JP2018134838A - Composite preform and method for producing the same, and composite container and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite preform which can efficiently heat a preform without aggravation of appearance of a plastic member surface even by near-infrared heating before blow molding.SOLUTION: A composite preform includes a mouth part, a body part connected to the mouth part and a bottom part connected to the body part, and includes a preform of a single layer structure, and a heat-shrinkable plastic member provided so as to surround the outside of the preform, where the heat-shrinkable plastic member has a colorant layer containing a colorant and a gas barrier layer, and a near-infrared transmittance of the heat-shrinkable plastic member is 50% or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composite preform and a manufacturing method thereof, and a composite container and a manufacturing method thereof.

  Recently, plastic bottles for storing content liquids such as foods and drinks have become common, and such plastic bottles store contents such as beverages.

  A plastic bottle that contains such contents is manufactured by inserting a preform into a mold and biaxially stretch blow molding.

  By the way, in the conventional biaxial stretch blow molding method, for example, it is molded into a container shape using a preform including a single layer material such as polyethylene terephthalate (PET) or polypropylene (PP), a multilayer material or a blend material. However, in the conventional biaxial stretch blow molding method, the preform is generally simply formed into a container shape. For this reason, when the container has various functions and characteristics (gas barrier properties such as oxygen barrier properties, carbon dioxide barrier properties, water vapor barrier properties, and heat retaining properties), for example, the material constituting the preform is changed. The means are limited. In particular, it is difficult to have different functions and characteristics depending on the part of the container (for example, the trunk and the bottom).

  In the previous application (Japanese Patent Application Laid-Open No. 2015-128858), the present applicant has proposed a composite container capable of imparting various functions and characteristics to the container.

JP2015-128858A

The composite container disclosed in Japanese Patent Application Laid-Open No. 2015-128858 is manufactured by heating a composite preform with near infrared rays and then blow-molding, but depending on the type of colorant contained in the plastic member, etc. Only the outer plastic member was heated and melted, deteriorating its appearance.
Moreover, the preform could not be efficiently heated, and there was room for improvement in productivity.

  The present invention has been made on the basis of such knowledge, and a composite capable of efficiently heating an inner preform without deteriorating the appearance of a plastic member surface even by near-infrared heating before blow molding. It is an object of the present invention to provide a preform and a manufacturing method thereof, a composite container which is a blow-molded product of the composite preform, and a manufacturing method thereof.

  The composite preform of the present invention is provided so as to surround the outside of the preform having a mouth portion, a body portion connected to the mouth portion, and a bottom portion connected to the body portion, and a preform. A heat-shrinkable plastic member, the heat-shrinkable plastic member has a colored layer containing a colorant, and a gas barrier layer, and the heat-shrinkable plastic member has a near infrared transmittance of 50% or more. It is characterized by.

  In the said aspect, it is preferable that a colored layer contains polyolefin resin.

  In the said aspect, it is preferable that a colorant is a brown pigment and the content is 0.1 to 30 mass%.

  In the above embodiment, the gas barrier layer comprises metaxylene 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 (PAN), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE) and styrene- It is preferable to include one or more gas barrier resins selected from the group consisting of isobutylene-styrene copolymers.

  In the said aspect, it is preferable to further provide an adhesive layer between the colored layer and the gas barrier layer.

  In the said aspect, it is preferable to have a structure of a colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer.

  In the said aspect, it is preferable that the end of the plastic member of the bottom part side of a preform is crimped | bonded.

  In the said aspect, it is preferable that the crimped | bonded part of the heat shrinkable plastic member is twisted and forms the twist part.

  In the above aspect, it is preferable that the heat-shrinkable plastic member has one end thereof and at least one notch at one end close to the mouth of the preform.

  In the above aspect, the specific gravity of the heat-shrinkable plastic member is preferably less than 1, and the specific gravity of the preform is preferably more than 1.

  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 container body having a single layer structure, a heat shrinkable plastic member provided in close contact with the outside of the container body, and an inner surface of the container body. The heat-shrinkable plastic member includes a colored layer and a gas barrier layer, and one end of the plastic member on the bottom side of the container body is pressure-bonded to form the bottom. To do.

  In the said aspect, it is preferable that it is a composite container for filling beer as a content whose transmittance | permeability of visible light with a wavelength of 400-500 nm is 20% or less.

  In the said aspect, it is preferable that the bottom part shape of a container main body is a petaloid shape.

In the said aspect, it is preferable that oxygen permeability is 0.5 cc / m < ² > * day * 0.21 atm or less.

  In the said aspect, it is preferable that the label is attached to the container main body and / or the plastic member.

  In the said aspect, it is preferable that a label is a shrink label, a stretch label, a roll label, a tack label, or a paper label.

  In the said aspect, it is preferable that printing is given to the label.

  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, a preform and a heat-shrinkable plastic Heating the member made and heat shrinking the member made of heat-shrinkable plastic.

  In the said aspect, it is preferable that the heat-shrinkable plastic member further includes a step of having a blank portion at an end opposite to the one end into which the fitting is performed, and thermocompression bonding the blank portion.

  In the said aspect, it is preferable to further include the process of twisting the blank part which carried out thermocompression bonding and forming a twist part.

  In the said aspect, it is preferable to further include the process of preheating a preform before a fitting process.

  In the said aspect, it is preferable to further include the process of providing a notch in a plastic member.

  In the said aspect, it is preferable to further include the process of performing a sterilization process with respect to a preform and / or a plastic member before and / or after an insertion process.

  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 above-mentioned composite container is filled with contents, and a cap is screwed into the mouth of the container body.

