WO2018155653A1 - 複合プリフォームおよびその製造方法、複合容器およびその製造方法、並びに複合容器にビールを充填した製品 - Google Patents
複合プリフォームおよびその製造方法、複合容器およびその製造方法、並びに複合容器にビールを充填した製品 Download PDFInfo
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- WO2018155653A1 WO2018155653A1 PCT/JP2018/006815 JP2018006815W WO2018155653A1 WO 2018155653 A1 WO2018155653 A1 WO 2018155653A1 JP 2018006815 W JP2018006815 W JP 2018006815W WO 2018155653 A1 WO2018155653 A1 WO 2018155653A1
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- Prior art keywords
- preform
- plastic member
- heat
- composite
- shrinkable plastic
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- B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
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- B65D41/3447—Threaded or like caps or cap-like covers provided with tamper elements formed in, or attached to, the closure skirt with rigid bead or projections formed on the tamper element and coacting with bead or projections on the container the tamper element being integrally connected to the closure by means of bridges
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1372—Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
Definitions
- the present invention relates to a composite preform and a manufacturing method thereof, a composite container and a manufacturing method thereof, and a product in which a composite container is filled with beer.
- plastic containers have become common as containers for storing liquid contents such as food and drinks.
- a plastic container is manufactured by inserting a preform into a mold and biaxially stretching.
- a preform containing a resin material such as PET or PP is molded to manufacture a container.
- the preform is generally simply formed into a container shape.
- the means is limited, for example, the material constituting the preform is changed.
- a composite container disclosed in Japanese Patent Application Laid-Open No. 2015-128858 discloses a composite container including a preform and a heat-shrinkable plastic member provided so as to surround the outside of the preform. Manufactured by molding. However, depending on the type of resin material and colorant contained in the plastic member, only the outer plastic member has been heated. For this reason, the surface of the plastic member may be dissolved, and the appearance may be impaired. Moreover, the preform could not be efficiently heated, and there was room for improvement in productivity.
- the present invention has been made based on such knowledge, and can effectively prevent deterioration of the appearance of the plastic member surface due to near-infrared heating before blow molding, and efficiently perform the inner preform. It is an object to provide a composite preform that can be heated and a method for producing the same, a composite container that is a blow-molded product of the composite preform and a method for producing the same, and a product in which the composite container is filled with beer. .
- the composite preform of the present invention is provided so as to surround the outside of the preform, a preform having a mouth, a body connected to the mouth, a bottom connected to the body, and a resin material and coloring
- a heat-shrinkable plastic member having at least a colored layer containing an agent, and the near-infrared transmittance of the heat-shrinkable plastic member is 50% or more.
- the heat-shrinkable plastic member further includes a gas barrier layer.
- the colored layer includes a polyolefin-based resin.
- the colorant is a brown pigment, and the content thereof is 0.1% by mass or more and 30% by mass or less.
- the preform has a multilayer structure including at least a gas barrier layer.
- one end of the plastic member on the bottom side of the preform is crimped.
- the crimped portion of the heat shrinkable plastic member is twisted to form a twisted portion.
- the composite container of the present invention is a blow molded product of the composite preform, and includes a mouth, a neck provided below the mouth, a shoulder provided below the neck, and a trunk provided below the shoulder.
- a heat-shrinkable plastic member provided with at least a colored layer containing a resin material and a colorant, and a container main body provided with a portion and a bottom provided below the body portion; And one end of the plastic member on the bottom side of the container body is crimped to form the bottom.
- the composite container has a transmittance of visible light having a wavelength of 400 to 500 nm of 20% or less.
- the composite container further includes a vapor deposition film on the inner surface of the container body.
- the composite container has an oxygen permeability of 0.5 cc / m 2 ⁇ day ⁇ 0.21 atm or less.
- the method for producing a composite preform of the present invention includes a step of preparing a preform and a heat-shrinkable plastic member, a step of fitting the preform from one end of the heat-shrinkable plastic member, and a heat-shrinkable plastic member. A step of thermocompression-bonding a blank portion having the step, and a step of heating the preform and the heat-shrinkable plastic member to heat-shrink the heat-shrinkable plastic member.
- the method for manufacturing the composite preform further includes a step of twisting the thermobonded blank portion to form a twisted portion.
- the method for manufacturing the composite preform further includes a step of preheating the preform before the fitting step.
- the method for producing a composite container according to the present invention includes a step of heating the composite preform and inserting the composite preform into a blow molding die, and performing blow molding on the composite preform after heating, so that the preform and the plastic are made. And a step of expanding the member as a unit.
- the product of the present invention is characterized in that the composite container is filled with beer, and a cap is attached to the mouth of the container body.
- the composite preform which can heat a preform efficiently, and its It is possible to provide a production method, a composite container which is a blow-molded product of this composite preform, a production method thereof, and a product in which the composite container is filled with beer.
- FIG. 1 is a partial vertical cross-sectional view of a composite preform of the present invention in one embodiment.
- FIG. 2 is a perspective view of the composite preform of the present invention in one embodiment.
- FIG. 3 is a front view of a composite preform having a twisted portion.
- FIG. 4 is a schematic view showing an embodiment of a method for producing a heat-shrinkable plastic member.
- FIG. 5 is a vertical sectional view showing a state in which the preform is fitted into a heat-shrinkable plastic member.
- FIG. 6 is a front view of a heat-shrinkable plastic member.
- FIG. 7 is a front view of the preform.
- FIG. 8 is a perspective view showing a crimping instrument according to an embodiment.
- FIG. 9 is a partial vertical sectional view showing a composite container manufactured using the composite preform of the present invention in one embodiment.
- FIG. 10 is a horizontal sectional view of the composite container shown in FIG.
- FIG. 11 is a schematic view showing a method for manufacturing a composite container.
- FIG. 12 is a schematic diagram illustrating a composite container manufacturing apparatus according to an embodiment.
- FIG. 13 is a schematic cross-sectional view showing a high-frequency plasma CVD apparatus.
- FIG. 14 is a partial vertical sectional view showing a product using a composite container in one embodiment.
- FIG. 15 is an enlarged partial vertical sectional view showing the vicinity of the mouth of a product using a composite container in one embodiment.
- the composite preform 70 includes a preform 10a and a heat-shrinkable plastic member 40a provided so as to surround the outside of the preform 10a.
- the composite preform 70 is biaxially stretched and blow molded, and the preform 10a of the composite preform 70 and the heat-shrinkable plastic member 40a are integrally expanded to obtain a composite container 10A.
- the preform 10a includes a mouth portion 11a, a body portion 20a connected to the mouth portion 11a, and a bottom portion 30a connected to the body portion 20a.
- the mouth portion 11 a corresponds to the mouth portion 11 of the container body 10 described above, and has substantially the same shape as the mouth portion 11.
- corresponds to the neck part 13, the shoulder part 12, and the trunk
- the bottom 30a corresponds to the bottom 30 of the container body 10 described above, and has a substantially hemispherical shape.
- the preform 10a included in the composite preform 70 of the present invention may have a single layer structure or a multilayer structure.
- Each layer provided in the preform 10a includes a thermoplastic resin, particularly a resin material such as PE (polyethylene), PP (polypropylene), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), and ionomer. be able to. Moreover, the blend resin which blended various resin mentioned above may be included.
- a resin material such as PE (polyethylene), PP (polypropylene), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), and ionomer.
- Each layer provided in the preform 10a may contain various additives as long as the characteristics of the present invention are not impaired.
- additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release agents, Examples include oxidants, ion exchangers, dispersants, ultraviolet absorbers, and color pigments.
- Each layer provided in the preform 10a may contain colorants such as red, blue, yellow, green, brown, black, and white. However, in consideration of recyclability, these layers are not included and are colorless. It is preferably transparent.
- the preform 10a has a multilayer structure including at least a gas barrier layer.
- the preform 10a may include two or more gas barrier layers. In this case, the configuration and thickness of each layer may be the same or different.
- the gas barrier layer comprises a gas barrier resin, such as metaxylene adipamide (MXD-6), nylon 6, nylon 6,6, nylon 6 / nylon 6,6 copolymer, ethylene-vinyl acetate copolymer Polymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), polyglycolic acid (PGA), polyvinylidene chloride copolymer (PVDC), polyacrylonitrile, polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE) and Examples thereof include styrene-isobutylene-styrene copolymers.
- the gas barrier layer may contain two or more kinds of the above gas barrier resins.
- the content of the gas barrier resin in the gas barrier layer is preferably 50% by mass or more, and more preferably 90% by mass or more. By setting the content of the gas barrier resin in the above numerical range, the gas barrier property of the composite container 10A can be further improved.
- the gas barrier layer may contain a resin material other than the gas barrier resin as long as the characteristics are not impaired.
- resins include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), polyethylene (LDPE, MDPE, HDPE, LLDPE), polypropylene (PP), ethylene-propylene Copolymers, polyolefin resins such as poly-4-methylpentene and poly-1-butene, vinyl chloride homopolymers, vinylidene chloride homopolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride or vinylidene chloride And vinyl resins such as copolymers with maleic acid derivatives and higher alkyl vinyl ethers, ionomer resins, and the like.
- the gas barrier layer comprises an oxidation promoter.
- the oxidation accelerator is not particularly limited as long as it promotes the reaction between the oxygen absorbent that can be auto-oxidized by molecular oxygen and molecular oxygen.
- a radical generator, a photo-oxidation catalyst, a transition Examples thereof include metal salts. Among these, a transition metal salt is preferable because a sufficient effect can be exhibited even in a small amount.
- the gas barrier layer contains an oxidation accelerator, the oxidation of the oxygen absorbent that can be auto-oxidized by molecular oxygen is promoted, and the oxygen absorption capacity is improved.
- metal salts include inorganic salts, organic salts, and complex salts.
- inorganic salts include halogenated salts, oxy salts, oxy acid salts, and silicates.
- organic acid salt include a carboxylate, a sulfonate, and a phosphonate.
- complex salts include complexes with ⁇ -diketone or ⁇ -keto acid ester.
- the content of the oxidation accelerator in the gas barrier layer is preferably 0.001% by mass or more and 3% by mass or less, more preferably 0.005% by mass or more and 2% by mass or less, and 0.01% by mass. % Or more and 1.5% by mass or less is more preferable.
- the gas barrier layer may contain an oxygen absorbent.
- the oxygen absorbent include iron-based oxygen absorbents and non-ferrous oxygen absorbents, and the non-ferrous oxygen absorbent is more preferable because the transparency of the preform 10a can be maintained.
- iron-based oxygen absorbents include iron powders such as reduced iron powder, interfacial iron powder, sprayed iron powder, iron grinding powder, electrolytic iron powder, and pulverized iron.
- non-ferrous oxygen absorbers include ethylenically unsaturated group-containing copolymers.
- the ethylenically unsaturated group-containing copolymer include polydienes such as polybutadiene, polychloroprene, poly (2-ethylbutadiene), and poly (2-butylbutadiene), which are mainly polymerized at the 1 and 4 positions, Ring-opening metathesis polymer of cycloolefin such as polyoctenylene, polypentenylene, polynorbornene, styrene-diene block copolymer such as styrene-isoprene block copolymer, styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer Among them, polybutadiene, polyoctenylene, and styrene-isoprene-styrene block copo
- the content of the oxygen absorbent in the gas barrier layer is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and 1% by mass or more. More preferably, it is 7.5 mass% or less.
- the specific layer structure includes, for example, a structure including a polyester resin layer / gas barrier layer / polyester resin layer from the innermost layer, and a polyester resin layer / gas barrier layer.
- the thing of the structure provided with / polyester-type resin layer / gas barrier layer / polyester-type resin layer is mentioned.
- More specific layer configurations include a layer comprising PET / a layer comprising MXD-6 / a layer comprising PET, a layer comprising PET / MXD-6 and a layer comprising an oxidation accelerator / PET.
- a layer comprising a layer, a layer comprising PEN / a layer comprising MXD-6 / a layer comprising a PEN, a layer comprising PEN / MXD-6 and a layer comprising an oxidation promoter / a layer comprising PEN The thing of the structure provided is mentioned.
- the preform 10a can be manufactured by injection molding a resin material or the like using a conventionally known apparatus.
- an inert gas nitrogen gas, argon gas
- a thermoplastic resin melt to form a foam preform having a foam cell diameter of 0.5 to 100 ⁇ m.
- the container body 10 may be manufactured by blow molding. Since such a container main body 10 contains the foam cell, the light shielding property of the container main body 10 whole can be improved.
- Heat-shrinkable plastic member 40a As shown in FIG. 1, the heat-shrinkable plastic member 40a is provided so as to surround the outside without being bonded to the preform 10a, and is in close contact with the preform 10a so as not to move or rotate. Or it is in close contact so that it does not fall under its own weight.
- the plastic member 40a has heat shrinkability, it is possible to prevent the foam 10 from being displaced from the preform 10a during the blow molding or from being generated between the container body 10 and the plastic member 40. And a composite container 10A having a good appearance can be obtained.
- the heat-shrinkable plastic member 40a is provided over the entire circumferential direction so as to surround the preform 10a. Further, as shown as a hatched portion in FIG. 1, one end of a heat-shrinkable plastic member 40a on the bottom 30a side of the preform 10a is thermocompression bonded, thereby forming a bottom portion that covers the bottom 30a of the preform 10a. It is preferable. Usually, it is difficult to cover the bottom 30a of the preform 10a with the heat-shrinkable plastic member 40a. However, by adopting such a configuration, after blow molding, the bottom of the container body 10 can be covered with a heat-shrinkable plastic member 40, and various functions can be applied to the bottom of the composite container 10A, such as gas barrier properties. Can be granted.
- thermocompression bonding is particularly preferably performed along the shape of the bottom 30a of the preform 10a.
- the plastic member 40a has a blank portion 80a.
- the blank portion 80a includes a bent portion 44 formed along the shape of the preform 10a and the bent portion 44.
- Each has a first opposing surface 46a and a second opposing surface 46b protruding.
- the first facing surface 46a and the second facing surface 46b are thermocompression bonded together.
- the first facing surface 46a and the second facing surface 46b each extend substantially in a straight line along the radial direction of the body portion 20a of the preform 10a when viewed from the bottom surface direction.
- the 1st opposing surface 46a and the 2nd opposing surface 46b are crimped
- the heat-shrinkable plastic member 40a may include a twisted portion 80 in which a thermocompression bonded portion is twisted (see FIG. 3). Since the heat-shrinkable plastic member 40a includes the twisted portion 80, not only can the bottom be formed, but also air bubbles can be formed between the container body 10 and the heat-shrinkable plastic member 40 included in the composite container 10A after blow molding. It is possible to prevent the occurrence of occurrence, and it is possible to prevent damage such as peeling off of the thermocompressed portion due to the force applied during blow molding.
- the heat-shrinkable plastic member 40a is one end of the body portion 41a, and when attached to the preform 10a, at least one cut is made at one end of the preform 10a on the side close to the mouth portion 11a. Have. By providing such a cut in the heat-shrinkable plastic member 40a, the plastic member 40 can be easily separated and removed from the composite container 10A after blow molding.
- the shape of the cut is not particularly limited, and may be a cut line, or may be a notch such as an arbitrary triangle or square.
- the length is not particularly limited, and may be appropriately changed in accordance with the shape of the container body 10, for example, 0.5 mm or more in the plastic member 40a before blow molding, It can be 5 mm or less.
- the heat-shrinkable plastic member 40a having a cut line having such a length is blow-molded together with the preform 10a, so that the heat-shrinkable plastic member 40 after blow molding has a cut of 3 mm or more and 15 mm or less. It will have a line and can be easily separated from the container body 10 based on this score line.
- the shape of the cutout is not particularly limited, and may be appropriately changed in consideration of the size and shape of the container body 10.
- the shape of the cutout may be a triangle shape, a square shape, a semicircular shape, a fan, or the like.
- Various shapes such as a shape combining curves such as shapes can be used.
- the vertical length can be 0.5 mm or more and 5 mm or less
- the horizontal length can be 0.1 mm or more and 8 mm or less. Absent.
- the heat-shrinkable plastic member 40a By blow-molding the heat-shrinkable plastic member 40a having such a notch together with the preform 10a, the heat-shrinkable plastic member 40 after blow molding has a vertical length of 1 mm or more, It has a triangular notch of 15 mm or less and a lateral length of 0.5 mm or more and 10 mm or less, and can be easily separated from the container body 10 based on the notch.
- the heat-shrinkable plastic member 40a has a knob portion connected to the cut.
- the material constituting the knob portion is not particularly limited, and may be made of a resin material used for manufacturing the heat-shrinkable plastic member 40a, and may be made of paper or metal. Also good.
- the near-infrared transmittance of the heat-shrinkable plastic member 40a included in the composite preform 70 of the present invention is 50% or more, more preferably 60% or more and 100% or less, still more preferably 70% or more, 100 % Or less.
