WO2018070157A1 - 容器用キャップ及びその製造方法 - Google Patents
容器用キャップ及びその製造方法 Download PDFInfo
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- WO2018070157A1 WO2018070157A1 PCT/JP2017/032521 JP2017032521W WO2018070157A1 WO 2018070157 A1 WO2018070157 A1 WO 2018070157A1 JP 2017032521 W JP2017032521 W JP 2017032521W WO 2018070157 A1 WO2018070157 A1 WO 2018070157A1
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- WIPO (PCT)
- Prior art keywords
- polyamide
- cap
- acid
- container
- polyolefin
- Prior art date
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Images
Classifications
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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
- B65D41/00—Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
- B65D41/02—Caps or cap-like covers without lines of weakness, tearing strips, tags, or like opening or removal devices
- B65D41/04—Threaded or like caps or cap-like covers secured by rotation
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1634—Making multilayered or multicoloured articles with a non-uniform dispersion of the moulding material in the article, e.g. resulting in a marble effect
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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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/164—The moulding materials being injected simultaneously
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/27—Sprue channels ; Runner channels or runner nozzles
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/27—Sprue channels ; Runner channels or runner nozzles
- B29C45/2701—Details not specific to hot or cold runner channels
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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
- B65D41/00—Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
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- B29K2995/0065—Permeability to gases
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- B29L2031/565—Stoppers or lids for bottles, jars, or the like, e.g. closures for containers
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- C08L2203/10—Applications used for bottles
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- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
Definitions
- the present invention relates to a container cap, and more particularly to a container cap in which a metaxylylene group-containing polyamide is dispersed as a gas barrier resin in a polyolefin, and a method for producing the same.
- gas barrier properties are imparted. It is known that gas barrier properties are imparted to the container body by providing a layer made of a gas barrier material such as a gas barrier resin or an aluminum foil when the container is made of resin. It is also known to impart gas barrier properties by dispersing a gas barrier resin in a layered manner in polyolefin or the like which is a main component of a resin container. Further, when a high gas barrier property is required, a glass container may be used.
- Patent Document 1 discloses a container cap in which a metaxylylene group-containing polyamide is dispersed in a layer form as a gas barrier resin in a polyolefin that is a main component of a resin cap.
- the gas barrier resin when the gas barrier resin is dispersed in the resin cap in layers, the gas barrier resin is usually dispersed not only on the top surface of the cap but also on the side surface of the cap.
- Polyamide constituting the gas barrier resin in particular, a metaxylylene group-containing polyamide having a high gas barrier property, has high hardness and low adhesion to polyolefin. Therefore, when the cap is tightened to seal the container, the side surface of the cap may be cracked due to the metaxylylene group-containing polyamide, which is a gas barrier resin, being peeled off from the polyolefin, resulting in poor sealing.
- the present invention has been made in view of the above circumstances, and while improving the gas barrier property of the cap, it is possible to prevent the gas barrier resin from being peeled off from the polyolefin when the cap is tightened and causing cracks on the side surface of the cap. Let it be an issue.
- the inventors of the present invention formed a cap for a container with a resin composition containing a polyolefin, an acid-modified polyolefin, and a metaxylylene group-containing polyamide at a predetermined blending ratio, and formed the metaxylylene group-containing polyamide on the top of the cap. It was found that the above problem can be solved by reducing the polyamide content on the side surface of the cap, and the following invention was completed. That is, the present invention provides the following (1) to (11).
- a container cap comprising: The ratio (X / Y) of the polyamide-derived nitrogen% (X) at the cap top surface portion measured by total nitrogen analysis to the polyamide-derived nitrogen% (Y) at the cap side surface portion is 1.2 to 3.0. Cap for container.
- the metaxylylene group-containing polyamide (C) is composed of a diamine unit containing 70 mol% or more of a structural unit derived from metaxylylenediamine, an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and isophthalic acid.
- the said resin composition is a manufacturing method of the cap for containers as described in said (8) injected
- the resin temperature at the nozzle tip of the injection molding machine for performing the injection molding is in the range of ⁇ 5 ° C. to + 15 ° C. with respect to the melting point of the metaxylylene group-containing polyamide (C) measured by DSC.
- the present invention it is possible to improve the gas barrier property of the cap and to prevent the gas barrier resin from being peeled off from the polyolefin when the cap is tightened and cracking on the side surface of the cap.
- the container cap according to the present invention contains a polyolefin (A), an acid-modified polyolefin (B), and a metaxylylene group-containing polyamide (C) (hereinafter, sometimes simply referred to as “polyamide (C)”). It consists of a molded body formed from a resin composition.
- polyamide (C) metaxylylene group-containing polyamide
- the polyolefin (A) includes various types, and any polyolefin (A) can be used as long as it can be used for an injection molded article.
- Specific examples of the polyolefin (A) include polyethylene resins such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; polypropylene resins such as homopolypropylene, block polypropylene, and propylene-ethylene random copolymer. Is used.
- Block polypropylene can be obtained, for example, by polymerizing propylene and other olefins such as ethylene in multiple stages.
- the block polypropylene includes a propylene-ethylene block copolymer, and a polypropylene having a sea-island structure in which polyethylene is dispersed in homopolypropylene and an ethylene-propylene rubber (EPR) phase is present around the polyethylene.
- EPR ethylene-propylene rubber
- homopolymers of ⁇ -olefins having 4 to 20 carbon atoms such as 1-butene and 1-methylpentene
- copolymers of ⁇ -olefins having 3 to 20 carbon atoms examples thereof also include copolymers of ⁇ -olefins having 3 to 20 carbon atoms and cyclic olefins.
- the polyolefin (A) is an unmodified polyolefin, that is, a polyolefin that has not been modified with an acid.
- polyethylene resin and polypropylene resin are preferable, and polypropylene resin is more preferable from the viewpoint of moldability and flexibility of the blend composition.
- polypropylene resin although a homopolypropylene and a block polypropylene are preferable, a block polypropylene is more preferable from a viewpoint of preventing the crack of a cap side surface more effectively.
- melt flow rate As an index of the melt viscosity and molecular weight of polyolefin, a melt flow rate (MFR) is representative.
- the polyolefin (A) preferably has a melt flow rate (MFR) of 3 to 28 g / 10 min at a load of, for example, 190 ° C. and 21.18 N (2.16 kgf).
- MFR melt flow rate
- an appropriate fluidity is imparted to the polyolefin (A) at the time of molding a container cap, and the moldability of the container cap becomes good.
- the MFR of the polyolefin (A) is more preferably 5 to 26 g / 10 minutes, and further preferably 6 to 24 g / 10 minutes. MFR refers to a value measured in accordance with JIS K7210-1: 2014.
- the acid-modified polyolefin (B) has a role of bonding the polyolefin (A) and the polyamide (C) constituting the resin composition.
- the adhesive strength between the polyolefin (A) and the polyamide (C) can be improved.
- the acid-modified polyolefin (B) is preferably one obtained by graft-modifying polyolefin with an unsaturated carboxylic acid or an anhydride thereof. Such acid-modified polyolefins are generally widely used as compatibilizing agents and adhesives.
- the polyolefin used for the acid-modified polyolefin (B) those similar to those listed above for the polyolefin (A) are used, and preferably a polypropylene resin and a polyethylene resin are used.
- the acid-modified polyolefin (B) is preferably a modified polyolefin of the same type as the polyolefin (A) used.
- the acid-modified polyolefin (B) is preferably a modified polyethylene resin, and if the polyolefin (A) is a polypropylene resin, the acid-modified polyolefin (B) is also modified from the polypropylene resin. Those are preferred. Accordingly, the acid-modified polyolefin (B) is more preferably a modified polypropylene resin.
- the unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, chloromaleic acid, butenyl succinic acid, and These acid anhydrides are mentioned. Of these, maleic acid and maleic anhydride are preferably used.
- various conventionally known methods can be used as a method for obtaining an acid-modified polyolefin by graft copolymerization of an unsaturated carboxylic acid or an anhydride thereof to a polyolefin.
- a method in which a polyolefin is melted with an extruder and a graft monomer is added for copolymerization or a method in which a polyolefin is dissolved in a solvent and a graft monomer is added for copolymerization, after the polyolefin is made into an aqueous suspension
- a method in which a graft monomer is added and copolymerized include a method in which a graft monomer is added and copolymerized.
- the melt flow rate (MFR) of the acid-modified polyolefin (B) at a load of 190 ° C. and 21.18 N (2.16 kgf) is preferably in the range of 1 to 25 g / 10 minutes.
- MFR of the acid-modified polyolefin (B) is adjusted within such a range, an appropriate fluidity is imparted to the acid-modified polyolefin (B) at the time of molding, the moldability of the container cap is improved, and the polyamide (C ) Are easily dispersed in layers. Furthermore, it becomes easy to make polyamide (C) unevenly distributed in a top
- the MFR of the acid-modified polyolefin (B) is more preferably 2 to 23 g / 10 minutes, and further preferably 4 to 20 g / 10 minutes.
- An acid value is mentioned as an index of the modification rate of the acid-modified polyolefin (B).
- the acid value of the acid-modified polyolefin (B) is measured according to the method described in JIS K0070: 1992.
- the acid value of the acid-modified polyolefin (B) is preferably higher than 15 mgKOH / g and not higher than 30 mgKOH / g. When the acid value is higher than 15 mgKOH / g, a large amount of the acid-modified polyolefin (B) is bonded to the terminal amino group of the polyamide (C) during cap molding.
- the fluidity of the polyamide (C) is suppressed at the time of molding, and the polyamide (C) is unevenly distributed on the cap top surface portion, and the ratio of the polyamide in the cap top surface portion is easily increased. Moreover, it becomes easy to disperse
- the acid value is 30 mgKOH / g or less, the fluidity of the polyolefin (A) and the polyamide (C) is moderated, and unevenness or unevenness of thickness on the cap surface is prevented.