  In the said aspect, it is preferable that an opening | mouth part has a flange part and a cap consists of an overcap which covers a flange part.

  In the said aspect, it is preferable to further provide the light shielding film which coat | covers a cap.

According to the present invention, a composite preform capable of efficiently heating a preform without deterioration of the appearance of the plastic member surface even by near infrared heating before blow molding, and a method for producing the same, and the composite It is possible to provide a composite container that is a blow-molded product of a preform and a method for manufacturing the same.
Furthermore, according to this invention, the composite preform which can manufacture the composite container excellent in gas barrier properties, such as oxygen barrier property, a carbon dioxide barrier property, and water vapor | steam barrier property, can be provided.

FIG. 1 is a partial vertical cross-sectional view of a composite preform of the present invention in one embodiment. FIG. 2 is a partial vertical sectional view showing a composite container manufactured using the composite preform of the present invention in one embodiment. FIG. 3 is a horizontal cross-sectional view of the composite container shown in FIG. 2 taken along line III-III. 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 front view of a composite preform having a twisted portion. FIG. 10 is a schematic view showing a method for manufacturing a composite container. FIG. 11 is a schematic diagram illustrating a composite container manufacturing apparatus according to an embodiment. FIG. 12 is a schematic cross-sectional view showing a high-frequency plasma CVD apparatus. FIG. 13 is a partial vertical sectional view showing a product using a composite container in one embodiment. FIG. 14 is an enlarged partial vertical sectional view showing the vicinity of the mouth of a product using a composite container in one embodiment.

Composite preform 70
In one embodiment, as shown in FIG. 1, a composite preform 70 includes a single-layered preform 10a and a heat shrink including at least a colored layer and a gas barrier layer provided so as to surround the outside of the preform 10a. And a plastic member 40a.

  2 is obtained by subjecting this composite preform 70 to biaxial stretch blow molding and inflating the preform 10a of the composite preform 70 and the heat-shrinkable plastic member 40a together. Can do.

Preform 10a
As shown in FIG. 1, 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. Of these, 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. Moreover, the trunk | drum 20a respond | corresponds to the neck part 13, the shoulder part 12, and the trunk | drum 20 of the container main body 10 mentioned above, and has a substantially cylindrical shape. The bottom 30a corresponds to the bottom 30 of the container body 10 described above, and has a substantially hemispherical shape.

The preform 10a includes a thermoplastic resin, particularly a resin material such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and ionomer. Moreover, the blend resin which blended various resin mentioned above may be included.
The preform 10a may contain colorants such as red, blue, yellow, green, brown, black, white, etc., but when considering recyclability, these preforms do not contain these colorants and are colorless and transparent. It is preferable.

The preform 10a can be manufactured by injection molding a resin material or the like using a conventionally known apparatus.
In one embodiment, an inert gas (nitrogen gas, argon gas) is mixed with a melt of a thermoplastic resin to form a foam preform having a foam cell diameter of 0.5 to 100 μm. The container body 10 may be produced 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.

  The preform 10a may contain various additives as long as the characteristics of the present invention are not impaired. Examples of 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.

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.
Since the heat-shrinkable plastic member 40a has heat-shrinkability, the blow-molding may cause a displacement with respect to the preform 10a, or air bubbles may be generated between the container body 10 and the heat-shrinkable plastic member 40. This can be prevented, 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.
In addition, as shown by the hatched portion in FIG. 1, one end of the 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 has been difficult to cover the bottom 30a of the preform 10a with the heat-shrinkable plastic member 40a. However, with such a configuration, it becomes possible to cover the bottom of the container body 10 with the heat-shrinkable plastic member 40 after blow molding, and various functions can be imparted to the bottom, such as gas barrier properties. .
This thermocompression bonding is particularly preferably performed along the shape of the bottom 30a of the preform 10a. Thereby, the bubble generation between the container main body 10 after blow molding and the heat-shrinkable plastic member 40 can be prevented, and the adhesion of the heat-shrinkable plastic member 40 to the container main body 10 can be improved. it can. Moreover, since there are no bubbles, the appearance of the composite container 10A can be improved.

In one embodiment, the heat-shrinkable plastic member 40a may include a twisted portion 80 in which a thermocompression bonded portion is twisted (see FIG. 9).
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 provided in the composite container 10A after blow molding. Can be prevented, and it is possible to prevent the thermocompression-bonded portion from being peeled off or damaged by the force applied during blow molding.

In one embodiment, 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.
Since the heat-shrinkable plastic member 40a has such a cut, 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 shape such as an arbitrary triangle or square.

When the cut is a cut line, 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.
Further, the shape of the cutout is not particularly limited, and may be appropriately changed in consideration of the size, shape, etc. of the container body 10. Various shapes such as a shape combining curves such as shapes can be used.
When the shape of the cutout is a triangle, for example, the vertical length can be 0.5 mm or more and 5 mm or less, and the horizontal length can be 0.1 mm or more and 8 mm or less. Absent.
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.

  In one embodiment, 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 is 50% or more, more preferably 60% or more and 100% or less, and further preferably 70% or more and 100% or less.
By setting the near-infrared transmittance of the heat-shrinkable plastic member 40a within the above numerical range, in the near-infrared heating of the blow molding process, the heat-shrinkable plastic member 40a that surrounds the preform 10a alone is heated to dissolve. It is possible to prevent the appearance from being deteriorated. Moreover, since the preform 10a can be efficiently heated, production efficiency can be increased.
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.
In the present invention, near infrared rays refer to light rays having a wavelength of 800 nm to 2500 nm.
Further, 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.
By setting the specific gravity of the heat-shrinkable plastic member 40a as described above, the heat-shrinkable plastic member 40 after blow molding can be easily separated from the container body 10 in water.
At this time, the specific gravity of the container body 10 is preferably more than 1, more preferably more than 1.2.
In the present invention, the specific gravity of the heat-shrinkable plastic member 40a refers to the specific gravity of the entire heat-shrinkable plastic member 40a having a multilayer structure.