- the near-infrared transmittance of the heat-shrinkable plastic member 40a can be adjusted by changing the type and content of a resin material and a colorant described later.
- near-infrared light means light having a wavelength of 800 nm to 2500 nm.
- the near-infrared transmittance being 50% or more means that the absorbance of the heat-shrinkable plastic member 40a is measured using a known spectrophotometer (for example, a spectroscope manufactured by Hamamatsu Photonics Co., Ltd.). In this case, the transmittance is 50% or more at 800 nm to 1500 nm.
- the heat-shrinkable plastic member 40a preferably has a specific gravity of less than 1 and more preferably less than 0.97.
- the specific gravity of the heat-shrinkable plastic member 40a is preferably more than 1, more preferably more than 1.2.
- the heat-shrinkable plastic member 40a provided in the composite preform 70 of the present invention may have a single layer structure or a multilayer structure.
- the heat-shrinkable plastic member 40a includes at least a colored layer containing a resin material and a colorant.
- the heat-shrinkable plastic member 40a contains a colorant, the infrared transmittance of the heat-shrinkable plastic member 40a can be adjusted. Further, the visible light transmittance of the composite container 10A after blow molding can be adjusted.
- the heat-shrinkable plastic member 40a may include two or more colored layers.
- the kind of material which comprises each colored layer, content, and the thickness of a colored layer may be the same, or may differ.
- a colored layer contains polyolefin resin as a resin material.
- polyolefin-based resins include polyethylene (LDPE, MDPE, HDPE, LLDPE), polypropylene, polybutene, polybutadiene, polyisoprene, and copolymers of these monomers (alkenes) with other monomers.
- a copolymer of ethylene and ⁇ -olefin having 4 or more carbon atoms ethylene- (meth) acrylic acid copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene-ethyl (meth) acrylate
- examples thereof include a copolymer, an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, and an ionomer resin.
- the heat-shrinkable plastic member 40a may contain one or more of the above-described polyolefin resins.
- the colored layer may contain a resin other than a polyolefin-based resin, for example, PET, PEN, poly-4-methylpentene-1, polystyrene, AS resin, ABS tree, polyvinyl chloride, Polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, diallyl phthalate resin, fluororesin, polymethyl methacrylate, polyacrylic acid, polymethyl acrylate, polyacrylonitrile, polyacrylamide, polybutadiene, polybutene 1, polyisoprene, polychloroprene, ethylene propylene rubber, butyl rubber, nitrile rubber, acrylic rubber, silicone rubber, fluorine rubber, nylon 6, nylon 6,6, MXD6, aromatic polyamide, polycarbonate, poly Ethylene phthalate, polybutylene terephthalate, ethylene polynaphthalene, U polymer, liquid crystal polymer, modified polyphenylene chloride
- the content of the resin material in the colored layer is preferably 70% by mass or more and 95% by mass or less, and more preferably 80% by mass or more and 90% by mass or less.
- the colorant contained in the colored layer may be a pigment or a dye, but a pigment is preferred from the viewpoint of light resistance.
- the color of the colorant is not particularly limited, and a colorant such as brown, black, green, white, blue, or red can be used.
- a plurality of colorants may be used. For example, a combination of red, yellow, and black colorants may be used, and the colorant may be brown.
- a brown colorant to the heat-shrinkable plastic member 40a, visible light having a wavelength of 400 to 500 nm can be cut, and the bitter components in the beer are decomposed by sunlight. It is possible to prevent a problem that 3-methyl-2-butene-1-thiol, which is an odor component, is generated.
- “beer” is defined in the Japanese liquor tax law, that is, “fermented using malt, hops and water as raw materials. Malt, hops, water and rice and other articles specified by a government ordinance. (However, the total weight of the articles specified in the relevant ordinance does not exceed 5/10 of the weight of the malt).
- the weight of malt in the raw material is (1) 67/100 or more of the weight of raw materials other than water, (2) 50/100 or more and less than 67/100, (3) 100 minutes Also included are those having 25 or more and less than 50/100, and (4) those having less than 25/100, so-called “third beer”, “beer-taste beverage”, and “miscellaneous sake”.
- the colored layer may contain one or more colorants, and the content thereof is preferably 0.1% by mass or more and 30% by mass or less, and 0.5% by mass or more and 10% by mass. % Or less is more preferable.
- a coloring agent can be favorably disperse
- the heat-shrinkable plastic member 40a can be easily manufactured.
- the colored layer may contain other additives as described above, as long as the effects of the present invention are not impaired.
- the thickness of the colored layer before blow molding is preferably 5 ⁇ m or more and 1000 ⁇ m or less, and more preferably 10 ⁇ m or more and 500 ⁇ m or less.
- the thickness of the colored layer may be uniform, but may be appropriately changed in consideration of the portion covering the container body 10 after blow molding.
- the heat-shrinkable plastic member 40a may further include a gas barrier layer.
- the heat-shrinkable plastic member 40a may include two or more gas barrier layers.
- the kind of material which comprises each gas barrier layer, content, and the thickness of a colored layer may be the same, or may differ.
- the gas barrier layer contains a gas barrier resin such as meta-xylene adipamide (MXD-6), nylon 6, nylon 6,6, nylon 6 / nylon 6,6 copolymer, ethylene-vinyl acetate copolymer ( EVA), ethylene-vinyl alcohol copolymer (EVOH), polyglycolic acid (PGA), polyvinylidene chloride copolymer (PVDC), polyacrylonitrile, polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE) and styrene- Examples include isobutylene-styrene copolymer.
- the gas barrier layer may contain two or more kinds of the above gas barrier resins.
- the content of the gas barrier resin in the gas barrier layer is preferably 50% by mass or more, and more preferably 90% by mass or more. Thereby, the gas barrier property of 10 A of composite containers can be improved more.
- the gas barrier layer may contain an oxygen absorbent.
- the oxygen absorbent is as described above.
- the content of the oxygen absorbent in the gas barrier layer is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and 0.1% by mass. % Or more and 2% by mass or less is more preferable.
- the gas barrier layer can contain an oxidation accelerator.
- the oxidation accelerator is not particularly limited as long as it promotes the reaction between the oxygen absorbent that can be auto-oxidized by molecular oxygen and molecular oxygen.
- a radical generator, a photo-oxidation catalyst, a transition Examples thereof include metal salts. Among these, a transition metal salt is preferable because a sufficient effect can be exhibited even in a small amount.
- the gas barrier layer contains an oxidation accelerator, the oxidation of the oxygen absorbent that can be auto-oxidized by molecular oxygen is promoted, and the oxygen absorption capacity is improved.
- metal salts include inorganic salts, organic salts, and complex salts.
- inorganic salts include halogenated salts, oxy salts, oxy acid salts, and silicates.
- organic acid salt include a carboxylate, a sulfonate, and a phosphonate.
- complex salts include complexes with ⁇ -diketone or ⁇ -keto acid ester.
- the content of the oxidation accelerator in the gas barrier layer is preferably 0.001% by mass or more and 2% by mass or less, more preferably 0.005% by mass or more and 1% by mass or less, and 0.01% by mass. % Or more and 0.5% by mass or less is more preferable.
- the gas barrier layer may contain the above-described resin materials and additives as long as the characteristics are not impaired.
- the thickness of the gas barrier layer before blow molding is preferably 10 ⁇ m or more and 300 ⁇ m or less, and more preferably 15 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the gas barrier layer may be uniform, but may be appropriately changed in consideration of the location covering the container body 10 after blow molding.
- the heat-shrinkable plastic member 40a may further include an adhesive layer between the colored layer and the gas barrier layer.
- Examples of the adhesive constituting the adhesive layer include a polyvinyl acetate adhesive, a polyacrylate adhesive, a cyanoacrylate adhesive, an ethylene copolymer adhesive, a cellulose adhesive, a polyester adhesive, Examples thereof include polyamide adhesives, polyimide adhesives, amino resin adhesives, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, rubber adhesives, and silicone adhesives.
- the thickness of the adhesive layer before blow molding is not particularly limited, but can be 5 ⁇ m or more and 150 ⁇ m or less.
- the specific layer structure includes, for example, a structure including a colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer from the innermost layer, coloring Examples include a layer / adhesive layer / gas barrier layer / adhesive layer / colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer.
- the heat-shrinkable plastic member 40a can be manufactured by a method including an extrusion process. More specifically, first, a resin composition containing the above-described resin material and colorant is heated and melted in an extrusion apparatus, and the molten resin material is continuously extruded from a ring die and cooled. The drawn extruded tube 1 is formed (see FIG. 4A). Next, one end of the extruded tube is closed by welding or bonding one end of the unstretched extruded tube. Further, the extruded tube 1 whose one end is closed is disposed in a mold 2 having an inner diameter larger than the outer diameter of the extruded tube 1 (see FIG. 4B).
- the blow device 3 is disposed (attached) to the other end of the extruded tube 1 (see FIG. 4C). At this time, it is preferable that the blower 3 is in close contact with the extruded tube 1 so that air does not leak between them.
- the extruded tube 1, the mold 2 and the blow device 3 are sent to the heating furnace 4 in this arrangement, and heated to 70 to 150 ° C. inside the heating furnace 4 (see FIG. 4D).
- a hot-air circulating heating furnace may be used in order to make the inside uniform. Or you may heat these by passing the extrusion tube 1, the metal mold
- the extruded tube 1, the mold 2 and the blow device 3 are taken out from the heating furnace 4, and air is blown into the extruded tube 1 from the blow device 3, whereby the inner surface of the extruded tube 1 is stretched under pressure.
- the extruded tube 1 expands and expands along the inner shape of the mold 2 (see FIG. 4E).
- the extruded tube 1 is cooled in cold water while air is blown out from the blower 3, and the extruded tube is taken out from the mold 2 (see FIG. 4 (f)).
- a heat-shrinkable plastic member 40a is obtained (see FIG. 4G).
- the heat-shrinkable plastic member 40a having a multilayer structure can be manufactured by co-extruding a resin composition containing a gas barrier resin and the like together with the resin composition.
- the heat-shrinkable plastic member 40a may be printed with images and characters. In this case, it is possible to display images and characters on the composite container 10A without separately providing a label or the like to the container body 10 after blow molding.
- Manufacturing method of composite preform 70 The manufacturing method of the composite preform 70 of the present invention includes: Preparing the preform 10a and the heat-shrinkable plastic member 40a; A step of fitting the preform 10a from the other end of the heat-shrinkable plastic member 40a; Heating the preform 10a and the heat-shrinkable plastic member 40a, and heat-shrinking the heat-shrinkable plastic member 40a.
- the method for manufacturing the composite preform 70 of the present invention may further include a step of thermocompression bonding the blank portion of the heat-shrinkable plastic member 40a.
- the method for manufacturing the composite preform 70 of the present invention may further include a step of twisting the blank portion subjected to thermocompression bonding to form the twisted portion 80.
- the manufacturing method of the composite preform 70 of this invention may include the process of providing a notch in the heat-shrinkable plastic member 40a.
- the method for manufacturing the composite preform 70 of the present invention may further include a step of sterilizing the preform 10a and / or the heat-shrinkable plastic member 40a.
- the method for manufacturing the composite preform 70 of the present invention may include a step of printing images, characters, etc. on the heat-shrinkable plastic member 40a.
- Step for preparing preform 10a and heat-shrinkable plastic member 40a As preform 10a and heat-shrinkable plastic member 40a, those manufactured by the above-described method may be used, and those that are commercially available are used. Also good.
- the length X of the heat-shrinkable plastic member 40a is preferably longer than the sum Y of the lengths of the body portion 20a and the bottom portion 30a of the preform 10a and has a blank portion. .
- the length of the blank portion is preferably 3 mm or more, and more preferably 5 mm or more and 20 mm or less.
- the length of the heat-shrinkable plastic member 40a refers to the length X before heat shrinkage, as shown in FIG. Further, the sum of the lengths of the body portion 20a and the bottom portion 30a of the preform 10a refers to the length Y shown in FIG.
- the method for manufacturing the composite preform 70 of the present invention includes a step of inserting the preform 10a from one end of the heat-shrinkable plastic member 40a.
- the preform 10a prior to the fitting step, is preferably preheated using near infrared rays or warm air. Thereby, the adhesiveness of the preform 10a and the heat-shrinkable plastic member 40a can be further improved.
- the preheating temperature of the surface of the preform 10a is not particularly limited, it is preferably heated to 40 ° C. or higher and 90 ° C. or lower, more preferably 50 ° C. or higher and 70 ° C. or lower. By setting the heating temperature within the above numerical range, the adhesion between the preform 10a and the heat-shrinkable plastic member 40a can be further improved.
- the method for manufacturing the composite preform 70 of the present invention includes a process of heating the preform 10a and the heat-shrinkable plastic member 40a to heat-shrink the heat-shrinkable plastic member 40a and closely adhere to the preform 10a. Including.
- the heating method of the preform 10a and the heat-shrinkable plastic member 40a is not particularly limited, and can be appropriately performed using near infrared rays, hot air, or the like.
- the heating temperature is preferably 60 ° C. or higher and 250 ° C. or lower, and more preferably 80 ° C. or higher and 150 ° C. or lower.
- the heating temperature is the surface temperature of the heat-shrinkable plastic member 40a at the time of heating, and is not an irradiation temperature such as near infrared rays or warm air.
- Thermocompression Bonding Process includes a process of thermocompression bonding one end (the other end) opposite to one end of the heat-shrinkable plastic member 40a into which the preform 10a has been fitted. Also good.
- thermocompression bonding of the heat-shrinkable plastic member 40a (hereinafter, sometimes referred to as a “crimping instrument”) is heated by the near-infrared ray or hot air, and then sandwiched, so that the end is clamped.
- a crimping instrument An instrument used for thermocompression bonding of the heat-shrinkable plastic member 40a (hereinafter, sometimes referred to as a “crimping instrument”) is heated by the near-infrared ray or hot air, and then sandwiched, so that the end is clamped.
- a metal or heat-resistant resin tool can be used, and these may be combined.
- compression-bonding instrument is not specifically limited, The thing made from a metal or a heat resistant resin can be used. Further, the surface of the crimping device may be flat or partially or entirely uneven. Moreover, the crimping
- the heating temperature of the surface of the crimping device is preferably, for example, 100 ° C. or more and 250 ° C. or less.
- the pressure during pressure bonding is preferably 50 N / cm 2 or more and 1000 N / cm 2 or less, more preferably 100 N / cm 2 or more and 500 N / cm 2 or less.
- the temperature of the heat-shrinkable plastic member 40a at the time of crimping is preferably changed as appropriate according to the configuration of the heat-shrinkable plastic member 40a.
- one end of the heat-shrinkable plastic member 40a after thermocompression bonding may be cut to an appropriate length as desired. Thereby, the external appearance of the bottom part at the time of setting it as a composite container becomes favorable. As shown in FIG. 1, the crimping portion may be cut in a straight line or in a shape along the shape of the bottom of the preform 10a (not shown).
- the method of this invention may include the process of twisting the thermocompression-bonded part and forming the twist part 80 shown in FIG.
- the method of the present invention includes the container body 10 included in the composite container 10A. And generation of bubbles between the heat-shrinkable plastic member 40 can be prevented. Further, during blow molding, it is possible to prevent peeling or breakage of the thermocompression-bonded portion of the heat-shrinkable plastic member 40a.
- the method for forming the twisted portion 80 is not particularly limited, and the twisted portion 80 can be formed by twisting a manually crimped portion using an instrument such as pliers. Moreover, it can carry out mechanically using the rotation apparatus etc. which hold
- the twisted portion 80 can be formed simultaneously with the thermocompression bonding. Thereby, a work process can be reduced and productivity can be improved more. Specifically, it can be performed by providing a rotation mechanism in the crimping tool, fixing the preform 10a and the heat-shrinkable plastic member 40a to the holding portion, and rotating the crimping tool. Moreover, it can also carry out by using the crimping instrument as a holding part and rotating the preform 10a and the heat-shrinkable plastic member 40a by the rotating part.
- the degree of twisting of the blank portion is not particularly limited, and may be about 0.25 to 30 rotations, and may be performed until the thread is cut off, but the appearance can be improved. And since it can prevent more effectively that the part which carried out thermocompression bonding is damaged by blow molding, it is preferable to carry out until it cuts off.
- incision may include the process of providing an incision in the heat-shrinkable plastic member 40a.
- the heat-shrinkable plastic member 40 can be easily separated and removed from the notch from the composite container 10A after blow molding.
- the position at which the cut is provided is not particularly limited, but is one end of the body portion 41a of the heat-shrinkable plastic member 40a and is close to the mouth portion 11a of the preform 10a when attached to the preform 10a. It is preferable to provide at one end of the side from the viewpoint of easy separation. Further, the number of cuts is not limited, and may have cuts at two or more places.