- the acid value of the acid-modified polyolefin (B) is more preferably from 17 to 25 mgKOH / g, and even more preferably from 18 to 25, from the viewpoint of appropriate fluidity and facilitating the uneven distribution of the polyamide (C) on the top surface of the cap. 22 mg KOH / g.
- the metaxylylene group-containing polyamide (C) has a gas barrier property by having a metaxylylene group.
- the metaxylylene group-containing polyamide (C) functions as a gas barrier resin, and can reduce gas permeability such as oxygen permeability of the container cap.
- the metaxylylene group-containing polyamide (C) includes a diamine unit and a dicarboxylic acid unit, and the diamine unit has a structural unit derived from metaxylylenediamine (metaxylylenediamine unit).
- the diamine unit in the polyamide (C) may have a diamine unit other than the metaxylylenediamine unit.
- Compounds that can constitute diamine units other than metaxylylenediamine units include aromatic diamines such as paraxylylenediamine and orthoxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis.
- Diamines having an alicyclic structure such as (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, nonane
- Examples include, but are not limited to, aliphatic diamines such as methylene diamine, 2-methyl-1,5-pentane diamine, polyoxyalkylene diamine, and polyether diamine. Moreover, you may use these individually or in combination of 2 or more types.
- the dicarboxylic acid unit in the polyamide (C) is an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (hereinafter simply referred to as “ ⁇ , ⁇ -dicarboxylic acid”) from the viewpoint of imparting appropriate crystallinity and flexibility. It is preferable to have a structural unit ( ⁇ , ⁇ -dicarboxylic acid unit) derived from an “acid”.
- Examples of ⁇ , ⁇ -dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12- Although dodecanedicarboxylic acid etc. can be illustrated, it is not limited to these. These can be used alone or in combination of two or more.
- the ⁇ , ⁇ -dicarboxylic acid is preferably an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 6 to 14 carbon atoms from the viewpoint of crystallinity, gas barrier properties, flexibility, etc., and ⁇ , ⁇ having 6 to 10 carbon atoms.
- -Linear aliphatic dicarboxylic acids are more preferred.
- adipic acid and sebacic acid are more preferred, and adipic acid is particularly preferred from the viewpoint of excellent gas barrier properties.
- the dicarboxylic acid unit may have a dicarboxylic acid unit other than the ⁇ , ⁇ -dicarboxylic acid unit.
- dicarboxylic acid units other than ⁇ , ⁇ -dicarboxylic acid units include aliphatic dicarboxylic acids other than ⁇ , ⁇ -dicarboxylic acids such as methylmalonic acid, methylsuccinic acid, malic acid, and tartaric acid, and 1,3- Examples include cycloaliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, xylylene dicarboxylic acid, and naphthalenedicarboxylic acid.
- dicarboxylic acids other than ⁇ , ⁇ -dicarboxylic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and isophthalic acid is more preferable.
- dicarboxylic acids, particularly isophthalic acid polyamide (C) excellent in gas barrier performance can be easily obtained without inhibiting the polycondensation reaction during the production of polyamide (C).
- examples thereof include polyamides containing 70 mol% or more of derived structural units, and having a molar ratio of structural units derived from ⁇ , ⁇ -dicarboxylic acid and structural units derived from isophthalic acid of 30:70 to 100: 0.
- Polyamide (C) makes it easier to improve the gas barrier performance by making 70 mol% or more of the diamine unit a metaxylylenediamine unit.
- polyamide (C) of the more preferable example may have a structural unit (isophthalic acid unit) derived from isophthalic acid or may not have, but by having an isophthalic acid unit, It becomes easy to improve gas barrier performance.
- the molar ratio of the ⁇ , ⁇ -dicarboxylic acid unit to the isophthalic acid unit is more preferably 50:50 to 100: 0, still more preferably 70:30 to 100: 0, and 90:10 to Even more preferably, it is 99: 1.
- the diamine unit in the polyamide (C) preferably contains 70% by mole or more of metaxylylenediamine units, more preferably 80 to 100% by mole, and still more preferably 90 to 100% by mole. It is particularly preferable that it is composed of a metaxylylenediamine unit (that is, a metaxylylenediamine unit is 100 mol%). As described above, when the content of the metaxylylenediamine unit is increased, the gas barrier performance is more easily improved.
- the total amount of ⁇ , ⁇ -dicarboxylic acid unit and isophthalic acid unit is preferably 70 mol% or more as described above, but it is contained 80 to 100 mol%.
- the dicarboxylic acid unit is preferably composed of an ⁇ , ⁇ -dicarboxylic acid unit, an isophthalic acid unit or these two components (that is, the total amount is 100 mol%).
- the ⁇ , ⁇ -dicarboxylic acid unit means a structural unit derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms as described above, and preferably has 6 to 14 carbon atoms.
- ⁇ , ⁇ -linear aliphatic dicarboxylic acid unit more preferably an ⁇ , ⁇ -linear aliphatic dicarboxylic acid unit having 6 to 10 carbon atoms, particularly preferably an adipic acid unit.
- the ratio of the content of diamine units and dicarboxylic acid units is preferably substantially the same from the viewpoint of the polymerization reaction, and the content of dicarboxylic acid units is preferably the same. More preferably, it is ⁇ 2 mol% of the content of the diamine unit.
- the content of the diamine unit is higher than the content of the dicarboxylic acid unit. Further preferred.
- the polyamide (C) may be composed of a diamine unit and a dicarboxylic acid unit, but may contain a copolymer unit other than the diamine unit and the dicarboxylic acid unit as long as the effects of the present invention are not impaired.
- Monomers that can constitute such a copolymer unit include lactams such as ⁇ -caprolactam and laurolactam, alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, t-leucine, isoleucine, serine, threonine.
- the ratio of copolymer units other than diamine units and dicarboxylic acid units is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less.
- a monofunctional compound may be reacted with the terminal amino group or terminal carboxyl group of polyamide (C).
- Such monofunctional compound may be any compound having reactivity with the terminal amino group or terminal carboxyl group of polyamide (C).
- monocarboxylic acid examples include monocarboxylic acids such as caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, and naphthalenecarboxylic acid.
- acid anhydrides such as monoamine and phthalic anhydride, monoisocyanate, monoacid halogen compound, monoester compound, monoalcohol compound and the like may be used.
- the relative viscosity of the polyamide (C) used in the present invention is preferably 1.5 to 4.2.
- the relative viscosity is preferably 1.5 to 4.2.
- the relative viscosity is more preferably 2.0 to 3.5, still more preferably 2.4 to 3.0.
- Polyamide (C) has a melting point of usually 200 to 255 ° C., preferably 210 to 250 ° C., more preferably 220 to 245 ° C. By setting the melting point of the polyamide (C) within these ranges, the melting point of the polyamide (C) can be made sufficiently higher than, for example, the melting points of the polyolefin (A) and the acid-modified polyolefin (B).
- the container cap is injection-molded, the components (A) and (B) are melted and mixed in a sufficiently fluidized state, while at least a part of the polyamide (C) is not melted. Can be injected into the cavity.
- the polyamide (C) is likely to be unevenly distributed on the top surface of the cap, and easily dispersed in a layered manner. Moreover, it can prevent making molding temperature higher than necessary by making melting
- fusing point is melting
- the terminal amino group concentration of the polyamide (C) is preferably 10 to 100 ⁇ eq / g.
- the terminal amino group concentration of the polyamide (C) is preferably 10 to 100 ⁇ eq / g.
- the terminal amino group concentration of the polyamide (C) is more preferably 12 to 50 ⁇ eq / g, and still more preferably 14 to 30 ⁇ eq / g.
- the method for adjusting the terminal amino group concentration of the polyamide (C) is not particularly limited. For example, when the polyamide (C) is produced by polycondensation, the amounts of diamine and dicarboxylic acid charged may be adjusted. Or you may adjust by making the above-mentioned monofunctional compound react with the terminal amino group etc. of polyamide (C). However, it is preferable to adjust the terminal amino group concentration by adjusting the amount of diamine and dicarboxylic acid charged.
- Polyamide (C) is obtained by polycondensation of the above diamine and dicarboxylic acid.
- the polymerization method include a melt polycondensation method.
- a nylon salt composed of a diamine and a dicarboxylic acid is heated under pressure in the presence of water, and the polymerization is performed in a molten state while removing added water and condensed water.
- diamine is continuously added to the dicarboxylic acid, while the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide.
- the polycondensation proceeds.
- a phosphorus atom-containing compound may be added in order to obtain an effect of promoting an amidation reaction and an effect of preventing coloration during polycondensation.
- Phosphorus atom-containing compounds include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, calcium hypophosphite, ethyl hypophosphite, phenyl Phosphonous acid, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate , Diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate
- metal hypophosphite metal salts such as sodium hypophosphite, potassium hypophosphite, lithium hypophosphite and the like are particularly preferable because they are highly effective in promoting amidation reaction and excellent in anti-coloring effect.
- sodium hypophosphite is particularly preferred
- the phosphorus atom-containing compounds that can be used in the present invention are not limited to these compounds.
- the amount of the phosphorus atom-containing compound added to the polycondensation system of the polyamide (C) is preferably in terms of the phosphorus atom concentration in the polyamide (C) from the viewpoint of preventing the polyamide (C) from being colored during the polycondensation. It is 1 to 500 ppm, more preferably 5 to 450 ppm, still more preferably 10 to 400 ppm.
- an alkali metal compound or an alkaline earth metal compound in combination with a phosphorus atom-containing compound.
- a sufficient amount of the phosphorus atom-containing compound needs to be present, but in order to adjust the amidation reaction rate, an alkali metal compound or an alkaline earth metal compound is required. Preferably coexist.
- hydroxides of alkali metals / alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and lithium acetate
- sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, barium acetate, and other alkali metal / alkaline earth metal acetates, etc. are not limited to these compounds.
- a value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus atom-containing compound is preferably 0.5 to 2. 0.0, more preferably 0.6 to 1.8.
