WO2019159528A1 - 酸素遮断性を有する容器蓋 - Google Patents
酸素遮断性を有する容器蓋 Download PDFInfo
- Publication number
- WO2019159528A1 WO2019159528A1 PCT/JP2018/046927 JP2018046927W WO2019159528A1 WO 2019159528 A1 WO2019159528 A1 WO 2019159528A1 JP 2018046927 W JP2018046927 W JP 2018046927W WO 2019159528 A1 WO2019159528 A1 WO 2019159528A1
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- WIPO (PCT)
- Prior art keywords
- molded body
- shell
- container lid
- top plate
- primary molded
- Prior art date
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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
- 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
- B65D51/00—Closures not otherwise provided for
- B65D51/24—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes
- B65D51/244—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes provided with oxygen absorbers
-
- 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
- B65D41/0407—Threaded or like caps or cap-like covers secured by rotation with integral sealing means
- B65D41/0414—Threaded or like caps or cap-like covers secured by rotation with integral sealing means formed by a plug, collar, flange, rib or the like contacting the internal surface of a container neck
- B65D41/0421—Threaded or like caps or cap-like covers secured by rotation with integral sealing means formed by a plug, collar, flange, rib or the like contacting the internal surface of a container neck and combined with integral sealing means contacting other surfaces of a container neck
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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
- B65D41/32—Caps or cap-like covers with lines of weakness, tearing-strips, tags, or like opening or removal devices, e.g. to facilitate formation of pouring openings
- B65D41/325—Caps or cap-like covers with lines of weakness, tearing-strips, tags, or like opening or removal devices, e.g. to facilitate formation of pouring openings with integral internal sealing means
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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
- B65D41/32—Caps or cap-like covers with lines of weakness, tearing-strips, tags, or like opening or removal devices, e.g. to facilitate formation of pouring openings
- B65D41/34—Threaded or like caps or cap-like covers provided with tamper elements formed in, or attached to, the closure skirt
- B65D41/3423—Threaded or like caps or cap-like covers provided with tamper elements formed in, or attached to, the closure skirt with flexible tabs, or elements rotated from a non-engaging to an engaging position, formed on the tamper element or in the closure skirt
- B65D41/3428—Threaded or like caps or cap-like covers provided with tamper elements formed in, or attached to, the closure skirt with flexible tabs, or elements rotated from a non-engaging to an engaging position, formed on the tamper element or in the closure skirt the tamper element being integrally connected to the closure by means of bridges
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Definitions
- the present invention relates to a container lid provided with a high-density polyethylene cap shell attached to a container mouth portion and an in-shell molded product formed by in-shell molding in the cap shell.
- plastic caps can be molded into various forms and are widely used as lid materials for containers of various forms.
- caps made of high-density polyethylene are not only highly crystalline and excellent in mechanical strength, but are also inexpensive, so their practical frequency is extremely high.
- plastic caps may be pursued with further added value.
- various functions such as improvement of barrier properties for the purpose of preventing deterioration of the content liquid are often required.
- a plastic cap has a low oxygen barrier property compared to a metal cap, and it is therefore an old problem to improve the oxygen barrier property.
- a container such as a plastic bottle has a multilayered structure and a gas barrier resin layer such as ethylene vinyl alcohol, an oxygen absorbing layer in which an oxidizable material is dispersed, and the like.
- a gas barrier resin layer such as ethylene vinyl alcohol, an oxygen absorbing layer in which an oxidizable material is dispersed, and the like.
- it is difficult to mold without impairing the cap opening and sealing performance of the cap, and it is not practical to adopt such a multilayer structure.
- this container lid is obtained by dispersing a hydrogen generating agent such as a metal hydride in a liner provided inside a plastic cap shell, generating hydrogen by contact with moisture in the container, This hydrogen reacts with oxygen through a catalyst to convert it into water, thereby reducing oxygen.
- a hydrogen generating agent such as a metal hydride
- such a container lid contains a hydrogen generating agent, if the moisture in the container directly contacts the liner, the hydrogen generating agent is immediately consumed and the oxygen barrier property is not exhibited. Accordingly, such a liner may require a cover member to prevent direct contact with the container contents.
- the above cover member needs to completely cover the liner without any gap, it must be provided in the cap shell by an in-shell mold. This is because mechanical means such as fitting will inevitably form a small gap, but hydrogen generated from the gap will leak or the liquid content will enter.
- a resin melt for forming a cover member is dropped on a hydrogen generator-containing liner provided in advance on the inner surface of the cap shell, and this resin melt is molded.
- the cover member is formed by pressing with a punch and shaping and then cooling.
- the problem here is that the resin melt for forming the cover member spreads quickly so as to completely cover the liner material by pressing with a punch, and must be fused directly to the inner surface of the cap shell at the periphery. It must be. That is, this cover member must be firmly fused and fixed to the inner surface of the cap shell at a small area of the peripheral portion at the same time that the resin melt is excellent in fluidity. Unless the fusion fixing property to the inner surface of the shell is improved, the excellent oxygen barrier property of the liner material cannot be exhibited, and improvement thereof is necessary.
- the above problems are problems that may exist even when an oxygen barrier property is provided using a liner formed using a gas barrier resin such as ethylene vinyl alcohol or an oxygen absorbent. .
- a similar cover member may be required.
- Patent No. 4601132 Special table 2013-523535 gazette
- an object of the present invention is to provide a container lid provided with a cap shell attached to the container mouth portion and an in-shell mold molded body provided on the inner surface of the cap shell.
- An object of the present invention is to provide an oxygen-blocking container lid in which direct contact with the container contents with a material exhibiting oxygen-blocking properties is reliably prevented and the oxygen-blocking property is stably maintained over a long period of time.
- Another object of the present invention is to provide a resin composition for an in-shell mold that can form a molded body that is firmly fused to the inner surface of the cap shell by an in-shell mold in the cap shell.
- a cap shell made of high-density polyethylene having a top plate portion and a skirt portion provided with an inner ring in close contact with the inner surface of the container mouth portion, and provided on a portion surrounded by the inner ring on the inner surface of the top plate portion.
- the in-shell mold molded body covers a primary molded body having an oxygen blocking function formed by an in-shell mold on the inner surface of the top plate portion, and covers the primary molded body with an in-shell mold on the primary molded body, and It consists of a secondary molded body that is fused and fixed to the inner surface of the top plate at the periphery,
- the secondary molded body contains linear low density polyethylene, has a melt flow rate at 190 ° C. of 1 to 10 g / 10 min, a density of 0.900 to 0.920 g / cm 3 , and JIS K-6922.
- a container lid characterized by being formed from a resin composition having a tensile fracture nominal strain specified in -2 in the range of 400% or more is provided.
- the secondary molded body contains a thermoplastic elastomer in addition to the linear low-density polyethylene, (2) The content of the thermoplastic elastomer in the secondary molded body is 30% by mass or less, Is preferred.
- the present invention is also composed of a blend of a linear low density polyethylene and a thermoplastic elastomer, having a melt flow rate at 190 ° C. of 1 to 10 g / 10 min and a density of 0.900 to 0.920 g /
- a resin composition for in-shell molding characterized by having a tensile fracture nominal strain defined by cm 3 and JIS K-69222-2 in the range of 400% or more.