- the method of forming the cut is not particularly limited.
- the cut of the heat-shrinkable plastic member 40a can be formed by using scissors or a knife. it can. Further, even after the preform 10a is fitted, a cut can be formed by using a laser beam or the like.
- the laser light to be used is not particularly limited, and examples thereof include He-Ne laser, Ar laser, carbon dioxide laser, excimer laser, metal vapor laser, fiber laser, YAG lasers including Nd: YAG laser, and the like. And higher harmonic lasers.
- the cut may be formed on the composite container 10A obtained by blow-molding the composite preform 70, and can be formed on the heat-shrinkable plastic member 40 using laser light or the like.
- the method of the present invention may include a step of providing a knob connected to the notch so that the heat-shrinkable plastic member 40 can be separated more easily.
- the knob can be bonded to the heat-shrinkable plastic member 40a with a conventionally known adhesive.
- a conventionally known adhesive for example, polyvinyl acetate adhesive, polyacrylate adhesive, cyanoacrylate adhesive, ethylene copolymer adhesive, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, Adhesives such as amino resin adhesives, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, rubber adhesives, and silicone adhesives can be used.
- the picking portion may be performed on the heat-shrinkable plastic member 40a before blow molding, or may be performed on the heat-shrinkable plastic member 40 after blow molding.
- the method of the present invention may include a step of sterilizing the inner and outer surfaces of the preform 10a and / or the inner and outer surfaces of the heat-shrinkable plastic member 40a.
- This sterilization treatment may be performed on the preform 10a and the heat-shrinkable plastic member 40a before fitting, or performed on the preform 10a and the heat-shrinkable plastic member 40a after fitting. It may be performed at both time points. Further, the sterilization treatment may be performed on the container body 10 and the heat-shrinkable plastic member 40 included in the composite container 10A after blow molding.
- sterilization treatment method examples include chemical sterilization treatment, light sterilization treatment, radiation sterilization treatment, hot water sterilization treatment, hot filling sterilization treatment, and pasteurizing sterilization treatment, and these may be combined.
- Hydrogen peroxide (H 2 O 2 ) sterilization treatment is one example of chemical sterilization treatment.
- a mist, gas or a mixture thereof containing a hydrogen peroxide component is generated, and the hydrogen peroxide mist, gas or a mixture thereof is converted into the preform 10a, the heat-shrinkable plastic member 40a, the composite plate.
- the sterilization process is performed by spraying on the reform 70 or the composite container 10A.
- the preform 10a, the heat-shrinkable plastic member 40a, and the composite preform 70 may be sterilized by blowing hot air after being immersed in hydrogen peroxide water.
- the microorganisms adhering to the surface of the preform 10a are sterilized or damaged.
- the attached hydrogen peroxide can be activated by spraying hot air on the preform 10a. Can be done effectively. Further, excess hydrogen peroxide can be removed by hot air treatment.
- Examples of the chemical sterilization treatment include peracetic acid (CH 3 COOH) sterilization treatment.
- This peracetic acid sterilization treatment is performed by spraying an aqueous peracetic acid solution in the form of liquid or gas onto the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A. .
- a chlorine sterilization treatment can be exemplified.
- an acidic cleaning liquid such as a chlorite aqueous solution is used, and the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A is cleaned and sterilized with such an acidic cleaning liquid. Processing is performed.
- an alkaline aqueous solution sterilization treatment using an alkaline aqueous solution can be used.
- the alkaline aqueous solution sterilization treatment is performed by washing the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70, or the composite container 10A with an alkaline aqueous solution made of, for example, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, or a sodium carbonate aqueous solution.
- a sterilization treatment is performed.
- an ozone sterilization treatment using ozone can be used as the chemical sterilization treatment.
- the ozone sterilization treatment is performed by injecting ozone into the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A.
- photo sterilization treatment examples include UV sterilization treatment and light pulse sterilization treatment.
- the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A is irradiated with light to perform the sterilization process.
- light for example, ultraviolet light having a wavelength of 150 to 2000 nm or light emitted from a xenon lamp can be used.
- a plasma sterilization process can be mentioned as the photo sterilization process.
- the plasma sterilization treatment low temperature plasma is generated in a decompression chamber, and the sterilization treatment is performed by irradiating the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A.
- EB sterilization treatment As one of the radiation sterilization treatments, an EB sterilization treatment can be used.
- the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A is irradiated with an electron beam (EB) to perform the sterilization treatment.
- EB electron beam
- Hot water sterilization treatment is performed by preparing hot water of, for example, 70 ° C. to 95 ° C. and spraying the hot water onto the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A. Is to be applied.
- the hot filling sterilization treatment is performed by, for example, preparing a medium temperature content liquid of 60 ° C. to 80 ° C. and filling the composite container 10A with the medium temperature content liquid to sterilize the composite container 10A. It is. This hot filling sterilization treatment can be performed simultaneously with the operation of filling the composite container 10A with the content liquid and the sterilization treatment.
- the composite container 10A can also be hot-filled and sterilized by preparing a high-temperature content liquid of, for example, 80 ° C. to 95 ° C.
- the preform can be heated to be sterilized.
- Printing on the heat-shrinkable plastic member 40a can be performed by a printing method such as an inkjet method, silk printing, gravure printing method, offset printing method, flexographic printing method, thermal transfer method, hot stamping (foil stamping).
- a printing method such as an inkjet method, silk printing, gravure printing method, offset printing method, flexographic printing method, thermal transfer method, hot stamping (foil stamping).
- a UV curable ink is applied to the heat-shrinkable plastic member 40a
- UV irradiation is applied to the heat-curable plastic member 40a.
- This printing may be performed on the heat-shrinkable plastic member 40a before being fitted into the preform 10a, or may be performed in a state where the heat-shrinkable plastic member 40a is provided outside the preform 10a. good.
- the heat-shrinkable plastic member 40 provided in the composite container 10A after blow molding may be printed.
- the composite container 10A of the present invention is a blow-molded product of the composite preform 70 described above. As shown in FIG. 9, the container body 10 positioned inside and the heat provided in close contact with the outside of the container body 10 are provided. A shrinkable plastic member 40. In one embodiment, the composite container 10 ⁇ / b> A of the present invention includes a vapor deposition film 21 formed on the inner surface of the container body 10.
- the heat-shrinkable plastic member 40 Since the heat-shrinkable plastic member 40 is not welded or bonded to the container body 10, it can be separated (separated) from the container body 10 and recovered. As a method of separating (peeling) the heat-shrinkable plastic member 40 from the container body 10, for example, the heat-shrinkable plastic member 40 is cut using a blade or the like, or is cut into the heat-shrinkable plastic member 40 in advance. A line and the above-mentioned notch are provided, and the heat-shrinkable plastic member 40 can be peeled along these.
- the composite container 10A is pulverized and then immersed in hot water, and the difference in specific gravity between the heat-shrinkable plastic member 40 and the container body 10 is used to separate and recover the heat-shrinkable plastic member 40. can do. Further, since the heat-shrinkable plastic member 40 has heat-shrinkability, it can be easily peeled off from the container body 10 in hot water. Since the heat-shrinkable plastic member 40 can be separated and removed from the container body 10 by the method as described above, the colorless and transparent container body 10 can be recycled as in the conventional case.
- Oxygen permeability of the composite container 10A is preferably not more than 0.5cc / m 2 ⁇ day ⁇ 0.21atm , more preferably not more than 0.3cc / m 2 ⁇ day ⁇ 0.21atm .
- the oxygen transmission rate is determined according to a pressure method such as JIS K 7126, an oxygen transmission rate measuring device (for example, manufactured by MOCON, trade name: OX-TRAN 2/20) 23 ° C., humidity 90% RH. It is a value measured according to the above condition, and is a value obtained by measuring the entire container of the composite container 10A whose mouth is closed with a jig and dividing by the surface area of the entire container excluding the mouth.
- the container body 10 includes a mouth part 11, a neck part 13 provided below the mouth part 11, a shoulder part 12 provided below the neck part 13, a trunk part 20 provided below the shoulder part 12, and a trunk part 20.
- the bottom part 30 provided below is provided.
- “upper” and “lower” refer to the upper side and the lower side in a state where the composite container 10A is erected (FIG. 9), respectively.
- the mouth portion 11 has a screw portion 14 attached to a cap (not shown) and a flange portion 17 provided below the screw portion 14.
- the shape of the mouth portion 11 may be a conventionally known shape, or may be a stopper-type mouth portion or a mouth portion having a shape on which a crown can be attached.
- the neck portion 13 is located between the flange portion 17 and the shoulder portion 12, and has a substantially cylindrical shape having a substantially uniform diameter.
- the shoulder 12 is located between the neck 13 and the trunk 20 and has a shape whose diameter gradually increases from the neck 13 toward the trunk 20.
- the body portion 20 has a cylindrical shape having a substantially uniform diameter as a whole.
- the present invention is not limited to this, and the body portion 20 may have a polygonal cylindrical shape such as a rectangular cylindrical shape or an octagonal cylindrical shape.
- drum 20 has a cylinder shape with a horizontal cross section which is not uniform toward upper direction from the downward direction.
- drum 20 may be provided with uneven structures, such as a panel or a groove
- the body portion 20 preferably does not have an uneven structure. Thereby, the deformation
- the bottom portion 30 has a concave portion 31 located in the center and a grounding portion 32 provided around the concave portion 31.
- the shape of the bottom portion 30 is not particularly limited, and may have a conventionally known bottom shape (for example, a petaloid bottom shape or a round bottom shape).
- the shape of the bottom 30 is preferably a petaloid shape.
- the container body 10 included in the composite container 10A of the present invention may have a single layer structure or a multilayer structure.
- the container body comprises a gas barrier layer.
- the type and content of the resin material contained in the gas barrier layer are as described above.
- the average thickness excluding the mouth portion 11 of the container body 10 is preferably 200 ⁇ m or more and 1000 ⁇ m or less, and more preferably 250 ⁇ m or more and 750 ⁇ m or less.
- the heat-shrinkable plastic member 40 is in close contact with the outer surface of the container main body 10 in a thinly extended state, and is attached to the container main body 10 without being easily moved or rotated. As shown in FIG. 10, the heat-shrinkable plastic member 40 is provided over the entire circumferential direction so as to surround the container body 10 and has a substantially circular horizontal cross section. One end of the plastic member 40 on the bottom 30 side of the container main body 10 is crimped to form a bottom portion that covers the bottom 30 of the container main body 10.
- One end of the heat-shrinkable plastic member 40 provided in the composite container 10A of the present invention is pressure-bonded to form a bottom part, and the shoulder part 12, the trunk part 20 and the bottom part 30 except for the mouth part 11 and the neck part 13 in the container body 10. It can provide so that it may cover. With such a configuration, desired functions and characteristics can be imparted to the shoulder portion 12, the trunk portion 20, and the bottom portion 30 of the container body 10. Further, as described above, the crimped portion may be twisted.
- the heat-shrinkable plastic member 40 included in the composite container 10A of the present invention includes at least a colored layer.
- the heat-shrinkable plastic member 40 includes a gas barrier layer.
- the type and content of the resin material included in each layer included in the heat-shrinkable plastic member 40 are as described above.
- the thickness of the heat-shrinkable plastic member 40 is preferably 5 ⁇ m or more and 200 ⁇ m or less, and more preferably 10 ⁇ m or more and 100 ⁇ m or less when attached to the container body 10. Further, the thickness of the heat-shrinkable plastic member 40 may be uniform as a whole, or may have a thickness that is appropriately different depending on the location covering the container body 10. Further, the thickness of the colored layer in the composite container 10A is preferably 5 ⁇ m or more and 100 ⁇ m or less, and more preferably 5 ⁇ m or more and 50 ⁇ m or less. Further, the thickness of the gas barrier layer in the composite container 10A is preferably 1 ⁇ m or more and 100 ⁇ m or less, and more preferably 1 ⁇ m or more and 20 ⁇ m or less.
- the heat-shrinkable plastic member 40 is provided so as to surround the outer side of the preform 10a, and the heat-shrinkable plastic member 40a closely adhered to the outer side of the preform 10a is biaxially stretched together with the preform 10a. It was obtained by blow molding.
- the heat-shrinkable plastic member 40 is required to have a function of cutting visible light having a wavelength of 400 to 500 nm.
- the transmittance of visible light having a wavelength of 400 to 500 nm of the composite container 10A including the heat-shrinkable plastic member 40 is preferably 15% or less, more preferably 5% or less, and further preferably 1% or less. preferable.
- the visible light transmittance can be adjusted by adjusting the type and content of the colorant contained in the heat-shrinkable plastic member 40.
- the transmittance of visible light can be measured at intervals of 0.5 nm using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer), and the light transmittance of visible light wavelength can be obtained. .
- the heat-shrinkable plastic member 40 may have a cut. This cut may be a cut line, or may be a notch such as an arbitrary triangle or square. For example, when a cut line is provided in the heat-shrinkable plastic member 40a before blow molding, the cut line has a shape pulled from the left and right by stretching of the heat-shrinkable plastic member 40a by blow molding. Moreover, the heat-shrinkable plastic member 40 may have a knob portion connected to the cut. Details of the notch and the picking portion have been described above, and are omitted here.
- the composite container 10 ⁇ / b> A of the present invention includes a vapor deposition film 21 on the inner surface of the container body 10.
- the vapor deposition film 21 is formed over the entire inner surface of the container body 10 with a substantially uniform thickness.
- the vapor deposition film 21 is preferably made of an inorganic oxide from the viewpoints of gas barrier properties such as oxygen and water vapor, and transparency.
- an inorganic oxide aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, or the like can be used.
- silicon oxide is particularly preferable from the viewpoints of gas barrier properties and production efficiency.
- carbon-added silicon oxide (SiOC) can also be used.
- the silicon oxide is represented by the general formula SiO X (where X represents a number from 0 to 2). From the viewpoint of gas barrier properties and transparency, X is 1 Preferably it represents a number from 3 to 1.9.
- the vapor deposition film 21 containing silicon oxide contains silicon oxide as a main component, and further contains at least one compound composed of one or more elements of carbon, hydrogen, silicon, and oxygen by a chemical bond or the like. Good.
- a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc.
- the organic silicon compound as a raw material or a derivative thereof is further chemically bonded. Etc. may be contained. Specific examples include hydrocarbons having a CH 3 site, hydrosilica such as SiH 3 silyl and SiH 2 silylene, and hydroxyl derivatives such as SiH 2 OH silanol.
- the vapor deposition film 21 may be a hard carbon film made of, for example, a DLC (Diamond Like Carbon) film.
- the hard carbon film made of a DLC film is a hard carbon film also called an i-carbon film or a hydrogenated amorphous carbon film (aC: H), which is an amorphous carbon film mainly composed of SP 3 bonds.
- the film thickness of the vapor deposition film 21 is preferably 0.002 ⁇ m or more and 0.4 ⁇ m or less, and more preferably 0.005 ⁇ m or more and 0.1 ⁇ m or less.
- a label may be attached to the container body 10 and / or the heat-shrinkable plastic member 40.
- This label may be provided so as to cover the entire container main body 10 or may be provided so as to cover a part thereof.
- a shrink label for example, a shrink label, a stretch label, a roll label, a tack label, a paper label, or a label suspended from the neck 13 of the composite container 10A with a string or the like (hereinafter referred to as “suspended label” in some cases). And so on.
- a shrink label, a stretch label or a roll label because of high productivity.
- the light shielding property may be further improved by using a conventionally known shrink label having a light shielding property, a paper label, or the like.
- the shrink label can be wound so as to cover the whole or a part of the container body 10 and / or the heat-shrinkable plastic member 40.
- the shrink label can be obtained by attaching to the container body 10 and / or the heat-shrinkable plastic member 40 and shrinking at a temperature of 80 to 90 degrees.
- Shrink labels are polylactic acid film, polystyrene film, polyester film, low density polyethylene film, medium density polyethylene film, high density polyethylene film, low density linear polyethylene film, cyclic polyolefin film, polypropylene film, ethylene-propylene Centrifugal polyolefin film, polyester-polystyrene multilayer film, non-woven fabric formed from resin such as copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer Laminated film of polyester and shrink film, polyester-polystyrene coextruded film, polyamide film such as 6-nylon film, 6,6-nylon film, chlorinated polyethylene Can be produced using a modified polyolefin film formed from a resin such as chlorinated polypropylene, a film formed from a vinyl chloride-vinyl acetate copolymer resin, or an acrylic resin film.
- the above film uses one or more of the resins constituting it, and is a single layer using a film forming method such as extrusion method, cast molding method, T-die method, cutting method, inflation method, etc.