In the present invention, the heat-shrinkable plastic member 40a has a multilayer structure including at least a colored layer and a gas barrier layer.
In one embodiment, the heat-shrinkable plastic member 40a further includes an adhesive layer between the colored layer and the gas barrier layer.
The plastic member 40a may have two or more colored layers and two or more gas barrier layers. In this case, the type and content of the material constituting each layer, the thickness of the layer, and the like may be the same or different. In addition, when the heat-shrinkable plastic member 40a includes two or more colored layers, the colors of the colored layers may be the same or different.
The specific layer structure of the plastic member 40a is as follows: colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer, colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer / adhesive layer / gas barrier layer / adhesive Layer / colored layer and the like.
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 μm or more and 150 μm or less.

Colored Layer In one embodiment, the colored layer comprises a resin material and a colorant.
As a resin material, the colored layer can contain a polyolefin-based resin, for example, polyethylene (LDPE, MDPE, HDPE, LLDPE), polypropylene, polybutene, polybutadiene, polyisoprene, and monomers (alkenes) constituting these. Copolymers with other monomers, for example, copolymers of ethylene and α-olefins having 4 or more carbon atoms, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid methyl copolymer Examples thereof include a copolymer, an ethylene- (meth) acrylate copolymer, an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, and an ionomer resin.
The colored layer may contain two or more kinds of polyolefin resins.

  In one embodiment, the colored layer includes, as a resin material, 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, Fluoro rubber, Nylon 6, Nylon 6, 6, MXD-6, Aromatic polyamide, Polycarbonate, Poly terephthalate, Poly terephthalate Polyethylene ethylene naphthalate, U polymer, liquid crystal polymer, modified polyphenylene ether, polyether ketone, polyether ether ketone, unsaturated polyester, alkyd resin, polyimide, polysulfone, polyphenylene sulfide, polyethersulfone, silicone resin, polyurethane, phenol Resin, urea resin, polyethylene oxide, polypropylene oxide, polyacetal, epoxy resin, ionomer resin and the like. The colored layer may contain two or more kinds of the resin materials described above.

  The content of the resin material in the colored layer is preferably 80% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less.

The colored layer contains a colorant. Thereby, the near-infrared transmittance of the heat-shrinkable plastic member 40a can be adjusted, and the visible light transmittance of the composite container 10A after blow molding can be adjusted.
As the colorant, a pigment or a dye may be used, but it is preferable to use a pigment 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.
When beer is filled in the composite container 10A as the contents, the plastic member 40 after blow molding is required to cut visible light having a wavelength of 400 to 500 nm.
In one embodiment, by adding 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. A problem that 3-methyl-2-butene-1-thiol, which is an odor component, is generated can be prevented.
In the present invention, “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. In addition to “fermented sake” under the liquor tax law. That is, the weight of malt in the raw material is (1) the weight of the raw material other than water is (1) 67/100 or more, (2) the 50/100 or more and less than 67/100, (3) 25/100 More than 50/100, and (4) less than 25/100, so-called “third beer”, “beer-taste beverage”, and “miscellaneous sake” are also included.

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.
By making content of a coloring agent into the said numerical range, a coloring agent can be favorably disperse | distributed in a coloring layer. Moreover, since the moldability can be maintained, the heat-shrinkable plastic member 40a can be easily produced.

  As long as the effects of the present invention are not impaired, the colored layer may contain other additives as described above.

The thickness of the colored layer before blow molding is preferably 5 μm or more and 1000 μm or less, and more preferably 10 μm or more and 500 μm or less. By setting the thickness of the colored layer within the above numerical range, the light shielding property can be improved while the blow moldability is good.
Further, 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.

Gas barrier layer 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 (EVA), ethylene-vinyl alcohol copolymer (EVOH), polyglycolic acid (PGA), polyvinylidene chloride copolymer (PVDC), polyacrylonitrile, polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE) ) And 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 is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. Thereby, the gas barrier property of 10 A of composite containers can be improved more.

  The gas barrier layer may contain an oxygen absorbent. Examples of the oxygen absorbent include an iron-based oxygen absorbent and a non-ferrous oxygen absorbent, and the non-ferrous oxygen absorbent is more preferable because the transparency of the plastic member 40a can be maintained.

  Examples of the iron-based oxygen absorbent include iron powders such as reduced iron powder, interfacial iron powder, sprayed iron powder, iron grinding powder, electrolytic iron powder, and pulverized iron.

  Examples of the non-ferrous oxygen absorber include an ethylenically unsaturated group-containing copolymer. Examples of the ethylenically unsaturated group-containing copolymer include polydienes such as polybutadiene, polychloroprene, poly (2-ethylbutadiene), and poly (2-butylbutadiene), which are mainly polymerized at positions 1 and 4, Ring-opening metathesis polymer of cycloolefin such as polyoctenylene, polypentenylene and 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 copolymer are preferable.

  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 comprise 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. For example, 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. When 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.

  Examples of metal salts include inorganic salts, organic salts, and complex salts. Examples of inorganic salts include halogenated salts, oxy salts, oxy acid salts, and silicates. Examples of the organic acid salt include a carboxylate, a sulfonate, and a phosphonate. Examples of the complex salt include complexes with β-diketone or β-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 material and additive as long as the characteristics are not impaired.