- the container lid of the present invention has a basic structure in which an in-shell mold molded body is provided on the inner surface of the top plate portion of a high density polyethylene (HDPE) cap shell.
- the secondary molded body is formed using a specific linear low density polyethylene (LLDPE).
- the primary molded body is an oxygen-blocking molded body containing a functional material having an oxygen-blocking function
- the secondary molded body has direct contact between the functional material in the primary molded body and the container contents.
- the secondary molded body is molded using a resin composition containing LLDPE and having a constant melt flow rate (MFR), density, and tensile fracture nominal strain.
- In-shell molding can completely cover the primary molded body, and it can be firmly fused and fixed to the inner surface of the cap shell made of HDPE, so that the functional material in the primary molded body exhibits oxygen.
- the blocking property can be exhibited stably over a long period of time.
- the side sectional view of the container lid of the present invention The figure which shows the process for shape
- this container lid is composed of a cap shell 1 and an in-shell mold molded body 3 formed by in-shell molding inside the cap shell 1. .
- the cap shell 1 has a top plate portion 5 and a skirt 7 descending from the periphery of the top plate portion 5.
- An inner ring 9 is formed on the inner surface of the top plate portion 5, and a short outer ring 11 is formed on the outer side of the inner ring 9, and further, between the inner ring 9 and the outer ring 11. Is provided with a flat annular small protrusion 13.
- the container mouth (not shown) enters the space between the inner ring 9 and the skirt 7, and the outer surface of the inner ring 9 is the upper end of the container mouth.
- the inner ring 9 has a form bulging outward.
- the outer ring 11 is slightly inclined inward, and is formed so as to be in close contact with the outer surface of the upper end portion of the container mouth portion that has entered between the inner ring 9 and the skirt 7.
- the container mouth is firmly held without rattling, and at the same time the seal by the inner ring 9 is reinforced.
- the annular small protrusion 13 is in close contact with the upper end surface of the container mouth portion that has entered between the inner ring 9 and the skirt 7 and further reinforces the seal by the inner ring 9.
- the inner surface of the skirt 7 is provided with a thread 15 that is threadedly engaged with the outer surface of the container mouth portion.
- the tamper-evidence band (TE band) 17 can be broken at the lower end of the skirt 7. 19 are connected.
- the TE band 17 is provided for preventing mischief and quality assurance of contents, and a flap piece 20 extending inward and upward is provided on the inner surface thereof.
- the container mouth part enters between the inner ring 9 and the skirt 7, whereby the cap shell 1 is fixed to the container mouth part.
- the flap piece 20 of the TE band 17 is located below the jaw part formed on the outer surface of the container mouth part.
- the skirt 7 rises along the outer surface of the container mouth. Because of the contact, the rise is prevented. Accordingly, the bridge 19 connecting the TE band 17 and the skirt 7 is broken, and as a result, the cap shell 1 is removed from the container mouth portion with the TE band 17 remaining on the container side.
- a general consumer sees the state that the TE band 17 is separated from the cap shell 1, and recognizes the opening history that the cap shell 1 has been removed from the container mouth. It is possible to prevent unauthorized use such as mischief.
- the TE band 17 is connected to the cap shell 1, it can be recognized that the cap shell 1 has never been removed from the container mouth, and the quality of the contents can be guaranteed. It can be done.
- the cap shell 1 described above is molded by injection molding or compression molding using high-density polyethylene.
- This high-density polyethylene has a high density of 0.942 g / cm 3 or more, has few branches, has high crystallinity, and is excellent in mechanical strength. It is very suitable for forming the cap shell 1 having the required part. Moreover, it is mainly used as a cap for Aseptic sterilization filling. Further, as such a high-density polyethylene, the cap shell 1 is formed by injection molding or compression molding. Therefore, in the so-called injection grade, for example, MFR (190 ° C.) is 2.0 to 12.0 g / 10 min. Are preferably used. For the compression grade, for example, an MFR (190 ° C.) of 0.5 to 10.0 g / 10 min is preferably used.
- an in-shell molded product 3 formed by an in-shell mold is provided in the cap shell 1, that is, in a portion surrounded by the inner ring 9 on the inner surface of the top plate portion 5.
- this in-shell mold product 3 exhibits oxygen barrier properties and can effectively prevent oxidative deterioration of the container contents. Furthermore, since it is molded by an in-shell mold in the portion inside the inner ring 9, there is no adverse effect on the cap opening and sealing performance of the cap.
- Such an in-shell mold molded body 3 has a two-layer structure, and a primary molded body 3a molded by the first-stage in-shell mold and a second stage on the molded primary molded body 3a.
- the secondary molded body 3b is formed so as to cover the primary molded body 3a by the in-shell mold.
- FIG. 2 which shows the process for shape
- resin or resin composition which forms the primary molded object 3a is made into the melt A about 250 degreeC, and an extruder. Etc., it is dropped to a region (particularly the central portion) surrounded by the inner ring 9 on the inner surface of the top plate portion 5 (see FIG. 2A).
- the primary molding jig 21 provided with the molding punch 21a is disposed in the cap shell 1 (see FIG. 2B).
- the molding punch 21a is lowered, the melt A is spread and pressed into a flat disk shape and cooled (see FIG. 2C).
- adhered to the inner surface of the top plate part 5 is shape
- the resin or resin composition forming the secondary molded body 3b is extruded onto the primary molded body 3a as a melt B having a temperature of about 250 ° C. Drop from a machine or the like (see FIG. 2D).
- the secondary molding jig 23 provided with the molding punch 23a is disposed in the cap shell 1 (see FIG. 2 (e)). In this state, the molding punch 23a is lowered, the melt B is spread and pressed into a flat disk shape and cooled (see FIG. 2 (f)).
- the in-shell mold molded body 3 having a two-layer structure is obtained by being in close contact with the inner surface of the top plate portion 5 so as to cover the primary molded body 3a.
- the primary molded product 3a exhibits oxygen barrier properties as described above.
- Such a primary molded body 3a is roughly classified into two types by means for exhibiting oxygen barrier properties.
- One type is called an active barrier type that removes oxygen using a chemical reaction, and there are oxygen absorber type and hydrogen generation type.
- the oxygen absorption type will be described.
- the oxygen absorbent used in the oxygen-absorbing resin composition exists as a layer containing an oxidizing polymer and a transition metal catalyst, as described in JP-A No. 2002-240813. By this action, the oxidizing polymer is oxidized by oxygen, thereby absorbing oxygen and blocking the permeation of oxygen.
- Such an oxidizable polymer and a transition metal catalyst are described in detail in the above-mentioned JP-A-2002-240813, etc., and details thereof are omitted, but representative examples of the oxidizable polymer include , An olefin resin having a tertiary carbon atom (for example, polypropylene, polybutene-1, or a copolymer thereof); a thermoplastic polyester or an aliphatic polyamide; And xylylene group-containing polyamide resin; ethylenically unsaturated group-containing polymer (for example, a polymer derived from polyene such as butadiene); and the like.