- the addition amount of the alkali metal compound or alkaline earth metal compound in the above range it is possible to suppress gel formation while obtaining the amidation reaction promoting effect by the phosphorus atom-containing compound.
- the above-described monofunctional compound may be added in order to adjust the molecular weight of the polyamide (C), the terminal amino group concentration, and the like.
- the polyamide (C) obtained by melt polycondensation is preferably taken out from a reaction system such as a reaction can and pelletized.
- the polyamide (C) obtained by melt polycondensation preferably the pelletized polyamide (C)
- a heating device used in drying or solid-phase polymerization a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum type heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer
- a conical heating apparatus provided with can be used suitably, a well-known method and apparatus can be used without being limited to these.
- a rotating drum type heating device among the above-mentioned devices is preferable because the inside of the system can be sealed and the polycondensation can easily proceed in a state where oxygen that causes coloring is removed. Used.
- the blending ratio of each material in the resin composition is 70 to 94% by mass of polyolefin (A), 3 to 15% by mass of acid-modified polyolefin (B), and 3 to 3% of polyamide (C) with respect to the total amount of the resin composition. 15% by mass.
- the polyolefin (A) is preferably 72 to 90% by mass
- the acid-modified polyolefin (B) is 5 to 14% by mass
- the polyamide (C) is 5 to 14% by mass with respect to the total amount of the resin composition.
- the polyolefin (A) is 74 to 88% by mass
- the acid-modified polyolefin (B) is 6 to 13% by mass
- the polyamide (C) is 6 to 13% by mass.
- the total of the three components (A) to (C) does not exceed 100% by mass.
- the total of the three components (A) to (C) with respect to the total amount of the resin composition is 76% by mass or more, preferably 76 to 100% by mass, more preferably 82 to 100% by mass, and still more preferably 86 to 100% by mass. More preferably, it is 90 to 100% by mass, still more preferably 95 to 100% by mass, and particularly preferably 100% by mass (that is, the resin composition consists of only three components (A) to (C)).
- the ratio (X / Y) can be easily set within a predetermined range as will be described later, and the gas barrier property of the cap is efficiently increased. Can do. Further, the ratio of the polyamide (C) in the side surface portion of the cap does not become higher than necessary, and the cap side surface portion is prevented from cracking when the cap is attached to the container and tightened.
- polyolefin (A), acid-modified polyolefin (B), and metaxylylene group-containing polyamide (C) various materials are blended in the resin composition as long as the effects of the present invention are not impaired. Can do.
- polyamides other than metaxylylene group-containing polyamide (C) such as nylon 6, nylon 66, nylon 666, nylon 610, nylon 11 and nylon 12; ionomers; ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, etc.
- polystyrene various polyesters such as polyethylene terephthalate; styrene-butadiene copolymers and hydrogenated products thereof; various thermoplastic elastomers may be added.
- antioxidants matting agents, heat stabilizers, weathering stabilizers, UV absorbers, nucleating agents, plasticizers, flame retardants, antistatic agents, anti-coloring agents, lubricants, anti-gelling agents, layered silicates
- Additives such as clay and nanofillers may be added. Each of these additives may be added to the molding machine in a state of being premixed with one or more of the components (A), (B), and (C).
- FIG. 1 is a cross-sectional view showing a container cap.
- the container cap 10 is a lid for closing the mouth portion of the container, and is suspended from the cap top surface portion 11 disposed above the mouth portion and the periphery of the cap top surface portion 11 so as to surround the outer periphery of the mouth portion.
- a cap side surface portion 12 disposed on the surface.
- the cap 10 for containers closes the mouth part of a container by screwing on the outer peripheral surface of the mouth part of the container provided with the external screw. Therefore, a female screw 13 that can be screwed with a male screw at the mouth of the container is formed on the inner peripheral surface of the cap side surface portion 12.
- the container cap 10 (that is, the cap top surface portion 11 and the cap side surface portion 12) is a molded body formed from the above resin composition.
- the molded body is preferably an injection molded body molded by injection molding described later, and the cap top surface portion 11 and the cap side surface portion 12 are integrally molded by injection molding.
- the polyamide (C) is not uniformly mixed with the polyolefin (A) and the acid-modified polyolefin (B) in the molded body, and is preferably dispersed in a granular or layered form so as to have a certain size. Are dispersed in layers. When the polyamide (C) is dispersed in layers, the gas barrier property of the container cap can be improved.
- the polyamide (C) may be dispersed in the cap top surface portion 11 in layers.
- the polyamide (C) dispersed in layers may partially form a continuous phase.
- the polyamide (C) dispersed in a layer may be in a dispersed state in which it exists alternately with the polyolefin (A) in the thickness direction.
- the polyamide (C) dispersed in layers usually spreads in layers or planes along the surface direction on the top surface of the cap.
- a seal portion 14 is provided on the inner surface of the cap top surface portion 11.
- the seal part 14 seals the container by being in close contact with the mouth of the container.
- the seal part 14 shows the example comprised by a cyclic
- the sheet-like member provided in the inner surface of the cap top surface part 11 may be sufficient, and it has another structure. May be.
- the seal portion 14 may be formed integrally with the cap top surface portion 11, but may be formed by a member different from the cap top surface portion 11.
- the seal portion 14 is molded by injection molding, which will be described later, together with the cap top surface portion 11 and the cap side surface portion 12 as a part of the molded body (that is, the cap top surface portion 11).
- the seal portion when the seal portion is formed as a separate member, it may be attached to the inner surface of the cap top surface portion of a molded body formed by injection molding, which will be described later, by adhesion, pressure bonding, fusion bonding, fitting, or the like.
- the ratio (X / Y) of the polyamide-derived nitrogen% (X) in the cap top surface portion 11 to the polyamide-derived nitrogen% (Y) in the cap side surface portion 12 is 1.2-3. .0.
- Nitrogen% (X) and (Y) serve as indexes indicating the ratio of polyamide in the cap top surface portion 11 and the cap side surface portion 12, respectively.
- the ratio (X / Y) is less than 1.2, the polyamide (C) is not sufficiently unevenly distributed on the cap top surface portion 11, and a large amount of polyamide (C) is present on the cap side surface portion 12.
- the polyamide (C) present on the side surface of the cap is peeled off from the polyolefin (A), and the cap is likely to crack.
- Such a crack on the side surface of the cap is likely to occur when the polyamide (C) is dispersed in a layered manner.
- the cap top surface portion 11 faces the space in the container closed by the container cap 10, but the cap side surface portion 12 is disposed on the outer peripheral side of the mouth portion of the container. Virtually not facing. Therefore, in order to improve the gas barrier property of the container closed by the container cap 10, it is better to increase the gas barrier property of the cap top surface portion 11.
- the ratio (X / Y) is less than 1.2, it is difficult to secure the gas barrier property of the cap top surface portion 11 and it is difficult to improve the gas barrier property of the container closed by the cap 10.
- the ratio (X / Y) is to be made larger than 3.0, it is difficult to manufacture the cap 10 by a manufacturing method described later.
- the ratio (X / Y) is preferably 1.4 to 2.8, more preferably 2.0 to 2.5, from the viewpoint of preventing cracking of the side surface of the cap, improving the gas barrier property of the top surface, and ease of manufacture. preferable.
- the nitrogen% (X) and (Y) derived from polyamide measured the nitrogen content of the cap top surface portion and the cap side surface portion by total nitrogen analysis, and determined the cap ceiling from the values. This is a calculation of the% nitrogen (mass%) derived from polyamide in each of the face part and the cap side part.
- ratio (X / Y) is calculated
- the resin composition may contain a compound having a nitrogen atom in addition to the polyamide (C).
- compounds having nitrogen atoms other than polyamide (C) are identified and quantified, and the amount of nitrogen derived from the compound is calculated. Then, the nitrogen amount is subtracted from the nitrogen amount obtained by the total nitrogen analysis, and the nitrogen% derived from the polyamide may be calculated.
- “polyamide” in nitrogen% (X) and (Y) derived from polyamide means that if a polyamide other than metaxylylene group-containing polyamide (C) is contained in the resin composition, nitrogen% derived from such polyamide. It is a value including.
- the diameter of the container cap (that is, a molded body formed from the resin composition) is preferably 10 to 200 mm, more preferably 20 to 100 mm. Further, the thickness (thickness of the cap top surface portion and the cap side surface portion of the molded body) is preferably 0.1 to 5 mm, and more preferably 0.5 to 2 mm.
- the polyamide (C) can be easily unevenly distributed on the top surface of the cap.
- the container cap may be used for a container formed of any material such as a resin container or a glass container, but is preferably used for a container having a high mouth hardness. Specifically, it is preferably used for a container having a mouth made of glass, such as a glass container. If the mouth has a high hardness, such as a glass mouth, the mouth hardly deforms when the container cap is attached to the mouth and tightened. Therefore, when the cap is tightened, a high stress acts on the side surface portion of the cap, and the above-described cracking is likely to occur. However, the container cap of the present invention has a low polyamide content in the side surface portion of the cap. Even when the hardness of the cap is high, cracking of the side surface portion of the cap hardly occurs.
- the manufacturing method according to an embodiment of the present invention is a method for obtaining a molded body constituting a container cap by injection molding the resin composition containing the components (A), (B) and (C) described above. is there.
- An example of the injection molding machine used for the injection molding of this manufacturing method is shown in FIG. As shown in FIG. 2, the injection molding machine 20 is connected to the heating cylinder 21, the nozzle 22 provided at the tip of the heating cylinder 21, the hopper 23 attached to the heating cylinder 21, and the tip of the nozzle 22.
- a mold 30 is provided.
- the heating cylinder 21 is not particularly limited as long as it has a structure that can be generally used in the injection molding machine 20.
- the heating cylinder 21 has a heater (not shown) for heating the inside of the cylinder and a screw 26 inside. Is used.
- the nozzle 22 is usually heated by a heater so that the resin composition passing through the nozzle 22 is maintained at a predetermined temperature.