The thickness of the gas barrier layer before blow molding is preferably 10 μm or more and 300 μm or less, and more preferably 15 μm or more and 100 μm or less. By setting the thickness of the gas barrier layer to the above numerical range, the gas barrier property of the composite container 10A can be improved.
Further, 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.

In one embodiment, the heat-shrinkable plastic member 40a can be produced by a method that includes an extrusion process.
More specifically, first, a resin composition for a colored layer containing at least a resin material and a colorant, a resin composition for a gas barrier layer containing at least a gas barrier resin, and an adhesive for an adhesive layer are combined from a ring die provided in the extrusion apparatus. By extruding and cooling, it is formed into an unstretched extruded tube 1 (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).
Next, 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.
Subsequently, 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). As the heating furnace 4, 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 | die 2, and the blow apparatus 3 in the heated liquid.
Next, 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. As a result, the extruded tube 1 expands and expands along the inner shape of the mold 2 (see FIG. 4E).
Thereafter, 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)). By cutting this into a desired size, a heat-shrinkable plastic member 40a is obtained (see FIG. 4G).

Further, the heat-shrinkable plastic member 40a may be designed or printed. 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.
The place where the design and printing are applied, not particularly limited, may be the outer surface or the inner surface.
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 stamping), or the like. For example, when the inkjet method is used, a print layer can be formed by applying UV curable ink to the heat-shrinkable plastic member 40a (40), irradiating it with UV, and curing it.
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. Further, the heat-shrinkable plastic member 40 provided in the composite container 10A after blow molding may be printed.

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 one 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.
In addition, 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.
In addition, 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.
Moreover, the manufacturing method of the composite preform 70 of this invention may include the process of providing the notch 90 in the heat-shrinkable plastic member 40a.
Furthermore, 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.

Step for preparing preform 10a and heat-shrinkable plastic member 40a As preform 10a and heat-shrinkable plastic member 40a, those prepared 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 heat-shrinkable plastic member 40a is longer than the sum Y of the lengths of the body 20a and the bottom 30a of the preform 10a, as shown in FIG. Is preferred. This facilitates thermocompression bonding of one end of the plastic member 40a (40) before and after blow molding.
The length of the blank portion is preferably 3 mm or more, and more preferably 5 mm or more and 20 mm or less.
By setting the length of the blank portion within the above numerical range, the thermocompression bonding process can be performed more easily. In addition, it is possible to prevent the margin part from being excessively provided, to reduce the material to be used, and to reduce the cost.
In the present invention, 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.

Inserting Step 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.

In a preferred embodiment, prior to the fitting step, the preform is preferably preheated using near infrared rays, warm air, or the like.
This reduces the risk of excessively heating the heat-shrinkable plastic member 40a in order to increase the temperature of the preform 10a during blow molding, and the surface of the heat-shrinkable plastic member 40a is melted. It is possible to prevent the appearance from being damaged.
Although the heating 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, and 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.

Heat Shrinkage Process 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 The manufacturing method of the composite preform 70 of the present invention includes a process of thermocompression bonding the end (blank part) opposite to one end of the heat-shrinkable plastic member 40a into which the preform 10a has been fitted. Also good.
An instrument used for thermocompression bonding (hereinafter, referred to as “crimping instrument” in some cases) is capable of crimping the end by, for example, sandwiching it after heating the crimping part with near infrared rays or warm air. There is no particular limitation, and for example, a metal or heat-resistant resin tool can be used, and these may be combined.
When the thermocompression bonding of the heat-shrinkable plastic member 40a is performed along the shape of the bottom portion 30a of the preform 10a, the heat-shrinkable plastic member 40a can be sandwiched between a pair of crimping instruments 90A and B as shown in FIG. The material of this crimping | 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 | compression-bonding instrument may have a heating mechanism in the surface. Thereby, the crimping strength can be further increased. 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 pressure bonding is preferably 80 ° C. or more and 200 ° C. or less, although it depends on the material.

Further, 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 when it is set as the composite container 10A 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).

Twist part formation process The method of this invention may include the process of twisting the thermocompression-bonded part and forming the twist part 80 shown in FIG.
By including such a step, the method of the present invention can not only form the bottom of the heat-shrinkable plastic member 40 after blow molding, but also the container body 10 and the heat-shrinkable plastic made of the composite container 10A. Air bubbles can be prevented from being generated between the member 40 and the force applied during blow molding can prevent the thermocompressed portion from being peeled off or being damaged. .

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 | maintain the preform 10a and the heat-shrinkable plastic member 40a, and a rotation part.
Alternatively, a combination of these methods may be used. Specifically, the thermocompression-bonded portion is sandwiched with a tool such as pliers, and the preform 10a and the heat-shrinkable plastic member 40a are rotated by the rotating portion. Thus, the twisted portion 80 can be formed.

In one embodiment, 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 a degree of rotation of 0.25 to 30 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.

The process of providing a notch | incision The method of this invention may include the process of providing an incision in the heat-shrinkable plastic member 40a.
By providing a notch 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 ease of 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. For example, before the preform 10a is fitted, 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.
Further, 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. 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.

Sterilization Treatment Step 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.

  Examples of the sterilization treatment method include chemical sterilization treatment, photo sterilization treatment, radiation sterilization treatment, hot water sterilization treatment, hot filling sterilization treatment, and pasteurizing sterilization treatment, and these may be combined.

  Next, each sterilization process will be described below.