- An olefin resin having a tertiary carbon atom for example, polypropylene, polybutene-1, or a copolymer thereof
- a thermoplastic polyester or an aliphatic polyamide for example, polypropylene, polybutene-1, or a copolymer thereof
- the inorganic salt, organic acid salt, or complex salt of transition metals such as iron, cobalt, and nickel
- transition metals such as iron, cobalt, and nickel
- the oxygen absorber as described above in order to ensure adhesion with the high-density polyethylene forming the cap shell 1, as in the case of the gas barrier resin described above, at a ratio that can maintain an appropriate oxygen barrier property, It can also be used by blending with an acid-modified olefin resin modified with polyethylene or maleic anhydride.
- the hydrogen generation type will be described.
- the hydrogen generating type is a material in which a hydrogen generating agent is dispersed in a resin as a functional material, and the hydrogen generating agent reacts with moisture moving from the content liquid in the container to generate hydrogen.
- Oxygen is captured by reacting with oxygen passing through the top plate portion 5 of the cap shell 1 or oxygen in the container via a catalyst to generate water, and as a result, oxygen barrier properties are exhibited. Is.
- Such a hydrogen-generating primary molded body 3a is known from Patent Document 1 described above.
- Typical examples of the hydrogen generator include metals or metal hydrides that generate hydrogen by reacting with water, for example, metals such as Na, Li, K, Ca, Mg, Mg, Zn, and Al, and hydrides of these metals. It is.
- sodium borohydride, lithium borohydride, tetramethyldisiloxane, trimethyltin hydride, organohydrogenpolysiloxane, and the like can be used. Select and use.
- Examples of the resin that serves as a matrix in which the hydrogen generator is dispersed include water-permeable resins such as olefin resins such as low, medium, high density polyethylene, and polypropylene, and styrene-ethylene-butylene copolymer.
- water-permeable resins such as olefin resins such as low, medium, high density polyethylene, and polypropylene, and styrene-ethylene-butylene copolymer.
- examples include coalesced (SEBS), polyamide, polystyrene, styrene- (meth) acrylate copolymer, ethylene vinyl acetate copolymer, and the like.
- an olefin resin particularly polyethylene having an MFR of about 1 to 10 g / 10 min is preferable.
- the LLDPE used for molding the secondary molded body 3b is most preferably used.
- the hydrogen generator described above is usually blended in an amount of about 5 to 20 parts by mass per 100 parts by mass of the resin.
- Another type is called a direct barrier type, called a passive barrier type, in which the resin itself prevents oxygen from entering from the outside.
- the primary molded body 3a of this type is formed from a gas barrier resin.
- the gas barrier resin examples include ethylene vinyl alcohol copolymers (saponified ethylene vinyl acetate copolymers) and aromatic polyamides, and ethylene vinyl alcohol copolymers are particularly preferable from the viewpoint of oxygen barrier properties. It is. Further, since such a gas barrier resin has poor adhesion to the polyolefin forming the cap shell 1, it is an acid-modified olefin modified with polyethylene or maleic anhydride at a ratio that can maintain an appropriate oxygen barrier property. It can also be used by blending with a resin.
- Any type of the primary molded body 3a described above is molded by an in-shell mold according to the process shown in FIG.
- the secondary molded body 3b provided so as to cover the primary molded body 3a described above prevents direct contact between the primary molded body 3a and the container contents. That is, the primary molded body 3a containing the hydrogen generating agent described above needs to prevent contact between the hydrogen generating agent and the contents of the container. That is, when the hydrogen generating agent and the contents of the container are in direct contact, the water contained in the container contents and the hydrogen generating agent react immediately, and the function of the hydrogen generating agent is immediately lost.
- the primary molded body 3a containing an oxygen absorbent In addition, gas barrier resins such as ethylene vinyl alcohol copolymer absorb moisture and the like, and the oxygen blocking function is greatly reduced. Therefore, the primary molded body 3a made of such a gas barrier resin also needs to prevent direct contact with the container contents.
- the secondary molded body 3b is provided in order to prevent direct contact with the primary molded body 3a and to continuously exhibit the oxygen barrier property. Therefore, the secondary molded body 3b needs to be fused and fixed to the inner surface of the top plate portion 5 in a state where the secondary molded body 3b is completely covered and sealed while being molded by the in-shell mold.
- the resin material (resin composition) used for molding the secondary molded body 3b needs to contain linear low density polyethylene (LLDPE).
- LLDPE linear low density polyethylene
- This LLDPE is a copolymer of ethylene with a small amount of ⁇ -olefin (generally having 4 or more carbon atoms), has few long-chain molecules, very high linearity, and almost no polymer chain entanglement. It has the property.
- the primary molded body 3a is completely covered by an in-shell mold on the primary molded body 3a, and a cap made of high-density polyethylene is formed at the peripheral edge. It can be firmly fused and fixed to the shell 1 (the inner surface of the top plate portion 5).
- the linearity of the molecule is high, it is easily entangled with the molecular chain of the high-density polyethylene, thereby being firmly fused and fixed to the inner surface of the top plate portion 5. Moreover, since the crystallinity is high, the barrier property against moisture is also high.
- the resin material of the secondary molded body 3b used in the present invention is required to have an MFR (190 ° C.) in the range of 1 to 10 g / 10 minutes. That is, when the MFR is higher than the above range, the above-described melt B is likely to flow, and it is difficult to effectively perform the embossing with the punch 23a. On the other hand, if the MFR is lower than the above range, the melt B is difficult to spread when being punched by the punch 23a, and molding is difficult.
- MFR 190 ° C.
- the temperature of the melt B can be increased to facilitate the spread of the melt B, but since the temperature of the melt B is excessively high, the primary plate 3a or the top plate portion of the cap shell 1 5 may cause inconveniences such as deformation and shape collapse of the inner surface of the plate 5 or resin burning.
- the resin material of the secondary molded body 3b needs to have a density in the range of 0.900 to 0.920 g / cm 3 and a tensile fracture nominal strain (JIS K-69222-2) of 400% or more. It is. That is, a resin material having such a density and a tensile fracture nominal strain is easy to stretch, can be adjusted to a thickness that allows water to permeate appropriately, and can prevent the disadvantage that the hydrogen generating agent is consumed at a stretch. .
- the melt B can be stretched so that the peripheral edge of the primary molded body 3a is completely covered, and embossing can be performed. At the peripheral edge, the secondary molded body 3b is firmly fused to the inner surface of the top plate part 5. Can be fixed.
- the secondary molded body 3b cannot be firmly fused and fixed to the inner surface of the top plate portion 5, and peeling or the like tends to occur.
- the moisture comes into contact at a stretch, the hydrogenating agent is consumed quickly, and it becomes difficult to trap oxygen by generating hydrogen from the hydrogen generating agent.
- the oxygen blocking function cannot be fully exhibited.
- the LLDPE as described above can be obtained by adjusting the type of ⁇ -olefin to be copolymerized, the amount of copolymerization, the molecular weight, etc.
- LLDPE having these physical properties is selected from commercially available LLDPE. And use it.
- LLDPE used in the present invention is marketed by Nippon Polyethylene Co., Ltd. under the trade name UF240.
- LLDPE can also be used independently as a resin material of the secondary molded object 3b, and it can also be used by blending with other resin or an elastomer.
- this blend satisfies the above-described conditions for MFR, density, and tensile fracture calling.
- thermoplastic elastomers include ethylene elastomers such as ethylene propylene copolymer rubber (EPR), ethylene butylene copolymer rubber (EBR), and ethylene-octene copolymer rubber (EOR).