- Various resin films formed by stretching in the biaxial direction can be used. Among these, a stretched film and a uniaxially stretched film in the flow direction is preferable.
- a stretched polyester film, a stretched polystyrene film, a stretched polyolefin film, a polylactic acid film, a foamed polyolefin film, a stretched polyester-polystyrene coextruded film or a foamed polystyrene film because of its high heat insulating properties
- a polyester-polystyrene multilayer film or the like can be preferably used.
- the laminated film of a nonwoven fabric and the said film can be used.
- the stretched film may be uniaxially stretched or biaxially stretched. In the case of a uniaxially stretched film, it may be longitudinally uniaxially stretched or laterally uniaxially stretched.
- the thickness of the shrink label is not limited to this, but can be, for example, about 10 ⁇ m to 80 ⁇ m when attached to the composite container 10A.
- the stretch label can be wound so as to cover the container body 10 and / or the whole or part of the heat-shrinkable plastic member 40, similarly to the shrink label.
- the stretch label can be manufactured by being fitted to the composite container 10A while being stretched in the circumferential direction, and then contracted by removing the pulling force, following the composite container 10A, and being wound.
- Stretch labels are thermoplastic resin films with moderate flexibility, such as single-layer or multilayer resin films made of polyolefin resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, low-density linear polyethylene, and polypropylene. Can be used. Among these, it is preferable to produce using a single layer film made of low density linear polyethylene and a multilayer film comprising a layer made of low density linear polyethylene. These films can be produced by the method described above.
- the thickness of the stretch label is not limited to this, but can be set to, for example, about 5 ⁇ m to 50 ⁇ m when attached to the composite container 10A.
- the roll label and the tack label can be wound so as to cover the entire region or a part of the container body 10 and / or the heat-shrinkable plastic member 40.
- a roll label can be manufactured by winding a resin film around a composite container and adhering or fusing the ends of the resin film.
- the tack label can be produced by directly attaching the resin film to the composite container via an adhesive or the like.
- the adhesive examples include a polyvinyl acetate adhesive, a polyacrylate adhesive, a cyanoacrylate adhesive, an ethylene copolymer adhesive, a cellulose adhesive, a polyester adhesive, a polyamide adhesive, Examples thereof include polyimide adhesives, amino resin adhesives, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, rubber adhesives, and silicone adhesives.
- the thicknesses of the roll label and the tack label are not limited to this, but can be set to, for example, about 5 ⁇ m to 100 ⁇ m when attached to the composite container 10A.
- the paper label can be wound so as to cover the entire area or a part of the container body 10 and / or the heat-shrinkable plastic member 40.
- a paper label can be manufactured by sticking a resin film directly to a composite container via an adhesive or the like, similar to a tack label.
- the paper label is preferably manufactured using paper having excellent water resistance impregnated with a polyisocyanate compound or the like.
- the thickness of the paper label is not limited to this, but it can be set to, for example, about 50 ⁇ m to 300 ⁇ m in a state of being attached to the composite container 10A.
- the hanging label can be manufactured by hanging a resin film or paper label from the neck 13 of the composite container 10A with a string or the like.
- the size / thickness of the label is not particularly limited, and a label of any size / thickness can be used.
- the label may be printed. Printing can be performed by a printing method such as an inkjet method, a gravure printing method, an offset printing method, a flexographic printing method, a thermal transfer method, a hot stamp (foil pressing), a silk screen printing method, or a pad printing method.
- the displayed items may include character information such as the name of the content liquid, the manufacturer, and the raw material name in addition to the design and the product name.
- the label may be partially or entirely colored in a color such as red, blue, yellow, green, brown, black, or white, and may be transparent or opaque.
- the manufacturing method of the composite container 10A of the present invention includes: Heating the composite preform 70 and inserting it into a blow mold; A step of inflating the preform 10a and the heat-shrinkable plastic member 40a integrally by performing blow molding on the composite preform 70 after heating; Comprising.
- the manufacturing method of the composite container 10 ⁇ / b> A of the present invention further includes a step of forming a vapor deposition film 21 on the inner surface of the container body 10.
- a step of sterilizing the composite container 10A may be included.
- the composite preform 70 is heated by the near infrared irradiation device 51 (see FIG. 11A). Note that the present invention is not limited to this, and heating with warm air, microwave, laser, or the like may be used. At this time, the composite preform 70 is evenly heated in the circumferential direction by the heating device 51 while rotating with the mouth portion 11a facing downward.
- the heating temperature of the preform 10a and the plastic member 40a in this heating step can be set to 90 ° C. to 130 ° C., for example.
- the composite preform 70 heated by the near infrared irradiation device 51 is sent to the blow molding die 50 (see FIG. 11B).
- the composite container 10 ⁇ / b> A is molded using this blow molding die 50.
- the blow mold 50 includes a pair of body molds 50a and 50b and a bottom mold 50c that are divided from each other (see FIG. 11B).
- the pair of body molds 50a and 50b are open to each other, and the bottom mold 50c is raised upward.
- the composite preform 70 is inserted between the pair of body molds 50a and 50b.
- the body molds 50a and 50b are heated to 30 ° C to 80 ° C, and the bottom mold 50c is cooled to 5 ° C to 25 ° C.
- the preform 10a of the composite preform 70 and the heat-shrinkable plastic member 40a are expanded as a unit.
- the preform 10a and the heat-shrinkable plastic member 40a are integrally formed into a shape corresponding to the inner surface of the blow molding die 50.
- the pair of body molds 50 a and 50 b and the bottom mold 50 c are separated from each other, and the composite container 10 ⁇ / b> A before the deposition film formation is taken out from the blow molding mold 50. .
- the composite container 10A may be manufactured by two-stage blow molding. Specifically, first, the composite preform 70 is blow-molded so as to be larger than the composite container 10A having the capacity to be manufactured, and then the composite container 10A is heated to be freely contracted. The composite container 10A having a desired capacity can be obtained by blow molding the contracted composite container 10A. By manufacturing the composite container 10A by such blow molding, the strength and heat resistance of the composite container 10A can be improved.
- a manufacturing apparatus 100 shown in FIG. 12 is an apparatus for manufacturing the above-described composite container 10A.
- the composite container 10A manufacturing apparatus 100 includes a molding unit 101, a plastic member mounting unit 102, a heating unit 103, and a blow molding unit 104.
- the molding unit 101, the plastic member mounting unit 102, the heating unit 103, and the blow molding unit 104 are integrated with each other in the manufacturing apparatus 100.
- the composite preform 70 and the composite container 10A can be manufactured in the same apparatus.
- the composite container manufacturing apparatus 100 further includes a control unit 105 that controls the molding unit 101, the plastic member mounting unit 102, the heating unit 103, and the blow molding unit 104.
- a control unit 105 that controls the molding unit 101, the plastic member mounting unit 102, the heating unit 103, and the blow molding unit 104.
- integrated means that a plurality of elements are physically connected and integrated, or are integrally controlled by one control unit (for example, the control unit 105). It means that
- the molding unit 101, the plastic member mounting unit 102, the heating unit 103, and the blow molding unit 104 are arranged in this order from the upstream side to the downstream side in the manufacturing apparatus 100.
- these units are arranged in a straight line, but the present invention is not limited to this, and they may be arranged in an annular shape.
- the molding unit 101 is for molding a preform 10a made of a plastic material.
- the molding unit 101 is, for example, an injection molding unit that performs injection molding.
- the molding unit 101 includes an injection unit 106 that melts and injects resin pellets, and a molding die 107 that molds the preform 10a. is doing.
- the molding unit 101 may be a compression molding unit that manufactures the preform 10a by compression molding or an injection compression molding unit that manufactures the preform 10a by injection compression molding.
- the plastic member mounting unit 102 is provided with a plastic member 40 a outside the preform 10 a molded by the molding unit 101.
- the plastic member mounting unit 102 includes a holding portion 108 that holds the preform 10a, and a mounting portion 109 that holds the plastic member 40a and attaches the plastic member 40a to the preform 10a. .
- the plastic member mounting unit 102 mounts one plastic member 40a on one preform 10a.
- the plastic member mounting unit 102 is not limited to this, and a plurality of plastic members 40a are stacked on one preform 10a. It may be what you do.
- the plastic member 40a may be thermally contracted by a heating mechanism (not shown).
- the heating unit 103 is for heating the preform 10a and the plastic member 40a to a temperature suitable for blow molding by heating the preform 10a and the plastic member 40a.
- the heating unit 51 is a near infrared heater. have.
- the blow molding unit 104 expands the preform 10a and the plastic member 40a integrally by performing blow molding on the preform 10a and the plastic member 40a. 10a and a stretching rod 110 for stretching the plastic member 40a.
- the control unit 105 controls the molding unit 101, the plastic member mounting unit 102, the heating unit 103, and the blow molding unit 104 as described above. In this case, one control unit 105 controls all units, but is not limited to this. A plurality of control units 105 may be provided, each control unit 105 may control one or more units, and each control unit 105 or each unit may exchange signals with each other.
- the composite container manufacturing apparatus 100 includes a cooling unit for cooling the preform 10a (composite preform 70), a temperature adjustment unit for adjusting the temperature of the preform 10a (composite preform 70), and a blow unit. You may have the standby unit etc. which make the preform 10a (composite preform 70) before shaping
- a printing unit (not shown) that performs printing on the plastic member 40 after blow molding may be provided on the downstream side of the blow molding unit 104.
- the printing unit may be integrated with the molding unit 101, the plastic member mounting unit 102, the heating unit 103, and the blow molding unit 104.
- the vapor deposition film 21 can be formed by a conventionally known method such as a plasma CVD method, a PVD method (such as an ion plating method), or a sputtering method.
- a plasma CVD method such as an ion plating method
- a PVD method such as an ion plating method
- a sputtering method a method for forming the vapor deposition film 21 by the plasma CVD method will be described with reference to FIG.
- the high-frequency plasma CVD apparatus 200 includes a base 201 and an external electrode 203 supported on the base 201 via an insulating plate 202.
- the external electrode 203 is composed of a plurality of members that are separable from each other so that the composite container 10A can be taken in and out.
- the external electrode 203 has a reaction chamber 204 that is a slightly larger space than the composite container 10A.
- an internal electrode 205 is disposed in the reaction chamber 204.
- the internal electrode 205 is made of a hollow body and has a plurality of source gas blowing holes 206.
- a source gas supply pipe 207 made of a conductive material is connected to the internal electrode 205.
- a vacuum source (not shown) is connected to the reaction chamber 204 via an exhaust pipe 208.
- a high-frequency power source 210 is connected to the external electrode 203 via a matching unit 209.
- the internal electrode 205 is grounded via the source gas supply pipe 207.
- a plurality of magnets 211 for generating a magnetic field in the reaction chamber 204 are arranged.
- the raw material gas supply pipe 207 provided continuously to the inner electrode 105, as shown by the arrow P 2, deposition monomer gas such as an organic silicon compound, oxygen gas, an inert gas, for deposition prepared using other A raw material gas composition gas is supplied.
- deposition monomer gas such as an organic silicon compound, oxygen gas, an inert gas
- the deposition source gas composition is supplied to the internal electrode 205 via the source gas supply pipe 207, the deposition source gas composition is blown out from the source gas blowing hole 206 provided in the internal electrode 205.
- the air in the reaction chamber 204 is exhausted by the vacuum source (vacuum pump) through the exhaust pipe 208.
- the vapor deposition film 21 is formed by first housing the composite container 10 ⁇ / b> A in the reaction chamber 204 of the external electrode 203. Next, a vacuum pump (not shown) connected to the exhaust pipe 208 evacuates the reaction chamber 204 to a pressure at which plasma can be generated, and the degree of vacuum is increased.
- an inert gas such as argon (Ar) or helium (He) is supplied into the container body 10 from the source gas supply pipe 207 and blown out from the source gas blowing hole 206.
- the external electrode 203 and the internal electrode 205 A high frequency voltage is applied during As a result, high-frequency glow discharge is generated in the reaction chamber 204 and a magnetic field is generated in the reaction chamber 204 by the magnet 211.
- the inert gas ejected from the raw material gas blowing holes 206 is turned into plasma in the reaction chamber 204 and collides with the inner surface of the container body 10 with acceleration, and fine irregularities are formed on the inner surface of the container body 10.
- reaction chamber 204 is evacuated again to a pressure at which plasma can be generated by the vacuum pump connected to the exhaust pipe 208, and the degree of vacuum in the reaction chamber 204 is increased in the same manner as described above.
- a source gas composition for vapor deposition prepared using a monomer gas for vapor deposition such as an organosilicon compound, oxygen gas, inert gas, or the like, through a source gas supply pipe 207 is appropriately placed in the reaction chamber 204. Supply at flow rate. Further, a high frequency voltage is applied between the external electrode 203 and the internal electrode 205 to generate a high frequency glow discharge in the reaction chamber 204, and a magnetic field is generated in the reaction chamber 204 by the magnet 211. At this time, the raw material gas composition for vapor deposition supplied into the reaction chamber 204 by the high-frequency glow discharge is subjected to a gas phase reaction in the reaction chamber 204 and is a reaction mainly composed of plasma-generated inorganic oxide such as silicon oxide.
- a monomer gas for vapor deposition such as an organosilicon compound, oxygen gas, inert gas, or the like
- a product is produced.
- This reaction product is deposited on the entire inner surface of the container body 10 with acceleration.
- the deposited reaction product can be efficiently deposited on the inner surface of the container body 10 by causing the reaction product to collide with acceleration.
- the supply of the vapor deposition source gas composition to the reaction chamber 204 via the source gas supply pipe 207 is stopped, and then the atmosphere is supplied to the reaction chamber 204. Introduce.
- the composite container 10A in which the vapor deposition film 21 is formed on the entire inner surface of the container body 10 is obtained.
- the product of the present invention is a product in which the above-mentioned composite container 10A is filled with contents, A cap 18 is attached to the mouth 11 of the container body 10 (see FIG. 14).
- the cap 18 included in the product of the present invention may be an overcap that covers the flange portion of the mouth portion 11 of the container body. Since the cap 18 included in the product of the present invention is an overcap having light shielding properties, the light shielding properties can be further improved, and the storage stability of the contents can be further improved.
- the mouth portion 11 includes a screw portion 14 to which a cap 18 is attached and a flange portion 17 provided below the screw portion 14.
- the neck portion 13 described above is provided below the flange portion 17, and the heat-shrinkable plastic member 40 reaches the lower surface of the flange portion 17 (see FIG. 15).
- the cap 18 includes a substantially cylindrical side wall portion 18a and a top surface portion 18b that is connected to the upper end of the side wall portion 18a and has a substantially planar shape.
- a screw portion 18c that engages with the screw portion 14 of the mouth portion 11 and an annular inner peripheral projection 18d that is positioned below the screw portion 18c are formed.
- a weakening line 18e is formed at the upper end of the inner peripheral projection 18d, and the weakening line 18e can be broken when the cap 18 is loosened.
- a support ring 18f and an annular engagement protrusion 18g extending inward from the lower end of the support ring 18f are formed at the lower portion of the side wall 18a.
- the engaging protrusion 18 g is engaged with the lower surface of the flange portion 17. Thereby, when the cap 18 is loosened and the weakening line 18e is broken, the engaging projection 18g engages with the flange portion 17, so that the support ring 18f remains on the mouth portion 11 side. If the inner peripheral projection 18d is provided, the weakening line 18e can be broken even if the engaging projection 18g is not engaged with the flange portion 17, so that the engaging projection 18g is formed on the flange portion 17. It may be engaged or not engaged (see FIG. 15).
- the cap 18 and / or the flange part 17 are covered with the light shielding film.
- the light shielding property of the composite container 10A can be further improved, and the storage stability of the contents can be further improved.
- the light shielding film an opaque film having a light shielding property is used.
- the material for the light shielding film include polyethylene terephthalate (PET), polystyrene (PS), polypropylene (PP), and polyethylene (PE).
- PET polyethylene terephthalate
- PS polystyrene
- PP polypropylene
- PE polyethylene
- the light-shielding film is preferably a heat-shrinkable cylindrical film.
- the content to be filled in the product of the present invention is not particularly limited, and in addition to the above-mentioned beer, it is filled with alcohols such as sake and wine, soft drinks such as sports drinks, vegetable juices and smoothies. be able to. Moreover, it is not limited to a drink, You may fill with a shampoo, rinse, cosmetics, a pharmaceutical etc.
- Example 1-1> (Step of preparing the preform 10a) Using an injection molding machine, a PET preform 10a having a single layer structure as shown in FIG. 7 was produced. The weight of this preform 10a was 30.0 g, and its length Y was 90 mm.
- the near-infrared transmittance of the heat-shrinkable plastic member 40a was measured using a spectroscope manufactured by Hamamatsu Photonics, it was 64%.
- the length X of the heat-shrinkable plastic member 40a was 100 mm.