<Drug sterilization treatment>
(1) Hydrogen peroxide (H ₂ O ₂ ) sterilization treatment is one example of chemical sterilization treatment. In the hydrogen peroxide 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.
By contacting and adhering hydrogen peroxide, the microorganisms adhering to the surface of the preform 10a are sterilized or damaged. The preform may be preheated by blowing hot air on the preform immediately before spraying the mist, gas or a mixture thereof on the preform, or immediately after blowing hot air on the preform. Hydrogen peroxide adhering to the inner surface and / or outer surface of the composite preform 70 is activated by the heat of hot air, thereby sterilizing the microorganisms of the preform. Further, excess hydrogen peroxide adhering to the preform by blowing hot air is quickly removed from the surface of the preform 1.

(2) 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. .

(3) As the chemical sterilization treatment, a chlorine sterilization treatment can be exemplified. In this chlorine sterilization treatment, for example, an acidic cleaning solution made of a chlorite aqueous solution or the like is used, and the preform 10a, the heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A is cleaned with such an acidic cleaning solution. A sterilization treatment is performed.

(4) As the chemical sterilization treatment, 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.

(5) As the chemical sterilization treatment, an ozone sterilization treatment using ozone (O ₃ ) can be used. 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.

<Photodisinfection treatment>
(1) Examples of the photo sterilization treatment include UV sterilization treatment and light pulse sterilization treatment. In this sterilization process, 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. As such light, for example, ultraviolet light having a wavelength of 150 to 2000 nm or light emitted from a xenon lamp can be used.

(2) A plasma sterilization process can be mentioned as the photo sterilization process. In 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.

<Radiation sterilization treatment>
As one of the radiation sterilization treatments, an EB sterilization treatment can be used. In the EB sterilization treatment, 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.

<Hot water sterilization treatment>
(1) The hot water sterilization treatment is performed by preparing hot water of 70 ° C. to 95 ° C., for example, 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.

<Hot filling sterilization>
(1) 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.

(2) Further, for example, a high-temperature content liquid of 80 ° C. to 95 ° C. is prepared, and the composite container 10A can be subjected to hot filling sterilization treatment by filling and overturning the high-temperature content liquid in the composite container 10A.

(3) Moreover, after making water vapor adhere to the preform 10a, the heat-shrinkable plastic member 40a, and the composite preform 70, the preform can be heated to be sterilized.

<Pastorizing sterilization treatment>
(1) As another sterilization treatment, a pasteurizing sterilization treatment in which the content liquid is filled in the composite container 10A and then the composite container 10B containing the content liquid is sterilized can be mentioned.

Composite container 10A
The composite container 10A of the present invention is a blow-molded product of the composite preform 70 described above. As shown in FIG. 1, the container main body 10 located on the inner side and the heat provided in close contact with the outer side of the container main body 10 are provided. A shrinkable plastic member 40 and a vapor deposition film 21 formed on the inner surface of the container body 10 are provided.

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 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.
In another embodiment, 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 .
In the present invention, the oxygen permeability is in accordance with JIS K 7126 isobaric method, oxygen permeability 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.

Container body 10
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. In the present specification, “upper” and “lower” refer to the upper side and the lower side in a state where the composite container 10A is erected (FIG. 1), respectively.

  The mouth portion 11 has a screw portion 14 screwed 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 mouthpiece type mouth portion.

  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.

  Furthermore, the trunk | drum 20 has a cylindrical shape with a substantially uniform diameter as a whole. However, 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. Or the trunk | drum 20 may have a cylinder shape with a horizontal cross section which is not uniform toward upper direction from the downward direction. Moreover, in this Embodiment, although the unevenness | corrugation is not formed in the trunk | drum 20, and has a substantially flat surface, it is not restricted to this. For example, unevenness such as a panel or a groove may be formed on the body portion 20.

  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 30 is not particularly limited, and may have a conventionally known bottom shape (for example, a petaloid bottom shape or a round bottom shape). When filling the composite container 10A with beer or carbonated beverages such as carbonated water as the contents, the shape of the bottom 30 is preferably a petaloid shape.

  Moreover, although the thickness of the container main body 10 in the trunk | drum 20 is not limited to this, For example, it can be made thin to about 100 micrometers-400 micrometers. Further, the weight of the container main body 10 is not limited to this, but for example, when the inner volume of the container main body 10 is 500 mL, it can be 10 g to 50 g. Thus, by reducing the thickness of the container main body 10, the weight of the container main body 10 can be reduced.

Plastic member 40
The heat-shrinkable plastic member 40 has a multilayer structure including at least a colored layer and a gas barrier layer, is in close contact with the outer surface of the container body 10 in a thinly extended state, and easily moves relative to the container body 10. Or installed without rotating. As shown in FIG. 3, 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. Therefore, it is possible to give a function such as a gas barrier property to the bottom of the composite container 10A, which is difficult when the conventional heat-shrinkable plastic member 40 is used.
In addition, since it mentioned above as a structure of a colored layer and a gas barrier layer, it abbreviate | omits here.

Since one end of the heat-shrinkable plastic member 40 included in the composite container 10A of the present invention is pressure-bonded to form a bottom portion, the shoulder portion 12 and the trunk portion of the container body 10 excluding the mouth portion 11 and the neck portion 13 are included. 20 and the bottom 30 can be provided. 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 thickness of the heat-shrinkable plastic member 40 is not limited to this, but can be set to, for example, about 5 μm to 200 μm when attached to the container body 10. In addition, 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 after blow molding is preferably 5 μm or more and 150 μm or less, and more preferably 5 μm or more and 100 μm or less.
The thickness of the gas barrier layer after blow molding is preferably 1 μm or more and 100 μm or less, and more preferably 1 μm or more and 20 μm or less.