- the temperature of the heater of the cylinder 21 and the nozzle 22 is set to 200 to 300 ° C., preferably 210 to 270 ° C., for example. By setting these temperature ranges, it becomes easy to adjust the resin temperature at the tip of the nozzle 22 to a temperature range described later.
- the mold 30 has a cavity 33 formed therein, and has a sprue 31 connected to the nozzle 22 and a runner 34 connected to the sprue 31.
- the runner 34 is connected to the cavity 33 via a pinpoint gate 35.
- One pinpoint gate 35 is connected to the cavity 33. That is, the pinpoint gate 35 is called a one-point gate. Normally, the mold 30 is not heated, and the runner 34 is a cold runner.
- the mold 30 is a three-sheet mold including a fixed mold 30A, an intermediate mold 30B, and a movable mold 30C, for example.
- a cavity 33 is formed between the movable mold 30C and the intermediate mold 30B.
- a sprue 31 is provided in the fixed mold 30A
- a runner 34 is provided in the intermediate mold 30B.
- the three molds 30A, 30B, and 30C are separated and pushed out by a sleeve ejecting mechanism including an ejector pin 36 provided inside the movable mold 30C to take out the molded product. It is.
- a screw portion can be rotated by a motor and can be ejected by using a sleeve projecting mechanism together.
- the mold 30 is not limited to the three-sheet mold and may be another type of mold. In FIG. 2, only one cavity 33 is provided in the mold 30, but a plurality of cavities 33 may be provided. In that case, a plurality of runners 34 are connected to the sprue 31, and each runner 34 is connected to the cavity 33 via the pinpoint gate 35.
- the cavity 33 includes a top surface hollow portion 33A for molding the cap top surface portion and the cap side surface portion, and a side surface hollow portion 33B, and the pinpoint gate 35 is connected to the top surface hollow portion 33A. Therefore, the resin composition is injected into the cavity 33 from the top surface of the cap by a one-point gate.
- the pinpoint gate 35 may be provided at a position corresponding to the center of the cap top surface portion, but may be provided at a position other than the position corresponding to the center.
- the gate diameter of the pinpoint gate 35 (one-point gate) is preferably 0.5 to 1.2 mm, and more preferably 0.6 to 1.0 mm.
- the gate diameter is 1.2 mm or less, the polyamide (C) is less likely to flow into the side hollow portion 33B as will be described later, and the ratio (X / Y) is easily within the above range. Moreover, when the gate diameter is 0.5 mm or more, it is difficult for each component constituting the resin composition, in particular, polyamide (C), to fail to pass through the pinpoint gate 35.
- the components constituting the resin composition such as the components (A), (B) and (C) are charged from the hopper 23 and heated in the heating cylinder 21 (A), The components (B) and (C) are mixed while being plasticized, and at least a part thereof is melted as necessary. Then, the resin composition is injected into the cavity 33 through the nozzle 22, the sprue 31, the runner 34, and the pinpoint gate 35. The resin composition injected into the cavity 33 is cooled and solidified to form an injection molded body. The injection molded body is taken out from the mold 30 as described above.
- the behavior of the components (A), (B), and (C) in the injection molding machine 20 is, for example, as follows.
- the components (A), (B), and (C) are softened and plasticized by the heat received from the heater in the cylinder 21.
- the polyolefin (A) and the acid-modified polyolefin (B) are sufficiently melted or fluidized and mixed in the cylinder 21.
- the polyamide (C) is stretched in layers by, for example, shear stress due to the screw 26 inside the cylinder 21, but since the melting point is high, it does not reach a state of being melted and uniformly mixed in the component (A).
- the liquid is injected into the cavity 33 while maintaining a certain size, preferably in a layered state. Therefore, the polyamide (C) is dispersed in a granular or layered form so as to have a certain size, and preferably in a state of being dispersed in a layered form.
- the temperature of the heating cylinder 21 may be adjusted so that the resin temperature at the tip of the nozzle 22 falls within a temperature range of ⁇ 5 ° C. to + 15 ° C. with respect to the melting point of the polyamide (C). Further, this temperature range is preferably ⁇ 5 ° C. to + 10 ° C., more preferably ⁇ 5 ° C. to + 5 ° C., in order to disperse the polyamide (C) in a layered state more appropriately in the molded body.
- the resin temperature at the tip of the nozzle 22 may be confirmed by measuring the actual temperature with a thermocouple attached to the tip of the nozzle 22.
- the actual temperature can be estimated from the heater temperature of the heating cylinder 21 or the like without being measured, it may be obtained by estimation.
- the acid value of the acid-modified polyolefin (B), the terminal amino group concentration of the polyamide (C), etc. are within a certain range, and a certain amount or more of the polyamide (C) is bonded to the acid-modified polyolefin (B).
- the fluidity of polyamide (C) during molding can be kept low. Then, when the polyamide (C) having such a bonded state and not completely melted is passed through the pinpoint gate 35 having a predetermined diameter, the polyamide (C) is moderate in the pinpoint gate 35. It is considered that shear resistance acts, and as a result, it flows into the top surface hollow portion 33A, but tends not to flow into the side surface hollow portion 33B. Further, the polyamide (C) is easily injected into the cavity 33 while being dispersed in layers.
- the preferable range of the pin diameter of the pinpoint gate is as described above. However, in order to achieve the ratio (X / Y), not only the adjustment method shown above but also other adjustment methods can be adopted.
- Relative viscosity t / t 0 (2) (4) Melting point Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-60), the sample was melted from room temperature to 260 ° C at a heating rate of 10 ° C / min under a nitrogen stream. After that, the measurement sample was rapidly cooled using liquid nitrogen, and the temperature was increased again from room temperature to 260 ° C. at a rate of 10 ° C./min. Next, the melting peak apex temperature was read from the obtained chart to obtain the melting point.
- DSC-60 differential scanning calorimeter
- Terminal amino group concentration 0.3-0.5 g of polyamide was precisely weighed and dissolved in 30 mL of a phenol / ethanol mixed solution (mixing volume ratio 4: 1) with stirring at room temperature. After complete dissolution, the solution was neutralized and titrated with a 0.01 mol / L hydrochloric acid aqueous solution while stirring to obtain the terminal amino group concentration; ⁇ equivalent / g ([NH 2 ]).
- the nitrogen content of the top surface portion and the nitrogen content of the side surface portion were measured at a reference flow rate: 100 mL / min.
- the ratio (X / Y) was calculated using these nitrogen contents as% nitrogen (X) derived from polyamide and% nitrogen (Y) derived from polyamide.
- AD-1 manufactured by Mitsui Chemicals, Inc., trade name: Admer QE800, maleic anhydride-modified polypropylene, MFR: 9 g / 10 min, acid value: 20 mgKOH / g
- AD-2 manufactured by Mitsubishi Chemical Corporation, trade name: Modic P555, maleic anhydride-modified polypropylene, MFR: 7 g / 10 min, acid value: 7.7 mg KOH / g
- IPA isophthalic acid
- sodium acetate 5.68 g (0.07 mol) was sufficiently purged with nitrogen, the inside of the melt polymerization kettle was sealed, and the temperature was raised to 170 ° C. with stirring while keeping the inside of the melt polymerization kettle at 0.4 MPaG.
- melt polymerization kettle After completion of the dropwise addition of metaxylylenediamine, the inside of the melt polymerization kettle was gradually returned to normal pressure, and then the melt polymerization kettle was decompressed to 80 kPa using an aspirator to remove condensed water. Observe the stirring torque of the stirrer during decompression, stop the stirring when it reaches the predetermined torque, pressurize the inside of the melt polymerization kettle with nitrogen, open the bottom drain valve, pelletize it and pelletize isophthalic acid A melt polymerized product (relative viscosity 2.1) of polymerized polymetaxylylene adipamide was obtained. Next, this pellet was charged into a stainless steel drum-type heating device and rotated at 5 rpm.
- the atmosphere in the reaction system was raised from room temperature to 140 ° C. under a small nitrogen flow.
- the pressure was reduced to 1 torr or less, and the internal temperature was further increased to 190 ° C. in 130 minutes.
- the solid state polymerization reaction was continued for 60 minutes at the same temperature.
- the pressure reduction was terminated and the system temperature was lowered under a nitrogen stream.
- the pellet was taken out, and a high molecular weight isophthalic acid copolymer polymetaxylylene adipamide (PA-1) was obtained.
- the obtained polyamide (PA-1) had a relative viscosity of 2.8, a melting point of 229 ° C., an isophthalic acid copolymerization ratio of 6 mol%, and a terminal amino group concentration ([NH 2 ]) of 15 ⁇ eq / g.
- Production Example 2 (Production of polyamide (PA-2)) Instead of charging 12120 g of adipic acid and 880 g of isophthalic acid into the reaction vessel, the same procedure as in Production Example 1 was carried out except that 12893 g (88.23 mol) of adipic acid was charged, and polymetaxylylene adipamide (polyamide (PA-2)) Got.
- Polyamide (PA-2) had a relative viscosity of 2.7, a melting point of 238 ° C., and a terminal amino group concentration ([NH 2 ]) of 19 ⁇ eq / g.
- Example 1 An injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., trade name “NEX80”, screw: 36 mm ⁇ , mold clamping force: 80 tons), blending ratio shown in Table 1, polyolefin (A), acid-modified polyolefin (B) Then, the polyamide (C) obtained in Production Example 1 was introduced, and a container cap having a diameter of 40 mm and a thickness of 1.5 mm was produced by an injection molding method. The mold used in the injection molding machine was not heated and was installed at room temperature. The sprue was gradually expanded from 3.5 mm to 5 mm in diameter and 4 cm in length, 4 mm in diameter, and 5 cm in length.
- the resin composition was injected from At the time of injection molding, the cylinder of the injection molding machine is heated by four heaters in order from the upstream side, and the heater temperature of each heater and nozzle (C1 / C2 / C3 / C4 / nozzle) is set to 220/225/225 / The resin temperature at the nozzle tip was set to the temperature shown in Table 1 at 225/220 (° C.).