- EPR ethylene propylene copolymer rubber
- EBR ethylene butylene copolymer rubber
- EOR ethylene-octene copolymer rubber
- a styrene-type elastomer and a propylene-type elastomer can also be used.
- ethylene butylene copolymer rubber (EBR) is preferably used to promote hydrogen permeability.
- the blending of the thermoplastic elastomer described above is advantageous for improving the adhesion to the inner surface of the primary molded body 3a and the top plate portion 5, but if excessively blended, the above-described melt B is dropped to form a secondary.
- the blending amount of the thermoplastic elastomer is preferably 30% by mass or less, particularly 10 to 30% by mass in the formed secondary molded body 3b.
- the MFR (190 ° C.) of the resin material of the secondary molded body 3b is in the range of 2.3 to 4.0 g / 10 min. Is desirable.
- the resin composition containing the LLDPE and the thermoplastic elastomer described above can form a molded body having excellent adhesion to various olefinic resins by an in-shell mold, not only for the secondary molded body 3b, It can also be used to form various in-shell molded articles.
- the melt B is very easy to stretch during the in-shell molding.
- the secondary molded body 3b is outside the portion covering the peripheral edge of the primary molded body 3a. It is optimal to have a configuration having a flange 30 that is widened in the direction. Thereby, not only can the primary molded body 3a be completely covered, but the area of contact with the inner surface of the top plate portion 5 can be set large, and the secondary molded body 3b can be more firmly attached to the inner surface of the top plate portion 5. It can be fused and fixed.
- LLDPE blended with the aforementioned thermoplastic elastomer is most suitable for forming the flange 30 as described above.
- a cap shell in the form of FIG. 1 was prepared by injection molding using high density polyethylene having a density of 0.960 g / cm 3 and MFR (190 ° C.) of 2.0 g / 10 min.
- the specifications of this cap shell are as follows.
- a primary molded body having a diameter of 14 mm and a thickness of 3 mm was molded by an inner mold using a resin composition having the following composition (molding temperature: 250 ° C.), and this was used as a test cap.
- Resin composition for primary molded body Linear low density polyethylene (LLDPE) 87.95 parts by mass Density: 0.919 g / cm 3 MFR: 5.7 g / 10 min (190 ° C.)
- Tensile fracture nominal strain JIS K-69222-2) 500% or more Hydrogen generator (sodium borohydride) 12 parts by weight
- Colorant phthalocyanine blue
- Example 1 The following LLDPE was prepared. LLDPE; UF240 manufactured by Nippon Polyethylene Corporation Density: 0.920 g / cm 3 MFR: 2.1 g / 10 min (190 ° C.) Melting point: 123.0 ° C Tensile fracture nominal strain (JIS K-69222-2) 500%
- the above LLDPE is charged into a melt extruder, melt extruded from a molten resin supply hole, and cut by a rotary blade provided at the outlet of the supply hole.
- the molten resin was stably dropped onto the center of the primary molded body, and the dripping property of the molten resin was extremely good.
- the molten resin could be stably cut, held stably without protruding from the primary molded body, and molded so as to completely cover the primary molded body without causing supply failure.
- the resulting container lid was subjected to an adhesion test of the secondary molded body.
- penetrating liquid colored liquid
- the top plate of the container lid is cut, and the penetration of the liquid between the secondary molded body and the top plate of the cap shell is confirmed.
- the coloring of the penetrating liquid was slightly observed (the part that was not adhered and peeled), this coloring did not reach the primary molded body, and the performance of the primary molded body was not affected.
- the top plate part of the obtained container lid was cut and caused using a hook needle on the flange of the secondary molded body, and the adhesive force was measured, it was 50 N or more.
- thermoplastic elastomer Thermoplastic elastomers (EBR); Ethylene butylene copolymer (A-4090S manufactured by Mitsui Chemicals, Inc.) Density: 0.893 g / cm 3 MFR: 3.6 g / 10 min (190 ° C.) Melting point: 77.0 ° C Tensile fracture nominal strain (JIS K-69222-2) 783%
- Example 1 90 parts by mass of LLDPE used in Example 1 and 10 parts by mass of thermoplastic elastomer were dry blended, melt kneaded using a melt extruder, extruded from a molten resin supply hole, and cut in the same manner as in Example 1. Then, a molten resin at 250 ° C. was dropped on the central part of the primary molded body of the test cap, and the secondary molded body having the form shown in FIG. 3 was molded by an in-shell mold to produce a container lid.
- the blend of LLDPE and thermoplastic elastomer had a density of 0.917 g / cm 3 , MFR (190 ° C.) of 2.3 g / 10 min, and a nominal tensile fracture strain of 528.3%. .
- the molten resin was stably dropped onto the center of the primary molded body as in Example 1, and the dripping property of the molten resin was extremely good. Further, similarly to Example 1, the molten resin could be stably cut, held stably without protruding from the primary molded body, and molded so as to completely cover the primary molded body without causing supply failure.
- Example 3 Except for dry blending 85 parts by mass of LLDPE and 15 parts by mass of thermoplastic elastomer (EBR), a secondary molded body was molded by an inner mold in the same manner as in Example 2 to obtain a container lid. Evaluation was performed.
- EBR thermoplastic elastomer
- the density of the blend of LLDPE and thermoplastic elastomer was 0.916 / cm 3 , MFR (190 ° C.) was 2.3 g / 10 min, and the tensile fracture nominal strain was 542.5%.
- the molten resin was stably dropped at the center of the primary molded body as in Example 1, and the dripping property of the molten resin was extremely good.
- the molten resin could be stably cut, held stably without protruding from the primary molded body, and molded so as to completely cover the primary molded body without causing supply failure.
- the obtained container lid was subjected to an adhesion test in the same manner as in Example 1, no peeling occurred between the inner surface of the cap top plate portion and the primary molded body.
- the adhesive force was 50N or more.
- Example 4 Except for dry blending 80 parts by mass of LLDPE and 20 parts by mass of thermoplastic elastomer (EBR), a secondary molded body was formed by an inner mold in the same manner as in Example 2 to obtain a container lid. Evaluation was performed.
- EBR thermoplastic elastomer
- the density of the blend of LLDPE and thermoplastic elastomer was 0.915 g / cm 3 , MFR (190 ° C.) was 2.4 g / 10 min, and the tensile fracture nominal strain was 556.6%.
- the molten resin was stably dropped at the center of the primary molded body as in Example 1, and the dripping property of the molten resin was extremely good. Further, similarly to Example 1, the molten resin could be stably cut, held stably without protruding from the primary molded body, and molded so as to completely cover the primary molded body without causing supply failure.
- Example 2 when the obtained container lid was subjected to an adhesion test in the same manner as in Example 1, no peeling occurred between the inner surface of the cap top plate portion and the primary molded body.
- the adhesive force was 50N or more.
- Example 5 Except for dry blending 70 parts by mass of LLDPE and 30 parts by mass of thermoplastic elastomer (EBR), a secondary molded body was molded by an inner mold in the same manner as in Example 2 to obtain a container lid. Evaluation was performed.