  As will be described later, 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.

As described above, when beer is filled as the contents, the heat-shrinkable plastic member 40 is required to cut 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 changing the type and content of the resin material and the colorant.
Further, 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.

Deposition film 21
In the composite container 10A of the present invention, a vapor deposition film 21 is formed on the inner surface of the container body 10. In this case, the vapor deposition film 21 is formed over the entire inner surface of the container body 10 with a substantially uniform thickness. By providing the composite container 10A of the present invention with the vapor deposition film 21, the oxygen, carbon dioxide, and water vapor barrier properties can be improved.

In one embodiment, the vapor deposition film 21 is preferably made of an inorganic oxide from the viewpoint of gas barrier properties such as oxygen and water vapor, and transparency.
As such 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. Among these, silicon oxide is particularly preferable from the viewpoints of gas barrier properties and production efficiency.
In one embodiment, carbon-added silicon oxide (SiOC) can also be used.

When the deposited film 21 contains silicon oxide, 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 It is preferable to represent a number from 3 to 1.9.
Moreover, 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. For example, when 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, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.

In another embodiment, the vapor deposition film 21 may be a hard carbon film made of, for example, a DLC (Diamond Like Carbon) film. A hard carbon film made of a DLC film is a hard carbon film 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 about 0.002 μm to 0.4 μm, and specifically about 0.005 to 0.1 μm. . By setting the thickness of the vapor deposition film 21 to 0.1 μm, and further to 0.4 μm or less, it is possible to prevent a problem that a crack or the like easily occurs in the vapor deposition film 21. On the other hand, when the thickness of the vapor deposition film 21 is 0.005 μm, further 0.002 μm or more, the gas barrier effect can be surely exhibited. In FIG. 1 and FIG. 2, the vapor deposition film 21 is exaggerated in the thickness direction.

In the composite container 10A of the present invention, 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.
This label is, 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. Among these, it is preferable to use a shrink label, a stretch label or a roll label because of high productivity.
Further, 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.

  A shrink label can be wound so that the container main body 10 and / or the heat shrinkable plastic member 40 whole region or a part may be covered. 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 Laminate film of polyester and shrink film, polyester-polystyrene coextruded film, polyamide film such as 6-nylon film, 6,6-nylon film, chlorinated polyethylene , Modified polyolefin film formed as a film of a resin such as chlorinated polypropylene, vinyl chloride - can be produced using was film-formed from a resin of vinyl acetate copolymer film, a resin film such as 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. Film formed, multilayered by co-extrusion using two or more types of resin, or formed by mixing two or more types of resin, and uniaxial or tenter or tubular Various resin films that are stretched in a biaxial direction can be used, but a stretched film, preferably a uniaxially stretched film in the flow direction. These films may be foamed films.

  In the present invention, 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 insulation properties, A polyester-polystyrene multilayer film or the like can be suitably used, or a laminated film of a nonwoven fabric and the film may 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.

  Although the thickness of a shrink label is not limited to this, For example, it can be set as about 10 micrometers-about 80 micrometers in the state attached to 10 A of composite containers.

  Like a shrink label, a stretch label can be wound so that the container main body 10 and / or the heat shrinkable plastic member 40 whole region or a part may be covered. The stretch label can be obtained 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 provided with a layer made of low density linear polyethylene. These films can be produced by the method described above.

  Although the thickness of a stretch label is not limited to this, For example, it can be set as about 5 micrometers-50 micrometers in the state attached to 10 A of composite containers.

  Similarly to the shrink label, 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. The roll label can be obtained by winding a resin film around a composite container and bonding or fusing the end of the resin film. The tack label can be obtained by directly attaching the resin film to the composite container via an adhesive or the like.

  The roll label and the tack label can be produced by using the above-described resin film. Examples of the adhesive 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.

  Although the thickness of a roll label and a tack label is not limited to this, For example, it can be set as about 5 micrometers-about 100 micrometers in the state attached to 10 A of composite containers.

  Similarly to the shrink label, the paper 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 paper label can be obtained by sticking the resin film directly to the composite container via an adhesive or the like, like the tack label.

  The paper label is preferably produced using paper having excellent water resistance impregnated with a polyisocyanate compound or the like.

  Although the thickness of a paper label is not limited to this, For example, it can be set as about 50 micrometers-300 micrometers in the state attached to 10 A of composite containers.

  The suspended label can be obtained 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 stamping), or the like. The displayed items may be character information such as the name of the content liquid, the manufacturer, the raw material name, etc. 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, and white, and may be transparent or opaque.

Manufacturing method of composite container 10A The manufacturing method of the composite container 10A according to 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;
Forming a vapor deposition film 21 on the inner surface of the container body 10.
In addition, as described above, a step of sterilizing the composite container 10A may be included.

  The blow molding method of the composite preform 70 of the present invention will be described in more detail with reference to FIGS.

In one embodiment, the composite preform 70 is heated by the near infrared irradiation device 51 (see FIG. 10A). Note that the present invention is not limited to this, and heating with warm air or microwaves 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 may be, for example, 90 ° C. to 130 ° C.

  Subsequently, the composite preform 70 heated by the near infrared irradiation device 51 is sent to the blow molding die 50 (see FIG. 10B).

The composite container 10 </ b> A is molded using this blow molding die 50.
In one embodiment, 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. 10B). In FIG. 10B, the pair of body molds 50a and 50b are open to each other, and the bottom mold 50c is raised upward. In this state, the composite preform 70 is inserted between the pair of body molds 50a and 50b.