- Injection molding was performed under the conditions of a screw rotation speed of 100 rpm, a plasticizing time: 2.37 seconds, a back pressure: 5 MPa, V / P switching: 10 mm, a cushion amount: 6 mm, and a mold temperature: 25 ° C.
- the evaluation results of the obtained container cap are shown in Table 1.
- the container cap of Example 1 is cut, diluted iodine tincture is applied to the cross section to stain the metaxylylene group-containing polyamide portion, and a photograph taken by enlarging the cross section is shown in FIG.
- Example 2 A container cap was produced in the same manner as in Example 1 except that the type of polyolefin (A) was changed as shown in Table 1.
- Example 4 The type of polyamide (C) was changed as shown in Table 1, and the heater temperature (C1 / C2 / C3 / C4 / nozzle) of each heater and nozzle in the cylinder was 230/235/235/235/230 (° C.
- the container cap was manufactured in the same manner as in Example 1 except that the resin temperature at the nozzle tip was set to the temperature shown in Table 1.
- Comparative Example 1 A cap for a container was produced in the same manner as in Example 1 except that the type of the acid-modified polyolefin (B) was changed as shown in Table 1. Comparative Example 2 The heater temperature of each heater and nozzle in the cylinder (C1 / C2 / C3 / C4 / nozzle) is 240/245/245/245/240 (° C.), and the resin temperature at the nozzle tip is the temperature shown in Table 1.
- a container cap was produced in the same manner as in Example 1 except that.
- FIG. 4 shows a photograph taken by enlarging the cross section after cutting the container cap of Comparative Example 2, applying diluted iodine tincture to the cross section and dyeing the metaxylylene group-containing polyamide portion.
- Comparative Example 3 A container cap was produced in the same manner as in Example 1 except that the type of polyamide (C) was changed as shown in Table 1. Comparative Examples 4 and 5 The same procedure as in Example 1 was carried out except that the acid-modified polyolefin (B) and polyamide (C) were not used, and various polyolefins (A) shown in Table 1 were used as resins.
- the polyamide content in Table 1 was calculated by dividing the nitrogen content of the top and side surfaces by the nitrogen ratio in the polyamide (C).
- the nitrogen ratio in the polyamides (PA-1) and (PA-3) is 9.9% by mass, and the nitrogen ratio in the polyamide (PA-2) is 10.6% by mass.
- Example 1 to 4 the ratio (X / Y) was increased so that the polyamide (C) was unevenly distributed on the top surface of the cap, and the polyamide (C) was dispersed in layers. For this reason, the oxygen permeability was lowered, and the gas barrier property of the cap was improved. Moreover, the strength of the side surface portion of the cap became good, and when the cap was attached to the container and tightened, the polyamide (C) was prevented from being peeled off and the occurrence of cracking could be suppressed.
- Comparative Examples 1 and 3 since the ratio (X / Y) was low and the polyamide (C) was not unevenly distributed on the top surface portion of the cap, the strength of the side surface portion of the cap was low, and the cap was attached to the container and tightened. Occasionally, the polyamide (C) peeled easily.
- Comparative Example 2 since the resin temperature was high, the ratio (X / Y) was low, and the polyamide (C) was not dispersed in the layered dispersion but was dispersed in a granular manner. Therefore, the strength of the side surface portion of the cap was relatively good, but the oxygen permeability was high and the gas barrier property was insufficient. Similarly, in Comparative Examples 4 and 5, since polyamide (C) was not used, it was difficult for the cap side surface to crack, but the oxygen permeability of the cap was high and the gas barrier properties were insufficient.
Abstract
Description
(1)ポリオレフィン(A)70~94質量%、酸変性ポリオレフィン(B)3~15質量%、及びメタキシリレン基含有ポリアミド(C)3~15質量%を含有する樹脂組成物から形成される成形体からなる容器用キャップであって、
全窒素分析により測定されるキャップ天面部におけるポリアミド由来の窒素%(X)のキャップ側面部におけるポリアミド由来の窒素%(Y)に対する比(X/Y)が、1.2~3.0である容器用キャップ。
(2)メタキシリレン基含有ポリアミド(C)は、メタキシリレンジアミン由来の構成単位を70モル%以上含むジアミン単位と、炭素数4~20のα,ω-直鎖脂肪族ジカルボン酸及びイソフタル酸からなる群から選択されるジカルボン酸由来の構成単位を70モル%以上含み、かつ炭素数4~20のα,ω-直鎖脂肪族ジカルボン酸由来の構成単位とイソフタル酸由来の構成単位のモル比率が30:70~100:0であるジカルボン酸単位とを含む、上記(1)に記載の容器用キャップ。
(3)酸変性ポリオレフィン(B)の酸価が、15mgKOH/gより高く30mgKOH/g以下である上記(1)又は(2)に記載の容器用キャップ。
(4)メタキシリレン基含有ポリアミド(C)の末端アミノ基濃度が10~100μ当量/gである上記(1)~(3)のいずれか1項に記載の容器用キャップ。
(5)ポリオレフィン(A)が、ポリプロピレン樹脂である上記(1)~(4)のいずれか1項に記載の容器用キャップ。
(6)メタキシリレン基含有ポリアミド(C)が、キャップ天面部において層状に分散する上記(1)~(5)のいずれか1項に記載の容器用キャップ。
(7)前記成形体が、射出成形体である上記(1)~(6)のいずれか1項に記載の容器用キャップ。
(8)上記(1)~(7)のいずれか1項に記載の容器用キャップの製造方法であって、前記樹脂組成物を射出成形して前記成形体を得る容器用キャップの製造方法。
(9)前記樹脂組成物は、キャップ天面部側から1点ゲートにより射出される上記(8)に記載の容器用キャップの製造方法。
(10)前記1点ゲートのゲート径が、0.5~1.2mmである上記(9)に記載の容器用キャップの製造方法。
(11)前記射出成形を行う射出成形機のノズル先端における樹脂温度が、DSCにより測定されるメタキシリレン基含有ポリアミド(C)の融点に対して-5℃~+15℃の範囲にある上記(8)~(10)のいずれか1項に記載の容器用キャップの製造方法。