- EBR thermoplastic elastomer
- the density of the blend of LLDPE and thermoplastic elastomer was 0.912 g / cm 3 , MFR (190 ° C.) was 2.6 g / 10 min, and the tensile fracture nominal strain was 584.9%.
- the molten resin was stably dropped at the center of the primary molded body as in Example 1, and the dripping property of the molten resin was extremely good.
- the molten resin could be stably cut, held stably without protruding from the primary molded body, and molded so as to completely cover the primary molded body without causing supply failure.
- the adhesion test on the obtained container lid no peeling occurred between the cap top plate inner surface and the primary molded body.
- the adhesive force was 50N or more.
- Example 6 Except for dry blending 65 parts by mass of LLDPE and 35 parts by mass of thermoplastic elastomer (EBR), a secondary molded body was molded by an inner mold in the same manner as in Example 2 to obtain a container lid. Evaluation was performed.
- the density of the blend of LLDPE and thermoplastic elastomer was 0.911 g / cm 3 , MFR (190 ° C.) was 2.6 g / 10 min, and the tensile fracture nominal strain was 599.5%.
- MFR 190 ° C.
- MFR 2.6 g / 10 min
- the tensile fracture nominal strain was 599.5%.
- the dripping property of the molten resin is unstable, and the molten resin can be molded so as to completely cover the primary molded body, but it is dropped from the central part of the primary molded body and cutting of the molten resin is not possible. It was stable. Further, in the adhesion test on the obtained container lid, no peeling occurred between the cap top plate inner surface and the primary molded body.
- the adhesive force was 50N or more.
- Example 7 Except for dry blending 60 parts by mass of LLDPE and 40 parts by mass of thermoplastic elastomer (EBR), a secondary molded body was molded by an inner mold in the same manner as in Example 2 to obtain a container lid. Evaluation was performed.
- EBR thermoplastic elastomer
- the density of the blend of LLDPE and thermoplastic elastomer was 0.909 g / cm 3 , MFR (190 ° C.) was 2.7 g / 10 min, and the tensile fracture nominal strain was 613.2%.
- MFR 190 ° C.
- MFR 2.7 g / 10 min
- the tensile fracture nominal strain was 613.2%.
- the dripping property of the molten resin is unstable, and the molten resin can be molded so as to completely cover the primary molded body, but it is dropped from the central part of the primary molded body and cutting of the molten resin is not possible. It was stable. Further, in the adhesion test on the obtained container lid, no peeling occurred between the cap top plate inner surface and the primary molded body.
- the adhesive force was 50N or more.
- thermoplastic elastomer Thermoplastic elastomers (EBR); Ethylene butylene copolymer (A-4070S manufactured by Mitsui Chemicals, Inc.) Density: 0.870 g / cm 3 MFR: 3.6 g / 10 min (190 ° C.) Melting point: 55.0 ° C Tensile fracture nominal strain (JIS K-69222-2) 1000%
- thermoplastic elastomer Except that 30 parts by mass of the above-mentioned thermoplastic elastomer was dry blended with 70 parts by mass of LLDPE, a secondary molded body was molded by an inner mold in the same manner as in Example 2 to obtain a container lid, and its evaluation was performed. It was.
- the density of the blend of LLDPE and thermoplastic elastomer was 0.905 g / cm 3 , MFR (190 ° C.) was 2.6 g / 10 min, and the tensile fracture nominal strain was 650%.
- the molten resin was stably dropped at the center of the primary molded body as in Example 1, and the dripping property of the molten resin was extremely good. Further, similarly to Example 1, the molten resin could be stably cut, held stably without protruding from the primary molded body, and molded so as to completely cover the primary molded body without causing supply failure. Further, in the adhesion test on the obtained container lid, no peeling occurred between the cap top plate inner surface and the primary molded body. The adhesive force was 50N or more.
- thermoplastic elastomer by blending the thermoplastic elastomer with LLDPE, the adhesion to the inner surface of the cap top plate portion and the primary molded body is improved. It can be seen that the amount of the thermoplastic elastomer blended is 15 to 30% by mass.
- LLDPE LLDPE
- FV104 manufactured by Sumitomo Chemical Co., Ltd.
- Density 0.913 g / cm 3
- MFR 1.0 g / 10 min (190 ° C.)
- Melting point 121.0 ° C
- LLDPE LLDPE
- FV201 manufactured by Sumitomo Chemical Co., Ltd.
- Density 0.916 g / cm 3
- MFR 2.3 g / 10 min (190 ° C.)
- Melting point 117.0 ° C
- VLDPE very low density polyethylene
- VLDPE very low density polyethylene
- Density 0.900 g / cm 3
- MFR 2.0 g / 10 min (190 ° C.)
- Melting point 115.0 ° C
- LDPE low density polyethylene
- Ube Maruzen Polyethylene Co., Ltd. F120N Density: 0.920 g / cm 3 MFR: 1.2 g / 10 min (190 ° C.) Melting point: 94.0 ° C
- the secondary molded body was formed by the inner mold in exactly the same manner as in Example 3 except that the LDPE used in Comparative Example 7 was used, and 85 parts by mass of LDPE was dry blended with 15 parts by mass of thermoplastic elastomer (EBR). Was molded to obtain a container lid, which was evaluated.
- the density of the blend of the LDPE and the thermoplastic elastomer was 0.916 g / cm 3 , the MFR (190 ° C.) was 1.6 g / 10 min, and the nominal tensile fracture strain was 190.9%.
- HDPE high density polyethylene
- 2200J made by Prime Polymer Co., Ltd.
- Density 0.964 g / cm 3
- MFR 5.2 g / 10 min (190 ° C.)
- Melting point 135 ° C
- Tensile fracture nominal strain JIS K-69222-2
- ⁇ Comparative Example 10> A secondary molded body by an inner mold in exactly the same manner as in Example 3 except that HDPE used in Comparative Example 9 was used, and 85 parts by mass of HDPE was dry blended with 15 parts by mass of a thermoplastic elastomer (EBR). Was molded to obtain a container lid, which was evaluated.
- the density of the blend of HDPE and thermoplastic elastomer was 0.953 g / cm 3 , MFR (190 ° C.) was 5.0 g / 10 min, and the tensile fracture nominal strain was 303%.
- HDPE high density polyethylene
- the secondary molded body was molded by an inner mold in exactly the same manner as in Example 1 to obtain a container lid, and the evaluation was performed.
- the secondary molded body was formed by an inner mold in the same manner as in Example 3 except that HDPE used in Comparative Example 11 was used, and 85 parts by mass of HDPE was dry blended with 15 parts by mass of thermoplastic elastomer (EBR). Was molded to obtain a container lid, which was evaluated.
- the density of the blend of HDPE and thermoplastic elastomer was 0.944 g / cm 3 , MFR (190 ° C.) was 4.8 g / 10 min, and the tensile fracture nominal strain was 455.4%.