  Next, as shown in FIG. 10C, after the bottom mold 50c is lowered, the pair of body molds 50a and 50b are closed, and the pair of body molds 50a and 50b and the bottom mold 50c are used. A sealed blow molding die 50 is configured. Next, a rod for stretching in the longitudinal direction enters from the mouth direction, contacts the bottom of the inner surface of the preform, and stretches as it is, and then air is pressed into the preform 10 a, and 2 to the composite preform 70. Axial stretch blow molding is performed.

  As a result, the container body 10 is obtained from the preform 10 a in the blow molding die 50. During this time, 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. At this time, in the blow mold 50, the preform 10a of the composite preform 70 and the heat-shrinkable plastic member 40a are expanded as a unit. Thus, 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.

  Next, as shown in FIG. 10D, 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. .

It is not limited to the above-described method, and 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.

One embodiment of an apparatus used for blow molding will be described below with reference to FIG.
A composite container manufacturing apparatus 100 shown in FIG. 11 is an apparatus for manufacturing the above-described composite container 10A. The composite container 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.
By using this apparatus, 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. In the present specification, “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. In FIG. 11, 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. In this case, 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. doing. The molding unit 101 may be a compression molding unit that produces the preform 10a by compression molding or an injection compression molding unit that produces 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. However, 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.

  In addition, after the mounting part 109 loosely inserts the plastic member 40a into the preform 10a, 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. For example, 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.

  As described above, 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. 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.

  Although not shown, 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 | molding wait.

  Furthermore, 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. In this case, 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.
Hereinafter, a method for forming the vapor deposition film 21 by the plasma CVD method will be described with reference to FIG.

First, the configuration of the high-frequency plasma CVD apparatus 200 will be described. 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 may be composed of a plurality of members 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. In addition, 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. On the other hand, the internal electrode 205 is grounded via the source gas supply pipe 207. Around the external electrode 203, 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. When 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.

Further, as shown by an arrow P ₁ , the air in the reaction chamber 204 is exhausted by the vacuum source (vacuum pump) through the exhaust pipe 208.

  First, the composite container 10 </ b> A is accommodated 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.

  Next, 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, and at the same time, 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. At that time, by generating a magnetic field by the magnet 211 inside the reaction chamber 204, it becomes possible not only to generate high-quality high-quality inert gas plasma, but also to plasma the inner surface of the container body 10. It is possible to collide the inert gas with acceleration and to form fine irregularities on the inner surface of the container body 10 efficiently.

  Next, the inside of the reaction chamber 204 is again exhausted 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 as described above.

  Next, 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 vapor deposition source gas composition 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 product is produced. This reaction product is deposited on the entire inner surface of the container body 10 with acceleration. At that time, by generating a magnetic field by the magnet 211 inside the reaction chamber 204, it becomes possible not only to generate a high-quality and high-quality plasma reaction product, but also to generate plasma on the inner surface of the container body 10. 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.

  After a sufficient time to form the vapor deposition film 21, 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. In this way, a composite container 10A (see FIG. 2) in which the vapor deposition film 21 is formed on the entire inner surface of the container body 10 is obtained.

Product Using Composite Container 10A 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 screwed to the mouth portion 11 of the container body 10 (see FIG. 13).

  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.

  In one embodiment, the mouth portion 11 includes a screw portion 14 to which the cap 18 is screwed, 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. 14).

  In one embodiment, the cap 18 has a substantially cylindrical side wall portion 18a and a top surface portion 18b connected to the upper end of the side wall portion 18a and having a substantially circular plane. On the inner surface of the side wall portion 18a, 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. 14).

Moreover, in one Embodiment, the cap 18 and / or the flange part 17 are covered with the light shielding film. With such a configuration, the light shielding property of the composite container 10A can be further improved, and the storage stability of the contents can be further improved.
As the light shielding film, an opaque film having a light shielding property is used. Examples of the material for the light shielding film include polyethylene terephthalate (PET), polystyrene (PS), polypropylene (PP), and polyethylene (PE). The light-shielding film is preferably a heat-shrinkable cylindrical film.

  The contents filled in the product of the present invention are not particularly limited, and in addition to the beer described above, alcohol such as sake and wine, soft drinks such as sports drinks, vegetable juice and smoothies are filled. be able to. Moreover, it is not limited to a drink, You may fill a shampoo, rinse, cosmetics, a pharmaceutical, etc.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Example 1>
(Step of preparing the preform 10a)
A PET preform 10a shown in FIG. 7 was produced using an injection molding machine. The weight of this preform 10a was 30.0 g, and its length Y was 90 mm.

(Process for preparing the heat-shrinkable plastic member 40a)
A colored layer resin composition containing polyethylene and a brown colorant as a polyolefin-based resin, EVOH, and an adhesive were coextruded from a ring-shaped die. Next, heat-shrinkable plastic having a configuration of colored layer / adhesive layer / gas barrier layer (EVOH) / adhesive layer / colored layer is performed by pressurizing the inner surface of the extruded tube or expanding the outer surface of the tube by applying a negative pressure from the inner surface. A member 40a was produced.
When 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 produced heat-shrinkable plastic member 40a was 100 mm.
In addition, content of the coloring agent in a colored layer was 5 mass%.

(Fitting process)
Next, the preform 10a was fitted from one end of the heat-shrinkable plastic member 40a by manual work.

(Heat shrinkage and thermocompression process)
After fitting, 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. Next, using a metal plate heated to 100 ° C., the blank portion was sandwiched at a pressure of 300 N / cm ² and thermocompression bonded to obtain a composite preform 70.