本発明に係る容器用キャップは、ポリオレフィン(A)、酸変性ポリオレフィン(B)、及びメタキシリレン基含有ポリアミド(C)(なお、以下では、単に「ポリアミド(C)」ということがある。)を含有する樹脂組成物から形成される成形体からなる。以下、これら(A)~(C)成分について詳細に説明する。
ポリオレフィン(A)は、種々のものが挙げられ、射出成形体に利用できるものであれば制限無く使用することができる。具体的なポリオレフィン(A)としては、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン等のポリエチレン樹脂;ホモポリプロピレン、ブロックポリプロピレン、プロピレン-エチレンランダム共重合体等のポリプロピレン樹脂が使用される。ブロックポリプロピレンは、例えば、プロピレンと、エチレン等の他のオレフィンとを多段で重合することにより得られる。また、ブロックポリプロピレンには、プロピレン-エチレンブロック共重合体や、ホモポリプロピレン中にポリエチレンが分散され、かつポリエチレンの周りにエチレンプロピレンゴム(EPR)相がある海島構造を有するもの等が含まれる。
また、上記したポリエチレン樹脂、ポリプロピレン樹脂以外にも、1-ブテン、1-メチルペンテン等の炭素数4~20のα-オレフィンの単独重合体、炭素数3~20のα-オレフィンの共重合体、炭素数3~20のα-オレフィンと環状オレフィンの共重合体等も例示される。なお、ポリオレフィン(A)は、未変性ポリオレフィンであり、すなわち、酸により変性されていないポリオレフィンである。
酸変性ポリオレフィン(B)は、樹脂組成物を構成するポリオレフィン(A)とポリアミド(C)とを接着する役割を有する。容器用キャップにおいて酸変性ポリオレフィン(B)を用いることで、ポリオレフィン(A)とポリアミド(C)との接着強度を向上させることができる。また、酸変性ポリオレフィン(B)を使用することでポリアミド(C)を層状に分散させやすくなり、ガスバリア性をより一層向上させやすくなる。さらには、天面部にポリアミド(C)を偏在させやすくなる。
不飽和カルボン酸又はその無水物をポリオレフィンにグラフト共重合して酸変性ポリオレフィンを得る方法としては、従来公知の種々の方法を用いることができる。例えば、ポリオレフィンを押出機等で溶融させ、グラフトモノマーを添加して共重合させる方法、あるいはポリオレフィンを溶媒に溶解させてグラフトモノマーを添加して共重合させる方法、ポリオレフィンを水懸濁液とした後グラフトモノマーを添加して共重合させる方法等を挙げることができる。
酸価が15mgKOH/gより高いと、キャップ成形時に、酸変性ポリオレフィン(B)がポリアミド(C)の末端アミノ基に多く結合する。そのため、成形時にポリアミド(C)の流動性が抑制されることになり、ポリアミド(C)がキャップ天面部に偏在し、キャップ天面部におけるポリアミドの割合を高めやすくなる。また、ポリアミド(C)が層状に分散しやすくなるとともに、ポリオレフィン(A)に対するポリアミド(C)の接着強度を向上させやすくなる。また、酸価が30mgKOH/g以下であると、ポリオレフィン(A)及びポリアミド(C)の流動性を適度なものにし、キャップ表面に凹凸が生じたり、厚みムラが生じたりすることを防止する。
流動性を適度なものとし、かつポリアミド(C)をキャップ天面により偏在しやすくする観点から、酸変性ポリオレフィン(B)の酸価は、より好ましくは17~25mgKOH/g、さらに好ましくは18~22mgKOH/gである。
メタキシリレン基含有ポリアミド(C)は、メタキシリレン基を有することでガスバリア性が良好となる。メタキシリレン基含有ポリアミド(C)は、ガスバリア性樹脂として機能するものであり、容器用キャップの酸素透過性などのガス透過性を低くすることが可能である。メタキシリレン基含有ポリアミド(C)は、ジアミン単位及びジカルボン酸単位を含み、かつジアミン単位がメタキシリレンジアミン由来の構成単位(メタキシリレンジアミン単位)を有する。
α,ω-ジカルボン酸としては、結晶性、ガスバリア性、柔軟性等の観点から、炭素数6~14のα,ω-直鎖脂肪族ジカルボン酸が好ましく、炭素数6~10のα,ω-直鎖脂肪族ジカルボン酸がより好ましい。また、中でもアジピン酸、セバシン酸がより好ましく、ガスバリア性を優れたものとする観点からアジピン酸が特に好ましい。
α,ω-ジカルボン酸以外のジカルボン酸としては、イソフタル酸、2,6-ナフタレンジカルボン酸が好ましく、イソフタル酸がより好ましい。これらのジカルボン酸、特にイソフタル酸を使用することで、ポリアミド(C)製造時における重縮合反応を阻害することなく、ガスバリア性能に優れるポリアミド(C)を容易に得ることができる。
ポリアミド(C)は、ジアミン単位の70モル%以上をメタキシリレンジアミン単位とすることで、ガスバリア性能をより高めやすくなる。また、ジカルボン酸単位として、上記のようにα,ω-ジカルボン酸単位を所定量以上含むことで、ガスバリア性能を低くすることなく、ポリアミド(C)の柔軟性、結晶性等を向上させやすくなる。また、上記のより好適な例のポリアミド(C)は、イソフタル酸由来の構成単位(イソフタル酸単位)を有してもよいし、有さなくてもよいが、イソフタル酸単位を有することで、ガスバリア性能を向上させやすくなる。
上記のα,ω-ジカルボン酸単位とイソフタル酸単位のモル比率は、50:50~100:0であることがより好ましく、70:30~100:0であることがさらに好ましく、90:10~99:1であることがよりさらに好ましい。
ポリアミド(C)において、ジアミン単位及びジカルボン酸単位以外の共重合体単位の比率は、好ましくは30モル%以下、より好ましくは20モル%以下、さらに好ましくは15モル%以下である。
なお、ここで言う相対粘度は、ポリアミド0.2gを96%硫酸20mLに溶解し、キャノンフェンスケ型粘度計にて25℃で測定した落下時間(t)と、同様に測定した96%硫酸そのものの落下時間(t0)の比であり、次式で示される。
相対粘度=t/t0
なお、融点は、示差走査熱量計(DSC)により測定される融点であり、詳細な測定条件は後述する実施例で記載されたとおりである。
これらの観点から、ポリアミド(C)の末端アミノ基濃度は、12~50μ当量/gであることがより好ましく、14~30μ当量/gであることがさらに好ましい。
ポリアミド(C)の末端アミノ基濃度を調整する方法は、特に限定されないが、例えば、重縮合によりポリアミド(C)を製造するとき、ジアミンとジカルボン酸の仕込み量を調整すればよい。あるいは、上記した単官能性の化合物を、ポリアミド(C)の末端アミノ基等と反応させることで調整してもよい。ただし、ジアミンとジカルボン酸の仕込み量を調整して末端アミノ基濃度を調整することが好ましい。
リン原子含有化合物としては、ジメチルホスフィン酸、フェニルメチルホスフィン酸、次亜リン酸、次亜リン酸ナトリウム、次亜リン酸カリウム、次亜リン酸リチウム、次亜リン酸カルシウム、次亜リン酸エチル、フェニル亜ホスホン酸、フェニル亜ホスホン酸ナトリウム、フェニル亜ホスホン酸カリウム、フェニル亜ホスホン酸リチウム、フェニル亜ホスホン酸エチル、フェニルホスホン酸、エチルホスホン酸、フェニルホスホン酸ナトリウム、フェニルホスホン酸カリウム、フェニルホスホン酸リチウム、フェニルホスホン酸ジエチル、エチルホスホン酸ナトリウム、エチルホスホン酸カリウム、亜リン酸、亜リン酸水素ナトリウム、亜リン酸ナトリウム、亜リン酸トリエチル、亜リン酸トリフェニル、ピロ亜リン酸等が挙げられる。これらの中でも特に次亜リン酸ナトリウム、次亜リン酸カリウム、次亜リン酸リチウム等の次亜リン酸金属塩がアミド化反応を促進する効果が高く、かつ着色防止効果にも優れるため好ましく用いられ、特に次亜リン酸ナトリウムが好ましいが、本発明で使用できるリン原子含有化合物はこれらの化合物に限定されない。
ポリアミド(C)の重縮合系内に添加するリン原子含有化合物の添加量は、重縮合中のポリアミド(C)の着色を防止する観点から、ポリアミド(C)中のリン原子濃度換算で好ましくは1~500ppm、より好ましくは5~450ppm、さらに好ましくは10~400ppmである。
例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム等のアルカリ金属/アルカリ土類金属の水酸化物や、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸ルビジウム、酢酸セシウム、酢酸マグネシウム、酢酸カルシウム、酢酸バリウム等のアルカリ金属/アルカリ土類金属の酢酸塩等が挙げられるが、これらの化合物に限定されることなく用いることができる。
ポリアミド(C)の重縮合系内にアルカリ金属化合物又はアルカリ土類金属化合物を添加する場合、該化合物のモル数をリン原子含有化合物のモル数で除した値が、好ましくは0.5~2.0、より好ましくは0.6~1.8である。アルカリ金属化合物又はアルカリ土類金属化合物の添加量を上述の範囲とすることでリン原子含有化合物によるアミド化反応促進効果を得つつゲルの生成を抑制することが可能となる。
さらに、重縮合系内には、ポリアミド(C)の分子量や、末端アミノ基濃度等を調整するために、上記した単官能性の化合物を添加してもよい。また、必要に応じて、ジアミン単位及びジカルボン酸単位以外の共重合体単位を構成し得るモノマーを適宜添加してもよい。
樹脂組成物における各材料の配合比率は、樹脂組成物全量に対して、ポリオレフィン(A)が70~94質量%、酸変性ポリオレフィン(B)が3~15質量%、ポリアミド(C)が3~15質量%である。また、樹脂組成物全量に対して、ポリオレフィン(A)が72~90質量%、酸変性ポリオレフィン(B)が5~14質量%、ポリアミド(C)が5~14質量%であることが好ましく、ポリオレフィン(A)が74~88質量%、酸変性ポリオレフィン(B)が6~13質量%、ポリアミド(C)が6~13質量%であることがより好ましい。ただし、(A)~(C)の3成分の合計が100質量%を超えることはない。樹脂組成物全量に対する(A)~(C)の3成分の合計は76質量%以上であり、好ましくは76~100質量%、より好ましくは82~100質量%、さらに好ましくは86~100質量%、よりさらに好ましくは90~100質量%、よりさらに好ましくは95~100質量%であり、特に好ましくは100質量%(すなわち、樹脂組成物が(A)~(C)の3成分のみからなる)である。
本発明においては、上述の範囲に各材料の配合比率を設定することによって、後述するように比(X/Y)を所定の範囲に設定しやすくなり、キャップのガスバリア性を効率的に高めることができる。また、キャップ側面部におけるポリアミド(C)の割合が必要以上に高くならず、キャップを容器に取り付け締め付けたときに、キャップ側面部に割れが生じたりすることを防止する。