- cap shell 3 in-shell molded body 3a: primary molded body 3b: secondary molded body 5: top plate portion 7: skirt 9: inner ring 11: outer ring 13: annular small protrusion 15: screw 17: TE band 19: Bridge 20: Flap piece 21: Primary molding jig 21a: Punch 23: Secondary molding jig 23 23a: Punch 30: Flange
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Abstract
Description
また、内容液充填後の容器内部のヘッドスペース中の酸素を除去するため、キャップ内面に酸素吸収剤配合樹脂の成形体を設けた種々の容器蓋も提案されている。このような容器蓋においては、キャップシェル内面側にインシェルモールドで設けられたライナー材に酸素吸収剤を配合するのが一般的である(例えば特許文献1)。
即ち、この容器蓋は、プラスチック製のキャップシェルの内部に設けられるライナーの内部に水素化金属などの水素発生剤を分散させたものであり、容器内の水分との接触により水素を発生させ、この水素が触媒を介し酸素と反応して水に転換させることにより酸素を低減するというものである。
ここで問題となるのは、カバー部材形成用の樹脂溶融物は、パンチによる押圧によってライナー材を完全に被覆するように速やかに広がり、且つ周縁部分において、キャップシェルの内面に直接融着しなければならないということである。即ち、このカバー部材は、樹脂溶融物が流動性に優れていると同時に、周縁部の小面積の部分でしっかりとキャップシェル内面に融着固定されなければならず、このような流動性及びキャップシェル内面への融着固定性を高めない限り、ライナー材が有する優れた酸素遮断性を発揮させることができず、その改善が必要となっている。
本発明の他の目的は、キャップシェル内でのインシェルモールドによってキャップシェルの内面に強固に融着する成形体を形成し得るインシェルモールド用樹脂組成物を提供することにある。
前記インシェルモールド成形体は、前記頂板部内面上でのインシェルモールドにより形成された酸素遮断機能を有する一次成形体と、該一次成形体上でのインシェルモールドにより該一次成形体を覆い且つ周縁部で前記頂板部内面に融着固定されている二次成形体とからなり、
前記二次成形体は、直鎖状低密度ポリエチレンを含み、且つ190℃でのメルトフローレートが1~10g/10分、密度が0.900~0.920g/cm3、及びJIS K-6922-2に規定された引張破壊呼び歪みが400%以上の範囲にある樹脂組成物から形成されていることを特徴とする容器蓋が提供される。
(1)前記二次成形体は、前記直鎖状低密度ポリエチレンに加えて、熱可塑性エラストマーを含有していること、
(2)前記二次成形体中の前記熱可塑性エラストマーの含有量が30質量%以下であること、
が好ましい。
本発明では、上記の二次成形体が、LLDPEを含み、且つ一定のメルトフローレート(MFR)、密度及び引張破壊呼び歪みを有する樹脂組成物を用いて成形されているため、一次成形体上でのインシェルモールドにより一次成形体を完全に被覆することができ、しかも、HDPE製のキャップシェルの内面に強固に融着固定することができるため、一次成形体中の機能性材料が示す酸素遮断性を長期にわたって安定に発揮することができる。
また、アウターリング11は、若干、内方側に傾斜しており、インナーリング9とスカート7との間に侵入した容器口部の上端部外面に密着するように形成されており、これにより、容器口部をがたつきなく、しっかりと保持し、同時にインナーリング9によるシールを補強する。
さらに、環状小突起13は、インナーリング9とスカート7との間に侵入した容器口部の上端面に密着するものであり、インナーリング9によるシールをさらに補強する。
このTEバンド17は、いたずら防止及び内容物の品質保証のために設けられるものであり、その内面には、内方かつ上方に延びているフラップ片20が設けられている。
このようにして、一般の消費者は、TEバンド17がキャップシェル1から分離している状態を見て、このキャップシェル1は容器口部から取り除かれたことがあるという開封履歴を認識することができ、いたずら等の不正使用を防止することができる。また、TEバンド17がキャップシェル1に連結されている場合には、このキャップシェル1は容器口部から取り外されたことがないものであることを認識でき、内容物の品質を保証することができるわけである。
また、このような高密度ポリエチレンとしては、射出成形や圧縮成形によりキャップシェル1を成形することから、所謂射出グレードのものでは、例えば、MFR(190℃)が2.0~12.0g/10minのものが好適に使用される。また、圧縮グレードのものでは、例えば、MFR(190℃)が0.5~10.0g/10minのものが好適に使用される。
次いで、成形用パンチ21aを備えた一次成形用治具21をキャップシェル1内に配置する(図2(b)参照)。
この状態で、成形用パンチ21aを降下させ、上記の溶融物Aを押し広げて平板円盤形状に押圧成形して冷却する(図2(c)参照)。これにより、頂板部5の内面に密着した一次成形体3aが成形される。
次いで、成形用パンチ23aを備えた二次成形用治具23をキャップシェル1内に配置する(図2(e)参照)。
この状態で、成形用パンチ23aを降下させ、上記の溶融物Bを押し広げて平板円盤状に押圧成形して冷却する(図2(f)参照)。これにより、一次成形体3aを覆うようにして頂板部5の内面に密着して成形され、二層構造のインシェルモールド成形体3が得られる。
上述した本発明の容器蓋が有するインシェルモールド成形体3において、一次成形体3aは、先にも述べたように、酸素遮断性を発揮するものである。
このような一次成形体3aは、酸素遮断性を発揮させる手段によって大きく2つのタイプに分けられる。
キシリレン基含有ポリアミド樹脂;エチレン系不飽和基含有重合体(例えばブタジエン等のポリエンから誘導される重合体);などが挙げられる。また、遷移金属系触媒としては、鉄、コバルト、ニッケル等の遷移金属の無機塩、有機酸塩或いは錯塩が代表的である。
上記のような酸素吸収剤には、キャップシェル1を形成する高密度ポリエチレンとの密着性を確保するために、前述したガスバリア性樹脂と同様、適度な酸素遮断性を維持できる程度の割合で、ポリエチレンや無水マレイン酸で変性された酸変性オレフィン系樹脂とブレンドして使用することもできる。
水素発生剤としては、水と反応して水素発生する金属または金属水素化物、例えば、Na,Li,K、Ca,Mg,Mg,Zn,Al等の金属、及びこれら金属の水素化物が代表的である。また、これら以外にも、水素化ホウ素ナトリウム、水素化ホウ素リチウム、テトラメチルジシロキサン、トリメチルスズ水素化物、オルガノハイドロジェンポリシロキサンなどを挙げることができ、内容物の種類に応じて適宜のものを選択して使用すればよい。
また、上記の水素発生剤が分散されるマトリックスとなる樹脂としては、水分透過性を有する樹脂、例えば、低、中、高密度ポリエチレン、ポリプロピレン等のオレフィン系樹脂や、スチレン-エチレン-ブチレン共重合体(SEBS)、ポリアミド、ポリスチレン、スチレン-(メタ)アクリレート共重合体、エチレン酢酸ビニル共重合体などを例示することができる。特に、キャップシェル1の頂板部5の内面或いは二次成形体3bとの密着性、或いはインシェルモールド成形性の観点からオレフィン系樹脂、特にMFRが1~10g/10min程度のポリエチレンが好ましく、後述する二次成形体3bの成形に使用されるLLDPEが最も好適に使用される。
上述した水素発生剤は、インシェルモールド成形性を考慮して、通常、上記の樹脂100質量部当り5~20質量部程度の量で配合される。
また、このようなガスバリア性樹脂は、キャップシェル1を形成するポリオレフィンとの密着性が乏しいため、適度な酸素遮断性を維持できる程度の割合で、ポリエチレンや無水マレイン酸で変性された酸変性オレフィン系樹脂とブレンドして使用することもできる。