(Manufacture of composite containers)
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.
Next, 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.
Moreover, when the transmittance | permeability of visible light with a wavelength of 400-500 nm in the trunk | drum and bottom part of 10 A of composite containers was measured using the spectrophotometer (The Shimadzu Corporation make, ultraviolet visible spectrophotometer), both were 0. .5%.
Further, in accordance with the JIS K 7126 isobaric method, an oxygen gas permeability measuring device (manufactured by MOCON, trade name: OX-TRAN 2/20) is used to measure the composite container 10A under the conditions of 23 ° C. and humidity 90% RH. The oxygen transmission rate was measured and found to be 0.060 cc / m ² · day · 0.21 atm.

<Appearance test>
When the appearance of the composite container 10A after manufacture was visually evaluated, no bubbles were present between the container body 10 and the plastic member 40, and no peeling or breakage of the crimping part was observed. Thus, the bottom 30 of the container body 10 was completely covered.

<Comparative Example 1>
A composite container 10A was produced in the same manner as in Example 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.

<Comparative example 2>
A composite container 10A was produced in the same manner as in Example 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%, and the oxygen transmittance is 0.060 cc / m. ² · day · 0.21 atm.
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.

<Comparative Example 3>
A composite container 10A was produced in the same manner as in Example 1 except that the vapor deposition film was not 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.

Claims (27)

A preform having a single layer structure, comprising a mouth, a body connected to the mouth, and a bottom connected to the body;
A heat shrinkable plastic member provided so as to surround the outside of the preform,
The heat-shrinkable plastic member includes a colored layer containing a colorant, and a gas barrier layer,
A composite preform, wherein the heat-shrinkable plastic member has a near-infrared transmittance of 50% or more.   The composite preform according to claim 1, wherein the colored layer contains a polyolefin-based resin.   The composite preform according to claim 1 or 2, wherein the colorant is a brown pigment, and the content thereof is 0.1% by mass or more and 30% by mass or less.   The gas barrier layer is metaxylene 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 (PAN), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE) and styrene-isobutylene-styrene copolymer The composite preform according to any one of claims 1 to 3, comprising at least one gas barrier resin selected from the group consisting of polymers.   The composite preform according to any one of claims 1 to 4, further comprising an adhesive layer between the colored layer and the gas barrier layer.   The composite preform according to any one of claims 1 to 5, which has a structure of colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer.   The composite preform according to any one of claims 1 to 6, wherein one end of the plastic member on the bottom side of the preform is crimped.   The composite preform according to claim 7, wherein the crimped portion of the heat-shrinkable plastic member is twisted to form a twisted portion.   The composite preform according to any one of claims 1 to 8, wherein the heat-shrinkable plastic member has at least one cut at one end of the heat-shrinkable plastic member that is close to the mouth of the preform. .   The composite preform according to any one of claims 1 to 9, wherein the specific gravity of the heat-shrinkable plastic member is less than 1, and the specific gravity of the preform is more than 1. A composite container which is a blow molded product of the composite preform according to any one of claims 1 to 10,
A mouth, a neck provided below the mouth, a shoulder provided below the neck, a trunk provided below the shoulder, and a bottom provided below the trunk. A container body having a single-layer structure,
A heat-shrinkable plastic member provided in close contact with the outside of the container body;
A vapor deposition film formed on the inner surface of the container body,
The heat-shrinkable plastic member comprises a colored layer and a gas barrier layer;
One end of the plastic member on the bottom side of the container main body is crimped to form a bottom part.   The composite container according to claim 11 for filling beer as a content, wherein the visible light transmittance at a wavelength of 400 to 500 nm is 20% or less.   The composite container according to claim 11 or 12, wherein a bottom shape of the container body is a petaloid shape. The composite container according to any one of claims 11 to 13, wherein the oxygen permeability is 0.5 cc / m ² · day · 0.21 atm or less.   The composite container according to claim 11, wherein a label is attached to the container body and / or the plastic member.   The composite container according to claim 15, wherein the label is a shrink label, a stretch label, a roll label, a tack label, or a paper label.   The composite container according to claim 15 or 16, wherein the label is printed. A method for producing the composite preform according to any one of claims 1 to 10,
Preparing a preform and a heat-shrinkable plastic member;
Fitting the preform from one end of the heat-shrinkable plastic member;
Heating the preform and the heat-shrinkable plastic member to heat-shrink the heat-shrinkable plastic member;
A method for producing a composite preform, comprising: The heat-shrinkable plastic member has a blank portion at the end opposite to the end where the fitting is performed,
The method according to claim 18, further comprising a step of thermocompression bonding the blank portion.   The method according to claim 19, further comprising twisting the thermocompression-bonded blank portion to form a twisted portion.   The method according to any one of claims 18 to 20, further comprising a step of preheating the preform before the fitting step.   The method according to any one of claims 18 to 21, further comprising providing a notch in the plastic member.   The method according to any one of claims 18 to 22, further comprising a step of sterilizing the preform and / or the plastic member before and / or after the fitting step. It is a manufacturing method of the composite container according to any one of claims 11 to 17,
Heating the composite preform according to any one of claims 1 to 10 and inserting it into a blow mold; and
A method for producing a composite container, comprising: performing a blow molding on the composite preform after heating, and expanding the preform and the plastic member integrally. A product in which the composite container according to any one of claims 11 to 17 is filled with contents,
A product, characterized in that a cap is screwed onto the mouth of the container body. The mouth portion has a flange portion;
26. A product as set forth in claim 25 wherein the cap comprises an overcap covering the flange portion.   27. The product of claim 25 or 26, further comprising a light shielding film covering the cap.