- the preform 10a and the heat-shrinkable plastic member 40a were heated to 100 ° C. using a hot air dryer, and the heat-shrinkable plastic member 40a was heat-shrinked.
- the blank portion 80a was sandwiched and thermocompression bonded at a pressure of 300 N / cm 2 to obtain a composite preform 70.
- the composite preform 70 obtained as described above was heated to 100 ° C. using a near-infrared heater and conveyed to a blow molding die shown in FIG. 9b. In this blow molding die, the composite preform 70 was blow-molded to obtain a composite container 10A having a full injection capacity of 500 mL.
- a vapor deposition film 21 made of silicon oxide was formed on the inner surface of the container body 10 using the high-frequency plasma CVD apparatus 100 shown in FIG.
- the thickness of the deposited film was 150 nm.
- the transmittance of visible light having a wavelength of 400 to 500 nm at the body and bottom of the composite container 10A was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer). %Met. Further, in accordance with JIS K 7126, the oxygen transmission rate of the composite container 10A was measured using an oxygen gas transmission rate measuring device (manufactured by MOCON, trade name: OX-TRAN 2/20) under conditions of 23 ° C. and humidity 90% RH. When the rate was measured, it was 0.12 cc / m 2 ⁇ day ⁇ 0.21 atm.
- Example 1-1 A composite container 10A was manufactured in the same manner as in Example 1-1 except that the brown colorant was not used in manufacturing the heat-shrinkable plastic member 40a.
- the visible light transmittance at the body and bottom of the composite container 10A was 88%, and the oxygen transmittance was 0.12 cc / m 2 ⁇ day ⁇ 0.21 atm. Further, when the appearance was evaluated by visual observation, no bubbles were present between the container body 10 and the plastic member 40, and no peeling or breakage of the crimping portion was observed. The bottom 30 was completely covered.
- Example 1-2 A composite container 10A was manufactured in the same manner as in Example 1-1, except that the thermal compression bonding of the blank portion was not performed.
- the visible light transmittance in the body portion of the composite container 10A is 0.5%
- the visible light transmittance in the bottom portion not covered with the plastic member is 88%
- the oxygen transmittance is 0.12 cc / m. 2 ⁇ day ⁇ 0.21 atm.
- the bottom part 30 of the container main body 10 was not covered with the plastic member 40.
- Example 1-1 A composite container 10A was manufactured in the same manner as in Example 1-3, except that the vapor deposition film was not provided on the inner surface of the container body 10. Visible light transmittance at the trunk and bottom was 0.5%, and oxygen transmittance was 1.3 cc / m 2 ⁇ day ⁇ 0.21 atm. Further, when the appearance was evaluated by visual observation, no bubbles were present between the container body 10 and the plastic member 40, and no peeling or breakage of the crimping portion was observed. The bottom 30 was completely covered.
- Example 2-1> (Step of preparing the preform 10a) Using an injection molding machine, a PET preform 10a having a single layer structure as shown in FIG. 7 was produced. The weight of this preform 10a was 30.0 g, and its length Y was 90 mm.
- the near-infrared transmittance of the heat-shrinkable plastic member 40a was measured using a spectroscope manufactured by Hamamatsu Photonics, the near-infrared transmittance at 800 nm was 70%.
- the length X of the manufactured heat-shrinkable plastic member 40a was 100 mm.
- content of the coloring agent in a colored layer was 5 mass%.
- the preform 10a and the heat-shrinkable plastic member 40a were heated to 100 ° C. using a hot air dryer, and the heat-shrinkable plastic member 40a was heat-shrinked.
- the blank portion was sandwiched at a pressure of 300 N / cm 2 and thermocompression bonded to obtain a composite preform 70.
- the composite preform 70 obtained as described above was heated to 100 ° C. using a near-infrared heater and conveyed to a blow molding die shown in FIG. 9b.
- the composite preform 70 was blow-molded to obtain a composite container 10A having a full injection capacity of 500 mL.
- a vapor deposition film 21 made of silicon oxide was formed on the inner surface of the container body 10 using the high-frequency plasma CVD apparatus 100 shown in FIG. The thickness of the deposited film was 150 nm.
- the transmittance of visible light having a wavelength of 400 to 500 nm at the body and bottom of the composite container 10A was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer). .5%.
- the oxygen permeability of the composite container 10A was measured under the conditions of 23 ° C. and humidity 90% RH using an oxygen gas permeability measuring device (manufactured by MOCON, trade name: OX-TRAN 2/20). Was 0.060 cc / m 2 ⁇ day ⁇ 0.21 atm.
- Example 2-1 A composite container 10A was produced in the same manner as in Example 2-1, except that the brown colorant was not included in the colored layer resin composition.
- the visible light transmittance at the trunk and bottom of the composite container 10A was 88%, and the oxygen transmittance was 0.060 cc / m 2 ⁇ day ⁇ 0.21 atm. Further, when the appearance was evaluated by visual observation, no bubbles were present between the container body 10 and the plastic member 40, and no peeling or breakage of the crimping portion was observed. The bottom 30 was completely covered.
- Example 2-2 A composite container 10A was manufactured in the same manner as in Example 2-1, except that the thermal compression bonding of the blank portion was not performed.
- the visible light transmittance in the body portion of the composite container 10A is 0.5%
- the visible light transmittance in the bottom portion not covered with the plastic member is 88%
- the oxygen transmittance is 0.060 cc / m. 2 ⁇ day ⁇ 0.21 atm.
- the bottom part 30 of the container main body 10 was not covered with the plastic member 40.
- Example 2-1 A composite container 10A was produced in the same manner as in Example 2-1, except that no vapor deposition film was provided on the inner surface of the container body 10.
- the visible light transmittance at the trunk and the bottom was 0.5%, and the oxygen transmittance was 0.650 cc / m 2 ⁇ day ⁇ 0.21 atm. Further, when the appearance was evaluated by visual observation, no bubbles were present between the container body 10 and the plastic member 40, and no peeling or breakage of the crimping portion was observed. The bottom 30 was completely covered.
- a preform 10a having the shape shown in FIG. 7 and including, from the innermost layer, a layer made of PET / MXD-6 and a layer made of an oxidation accelerator / PE was made.
- the content of the oxidation accelerator was 1% by mass.
- the weight of this preform 10a was 30.0 g, and its length Y was 90 mm.
- the near-infrared transmittance of the heat-shrinkable plastic member 40a was measured using a spectroscope manufactured by Hamamatsu Photonics, it was 70%.
- the length X of the manufactured heat-shrinkable plastic member 40a was 100 mm.
- the preform 10a and the heat-shrinkable plastic member 40a were heated to 100 ° C. using a hot air dryer, and the heat-shrinkable plastic member 40a was heat-shrinked.
- the blank portion 80a was sandwiched and thermocompression bonded at a pressure of 300 N / cm 2 to obtain a composite preform 70.
- the composite preform 70 obtained as described above was heated to 100 ° C. using a near-infrared heater and conveyed to a blow molding die shown in FIG. 9b.
- the composite preform 70 was blow-molded to obtain a composite container 10A having a full injection capacity of 500 mL.
- the thickness of the gas barrier layer was 10 ⁇ m
- the thicknesses of the other layers were both 120 ⁇ m.
- the thickness of the colored layers was 10 ⁇ m
- the thickness of the adhesive layer was 2 ⁇ m
- the thickness of the gas barrier layer was 5 ⁇ m.
- the transmittance of visible light having a wavelength of 400 to 500 nm at the body and bottom of the composite container 10A was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer). %Met. Further, in accordance with JIS K 7126, the oxygen permeability of the composite container 10A was measured under the conditions of 23 ° C. and humidity 90% RH using an oxygen gas permeability measuring device (manufactured by MOCON, trade name: OX-TRAN 2/20). Was 0.075 cc / m 2 ⁇ day ⁇ 0.21 atm.
- Example 3-1 A composite container 10A was produced in the same manner as in Example 3-1, except that the brown colorant was not included in the colored layer resin composition.
- the visible light transmittance at the trunk and bottom of the composite container 10A was 88%, and the oxygen transmittance was 0.075 cc / m 2 ⁇ day ⁇ 0.21 atm. Further, when the appearance was evaluated by visual observation, no bubbles were present between the container body 10 and the plastic member 40, and no peeling or breakage of the crimping portion was observed. The bottom 30 was completely covered.
- Example 3-2 A composite container 10A was manufactured in the same manner as in Example 3-1, except that the thermocompression bonding of the blank portion was not performed.
- the visible light transmittance in the body portion of the composite container 10A is 0.5%
- the visible light transmittance in the bottom portion not covered with the plastic member is 88%
- the oxygen transmittance is 0.075 cc / m. 2 ⁇ day ⁇ 0.21 atm.
- the bottom part 30 of the container main body 10 was not covered with the plastic member 40.
- Example 4-1> (Step of preparing the preform 10a) Using an injection molding machine, a preform 10a having the shape shown in FIG. 7 and having a layer made of PET / MXD-6 and a layer made of an oxidation accelerator / a layer made of PET was produced. The content of the oxidation accelerator was 1% by mass. The weight of this preform 10a was 30.0 g, and its length Y was 90 mm.
- the preform 10a and the heat-shrinkable plastic member 40a were heated to 100 ° C. using a hot air dryer, and the heat-shrinkable plastic member 40a was heat-shrinked.
- the blank portion 80a was sandwiched and thermocompression bonded at a pressure of 300 N / cm 2 to obtain a composite preform 70.
- the composite preform 70 obtained as described above was heated to 100 ° C. using a near-infrared heater and conveyed to a blow molding die shown in FIG. 9b.
- the composite preform 70 was blow-molded to obtain a composite container 10A having a full injection capacity of 500 mL.
- the thickness of the gas barrier layer was 30 ⁇ m
- the thicknesses of the other layers were both 120 ⁇ m.
- the thickness of the plastic member 40 was 50 ⁇ m.
- the transmittance of visible light having a wavelength of 400 to 500 nm at the body and bottom of the composite container 10A was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer). %Met. Further, in accordance with JIS K 7126, the oxygen permeability of the composite container 10A was measured under the conditions of 23 ° C. and humidity 90% RH using an oxygen gas permeability measuring device (manufactured by MOCON, trade name: OX-TRAN 2/20). Was 0.51 cc / m 2 ⁇ day ⁇ 0.21 atm.
- Example 4-1 A composite container 10A was manufactured in the same manner as in Example 4-1, except that the brown colorant was not used for manufacturing the heat-shrinkable plastic member 40a.
- the visible light transmittance at the body and the bottom of the composite container 10A was 88%, and the oxygen transmittance was 0.51 cc / m 2 ⁇ day ⁇ 0.21 atm. Further, when the appearance was evaluated by visual observation, no bubbles were present between the container body 10 and the plastic member 40, and no peeling or breakage of the crimping portion was observed. The bottom 30 was completely covered.
- Example 4-2 A composite container 10A was manufactured in the same manner as in Example 4-1, except that the thermal compression bonding of the blank portion was not performed.
- the visible light transmittance at the body portion of the composite container 10A is 0.5%
- the visible light transmittance at the bottom not covered with the plastic member is 88%
- the oxygen transmittance is 0.51 cc / m. 2 ⁇ day ⁇ 0.21 atm.
- the bottom part 30 of the container main body 10 was not covered with the plastic member 40.
- Example 5-1> (Step of preparing the preform 10a) Using an injection molding machine, a PET preform 10a having a single layer structure as shown in FIG. 7 was produced. The weight of this preform 10a was 30.0 g, and its length Y was 90 mm.
- the preform 10a and the heat-shrinkable plastic member 40a were heated to 100 ° C. using a hot air dryer, and the heat-shrinkable plastic member 40a was heat-shrinked.
- the blank portion was sandwiched at a pressure of 300 N / cm 2 and thermocompression bonded to obtain a composite preform 70.
- the composite preform 70 obtained as described above was heated to 100 ° C. using a near-infrared heater and conveyed to a blow molding die shown in FIG. In this blow molding die, the composite preform 70 was blow-molded to obtain a composite container 10A having a full injection capacity of 500 mL. Further, the transmittance of visible light having a wavelength of 400 to 500 nm at the body and bottom of the composite container 10A was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer). .5%.
- Example 5-1 A composite container 10A was manufactured in the same manner as in Example 5-1, except that the brown colorant was not used in manufacturing the heat-shrinkable plastic member 40a.
- the visible light transmittance at the trunk and bottom of the composite container 10A was 88%. Further, when the appearance was evaluated by visual observation, no bubbles exist between the container body 10 and the plastic member 40, and no peeling or breakage of the thermocompression bonding portion is observed. Ten bottoms 30 were completely covered.
- Example 5-2> A composite container 10A was manufactured in the same manner as in Example 5-1, except that the thermal compression bonding of the blank portion was not performed. The visible light transmittance at the body portion of the composite container 10A was 0.5%. Moreover, when the external appearance was evaluated visually, the bottom part 30 of the container main body 10 was not covered with the plastic member 40.