上述した一次成形体3aを覆うように設けられる二次成形体3bは、一次成形体3aと容器内容物との直接の接触を防止するものである。
即ち、前述した水素発生剤を含む一次成形体3aは、水素発生剤と容器内容物の接触を防止する必要がある。即ち、水素発生剤と容器内容物とが直接接触すると、容器内容物に含まれる水分と水素発生剤とが直ちに反応してしまい、水素発生剤の機能が直ちに失われてしまうからである。これは、酸素吸収剤を含む一次成形体3aについても同様である。また、エチレンビニルアルコール共重合体等のガスバリア性樹脂は、水分等を吸収して酸素遮断機能が大きく低下してしまう。従って、このようなガスバリア性樹脂からなる一次成形体3aもまた、容器内容物との直接接触を防止する必要がある。
従って、この二次成形体3bは、インシェルモールドにより成形されると同時に、一次成形体3aを完全に覆い、シールした状態で頂板部5の内面に融着固定されることが必要である。
即ち、MFRが上記範囲よりも高いと、前述した溶融物Bが流れ易くなってしまい、パンチ23aによる型押しを効果的に行うことが困難となってしまう。また、MFRが上記範囲よりも低いと、パンチ23aによる型押しに際して、溶融物Bが拡がり難くなり、やはり成形が困難となってしまう。この場合、溶融物Bの温度を高温にして溶融物Bを拡がり易くすることはできるが、溶融物Bの温度が過度に高温となっているため、一次成形体3a或いはキャップシェル1の頂板部5の内面の変形や形状崩れ、あるいは樹脂焼けが発生するという不都合を生じてしまう。
このような熱可塑性エラストマーとしては、エチレンプロピレン共重合体ゴム(EPR)、エチレンブチレン共重合体ゴム(EBR)、エチレン-オクテン共重合体ゴム(EOR)などのエチレン系エラストマーを挙げることができる。また、スチレン系エラストマー、プロピレン系エラストマーを用いることもできる。特に一次成形体に水素発生剤を使用する場合、水素の透過性を促進するにはエチレンブチレン共重合体ゴム(EBR)が好適に用いられる。
また、一次成形体3aや頂板部5の内面との密着性向上の観点から、二次成形体3bの樹脂材料のMFR(190℃)は2.3~4.0g/10minの範囲にあることが望ましい。
密度が0.960g/cm3及びMFR(190℃)が2.0g/10minの高密度ポリエチレンを用いての射出成形により成形された図1の形態のキャップシェルを用意した。このキャップシェルの仕様は次のとおりである。
キャップ径(頂板部の外径):28mm
インナーリング付け根部の内径:18.5mm
次いで、以下の組成の樹脂組成物を用いてのインナーモールドにより(成形温度:250℃)、径が14mm、厚みが3mmの一次成形体を成形し、これを試験用キャップとした。
一次成形体用樹脂組成物;
直鎖状低密度ポリエチレン(LLDPE) 87.95質量部
密度:0.919g/cm3
MFR:5.7g/10min(190℃)
引張破壊呼び歪み(JIS K-6922-2) 500%以上
水素発生剤(水酸化ホウ素ナトリウム) 12質量部
着色剤(フタロシアニンブルー) 0.05質量部
以下のLLDPEを用意した。
LLDPE;
日本ポリエチレン(株)製UF240
密度:0.920g/cm3
MFR:2.1g/10min(190℃)
融点:123.0℃
引張破壊呼び歪み(JIS K-6922-2) 500%
下記の熱可塑性エラストマーを用意した。
熱可塑性エラストマー(EBR);
エチレンブチレン共重合体(三井化学(株)製A-4090S)
密度:0.893g/cm3
MFR:3.6g/10min(190℃)
融点:77.0℃
引張破壊呼び歪み(JIS K-69222-2) 783%
尚、上記のLLDPEと熱可塑性エラストマーとのブレンド物の密度は0.917g/cm3、MFR(190℃)は2.3g/10minであり、引張破壊呼び歪みは、528.3%であった。
85質量部のLLDPEと15質量部の熱可塑性エラストマー(EBR)とをドライブレンドした以外は、実施例2と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
また、上記の成形に際して、溶融樹脂は、実施例1と同様、一次成形体の中心部に安定に滴下され、溶融樹脂の滴下性は極めて良好であった。また、実施例1と同様、溶融樹脂を安定してカッティングでき且つ一次成形体上からはみ出すことなく安定に保持され、供給不良を生じることなく、一次成形体を完全に覆うように成形できた。
また、得られた容器蓋について、実施例1と同様、接着性試験を行ったところ、キャップ頂板部内面及び一次成形体との間に剥離は全く生じていなかった。接着力は50N以上であった。
80質量部のLLDPEと20質量部の熱可塑性エラストマー(EBR)とをドライブレンドした以外は、実施例2と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
また、上記の成形に際して、溶融樹脂は、実施例1と同様、一次成形体の中心部に安定に滴下され、溶融樹脂の滴下性は極めて良好であった。また、実施例1と同様、溶融樹脂を安定してカッティングでき且つ一次成形体上からはみ出すことなく安定に保持され、供給不良を生じることなく、一次成形体を完全に覆うように成形できた。
70質量部のLLDPEと30質量部の熱可塑性エラストマー(EBR)とをドライブレンドした以外は、実施例2と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
また、上記の成形に際して、溶融樹脂は、実施例1と同様、一次成形体の中心部に安定に滴下され、溶融樹脂の滴下性は極めて良好であった。また、実施例1と同様、溶融樹脂を安定してカッティングでき且つ一次成形体上からはみ出すことなく安定に保持され、供給不良を生じることなく、一次成形体を完全に覆うように成形できた。
また、得られた容器蓋についての接着性試験では、キャップ頂板部内面及び一次成形体との間に剥離は全く生じていなかった。接着力は50N以上であった。
65質量部のLLDPEと35質量部の熱可塑性エラストマー(EBR)とをドライブレンドした以外は、実施例2と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
上記の成形に際して、溶融樹脂の滴下性が不安定であり、一次成形体を完全に覆うように成形できたものの、一次成形体の中心部から外れて滴下されており、溶融樹脂のカッティングが不安定となっていた。
また、得られた容器蓋についての接着性試験では、キャップ頂板部内面及び一次成形体との間に剥離は全く生じていなかった。接着力は50N以上であった。
60質量部のLLDPEと40質量部の熱可塑性エラストマー(EBR)とをドライブレンドした以外は、実施例2と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
上記の成形に際して、溶融樹脂の滴下性が不安定であり、一次成形体を完全に覆うように成形できたものの、一次成形体の中心部から外れて滴下されており、溶融樹脂のカッティングが不安定となっていた。
また、得られた容器蓋についての接着性試験では、キャップ頂板部内面及び一次成形体との間に剥離は全く生じていなかった。接着力は50N以上であった。
下記の熱可塑性エラストマーを用意した。
熱可塑性エラストマー(EBR);
エチレンブチレン共重合体(三井化学(株)製A-4070S)
密度:0.870g/cm3
MFR:3.6g/10min(190℃)
融点:55.0℃
引張破壊呼び歪み(JIS K-69222-2) 1000%
上記の成形に際して、溶融樹脂は、実施例1と同様、一次成形体の中心部に安定に滴下され、溶融樹脂の滴下性は極めて良好であった。また、実施例1と同様、溶融樹脂を安定してカッティングでき且つ一次成形体上からはみ出すことなく安定に保持され、供給不良を生じることなく、一次成形体を完全に覆うように成形できた。
また、得られた容器蓋についての接着性試験では、キャップ頂板部内面及び一次成形体との間に剥離は全く生じていなかった。接着力は50N以上であった。
以下のLLDPEを用意した。
LLDPE;
(株)プライムポリマー社製SP2020
密度:0.923g/cm3
MFR:1.9g/10min(190℃)
