Technical field
[0001]The present invention is a composite preform and a manufacturing method thereof, a composite container, a method of manufacturing the same, and to products filled with beer composite container.
BACKGROUND
[0002]Recently, as a container for accommodating liquid contents, such as food and drink, as plastic have been generalized.
[0003]Plastic containers, inserts the preform in a mold, is manufactured by biaxial stretch blow molding.
[0004]
　Incidentally, in the conventional biaxial stretch blow molding method, a preform comprising a resin material such as PET or PP, is manufactured containers. However, in the conventional biaxial stretch blow molding method is simply common that only molding the preform into a container shape. Therefore, when to have various functions and characteristics relative to the container (such as barrier property and warmth), for example, such as changing the material constituting the preform, the means is limited. Especially, according to the site of vessel (e.g., the trunk section and the bottom), so it is difficult to have different functions and characteristics.
[0005]
　The Applicant has been made in view of the above problems, in the prior application (Japanese Patent Application Laid-Open No. 2015-128858) proposes a composite container capable of imparting various functions and characteristics to the container.
CITATION
Patent Document
[0006]
Patent Document 1: JP 2015-128858 JP
Disclosure of the Invention
Problems that the Invention is to Solve
[0007]
　JP composite container disclosed in 2015-128858 Patent Publication, and the preform was heated by near infrared composite preform comprising a heat-shrinkable plastic member provided so as to surround the outside of the preform, blow It is made by molding.
　However, such depending on the type of resin material or the colorant contained in the plastic member, only the outer plastic member has fallen into the heat. Therefore will dissolve the surface of the plastic member, there is a possibility that impairs the appearance. Further, it is impossible to heat the preform efficiently, had room for improvement in their productivity.
[0008]
　The present invention has been made based on the knowledge of, it is possible to effectively prevent the appearance deterioration of the plastic member surface due to the near-infrared heating before blow molding, the inner preform efficiently composite preform and method of manufacturing the same capable of heating the composite container, a manufacturing method thereof is blow-molded article of the composite preform, as well as to provide a product filled with beer to the composite container and its purpose .
[0009]
　Composite preform of the present invention includes a mouth portion, a body portion coupled to the mouth, and the preform comprising a bottom portion connected to the body portion, provided so as to surround the outer preform, resin material and coloring and at least comprises heat-shrinkable plastic member a coloring layer containing an agent, NIR transmittance of a heat shrinkable plastic member is equal to or less than 50%.
[0010]
　In one embodiment, the heat shrinkable plastic member further comprises a gas barrier layer.
[0011]
　In one embodiment, the colored layer comprises a polyolefin resin.
[0012]
　In one embodiment, the colorant is a brown pigment, the content thereof is 0.1 wt% or more and 30 mass% or less.
[0013]
　In one embodiment, the preform has a multilayer structure comprising at least a gas barrier layer.
[0014]
　In one embodiment, one end of the plastic member on the bottom side of said preform is crimped.
[0015]
　In one embodiment, the crimping portions of the heat shrinkable plastic member is twisted to form a twisted portion.
[0016]
　Cylinder composite container of the present invention is a blow-molded article of the composite preform, the mouth, and the mouth portion neck provided below, a shoulder portion provided on the neck downward, provided on the shoulder portion downwardly and parts, a bottom part provided in the body portion downward, and the container body with a, provided in close contact with the outside of the container body, and a heat shrinkable plastic member having at least a colored layer containing a resin material and a colorant, the provided, it is crimped to one end of a plastic member of the bottom side of the container body, characterized in that it forms the bottom.
[0017]
　In one embodiment, the composite container, visible light transmittance at a wavelength of 400 ~ 500 nm is 20% or less.
[0018]
　In one embodiment, the composite container, the inner surface of the container main body further comprises a deposited film.
[0019]
　In one embodiment, the composite container, oxygen permeability, 0.5 cc / m 2 or less · day · 0.21 atm.
[0020]
　The method of producing a composite preform of the present invention includes the steps of preparing a preform and heat shrinkable plastic member, a step of fitting the preform from one end of the heat shrinkable plastic member, the heat-shrinkable plastic member a step of the margin thermocompression bonding with, heating the preform and heat shrinkable plastic member, a heat-shrinkable plastic member, characterized in that it comprises a step of heat shrinking, the
[0021]
　In one embodiment, the manufacturing method of the composite preform, twisting the blank portion was heat pressed, further comprising the step of forming the twisted portion.