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Abstract
Description
しかしながら、プラスチック製部材に含有される樹脂材料や着色剤の種類などによっては、外側のプラスチック製部材ばかりが加熱されてしまっていた。そのためプラスチック製部材の表面が溶解してしまい、外観を損なってしまうというおそれがあった。また、プリフォームを効率的に加熱することができず、その生産性には改善の余地があった。
一実施形態において、図1に示すように、複合プリフォーム70は、プリフォーム10aと、プリフォーム10aの外側を取り囲むように設けられた、熱収縮性プラスチック製部材40aとを備える。
プリフォーム10aは、図1に示すように、口部11aと、口部11aに連結された胴部20aと、胴部20aに連結された底部30aとを備えている。このうち口部11aは、上述した容器本体10の口部11に対応するものであり、口部11と略同一の形状を有している。また、胴部20aは、上述した容器本体10の首部13、肩部12および胴部20に対応するものであり、略円筒形状を有している。底部30aは、上述した容器本体10の底部30に対応するものであり、略半球形状を有している。
さらに具体的な層構成としては、PETを含む層/MXD-6を含む層/PETを含む層を備える構成のもの、PETを含む層/MXD-6および酸化促進剤を含む層/PETを含む層を備える構成のもの、PENを含む層/MXD-6を含む層/PENを含む層を備える構成のもの、PENを含む層/MXD-6および酸化促進剤を含む層/PENを含む層を備える構成のものが挙げられる。
一実施形態において、熱可塑性樹脂の溶融物に不活性ガス(窒素ガス、アルゴンガス)を混ぜることで、0.5~100μmの発泡セル径を持つ発泡プリフォームを成形し、この発泡プリフォームをブロー成形することによって、容器本体10を製造しても良い。このような容器本体10は、発泡セルを内蔵しているため、容器本体10全体の遮光性を高めることができる。
図1に示すように、熱収縮性プラスチック製部材40aは、プリフォーム10aに接着されることなく、その外側を取り囲むように設けられ、プリフォーム10aに対して移動または回転しないほどに密着されているか、または自重で落下しない程度に密着されている。
プラスチック製部材40aが熱収縮性を有することにより、ブロー成形の際、プリフォーム10aに対するずれであったり、容器本体10とプラスチック製部材40との間に気泡が生じてしまうことを防止することができ、外観が良好な複合容器10Aを得ることができる。
また、図1に斜線部として示すように、プリフォーム10aの底部30a側の熱収縮性プラスチック製部材40aの一端が熱圧着され、これによりプリフォーム10aの底部30aを覆う底部を形成していることが好ましい。
通常、熱収縮性のプラスチック製部材40aにより、プリフォーム10aの底部30aを覆うことは困難であった。しかしながら、このような構成とすることにより、ブロー成形後、容器本体10の底部を熱収縮性のプラスチック製部材40で覆うことが可能となり、ガスバリア性など、複合容器10Aの底部に様々な機能を付与することができる。
熱収縮性プラスチック製部材40aがねじり部80を備えることにより、底部形成することができるだけではなく、ブロー成形後に複合容器10Aが備える容器本体10と熱収縮性プラスチック製部材40との間に気泡が発生してしまうことを防止することができると共に、ブロー成形時に加わる力によって、熱圧着した部分が剥がれてしまったりなど、破損してしまうことを防止することができる。
熱収縮性プラスチック製部材40aに対し、このような切り込みを設けておくことにより、ブロー成形後の複合容器10Aからプラスチック製部材40を容易に分離除去することができるようになる。
このような長さの切り込み線を有する熱収縮性プラスチック製部材40aを、プリフォーム10aと共に、ブロー成形することにより、ブロー成形後の熱収縮性プラスチック製部材40は、3mm以上、15mm以下の切り込み線を有することとなり、この切り込み線に基づき容易に容器本体10から分離することができる。
切り欠けの形状が三角形である場合、例えば、縦の長さを0.5mm以上、5mm以下、横の長さを0.1mm以上、8mm以下とすることができるがこれに限定されるものではない。
このような大きさの切り欠けを有する熱収縮性プラスチック製部材40aをプリフォーム10aと共に、ブロー成形することにより、ブロー成形後の熱収縮性プラスチック製部材40は、縦の長さを1mm以上、15mm以下、横の長さを0.5mm以上、10mm以下の三角形の切り欠けを有することとなり、この切り欠けに基づき容易に容器本体10から分離することができる。
熱収縮性プラスチック製部材40aの近赤外線透過率を上記数値範囲とすることにより、ブロー成形工程の近赤外線加熱において、プリフォーム10aを取り囲む熱収縮性プラスチック製部材40aばかりが温められ、溶解してしまい、その外観が劣化してしまうことを防止することができる。また、プリフォーム10aを効率良く加熱することができるため、生産効率を高めることができる。
熱収縮性プラスチック製部材40aの近赤外線透過率は、後述する樹脂材料や着色剤の種類や含有量などを変更することにより調整することができる。
なお、本発明において、近赤外線とは、波長が800nm~2500nmの光線のことを指す。
また、近赤外線透過率が50%以上であるとは、公知の分光光度計(例えば、浜松ホトニクス株式会社製の分光器)を用いて熱収縮性プラスチック製部材40aに対して吸光度の測定を行った際、800nm~1500nmでその透過率が50%以上となることをいう。
熱収縮性プラスチック製部材40aの比重を上記のようにすることで、複合容器10Aを粉砕後、水中に投入した際に、熱収縮性プラスチック製部材40を容器本体10から容易に分離することができる。
また、このとき、容器本体10の比重は、1超であることが好ましく、1.2超であることがより好ましい。
熱収縮性プラスチック製部材40aは、着色層を2層以上備えていてもよい。また、それぞれの着色層を構成する材料の種類、含有量、着色層の厚さは同一であっても、異なっていてもよい。
ポリオレフィン系樹脂としては、例えば、ポリエチレン(LDPE、MDPE、HDPE、LLDPE)、ポリプロピレン、ポリブテン、ポリブタジエン、ポリイソプレンや、これらを構成する単量体(アルケン)とその他の単量体との共重合体、例えば、エチレンと炭素数が4以上のαオレフィンとの共重合体、エチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸メチル共重合体、エチレン-(メタ)アクリル酸エチル共重合体、エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体、アイオノマー樹脂などが挙げられる。
熱収縮性プラスチック製部材40aは、上記したポリオレフィン系樹脂を1種または2種以上含んでいてもよい。
着色剤の色についても特に限定されるものではなく、茶色、黒色、緑色、白色、青色または赤色などの着色剤を使用することができる。なお、複数の色の着色剤を使用してもよく、例えば、赤色、黄色及び黒色の着色剤を組み合わせて使用し、茶色としてもよい。
内容物としてビールが複合容器10Aに充填される場合、ブロー成形後のプラスチック製部材40には、波長400~500nmの可視光線をカットすることが求められる。
一実施形態において、茶色の着色剤を熱収縮性プラスチック製部材40aに含有させることにより、波長400~500nmの可視光線をカットすることができ、ビール中の苦味成分が日光によって分解されて、日光臭成分である3-メチル-2-ブテン-1-チオールが生成される不具合を防止することができる。
なお、本発明において、「ビール」とは、日本の酒税法に定められたもの、すなわち「麦芽、ホップおよび水を原料として発酵させたもの。および麦芽、ホップ、水および米その他政令で定める物品を原料として発酵させたもの(但し、その原料中当該政令で定める物品の重量の合計が麦芽の重量の10分の5をこえないものに限る)。」のほか、酒税法上の「発泡酒」、すなわち原料中の麦芽の重量が水以外の原料の重量の(1)100分の67以上のもの、(2)100分の50以上100分の67未満のもの、(3)100分の25以上100分の50未満のもの、および(4)100分の25未満のものや、いわゆる「第3のビール」、「ビールテイスト飲料」、および「雑酒」も含む。
着色層における着色剤の含有量を上記数値範囲とすることにより、熱収縮性プラスチック製部材40a中において着色剤を良好に分散させることができる。また、成形性を維持することができるため、熱収縮性プラスチック製部材40aを容易に製造することができる。
また、着色層の厚さは、均一であってもよいが、ブロー成形後、容器本体10を覆う箇所を考慮し、適宜変更してもよい。
また、ガスバリア層の厚さは、均一であってもよいが、ブロー成形後、容器本体10を覆う箇所を考慮し、適宜変更してもよい。
より詳細には、まず、上記した樹脂材料および着色剤などを含む樹脂組成物を、押出装置内で加熱溶融し、溶融した樹脂材料などをリングダイより連続的に押し出し、冷却することにより、未延伸の押出チューブ1に成形する(図4(a)参照)。
次いで、この未延伸の押出チューブの一端を溶着または接着することによって、押出チューブの一端を閉鎖する。
さらに、この一端が閉鎖された押出チューブ1を、押出チューブ1の外径よりも大きい内径を有する金型2内に配置する(図4(b)参照)。
次いで、押出チューブ1の他端にブロー装置3を配置(装着)する(図4(c)参照)。このとき、ブロー装置3は、押出チューブ1と、これらの間からエアが漏れないよう密着させることが好ましい。
続いて、押出チューブ1、金型2およびブロー装置3を、この配置のまま加熱炉4に送り込み、加熱炉4の内部で70~150℃に加熱する(図4(d)参照)。加熱炉4としては、その内部を均一な温度にするために、熱風循環式加熱炉を用いても良い。あるいは押出チューブ1、金型2およびブロー装置3を、加熱した液体中を通過させることにより、これらを加熱しても良い。
次に、押出チューブ1、金型2およびブロー装置3を、加熱炉4から取り出し、ブロー装置3から押出チューブ1内にエアを噴出することにより、押出チューブ1の内面を加圧延伸する。これにより、押出チューブ1は、膨張し、金型2の内面形状に沿って拡径される(図4(e)参照)。
その後、ブロー装置3からエアを噴出した状態のまま、押出チューブ1を冷水中で冷却し、押出チューブを金型2から取り出す(図4(f)参照)。これを所望の大きさにカットすることにより熱収縮性プラスチック製部材40aが得られる(図4(g)参照)。
なお、多層構造の熱収縮性プラスチック製部材40aは、上記樹脂組成物と共に、ガスバリア性樹脂などを含む樹脂組成物を共押し出しすることにより製造することができる。
本発明の複合プリフォーム70の製造方法は、
プリフォーム10aおよび熱収縮性プラスチック製部材40aを準備する工程と、
プリフォーム10aを熱収縮性プラスチック製部材40aの他端から嵌め込む工程と、
プリフォーム10aおよび熱収縮性プラスチック製部材40aを加熱し、熱収縮性プラスチック製部材40aを熱収縮させる工程と、を含んでなる。
また、本発明の複合プリフォーム70の製造方法は、熱圧着した余白部をねじり,ねじり部80を形成する工程をさらに含んでいてもよい。
また、本発明の複合プリフォーム70の製造方法は、熱収縮性プラスチック製部材40aに切り込みを設ける工程を含んでいてもよい。
また、本発明の複合プリフォーム70の製造方法は、プリフォーム10aおよび/または熱収縮性プラスチック製部材40aを殺菌処理する工程をさらに含んでいてもよい。
さらに、本発明の複合プリフォーム70の製造方法は、熱収縮性プラスチック製部材40aに対し、画像や文字などの印刷を施す工程を含んでいてもよい。
プリフォーム10aおよび熱収縮性プラスチック製部材40aは、上記した方法により製造したものを使用してもよく、市販されるものを使用してもよい。
余白部の長さは、3mm以上であることが好ましく、5mm以上、20mm以下であることがより好ましい。
余白部の長さを上記数値範囲とすることにより、プラスチック製部材40a(40)の一端の熱圧着をより容易に行うことができる。また、過度に余白部を設けることが防止でき、使用する材料を減らすことができ、コストダウンを図ることができる。
なお、本発明において、熱収縮性プラスチック製部材40aの長さとは、図6に示されるように、熱収縮前の長さXをいう。また、プリフォーム10aの胴部20aおよび底部30aの長さの和とは、図7に示される長さYをいう。
本発明の複合プリフォーム70の製造方法は、熱収縮性プラスチック製部材40aの一端からプリフォーム10aを嵌め込む工程を含んでなる。
これにより、プリフォーム10aと、熱収縮性プラスチック製部材40aとの密着性をより向上させることができる。
プリフォーム10a表面の予備加熱温度は、特に限定されるものではないが、40℃以上、90℃以下に加熱することが好ましく、50℃以上、70℃以下に加熱することがより好ましい。加熱温度を上記数値範囲とすることにより、プリフォーム10aと、熱収縮性プラスチック製部材40aとの密着性をより向上させることができる。
本発明の複合プリフォーム70の製造方法は、プリフォーム10aおよび熱収縮性プラスチック製部材40aを加熱し、熱収縮性プラスチック製部材40aを熱収縮させ、プリフォーム10aに密着させる工程を含む。
本発明の複合プリフォーム70の製造方法は、プリフォーム10aの嵌め込みを行った熱収縮性プラスチック製部材40aの一端とは反対の端(他端)を熱圧着する工程を含んでいてもよい。
プリフォーム10aの底部30aの形状に沿って、熱収縮性プラスチック製部材40aの熱圧着を行う場合、図8に示すような形状を有する一対の圧着器具90A、Bにより挟み込むことにより行うことができる。この圧着器具の材質は特に限定されず、金属製や耐熱性の樹脂製のものを使用することができる。
また、圧着器具の表面は、平坦なものであってもよく、一部または全体に凹凸形状を有するものであっても良い。
また、圧着器具は、その表面に加熱機構を有していてもよい。これにより、圧着強度をより高めることができる。圧着器具表面の加熱温度は、例えば、100℃以上、250℃以下とすることが好ましい。
圧着部のカットは、図1に示すように、直線状に行ってもよく、プリフォーム10aの底部の形状に沿った形状に行ってもよい(図示せず)。
本発明の方法は、熱圧着した部分をねじり、図3に示すねじり部80を形成させる工程を含んでいてもよい。
本発明の方法が、熱圧着工程に加えて、ねじり部形成工程を含むことにより、ブロー成形後の熱収縮性プラスチック製部材40の底部を形成できることに加えて、複合容器10Aが備える容器本体10と熱収縮性プラスチック製部材40との間に気泡が発生してしまうことを防止することができる。また、ブロー成形の際に、熱収縮性プラスチック製部材40aの熱圧着した部分の剥がれや、破損を防止することができる。
また、プリフォーム10aおよび熱収縮性プラスチック製部材40aを保持する保持部および回転部を含む回転装置などを用いて機械的に行うことができる。
また、これらを組み合わせた方法により行ってもよく、具体的には、熱圧着した部分をペンチなどの器具を用いて挟み、プリフォーム10aおよび熱収縮性プラスチック製部材40aを回転部により回転させることによっても、ねじり部80を形成することができる。
具体的には、圧着器具に回転機構を設け、プリフォーム10aおよび熱収縮性プラスチック製部材40aを保持部に固定し、圧着器具を回転させることにより行うことができる。また、圧着器具を保持部として利用し、回転部によりプリフォーム10aおよび熱収縮性プラスチック製部材40aを回転させることによっても行うことができる。
本発明の方法は、熱収縮性プラスチック製部材40aに切り込みを設ける工程を含んでいてもよい。
熱収縮性プラスチック製部材40aに切り込みを設けることにより、ブロー成形後の複合容器10Aから熱収縮性プラスチック製部材40をこの切り込みから容易に分離除去することができるようになる。
使用するレーザー光は、特に限定されるものではなく、例えば、He-Neレーザー、Arレーザー、炭酸ガスレーザー、エキシマレーザー、金属蒸気レーザー、ファイバレーザー、Nd:YAGレーザーを含むYAGレーザー類、およびそれらの高調波レーザーなどが挙げられる。
なお、切り込みの形成は、複合プリフォーム70をブロー成形した複合容器10Aに対して行ってもよく、レーザー光などを利用して熱収縮性プラスチック製部材40に形成することができる。
摘まみ部は、従来公知の接着剤により熱収縮性プラスチック製部材40aに接着することができる。例えば、ポリ酢酸ビニル系接着剤、ポリアクリル酸エステル系接着剤、シアノアクリレート系接着剤、エチレン共重合体接着剤、セルロース系接着剤、ポリエステル系接着剤、ポリアミド系接着剤、ポリイミド系接着剤、アミノ樹脂系接着剤、フェノール樹脂系接着剤、エポキシ系接着剤、ポリウレタン系接着剤、ゴム系接着剤、シリコーン系接着剤などの接着剤を使用することができる。
本発明の方法は、プリフォーム10aの内外面および/または熱収縮性プラスチック製部材40a内外面を殺菌処理する工程を含んでいてもよい。
この殺菌処理は、嵌め込みを行う前のプリフォーム10a、熱収縮性プラスチック製部材40aに対して行ってもよく、嵌め込みを行った後のプリフォーム10a、熱収縮性プラスチック製部材40aに対して行ってもよく、両時点において行ってもよい。
さらに、殺菌処理は、ブロー成形後の複合容器10Aが備える容器本体10および熱収縮性プラスチック製部材40に対して行ってもよい。
(1)薬剤殺菌処理の一つとして、過酸化水素(H2O2)殺菌処理が挙げられる。過酸化水素殺菌処理は過酸化水素成分を含むミスト、ガスまたはこれらの混合物を生成し、この過酸化水素のミスト、ガスまたはこれらの混合物をプリフォーム10a、熱収縮性プラスチック製部材40a、複合プリフォーム70または複合容器10Aに対して噴射することにより殺菌処理を行なうものである。また、プリフォーム10a、熱収縮性プラスチック製部材40a、複合プリフォーム70に対しては、過酸化水素水に浸漬させた後、ホットエアーをブローすることで殺菌処理を行っても良い。
過酸化水素を接触、付着させることにより、プリフォーム10a表面に付着した微生物が殺菌され、あるいは傷付けられる。
なお、プリフォーム10aへのミスト、ガスまたはこれらの混合物の吹き付けの直前および/または直後に、プリフォーム10aに対して熱風を吹き付けることにより、付着した過酸化水素を活性化でき、殺菌処理をより効果的に行うことができる。また、熱風処理により、余分な過酸化水素を除去することができる。
この過酢酸殺菌処理は、プリフォーム10a、熱収縮性プラスチック製部材40a、複合プリフォーム70または複合容器10Aに対して過酢酸水溶液を液またはガス状で噴霧することにより殺菌処理を行なうものである。
(1)光殺菌処理として、UV殺菌処理や光パルス殺菌処理を挙げることができる。この殺菌処理は、プリフォーム10a、熱収縮性プラスチック製部材40a、複合プリフォーム70または複合容器10Aに対して光を照射して殺菌処理を施すものである。このような光としては、例えば波長150~2000nmの紫外線またはキセノンランプから発光する光を用いることができる。
放射線殺菌処理の一つとして、EB殺菌処理を用いることができる。このEB殺菌処理は、プリフォーム10a、熱収縮性プラスチック製部材40a、複合プリフォーム70または複合容器10Aに対して電子ビーム(EB)を照射して殺菌処理を行なうものである。
(1)温水殺菌処理は、例えば70℃~95℃の温水を準備し、この温水をプリフォーム10a、熱収縮性プラスチック製部材40a、複合プリフォーム70または複合容器10Aに噴射することにより殺菌処理を施すものである。
(1)ホット充填殺菌処理は、例えば60℃~80℃の中温の内容液を準備し、この中温の内容液を複合容器10Aに充填することにより、複合容器10Aに対して殺菌処理を施すものである。このホット充填殺菌処理は、複合容器10Aに内容液を充填する作業と、殺菌処理を同時に行なうことができる。
(1)その他の殺菌処理としては、複合容器10A内に内容液を充填し、その後に内容液入り複合容器10Aに対して殺菌処理を施すパストライジング殺菌処理が挙げられる。
熱収縮性プラスチック製部材40aへの印刷は、例えばインクジェット法、シルク印刷、グラビア印刷法、オフセット印刷法、フレキソ印刷法、熱転写法、ホットスタンプ(箔押し)などの印刷法により行うことができる。