融点:116.0℃
引張破壊呼び歪み(JIS K-6922-2) 346.2%
上記のLLDPEを用いた以外は、実施例1と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
以下のLLDPEを用意した。
LLDPE;
住友化学(株)製FV104
密度:0.913g/cm3
MFR:1.0g/10min(190℃)
融点:121.0℃
引張破壊呼び歪み(JIS K-6922-2) 236.2%
上記のLLDPEを用いた以外は、実施例1と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
比較例2で使用したLLDPEを使用し、このLLDPE85質量部に、15質量部の熱可塑性エラストマー(EBR)をドライブレンドした以外は、比較例2と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
上記のLLDPEと熱可塑性エラストマーとのブレンド物の密度は0.910g/cm3、MFR(190℃)は1.4g/10minであり、引張破壊呼び歪みは、325.6%であった。
以下のLLDPEを用意した。
LLDPE;
住友化学(株)製FV201
密度:0.916g/cm3
MFR:2.3g/10min(190℃)
融点:117.0℃
引張破壊呼び歪み(JIS K-6922-2) 331.2%
上記のLLDPEを用いた以外は、実施例1と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
比較例4で使用したLLDPEを使用し、このLLDPE70質量部に、30質量部の熱可塑性エラストマー(EBR)をドライブレンドした以外は、実施例5或いは実施例7と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
上記のLLDPEと熱可塑性エラストマーとのブレンド物の密度は0.909g/cm3、MFR(190℃)は2.7g/10minであり、引張破壊呼び歪みは、388.9%であった。
以下の超低密度ポリエチレン(VLDPE)を用意した。
VLDPE;
住友化学(株)製VL200
密度:0.900g/cm3
MFR:2.0g/10min(190℃)
融点:115.0℃
引張破壊呼び歪み(JIS K-6922-2) 900%
上記のVLDPEを用いた以外は、実施例1と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
以下の低密度ポリエチレン(LDPE)を用意した。
LDPE;
宇部丸善ポリエチレン(株)製F120N
密度:0.920g/cm3
MFR:1.2g/10min(190℃)
融点:94.0℃
引張破壊呼び歪み(JIS K-6922-2) 92.8%
上記のLDPEを用いた以外は、実施例1と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
比較例7で使用したLDPEを使用し、このLDPE85質量部に、15質量部の熱可塑性エラストマー(EBR)をドライブレンドした以外は、実施例3と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
上記のLDPEと熱可塑性エラストマーとのブレンド物の密度は0.916g/cm3、MFR(190℃)は1.6g/10minであり、引張破壊呼び歪みは、190.9%であった。
以下の高密度ポリエチレン(HDPE)を用意した。
HDPE;
(株)プライムポリマー社製2200J
密度:0.964g/cm3
MFR:5.2g/10min(190℃)
融点:135℃
引張破壊呼び歪み(JIS K-6922-2) 176.7%
上記のHDPEを用いた以外は、実施例1と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
比較例9で使用したHDPEを使用し、このHDPE85質量部に、15質量部の熱可塑性エラストマー(EBR)をドライブレンドした以外は、実施例3と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
上記のHDPEと熱可塑性エラストマーとのブレンド物の密度は0.953g/cm3、MFR(190℃)は5.0g/10minであり、引張破壊呼び歪みは、303%であった。
以下の高密度ポリエチレン(HDPE)を用意した。
HDPE;
日本ポリエチレン(株)HJ362N
密度:0.953g/cm3
MFR:5.0g/10min(190℃)
融点:132℃
引張破壊呼び歪み(JIS K-6922-2) 384.3%
上記のHDPEを用いた以外は、実施例1と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
比較例11で使用したHDPEを使用し、このHDPE85質量部に、15質量部の熱可塑性エラストマー(EBR)をドライブレンドした以外は、実施例3と全く同様にして、インナーモールドにより二次成形体を成形し、容器蓋を得、その評価を行った。
上記のHDPEと熱可塑性エラストマーとのブレンド物の密度は0.944g/cm3、MFR(190℃)は4.8g/10minであり、引張破壊呼び歪みは、455.4%であった。
しかしながら、得られた容器蓋についての接着性試験では、キャップ頂板部内面及び二次成形体との間に剥離が生じており、浸透液の着色が一次成形体まで到達し、二次成形体が一次成形体を被覆する機能が損なわれていた。
3:インシェルモールド成形体
3a:一次成形体
3b:二次成形体
5:頂板部
7:スカート
9:インナーリング
11:アウターリング
13:環状小突起
15:螺条
17:TEバンド
19:ブリッジ
20:フラップ片
21:一次成形用治具
21a:パンチ
23:二次成形用治具23
23a:パンチ
30:フランジ
Claims (5)
- 容器口部の内面に密着するインナーリングが設けられた頂板部とスカート部とを有する高密度ポリエチレン製キャップシェルと、該頂板部内面のインナーリングに囲まれた部分に設けられたインシェルモールド成形体とを備えた容器蓋において、
前記インシェルモールド成形体は、前記頂板部内面上でのインシェルモールドにより形成された酸素遮断機能を有する一次成形体と、該一次成形体上でのインシェルモールドにより該一次成形体を覆い且つ周縁部で前記頂板部内面に融着固定されている二次成形体とからなり、
前記二次成形体は、直鎖状低密度ポリエチレンを含み、且つ190℃でのメルトフローレートが1~10g/10分、密度が0.900~0.920g/cm3、及びJIS K-6922-2で規定された引張破壊呼び歪みが400%以上の範囲にある樹脂組成物から形成されていることを特徴とする容器蓋。 - 前記二次成形体は、前記直鎖状低密度ポリエチレンに加えて、熱可塑性エラストマーを含有している請求項1に記載の容器蓋。
- 前記二次成形体中の前記熱可塑性エラストマーの含有量が30質量%以下である請求項2に記載の容器蓋。
- 前記一次成形体は水素発生剤を含んでいる請求項1に記載の容器蓋。
- 直鎖状低密度ポリエチレンと熱可塑性エラストマーとのブレンド物からなり、190℃でのメルトフローレートが1~10g/10分、密度が0.900~0.920g/cm3、及びJIS K-6922-2で規定された引張破壊呼び歪みが400%以上の範囲にあることを特徴とするインシェルモールド用樹脂組成物。
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CN201880089678.8A CN111788120B (zh) | 2018-02-19 | 2018-12-20 | 具有阻氧性能的容器盖 |
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EP4001155A4 (en) * | 2019-07-16 | 2023-08-09 | Jin Hee Ahn | CONTAINER CAP AND CONTAINER COMBINED THEREOF |
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