樹脂組成物には、ポリオレフィン(A)、酸変性ポリオレフィン(B)、及びメタキシリレン基含有ポリアミド(C)の3成分の他に、本発明の効果を損なわない範囲で、様々な材料を配合することができる。例えば、ナイロン6、ナイロン66、ナイロン666、ナイロン610、ナイロン11、ナイロン12などのメタキシリレン基含有ポリアミド(C)以外のポリアミド;アイオノマー;エチレン-エチルアクリレート共重合体やエチレン-メチルアクリレート共重合体等の各種変性ポリエチレン;ポリスチレン;ポリエチレンテレフタレート等の各種ポリエステル;スチレン-ブタジエン共重合体やその水添化物;各種熱可塑性エラストマー等を加えてもよい。
また、酸化防止剤、艶消剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、核剤、可塑剤、難燃剤、帯電防止剤、着色防止剤、滑剤、ゲル化防止剤、層状ケイ酸塩等のクレイやナノフィラー等の添加剤を加えてもよい。これら各添加剤は、(A)、(B)及び(C)成分の1つ以上に予め混合された状態で成形機に投入してもよい。
図1は、容器用キャップを示す断面図である。以下、図1を用いて、容器用キャップ10の構造について図面を参照して詳細に説明する。容器用キャップ10は、容器の口部を閉じるための蓋体であって、口部上方に配置されるキャップ天面部11と、キャップ天面部11の周縁から垂下し、口部の外周を取り囲むように配置されるキャップ側面部12とを備える。容器用キャップ10は、雄螺子が設けられた容器の口部の外周面に螺着することで、容器の口部を閉じるものである。したがって、キャップ側面部12の内周面には、容器の口部の雄螺子と螺着可能な雌螺子13が形成されている。
層状に分散されるポリアミド(C)は、一部連続して連続相を形成してもよい。また、層状に分散したポリアミド(C)は、厚さ方向においてポリオレフィン(A)と交互に存在するような分散状態となっていてもよい。なお、層状に分散されたポリアミド(C)は、キャップ天面部においては、通常、その面方向に沿って層状ないし面状に広がるものである。
シール部14は、キャップ天面部11と一体的に成形されてもよいが、キャップ天面部11とは別部材により成形されてもよい。シール部14は、一体的に成形される場合には、キャップ天面部11とキャップ側面部12とともに、成形体(すなわち、キャップ天面部11)の一部として後述する射出成形等により成形される。一方で、シール部は、別部材として成形される場合、後述する射出成形等により成形された成形体のキャップ天面部の内面に、接着、圧着、融着、嵌合等により取り付ければよい。
なお、ポリアミド由来の窒素%(X),(Y)とは、後述する実施例に示すように、キャップ天面部及びキャップ側面部の窒素量を全窒素分析により測定して、その値からキャップ天面部及びキャップ側面部それぞれにおけるポリアミド由来の窒素%(質量%)を算出したものである。そして、比(X/Y)は、算出されたポリアミド由来の窒素%(X),(Y)から求められる。
また、ポリアミド由来の窒素%(X),(Y)における“ポリアミド”とは、メタキシリレン基含有ポリアミド(C)以外のポリアミドが樹脂組成物に含まれる場合には、そのようなポリアミド由来の窒素%も含めた値である。
以下、容器用キャップの製造方法の一実施形態について説明する。
本発明の一実施形態に係る製造方法は、上記した(A)、(B)及び(C)成分を含む樹脂組成物を、射出成形して、容器用キャップを構成する成形体を得るものである。
本製造方法の射出成形に使用する射出成形機の一例を図2に示す。図2に示すように、射出成形機20は、加熱シリンダー21と、加熱シリンダー21の先端に設けられたノズル22と、加熱シリンダー21に取り付けられたホッパー23と、ノズル22の先端に接続される金型30とを備える。
金型30は、内部にキャビティ33が形成されるとともに、ノズル22に接続されるスプルー31と、スプルー31に接続されるランナー34を有する。ランナー34は、ピンポイントゲート35を介してキャビティ33に接続される。キャビティ33に接続されるピンポイントゲート35は1つである。すなわち、ピンポイントゲート35は、1点ゲートと呼ばれるものである。なお、通常、金型30は加熱されておらず、ランナー34はコールドランナーである。
3枚型では、射出成形後に、3つの金型30A,30B,30Cが分離され、かつ可動金型30C内部に設けられるエジェクタピン36等から構成されるスリーブ突き出し機構により押し出されて成形体が取り出される。また、ネジ抜き装置としてモーターによりネジ部を回転させ、かつスリーブ突き出し機構を併用して突き出して取り出すこともできる。
ただし、金型30は、3枚型に限定されず他のタイプの金型であってもよい。また、図2には、金型30にキャビティ33が1つ設けられるのみであるが、複数のキャビティ33が設けられてもよい。その場合には、スプルー31に複数のランナー34が接続され、各ランナー34がピンポイントゲート35を介してキャビティ33に接続される。
ピンポイントゲート35(1点ゲート)のゲート径は、0.5~1.2mmであることが好ましく、0.6~1.0mmであることがより好ましい。ゲート径を1.2mm以下とすると、後述するようにポリアミド(C)が側面中空部33Bに流入しにくくなり、比(X/Y)を上記範囲内としやすくなる。また、ゲート径を0.5mm以上とすると、樹脂組成物を構成する各成分、特にポリアミド(C)がピンポイントゲート35を通過できなくなるなどの不具合が生じにくくなる。
なお、ノズル22の先端における樹脂温度は、ノズル22の先端に取り付けられた熱電対により、実温度を測定して確認すればよい。あるいは、実温度を測定せず、加熱シリンダー21のヒーター温度などから推定できる場合には推定により求めてもよい。
ポリアミド(C)を酸変性ポリオレフィン(B)に一定量結合させると、成形時のポリアミド(C)の流動性を低く抑えられる。そして、このような結合状態を有し、かつ完全に溶融しない状態のポリアミド(C)を所定の径を有するピンポイントゲート35を通過させると、ポリアミド(C)は、ピンポイントゲート35において適度なせん断抵抗が作用されると考えられ、結果として、天面中空部33Aには流入するが、側面中空部33Bには多く流入しない状態となりやすくなる。また、ポリアミド(C)は、層状分散したままキャビティ33内に射出されやすくなる。なお、ピンポイントゲートのゲート径の好ましい範囲は、上記したとおりである。
ただし、比(X/Y)を達成するためには、以上で示した調整方法に限らず、他の調整方法を採用することも可能である。
(1)ポリオレフィン(A)及び酸変性オレフィン(B)のMFR(g/10分)
(株)東洋精機製作所製メルトインデクサーを使用し、JIS K7210-1:2014に準拠して、190℃、2.16kgfの条件にて測定を行った。
(2)酸変性ポリオレフィン(B)の酸価(mgKOH/g)
JIS K0070:1992に準拠して、中和滴定により測定を行った。酸変性ポリオレフィン1gを精秤し、キシレン100mLに約120℃で撹拌溶解した。完全に溶解した後、フェノールフタレイン溶液を加え、予め正確な濃度を求めた0.1mol/L水酸化カリウムエタノール溶液を用いて中和滴定を行った。滴下量(T)、0.1mol/L水酸化カリウムエタノール溶液のファクター(f)、水酸化カリウムの式量56.11の1/10(5.611)、酸変性ポリオレフィンの質量(S)から以下の式(1)により酸価を算出した。
酸価=T×f×5.611/S ・・・(1)
ポリアミド(C)0.2gを精秤し、96%硫酸20mLに20~30℃で撹拌溶解した。完全に溶解した後、速やかにキャノンフェンスケ型粘度計に溶液5mLを取り、25℃の恒温層中で10分間放置後、落下時間(t)を測定した。また同様の条件で96%硫酸そのものの落下時間(t0)を測定した。t及びt0から以下の式(2)により相対粘度を算出した。
相対粘度=t/t0 ・・・(2)
(4)融点
示差走査熱量計((株)島津製作所製、商品名:DSC-60)を用い、窒素気流下にて、室温から260℃まで10℃/分の昇温速度で試料を融解させた後、液体窒素を用いて測定試料を急冷し、再度室温から260℃まで10℃/分の速度で昇温して測定を行った。次いで、得られたチャートから融解ピーク頂点の温度を読み取って融点とした。
(5)末端アミノ基濃度
ポリアミド0.3~0.5gを精秤し、フェノール/エタノール混合溶液(混合容積比4:1)30mLに室温で撹拌溶解した。完全に溶解した後、撹拌しつつ0.01モル/L塩酸水溶液で中和滴定して、末端アミノ基濃度;μ当量/g([NH2])を求めた。
得られたキャップより、天面部については、天面中心より天面半径の90%にあたる範囲を切り出し、側面部については、キャップの天面部の厚み部分を除いた、残り部分を側面部として切り出し、液体窒素を用いて凍結粉砕した。得られた粉砕品を、CHN元素分析計(サーモフィニガン製、商品名:EA1112)にて、燃焼炉温度:950℃、オーブン温度:65℃、キャリア流量:140mL/min、酸素流量:250mL/min、リファレンス流量:100mL/minにて、天面部の窒素含有率と側面部の窒素含有率を測定した。これら窒素含有率をポリアミド由来の窒素%(X)と、ポリアミド由来の窒素%(Y)として比(X/Y)を算出した。
CPP/アルミ箔/PET=50/9/12(μm)のフィルムからなる蓋体で、得られたキャップの開口部を覆いヒートシールした後、フィルム(蓋体)に穴を開けて、ガス導入管及びガス排出管を挿しこみ、挿しこみ部をエポキシ系接着剤で固めた。ガス導入管より窒素ガスを10mL/min流し、酸素透過率測定装置(Mocon社(米国)製、商品名:Ox-Tran2/61)を用いて温度23℃、内:0%RH、外:50%RHの条件でJIS K7126-2:2006に準じてキャップ一個当たりの酸素透過率(ml/キャップ・day・0.21atm)を求めた。
得られた容器用キャップをガラス製容器の口部に取り付け、締め付け力:10N、30Nでヘッドがパイプレンチタイプのトルクレンチ(東日製作所製、商品名:PHL50N)を用いて締め付けたときのキャップ側面部の状態を確認することでキャップ側面部の強度を以下の基準により評価した。
A:いずれの締め付け力で締め付けてもキャップ側面部に割れが生じない。
B:締め付け力10Nで締め付けてもキャップ側面部に割れが生じないが、30Nで締め付けるとポリアミド(C)の剥離等により割れが生じた。
C:いずれの締め付け力で締め付けても、ポリアミド(C)の剥離等により割れが生じた。
得られたキャップの天面部を切断し、断面をミクロトーム(REICHERT-JUNG LIMITED製、商品名:ULTRACUT E)を用いて平滑にした後、希ヨードチンキ(月島薬品(株)製)を断面に塗布してポリアミド部分を染色した。これをデジタル顕微鏡((株)キーエンス製、 デジタルマイクロスコープ VHX-1000)を用いてポリアミドの分散状態を観察し、以下の評価基準で評価した。
A:ポリアミドの殆どが層状に分散していた。
B:ポリアミドの一部が層状に分散しているものの、粒状に分散しているポリアミドが相当量見られた。
C:ポリアミドの殆ど全てが粒状に分散していた。
<ポリオレフィン(A)>
PO-1:住友化学(株)製、商品名:ノーブレン AW564、ブロックポリプロピレン、MFR:9g/10分
PO-2:日本ポリプロ(株)製、商品名:ノバテックPP MA3、ホモポリプロピレン、MFR:11g/10分
PO-3:日本ポリプロ(株)製、商品名:ノバテックPP MA1B、ホモポリプロピレン、MFR:21g/10分