例えば、インクジェット法を用いる場合、熱収縮性プラスチック製部材40aにUV硬化型インクを塗布し、これにUV照射を行い、硬化することにより、熱収縮性プラスチック製部材40aに画像や文字などの印刷を施すことができる。
この印刷は、プリフォーム10aに嵌め込む前の熱収縮性プラスチック製部材40aに対して施されても良く、プリフォーム10aの外側に熱収縮性プラスチック製部材40aを設けた状態で施されても良い。さらに、ブロー成形後の複合容器10Aが備える熱収縮性プラスチック製部材40に印刷が施されても良い。
本発明の複合容器10Aは、上記した複合プリフォーム70のブロー成形品であり、図9に示すように、内側に位置する容器本体10と、容器本体10の外側に密着して設けられた熱収縮性プラスチック製部材40と、を備えている。また、一実施形態において、本発明の複合容器10Aは、容器本体10の内面に形成された蒸着膜21を備えている。
熱収縮性プラスチック製部材40の容器本体10からの分離(剥離)の方法としては、例えば刃物などを用いて熱収縮性プラスチック製部材40を切除したり、熱収縮性プラスチック製部材40に予め切断線や上記した切り込みを設け、これらに沿って熱収縮性プラスチック製部材40を剥離したりすることができる。
別の態様においては、複合容器10Aを粉砕した後、熱水に浸け、熱収縮性プラスチック製部材40と、容器本体10との比重の差を利用し、熱収縮性プラスチック製部材40を分離回収することができる。また、熱収縮性プラスチック製部材40は熱収縮性を有しているため熱水中において、容器本体10から容易に剥離することができる。
上記のような方法により、熱収縮性プラスチック製部材40を容器本体10から分離除去することができるので、従来と同様に無色透明な容器本体10をリサイクルすることができる。
なお、本発明において、酸素透過率は、JIS K 7126など圧法に準拠して、酸素透過率測定装置(例えば、MOCON社製、商品名:OX-TRAN 2/20)23℃、湿度90%RHの条件により測定される値であり、口部をジグで塞いだ複合容器10Aの容器全体において測定し、口部を除いた容器全体の表面積で除した値である。
容器本体10は、口部11と、口部11下方に設けられた首部13と、首部13下方に設けられた肩部12と、肩部12下方に設けられた胴部20と、胴部20下方に設けられた底部30とを備えている。なお、本明細書中、「上」および「下」とは、それぞれ複合容器10Aを正立させた状態(図9)における上方および下方のことをいう。
また、胴部20は、パネルまたは溝などの凹凸構造を備えていてもよい。
内容物が、ビールや、炭酸水等の炭酸飲料の場合、胴部20は、凹凸構造を備えていないことが好ましい。これにより、容器本体10内圧の上昇に基づく、変形を防止することができる。
一実施形態において、容器本体は、ガスバリア層を備える。ガスバリア層に含まれる樹脂材料の種類や含有量などについては、上記した通りである。
熱収縮性プラスチック製部材40は、容器本体10の外面に薄く延ばされた状態で密着されており、容器本体10に対して容易に移動または回転しない状態で取付けられている。また、図10に示すように、熱収縮性プラスチック製部材40は、容器本体10を取り囲むようにその周方向全域にわたって設けられており、略円形状の水平断面を有している。
また、容器本体10の底部30側のプラスチック製部材40の一端は、圧着されており、容器本体10の底部30を覆う底部を形成している。
また、上記したように、この圧着された部分はねじられていてもよい。
また、一実施形態において、熱収縮性プラスチック製部材40は、ガスバリア層を備える。
熱収縮性プラスチック製部材40が備える各層に含まれる樹脂材料の種類や含有量などについては、上記した通りである。
また、複合容器10Aにおける着色層の厚さは、5μm以上、100μm以下であることが好ましく、5μm以上、50μm以下であることがより好ましい。
また、複合容器10Aにおけるガスバリア層の厚さは、1μm以上、100μm以下であることが好ましく、1μm以上、20μm以下であることがより好ましい。
熱収縮性プラスチック製部材40を備える複合容器10Aの波長400~500nmの可視光線の透過率は、15%以下であることが好ましく、5%以下であるとより好ましく、1%以下であると更に好ましい。
可視光線の透過率は、熱収縮性プラスチック製部材40に含まれる着色剤の種類や含有量などを調整することにより調整することができる。
また、可視光の透過率は、分光光度計(株式会社島津製作所製、紫外可視分光光度計)を使用して、0.5nm間隔で測定し、可視光線波長の光線透過率を求めることができる。
例えば、ブロー成形前の熱収縮性プラスチック製部材40aに切り込み線を設けていた場合、この切り込み線はブロー成形による熱収縮性プラスチック製部材40aの延伸により、左右から引張された形状となる。
また、熱収縮性プラスチック製部材40は、切り込みに連接する摘まみ部を有していてもよい。
切り込みおよび摘まみ部についての詳細は上記したためここでは省略する。
一実施形態において、本発明の複合容器10Aは、容器本体10の内面に、蒸着膜21を備える。
この場合、蒸着膜21は、略均一な厚みで、容器本体10の内面全域にわたって形成される。本発明の複合容器10Aが蒸着膜21を備えてなることにより、その酸素、二酸化炭素および水蒸気バリア性を向上させることができる。
このような無機酸化物としては、酸化アルミニウム、酸化ケイ素、酸化マグシウム、酸化カルシウム、酸化ジルコニウム、酸化チタン、酸化ホウ素、酸化ハフニウム、酸化バリウムなどを使用することができる。これらの中でもガスバリア性および生産効率の観点から、酸化ケイ素が特に好ましい。
また、一実施形態において、炭素添加シリコン酸化物(SiOC)を使用することもできる。
また、酸化ケイ素を含む蒸着膜21は、酸化ケイ素を主体とし、さらに炭素、水素、ケイ素、酸素の1種または2種以上の元素からなる化合物の少なくとも1種類を化学結合などにより含有してもよい。例えば、C-H結合を有する化合物、Si-H結合を有する化合物、炭素単位がグラファイト状、ダイヤモンド状、フラーレン状などになっている場合、更に、原料の有機珪素化合物やそれらの誘導体を化学結合などを含有してもよい。具体例を挙げると、CH3部位を持つハイドロカーボン、SiH3シリル、SiH2シリレンなどのハイドロシリカ、SiH2OHシラノールなどの水酸基誘導体などを挙げることができる。
蒸着膜21の厚みを、上記数値範囲内とすることにより、ガスバリア性を維持しつつ、蒸着膜21におけるクラックなどの発生を防止することができる。なお、図9および10において、蒸着膜21を厚み方向に誇張して描いている。
また、従来既知の遮光性を付与したシュリンクラベルや、紙ラベルなどを使用して更に遮光性を向上させても良い。
なお、延伸フィルムは、一軸延伸であっても、二軸延伸であってもよく、一軸延伸フィルムの場合は、縦一軸延伸であっても、横一軸延伸であってもよい。
タックラベルは、樹脂フィルムを複合容器に接着剤などを介し、直接貼り付けることにより製造することができる。
接着剤としては、例えば、ポリ酢酸ビニル系接着剤、ポリアクリル酸エステル系接着剤、シアノアクリレート系接着剤、エチレン共重合体接着剤、セルロース系接着剤、ポリエステル系接着剤、ポリアミド系接着剤、ポリイミド系接着剤、アミノ樹脂系接着剤、フェノール樹脂系接着剤、エポキシ系接着剤、ポリウレタン系接着剤、ゴム系接着剤、シリコーン系接着剤などが挙げられる。
本発明の複合容器10Aの製造方法は、
複合プリフォーム70を加熱するとともにブロー成形金型内に挿入する工程と、
加熱後の複合プリフォーム70に対してブロー成形を施すことにより、プリフォーム10aおよび熱収縮性プラスチック製部材40aを一体として膨張させる工程と、
を含んでなる。
また、一実施形態において、本発明の複合容器10Aの製造方法は、容器本体10の内面に蒸着膜21を形成する工程をさらに含む。
また、上記したように、複合容器10Aに対し、殺菌処理を施す工程を含んでいてもよい。
このとき、複合プリフォーム70は、口部11aを下に向けた状態で回転しながら、加熱装置51によって周方向に均などに加熱される。
この加熱工程におけるプリフォーム10aおよびプラスチック製部材40aの加熱温度は、例えば90℃~130℃とすることができる。
一実施形態において、ブロー成形金型50は、互いに分割された一対の胴部金型50a、50bと、底部金型50cとからなる(図11(b)参照)。図11(b)において、一対の胴部金型50a、50b間は互いに開いており、底部金型50cは上方に上がっている。この状態で一対の胴部金型50a、50b間に、複合プリフォーム70が挿入される。
具体的には、まず、複合プリフォーム70を、製造しようとする容量の複合容器10Aより大きくなるようにブロー成形し、次いで、この複合容器10Aを加熱することにより、自由収縮させる。そして、この収縮させた複合容器10Aをブロー成形することにより、所望の容量の複合容器10Aを得ることができる。このようなブロー成形により複合容器10Aを製造することにより、複合容器10Aの強度および耐熱性を向上させることができる。
図12に示す製造装置100は、上述した複合容器10Aを製造する装置である。この複合容器10Aの製造装置100は、成形ユニット101と、プラスチック製部材装着ユニット102と、加熱ユニット103と、ブロー成形ユニット104とを備えている。
これら成形ユニット101と、プラスチック製部材装着ユニット102と、加熱ユニット103と、ブロー成形ユニット104とは、製造装置100内で互いに一体化されている。
本装置を用いることにより、複合プリフォーム70および複合容器10Aの製造を同一装置内において行うことができる。
プラスチック製部材装着ユニット102は、1つのプリフォーム10aに対して1つのプラスチック製部材40aを装着するが、これに限らず、1つのプリフォーム10aに対して複数のプラスチック製部材40aを重ねて装着するものであっても良い。
以下、図13を参照し、プラズマCVD法により蒸着膜21を形成する方法を説明する。
一実施形態において、外部電極203は、複合容器10Aの出し入れが可能となるように、互いに分離可能な複数の部材から構成されている。この外部電極203は、複合容器10Aよりもやや大きめの空間である反応室204を有している。
また、一実施形態において、反応室204内に、内部電極205が配置されている。内部電極205は中空体からなり、且つ複数の原料ガス吹き出し孔206を有している。内部電極205には導電性材料からなる原料ガス供給管207が連設されている。また、反応室204には、排気管208を介して真空源(図示せず)が接続されている。
本発明の製品は、上記した複合容器10Aに内容物が充填されたものであり、
容器本体10の口部11にキャップ18が装着されていることを特徴とする(図14参照)。
遮光フィルムとしては、遮光性を有する不透明のものが用いられる。遮光フィルムの材料としては、例えばポリエチレンテレフタレート(PET)、ポリスチレン(PS)、ポリプロピレン(PP)、ポリエチレン(PE)が挙げられる。また、遮光フィルムは、熱収縮性の円筒状のフィルムであることが好ましい。
(プリフォーム10aを準備する工程)
射出成形機を使用して、図7に示す、単層構造を有する、PET製のプリフォーム10aを製造した。このプリフォーム10aの重量は、30.0gであり、その長さYは、90mmであった。
ポリオレフィン系樹脂としてポリエチレンおよび茶色着色剤を含む樹脂組成物を加熱溶融し、リング状のダイから押出した。次いで、押出されたチューブ内面を加圧、またはチューブ外面を内面より陰圧とし拡径を行い、単層構造を有する熱収縮性プラスチック製部材40aを製造した。なお、熱収縮性プラスチック製部材40aにおける茶色着色剤の含有量は、1.5質量%とした。
熱収縮性プラスチック製部材40aの近赤外線透過率を浜松ホトニクス製の分光器を使用して測定したところ、64%であった。
熱収縮性プラスチック製部材40aの長さXは、100mmであった。
次いで、手作業により、プリフォーム10aを、熱収縮性プラスチック製部材40aの一端から嵌め込んだ。
嵌め込み後、温風ドライヤーを用いて、プリフォーム10aおよび熱収縮性プラスチック製部材40aを100℃まで加熱し、熱収縮性プラスチック製部材40aを熱収縮させた。次いで、100℃に加熱した金属板を用いて余白部80aを300N/cm2の圧力で挟み込み熱圧着し、複合プリフォーム70を得た。
上記のようにして得られた複合プリフォーム70を近赤外線ヒーターを用いて、100℃まで加熱し、図9bに表されるブロー成形金型に搬送した。このブロー成形金型内において、複合プリフォーム70をブロー成形し、満注容量が500mLの複合容器10Aを得た。
また、JIS K 7126に準拠して、酸素ガス透過率測定装置(MOCON社製、商品名:OX-TRAN2/20)を用いて、23℃、湿度90%RHの条件により複合容器10Aの酸素透過率を測定したところ、0.12cc/m2・day・0.21atmであった。
製造後の複合容器10Aの外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
熱収縮性プラスチック製部材40aの製造において茶色着色剤を使用しなかった以外は、実施例1-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部および底部における可視光線の透過率は88%であり、酸素透過率は0.12cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
余白部の熱圧着を行わなかった以外は、実施例1-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部における可視光線の透過率は0.5%であり、プラスチック製部材で覆われていない底部の可視光線の透過率は88%であり、酸素透過率は0.12cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10の底部30はプラスチック製部材40で覆われていなかった。
容器本体10の内面に蒸着膜を設けなかった以外は、実施例1-3と同様にして複合容器10Aを製造した。
胴部および底部の可視光線の透過率は0.5%であり、酸素透過率は1.3cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
(プリフォーム10aを準備する工程)
射出成形機を使用して、図7に示す、単層構造を有する、PET製のプリフォーム10aを製造した。このプリフォーム10aの重量は30.0gであり、その長さYは90mmであった。
ポリオレフィン系樹脂としてポリエチレンおよび茶色着色剤を含む着色層用樹脂組成物、EVOHおよび接着剤をリング状のダイから共押し出した。次いで、押出されたチューブ内面を加圧、またはチューブ外面を内面より陰圧とし拡径を行い、着色層/接着層/ガスバリア層(EVOH)/接着層/着色層の構成を有する熱収縮性プラスチック製部材40aを製造した。
熱収縮性プラスチック製部材40aの近赤外線透過率を浜松ホトニクス製の分光器を使用して測定したところ、800nmの近赤外線透過率は70%であった。
製造した熱収縮性プラスチック製部材40aの長さXは、100mmであった。
なお、着色層における着色剤の含有量は、5質量%とした。
次いで、手作業により、プリフォーム10aを、熱収縮性プラスチック製部材40aの一端から嵌め込んだ。
嵌め込み後、温風ドライヤーを用いて、プリフォーム10aおよび熱収縮性プラスチック製部材40aを100℃まで加熱し、熱収縮性プラスチック製部材40aを熱収縮させた。次いで、100℃に加熱した金属板を用いて余白部を300N/cm2の圧力で挟み込み熱圧着し、複合プリフォーム70を得た。
上記のようにして得られた複合プリフォーム70を近赤外線ヒーターを用いて、100℃まで加熱し、図9bに表されるブロー成形金型に搬送した。このブロー成形金型内において、複合プリフォーム70をブロー成形し、満注容量が500mLの複合容器10Aを得た。
次いで、図11に示される高周波プラズマCVD装置100を用いて、容器本体10内面に酸化ケイ素からなる蒸着膜21を形成した。蒸着膜の厚さは、150nmであった。
また、複合容器10Aの胴部および底部における、波長400~500nmの可視光線の透過率を、分光光度計(株式会社島津製作所製、紫外可視分光光度計)を使用して測定したところ、共に0.5%であった。
また、JIS K 7126に準拠し、酸素ガス透過率測定装置(MOCON社製、商品名:OX-TRAN2/20)を用いて、23℃、湿度90%RHの条件により複合容器10Aの酸素透過率を測定したところ、0.060cc/m2・day・0.21atmであった。
製造後の複合容器10Aの外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
着色層用樹脂組成物に茶色着色剤を含有させなかった以外は、実施例2-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部および底部における可視光線の透過率は88%であり、酸素透過率は0.060cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
余白部の熱圧着を行わなかった以外は、実施例2-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部における可視光線の透過率は0.5%であり、プラスチック製部材で覆われていない底部の可視光線の透過率は88%であり、酸素透過率は0.060cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10の底部30はプラスチック製部材40で覆われていなかった。
容器本体10の内面に蒸着膜を設けなかった以外は、実施例2-1と同様にして複合容器10Aを製造した。
胴部および底部の可視光線の透過率は0.5%であり、酸素透過率は0.650cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
(プリフォーム10aを準備する工程)
射出成形機を使用して、図7に示す形状を有し、最内層から、PETからなる層/MXD-6および酸化促進剤からなる層/PEからなる層を備えるプリフォーム10aを製造した。酸化促進剤の含有量は、1質量%とした。
このプリフォーム10aの重量は、30.0gであり、その長さYは、90mmであった。
ポリオレフィン系樹脂としてポリエチレンおよび茶色着色剤を含む着色層用樹脂組成物、EVOHおよび接着剤をリング状のダイから共押し出した。次いで、押出されたチューブ内面を加圧、またはチューブ外面を内面より陰圧とし拡径を行い、最内層から着色層/接着層/ガスバリア層(EVOH)/接着層/着色層を備える熱収縮性プラスチック製部材40aを製造した。着色層における茶色着色剤の含有量は、5質量%とした。
熱収縮性プラスチック製部材40aの近赤外線透過率を浜松ホトニクス製の分光器を使用して測定したところ、70%であった。
製造した熱収縮性プラスチック製部材40aの長さXは、100mmであった。
次いで、手作業により、プリフォーム10aを、熱収縮性プラスチック製部材40aの一端から嵌め込んだ。
嵌め込み後、温風ドライヤーを用いて、プリフォーム10aおよび熱収縮性プラスチック製部材40aを100℃まで加熱し、熱収縮性プラスチック製部材40aを熱収縮させた。次いで、100℃に加熱した金属板を用いて余白部80aを300N/cm2の圧力で挟み込み熱圧着し、複合プリフォーム70を得た。
上記のようにして得られた複合プリフォーム70を近赤外線ヒーターを用いて、100℃まで加熱し、図9bに表されるブロー成形金型に搬送した。このブロー成形金型内において、複合プリフォーム70をブロー成形し、満注容量が500mLの複合容器10Aを得た。
なお、容器本体10において、ガスバリア層の厚さは10μmであり、その他の層(ポリエステル系樹脂層)の厚さは共に120μmであった。
また、プラスチック製部材40において、着色層の厚さは共に10μmであり、接着層の厚さは共に2μmであり、ガスバリア層の厚さは5μmであった。
また、JIS K 7126に準拠し、酸素ガス透過率測定装置(MOCON社製、商品名:OX-TRAN2/20)を用いて、23℃、湿度90%RHの条件により複合容器10Aの酸素透過率を測定したところ、0.075cc/m2・day・0.21atmであった。
製造後の複合容器10Aの外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
着色層用樹脂組成物に茶色着色剤を含有させなかった以外は、実施例3-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部および底部における可視光線の透過率は88%であり、酸素透過率は0.075cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
余白部の熱圧着を行わなかった以外は、実施例3-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部における可視光線の透過率は0.5%であり、プラスチック製部材で覆われていない底部の可視光線の透過率は88%であり、酸素透過率は0.075cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10の底部30はプラスチック製部材40で覆われていなかった。
(プリフォーム10aを準備する工程)
射出成形機を使用して、図7に示す形状を有し、PETからなる層/MXD-6および酸化促進剤からなる層/PETからなる層を備えるプリフォーム10aを製造した。酸化促進剤の含有量は、1質量%とした。
このプリフォーム10aの重量は、30.0gであり、その長さYは、90mmであった。
ポリオレフィン系樹脂としてポリエチレンおよび茶色着色剤を含む混合物をリング状のダイから押し出した。次いで、押出されたチューブ内面を加圧、またはチューブ外面を内面より陰圧とし拡径を行い、単層構造を有する、熱収縮性プラスチック製部材40aを製造した。
着色層における茶色着色剤の含有量は、5質量%とした。
熱収縮性プラスチック製部材40aの近赤外線透過率を浜松ホトニクス製の分光器を使用して測定したところ、70%であった。
製造した熱収縮性プラスチック製部材40aの長さXは、100mmであった。
次いで、手作業により、プリフォーム10aを、熱収縮性プラスチック製部材40aの一端から嵌め込んだ。
嵌め込み後、温風ドライヤーを用いて、プリフォーム10aおよび熱収縮性プラスチック製部材40aを100℃まで加熱し、熱収縮性プラスチック製部材40aを熱収縮させた。次いで、100℃に加熱した金属板を用いて余白部80aを300N/cm2の圧力で挟み込み熱圧着し、複合プリフォーム70を得た。
上記のようにして得られた複合プリフォーム70を近赤外線ヒーターを用いて、100℃まで加熱し、図9bに表されるブロー成形金型に搬送した。このブロー成形金型内において、複合プリフォーム70をブロー成形し、満注容量が500mLの複合容器10Aを得た。
なお、容器本体10において、ガスバリア層の厚さは30μmであり、その他の層(ポリエステル系樹脂層)の厚さは共に120μmであった。
また、プラスチック製部材40の厚さは50μmであった。
また、JIS K 7126に準拠し、酸素ガス透過率測定装置(MOCON社製、商品名:OX-TRAN2/20)を用いて、23℃、湿度90%RHの条件により複合容器10Aの酸素透過率を測定したところ、0.51cc/m2・day・0.21atmであった。
製造後の複合容器10Aの外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
熱収縮性プラスチック製部材40aの製造に茶色着色剤を使用しなかった以外は、実施例4-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部および底部における可視光線の透過率は88%であり、酸素透過率は0.51cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
余白部の熱圧着を行わなかった以外は、実施例4-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部における可視光線の透過率は0.5%であり、プラスチック製部材で覆われていない底部の可視光線の透過率は88%であり、酸素透過率は0.51cc/m2・day・0.21atmであった。
また、その外観を目視により評価したところ、容器本体10の底部30はプラスチック製部材40で覆われていなかった。
(プリフォーム10aを準備する工程)
射出成形機を使用して、図7に示す、単層構造を有する、PET製のプリフォーム10aを製造した。このプリフォーム10aの重量は、30.0gであり、その長さYは、90mmであった。
ポリオレフィン系樹脂としてポリエチレンおよび茶色着色剤を含む混合物を加熱溶融し、リング状のダイから押出した。次いで、押出されたチューブ内面を加圧、またはチューブ外面を内面より陰圧とし拡径を行い、熱収縮性プラスチック製部材40aを製造した。
熱収縮性プラスチック製部材40aにおける茶色着色剤の含有量は、1.5質量%とした。
熱収縮性プラスチック製部材40aの近赤外線透過率を浜松ホトニクス製の分光器を使用して測定したところ、64%であった。
製造した熱収縮性プラスチック製部材40aの長さXは、100mmであった。
次いで、手作業により、プリフォーム10aを、熱収縮性プラスチック製部材40aの一端から嵌め込んだ。
嵌め込み後、温風ドライヤーを用いて、プリフォーム10aおよび熱収縮性プラスチック製部材40aを100℃まで加熱し、熱収縮性プラスチック製部材40aを熱収縮させた。次いで、100℃に加熱した金属板を用いて余白部を300N/cm2の圧力で挟み込み熱圧着し、複合プリフォーム70を得た。
上記のようにして得られた複合プリフォーム70を近赤外線ヒーターを用いて、100℃まで加熱し、図12(b)に表されるブロー成形金型に搬送した。このブロー成形金型内において、複合プリフォーム70をブロー成形し、満注容量が500mLの複合容器10Aを得た。
また、複合容器10Aの胴部および底部における、波長400~500nmの可視光線の透過率を、分光光度計(株式会社島津製作所製、紫外可視分光光度計)を使用して測定したところ、共に0.5%であった。
製造後の複合容器10Aの外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、熱圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
熱収縮性プラスチック製部材40aの製造において茶色着色剤を使用しなかった以外は、実施例5-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部および底部における可視光線の透過率は88%であった。
また、その外観を目視により評価したところ、容器本体10とプラスチック製部材40との間に気泡は存在せず、また、熱圧着部の剥がれや破損は見られず、プラスチック製部材40により容器本体10の底部30が完全に覆われていた。
余白部の熱圧着を行わなかった以外は、実施例5-1と同様にして複合容器10Aを製造した。
複合容器10Aの胴部における可視光線の透過率は0.5%であった。
また、その外観を目視により評価したところ、容器本体10の底部30はプラスチック製部材40で覆われていなかった。
Claims (16)
- 口部と、前記口部に連結された胴部と、前記胴部に連結された底部を備えるプリフォームと、
前記プリフォームの外側を取り囲むように設けられ、樹脂材料および着色剤を含む着色層を少なくとも備える熱収縮性プラスチック製部材とを備え、
前記熱収縮性プラスチック製部材の近赤外線透過率が50%以上であることを特徴とする、複合プリフォーム。 - 前記熱収縮性プラスチック製部材が、ガスバリア層をさらに備える、請求項1に記載の複合プリフォーム。
- 前記着色層が、ポリオレフィン系樹脂を含む、請求項1または2に記載の複合プリフォーム。
- 前記着色剤が、茶色顔料であり、含有量が0.1質量%以上、30質量%以下である、請求項1~3のいずれか一項に記載の複合プリフォーム。
- 前記プリフォームが、少なくともガスバリア層を備える多層構造を有する、請求項1~4のいずれか一項に記載の複合プリフォーム。
- 前記プリフォームの底部側の前記プラスチック製部材の一端が圧着されている、請求項1~5のいずれか一項に記載の複合プリフォーム
- 前記熱収縮性プラスチック製部材の圧着された部分が、ねじられ、ねじり部を形成している、請求項6に記載の複合プリフォーム。
- 請求項1~7のいずれか一項に記載の複合プリフォームのブロー成形品である複合容器であって、
口部と、前記口部下方に設けられた首部と、前記首部下方に設けられた肩部と、前記肩部下方に設けられた胴部と、前記胴部下方に設けられた底部と、を備える容器本体と、
前記容器本体の外側に密着して設けられ、樹脂材料および着色剤を含む着色層を少なくとも備える熱収縮性プラスチック製部材と、を備え、
前記容器本体の底部側の前記プラスチック製部材の一端が圧着され、底部を形成していることを特徴とする、複合容器。 - 波長400~500nmの可視光線の透過率が20%以下である、請求項8に記載の複合容器。
- 前記容器本体の内面に、蒸着膜をさらに備える、請求項8または9に記載の複合容器。
- 酸素透過率が、0.5cc/m2・day・0.21atm以下である、請求項8~10のいずれか一項に記載の複合容器。
- 請求項1~7のいずれか一項に記載の複合プリフォームを製造する方法であって、
プリフォームおよび熱収縮性プラスチック製部材を準備する工程と、
前記プリフォームを前記熱収縮性プラスチック製部材の一端から嵌め込む工程と、
前記熱収縮性プラスチック製部材が有する余白部を熱圧着する工程と、
前記プリフォームおよび前記熱収縮性プラスチック製部材を加熱し、前記熱収縮性プラスチック製部材を熱収縮させる工程と、
を含むことを特徴とする、複合プリフォームの製造方法。 - 前記熱圧着した余白部をねじり、ねじり部を形成する工程をさらに含む、請求項12に記載の方法。
- 前記嵌め込み工程前に、前記プリフォームを予備加熱する工程をさらに含む、請求項12または13に記載の方法。
- 請求項8~10のいずれか一項に記載の複合容器の製造方法であって、
請求項1~7のいずれか一項に記載の複合プリフォームを加熱するとともにブロー成形金型内に挿入する工程と、
加熱後の前記複合プリフォームに対してブロー成形を施すことにより、プリフォームおよびプラスチック製部材を一体として膨張させる工程とを含んでなることを特徴とする、複合容器の製造方法。 - 請求項8~10のいずれか一項に記載の複合容器にビールが充填された製品であって、前記容器本体の口部にキャップが装着されていることを特徴とする、製品。
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| ES18758071T ES2928186T3 (es) | 2017-02-23 | 2018-02-23 | Preforma de composite y el método para producirla, recipiente de composite y el método para producirlo, y producto de recipiente de composite cargado con cerveza |
| KR1020197026550A KR102360734B1 (ko) | 2017-02-23 | 2018-02-23 | 복합 프리폼 및 그 제조 방법, 복합 용기 및 그 제조 방법, 그리고 복합 용기에 맥주를 충전한 제품 |
| CA3053731A CA3053731A1 (en) | 2017-02-23 | 2018-02-23 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
| MX2019009917A MX2019009917A (es) | 2017-02-23 | 2018-02-23 | Preforma compuesta y metodo para producir la misma, contenedor compuesto y metodo para producir el mismo, y producto de contenedor compuesto cargado con cerveza. |
| BR112019017293-9A BR112019017293B1 (pt) | 2017-02-23 | 2018-02-23 | Pré-forma compósita e método para produzir a mesma, recipiente compósito e método para produzir o mesmo, e produto de recipiente compósito carregado com cerveja |
| SG11201907617TA SG11201907617TA (en) | 2017-02-23 | 2018-02-23 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
| EP18758071.7A EP3587070B1 (en) | 2017-02-23 | 2018-02-23 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
| KR1020227003879A KR102494109B1 (ko) | 2017-02-23 | 2018-02-23 | 복합 프리폼 및 그 제조 방법, 복합 용기 및 그 제조 방법, 그리고 복합 용기에 맥주를 충전한 제품 |
| KR1020237003051A KR102657860B1 (ko) | 2017-02-23 | 2018-02-23 | 복합 프리폼 및 그 제조 방법, 복합 용기 및 그 제조 방법, 그리고 복합 용기에 맥주를 충전한 제품 |
| US16/485,249 US11136158B2 (en) | 2017-02-23 | 2018-02-23 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
| CN201880012566.2A CN110312607A (zh) | 2017-02-23 | 2018-02-23 | 复合预成型体及其制造方法、复合容器及其制造方法、以及在复合容器中填充有啤酒的产品 |
| US17/444,406 US11866222B2 (en) | 2017-02-23 | 2021-08-04 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
| US17/444,403 US12157601B2 (en) | 2017-02-23 | 2021-08-04 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
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| JP2017-032315 | 2017-02-23 | ||
| JP2017-032328 | 2017-02-23 | ||
| JP2017032315A JP6891534B2 (ja) | 2017-02-23 | 2017-02-23 | 複合プリフォームおよびその製造方法、並びに複合容器およびその製造方法 |
| JP2017032328A JP6913296B2 (ja) | 2017-02-23 | 2017-02-23 | 複合プリフォームおよびその製造方法、並びに複合容器およびその製造方法 |
| JP2017-091340 | 2017-05-01 | ||
| JP2017091345A JP7013678B2 (ja) | 2017-05-01 | 2017-05-01 | 複合容器およびその製造方法 |
| JP2017091340A JP6994168B2 (ja) | 2017-05-01 | 2017-05-01 | 複合プリフォームおよびその製造方法、並びに複合容器およびその製造方法 |
| JP2017-091345 | 2017-05-01 | ||
| JP2017-091341 | 2017-05-01 | ||
| JP2017091341A JP7003441B2 (ja) | 2017-05-01 | 2017-05-01 | 複合プリフォームおよびその製造方法、並びに複合容器およびその製造方法 |
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| US16/485,249 A-371-Of-International US11136158B2 (en) | 2017-02-23 | 2018-02-23 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
| US17/444,406 Division US11866222B2 (en) | 2017-02-23 | 2021-08-04 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
| US17/444,403 Division US12157601B2 (en) | 2017-02-23 | 2021-08-04 | Composite preform and method for producing the same, composite container and method for producing the same, and composite container product loaded with beer |
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| Country | Link |
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| US (3) | US11136158B2 (ja) |
| EP (1) | EP3587070B1 (ja) |
| KR (3) | KR102494109B1 (ja) |
| CN (1) | CN110312607A (ja) |
| BR (1) | BR112019017293B1 (ja) |
| CA (1) | CA3053731A1 (ja) |
| ES (1) | ES2928186T3 (ja) |
| MX (1) | MX2019009917A (ja) |
| MY (1) | MY199475A (ja) |
| SG (1) | SG11201907617TA (ja) |
| TW (1) | TWI787237B (ja) |
| WO (1) | WO2018155653A1 (ja) |
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| BR112019017293A2 (pt) | 2020-03-31 |
| KR102494109B1 (ko) | 2023-01-31 |
| CA3053731A1 (en) | 2018-08-30 |
| SG11201907617TA (en) | 2019-09-27 |
| US11136158B2 (en) | 2021-10-05 |
| KR102657860B1 (ko) | 2024-04-16 |
| EP3587070A1 (en) | 2020-01-01 |
| US12157601B2 (en) | 2024-12-03 |
| EP3587070A4 (en) | 2020-12-09 |
| BR112019017293B1 (pt) | 2023-02-14 |
| KR102360734B1 (ko) | 2022-02-10 |
| MX2019009917A (es) | 2019-11-05 |
| US20190375547A1 (en) | 2019-12-12 |
| KR20220020435A (ko) | 2022-02-18 |
| TW201838782A (zh) | 2018-11-01 |
| US20210394948A1 (en) | 2021-12-23 |
| ES2928186T3 (es) | 2022-11-16 |
| EP3587070B1 (en) | 2022-09-07 |
| US11866222B2 (en) | 2024-01-09 |
| KR20230019504A (ko) | 2023-02-08 |
| KR20190117619A (ko) | 2019-10-16 |
| CN110312607A (zh) | 2019-10-08 |
| US20210362901A1 (en) | 2021-11-25 |
| TWI787237B (zh) | 2022-12-21 |
| MY199475A (en) | 2023-10-31 |
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