AD-1:三井化学(株)製、商品名:アドマー QE800、無水マレイン酸変性ポリプロピレン、MFR:9g/10分、酸価:20mgKOH/g
AD-2:三菱化学(株)製、商品名:モディック P555、無水マレイン酸変性ポリプロピレン、MFR:7g/10分、酸価:7.7mgKOH/g
製造例1(ポリアミド(PA-1)の製造)
撹拌機、分縮器、全縮器、圧力調整器、温度計、滴下槽、ポンプ、アスピレーター、窒素導入管、底排弁、及びストランドダイを備えた内容積50Lの耐圧溶融重合釜に、精秤したアジピン酸(AA)12120g(82.94mol)、イソフタル酸(IPA)880g(5.29mol)、次亜リン酸ナトリウム10.96g(0.10mol)、及び酢酸ナトリウム5.68g(0.07mol)を入れ、十分に窒素置換した後、溶融重合釜内を密閉し、溶融重合釜内を0.4MPaGに保ちながら撹拌下170℃まで昇温した。
170℃に到達後、溶融重合釜内の溶融した原料に対し、滴下槽に貯めたメタキシリレンジアミン(MXDA)11962g(87.83mol)(ジアミン成分/ジカルボン酸成分の仕込みモル比(MXDA/(AA+IPA))=0.9955)の滴下を開始し、溶融重合釜内の圧力を0.4MPaGに保ち、生成する縮合水を系外へ除きながら、溶融重合釜内を連続的に260℃まで昇温した。
メタキシリレンジアミンの滴下終了後、溶融重合釜内を徐々に常圧に戻し、次いでアスピレーターを用いて溶融重合釜内を80kPaに減圧して縮合水を除いた。減圧中に撹拌機の撹拌トルクを観察し、所定のトルクに達した時点で撹拌を止め、溶融重合釜内を窒素で加圧し、底排弁を開け抜き出し、ペレット化してペレット状のイソフタル酸共重合ポリメタキシリレンアジパミドの溶融重合品(相対粘度2.1)を得た。
次にこのペレットをステンレス製の回転ドラム式の加熱装置に仕込み、5rpmで回転させた。十分窒素置換し、さらに少量の窒素気流下にて反応系内を室温から140℃まで昇温した。反応系内温度が140℃に達した時点で1torr以下まで減圧を行い、更に系内温度を130分間で190℃まで昇温した。系内温度が190℃に達した時点から、同温度にて60分間、固相重合反応を継続した。
反応終了後、減圧を終了し窒素気流下にて系内温度を下げ、60℃に達した時点でペレットを取り出し、高分子量化されたイソフタル酸共重合ポリメタキシリレンアジパミド(PA-1)を得た。
得られたポリアミド(PA-1)は、相対粘度2.8、融点229℃、イソフタル酸共重合比率6mol%、末端アミノ基濃度([NH2])15μ当量/gであった。
反応容器にアジピン酸12120g及びイソフタル酸880gを仕込む代わりに、アジピン酸12893g(88.23mol)を仕込んだこと以外は製造例1と同様にし、ポリメタキシリレンアジパミド(ポリアミド(PA-2))を得た。ポリアミド(PA-2)は、相対粘度2.7、融点238℃、末端アミノ基濃度([NH2])19μ当量/gであった。
各モノマーの仕込みがメタキシリレンジアミン:アジピン酸:イソフタル酸=87.39:82.94:5.29(mol)(ジアミン成分/ジカルボン酸成分の仕込みモル比(MXDA/(AA+IPA))=0.9905)となるようにし、さらに、固相重合反応時間を300分とした以外は製造例1と同様にして、イソフタル酸共重合比率6mol%のイソフタル酸共重合ポリメタキシリレンアジパミド(ポリアミド(PA-3))を得た。ポリアミド(PA-3)は、相対粘度2.5、融点229℃、末端アミノ基濃度([NH2])6μ当量/gであった。
射出成形機(日精樹脂工業(株)製、商品名「NEX80」、スクリュー:36mmφ、型締力:80トン)に、表1に示す配合比率で、ポリオレフィン(A)、酸変性ポリオレフィン(B)及び製造例1で得られたポリアミド(C)を投入して、射出成形法により直径40mm、厚さ1.5mmの容器用キャップを作製した。
また、射出成形機で使用した金型は、加熱されず室温下に設置されたものであり、直径3.5mmから5mmに漸次拡径されかつ長さが4cmのスプルー、直径4mm、長さ5cmのコールドランナー、ゲート径0.7mm、断面形状:丸、長さ1.5mmのピンポイントゲート(1点ゲート)を有する3枚型であり、図2に示すとおり、キャビティ内には天面部側から樹脂組成物を射出した。射出成形時、射出成形機のシリンダーは、上流側から順に4つのヒーターによって加熱されており、その各ヒーター及びノズルのヒーター温度(C1/C2/C3/C4/ノズル)を220/225/225/225/220(℃)とし、ノズル先端における樹脂温度を表1に示す温度になるようにした。また、射出成形は、スクリュー回転数100rpm、可塑化時間:2.37秒、背圧:5MPa、V/P切り替え:10mm、クッション量:6mm、金型温度:25℃の条件下で行った。得られた容器用キャップの評価結果を表1に示す。また、実施例1の容器用キャップを切断し、希ヨードチンキを断面に塗布してメタキシリレン基含有ポリアミド部分を染色した後、その断面を拡大して撮影した写真を図3に示す。
ポリオレフィン(A)の種類を表1に示したように変更したこと以外は実施例1と同様にして容器用キャップを製造した。
実施例4
ポリアミド(C)の種類を表1に示したように変更し、かつシリンダーにおける各ヒーター及びノズルのヒーター温度(C1/C2/C3/C4/ノズル)を230/235/235/235/230(℃)とし、ノズル先端における樹脂温度を表1に示す温度になるようにした以外は実施例1と同様にして容器用キャップを製造した。
酸変性ポリオレフィン(B)の種類を表1に示したように変更したこと以外は実施例1と同様にして容器用キャップを製造した。
比較例2
シリンダーにおける各ヒーター及びノズルのヒーター温度(C1/C2/C3/C4/ノズル)を240/245/245/245/240(℃)とし、ノズル先端における樹脂温度を表1に示す温度になるようにした以外は実施例1と同様にして容器用キャップを製造した。比較例2の容器用キャップを切断し、希ヨードチンキを断面に塗布してメタキシリレン基含有ポリアミド部分を染色した後、その断面を拡大して撮影した写真を図4に示す。
比較例3
ポリアミド(C)の種類を表1に示したように変更したこと以外は実施例1と同様にして容器用キャップを製造した。
比較例4、5
酸変性ポリオレフィン(B)、及びポリアミド(C)を使用せず、樹脂として表1に示す各種のポリオレフィン(A)を使用した点を除いて実施例1と同様に実施した。
それに対して、比較例1、3では、比(X/Y)が低く、ポリアミド(C)がキャップ天面部に偏在しなかったため、キャップ側面部の強度が低くなり、キャップを容器に取り付け締め付けたときに、ポリアミド(C)の剥離が生じやすくなった。また、比較例2では、樹脂温度が高いため、比(X/Y)が低く、かつポリアミド(C)が層状分散に留まらず粒状分散した。そのため、キャップ側面部の強度は比較的良好となったが、酸素透過率が高くなり、ガスバリア性が不十分であった。同様に、比較例4、5では、ポリアミド(C)を使用しなかったため、キャップ側面部に割れが生じにくかったが、キャップの酸素透過率が高くなりガスバリア性が不十分であった。
11 キャップ天面部
12 キャップ側面部
20 射出成形機
22 ノズル
30 金型
31 スプルー
33 キャビティ
34 ランナー
35 ピンポイントゲート
Claims (11)
- ポリオレフィン(A)70~94質量%、酸変性ポリオレフィン(B)3~15質量%、及びメタキシリレン基含有ポリアミド(C)3~15質量%を含有する樹脂組成物から形成される成形体からなる容器用キャップであって、
全窒素分析により測定されるキャップ天面部におけるポリアミド由来の窒素%(X)のキャップ側面部におけるポリアミド由来の窒素%(Y)に対する比(X/Y)が、1.2~3.0である容器用キャップ。 - メタキシリレン基含有ポリアミド(C)は、メタキシリレンジアミン由来の構成単位を70モル%以上含むジアミン単位と、炭素数4~20のα,ω-直鎖脂肪族ジカルボン酸及びイソフタル酸からなる群から選択されるジカルボン酸由来の構成単位を70モル%以上含み、かつ炭素数4~20のα,ω-直鎖脂肪族ジカルボン酸由来の構成単位とイソフタル酸由来の構成単位のモル比率が30:70~100:0であるジカルボン酸単位とを含む、請求項1に記載の容器用キャップ。
- 酸変性ポリオレフィン(B)の酸価が、15mgKOH/gより高く30mgKOH/g以下である請求項1又は2に記載の容器用キャップ。
- メタキシリレン基含有ポリアミド(C)の末端アミノ基濃度が10~100μ当量/gである請求項1~3のいずれか1項に記載の容器用キャップ。
- ポリオレフィン(A)が、ポリプロピレン樹脂である請求項1~4のいずれか1項に記載の容器用キャップ。
- メタキシリレン基含有ポリアミド(C)が、キャップ天面部において層状に分散する請求項1~5のいずれか1項に記載の容器用キャップ。
- 前記成形体が、射出成形体である請求項1~6のいずれか1項に記載の容器用キャップ。
- 請求項1~7のいずれか1項に記載の容器用キャップの製造方法であって、前記樹脂組成物を射出成形して前記成形体を得る容器用キャップの製造方法。
- 前記樹脂組成物は、キャップ天面部側から1点ゲートにより射出される請求項8に記載の容器用キャップの製造方法。
- 前記1点ゲートのゲート径が、0.5~1.2mmである請求項9に記載の容器用キャップの製造方法。
- 前記射出成形を行う射出成形機のノズル先端における樹脂温度が、DSCにより測定されるメタキシリレン基含有ポリアミド(C)の融点に対して-5℃~+15℃の範囲にある請求項8~10のいずれか1項に記載の容器用キャップの製造方法。
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- 2017-09-08 KR KR1020197010187A patent/KR102398805B1/ko active IP Right Grant
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KR20190069419A (ko) | 2019-06-19 |
JP6344536B1 (ja) | 2018-06-20 |
TWI745429B (zh) | 2021-11-11 |
CN109803901B (zh) | 2020-06-19 |
EP3527503A4 (en) | 2019-09-18 |
JPWO2018070157A1 (ja) | 2018-10-11 |
US10543961B2 (en) | 2020-01-28 |
EP3527503A1 (en) | 2019-08-21 |
KR102398805B1 (ko) | 2022-05-17 |
US20190256256A1 (en) | 2019-08-22 |
TW201821513A (zh) | 2018-06-16 |
EP3527503B1 (en) | 2021-08-18 |
CN109803901A (zh) | 2019-05-24 |
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