[0022]
　In one embodiment, the manufacturing method of the composite preform, before fitting step, further comprising the step of preheating the preform.
[0023]
　Method of manufacturing a composite container of the present invention includes the steps of inserting into the blow mold while heating the composite preform, by performing blow molding the composite preform after heating, preforms and plastic member, characterized by comprising a step of inflating integrally.
[0024]
　Products of the present invention has beer filled in the composite container, wherein the cap to the mouth portion of the container body is mounted.
The invention's effect
[0025]
　According to the present invention, it is possible to effectively prevent the appearance deterioration of the plastic member surface due to the near-infrared heating before blow molding, the composite preform and capable of heating the preform efficiently production method, the composite container, a manufacturing method thereof is blow-molded article of the composite preform, as well as to provide a product filled with beer composite container.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026]
[1] Figure 1 is a partial vertical sectional view of a composite preform of the present invention in one embodiment.
FIG. 2 is a perspective view of a composite preform of the present invention in one embodiment.
FIG. 3 is a front view of a composite preform forming the twisted portion.
[4] FIG. 4 is a schematic diagram illustrating one embodiment of a method for producing a heat-shrinkable plastic member.
FIG. 5 is a vertical cross-sectional view showing a state in which fitting the preform to the heat shrinkable plastic member.
FIG. 6 is a front view of a heat shrinkable plastic member.
[7] FIG. 7 is a front view of the preform.
[8] FIG. 8 is a perspective view showing a crimping tool in one embodiment.
[9] FIG. 9 is a partial vertical sectional view showing a composite container produced by using the composite preform of the present invention in one embodiment.
[10] FIG 10 is a x-x line horizontal sectional view of the composite container shown in FIG.
[11] FIG 11 is a schematic diagram showing a method for manufacturing a composite container.
[12] FIG 12 is a schematic diagram showing an apparatus for manufacturing a composite container in one embodiment.
[13] FIG 13 is a schematic sectional view showing a high-frequency plasma CVD apparatus.
[14] FIG. 14 shows, in an embodiment, is a partial vertical cross-sectional view showing a product using the composite container.
[15] FIG. 15 shows, in an embodiment, is an enlarged partial vertical cross-section of an article mouth near using the composite container.
DESCRIPTION OF THE INVENTION
[0027]
　 Composite preform 70
　in one embodiment, as shown in FIG. 1, the composite preform 70 includes a preform 10a, provided so as to surround the outer preform 10a, and a heat-shrinkable plastic member 40a .
[0028]
　For this composite preform 70 is subjected to biaxial stretch blow molding, by expanding the preform 10a and the heat-shrinkable plastic member 40a of the composite preform 70 integrally, it is possible to obtain a composite container 10A.
[0029]
　　 Preform 10a
　preform 10a, as shown in FIG. 1 comprises a mouth portion 11a, a body portion 20a which is connected to the mouth portion 11a, a bottom portion 30a which is connected to the body portion 20a. Among the mouth portion 11a, which corresponds to the mouth portion 11 of the container body 10 described above, and has a mouth portion 11 substantially the same shape. Further, the body portion 20a has a neck portion 13 of the container body 10 described above, which corresponds to the shoulder portion 12 and body portion 20 has a substantially cylindrical shape. Bottom 30a, which corresponds to the bottom 30 of the container body 10 described above, has a substantially hemispherical shape.
[0030]
　The preform 10a having a composite preform 70 of the present invention also have a single-layer structure, it may have a multilayer structure.
[0031]
　Each layer comprising the preform 10a is a thermoplastic resin, particularly PE (polyethylene), PP (polypropylene), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), comprises a resin material such as ionomer be able to. It may also include a blend resin obtained by blending various resins described above.
[0032]
　Each layer comprising the preform 10a is, to the extent that the characteristics of the present invention are not impaired, may contain various additives. As the additives, such as plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agent, slip agents, release agents, anti oxidizing agents, ion exchange agents, dispersing agents, UV absorbers and coloring pigments.
[0033]
　Further, each layer comprising preform 10a is red, blue, yellow, green, brown, black, may contain a colorant such as white, but when considering recyclability, without them colorants, colorless it is preferably transparent.
[0034]
　In one embodiment, the preform 10a has a multilayer structure comprising comprising at least a gas barrier layer. Further, the preform 10a may be one comprising a gas barrier layer 2 or more layers, in this case, be the same for such configuration and thickness of each layer may be different.
[0035]
　Gas barrier layer comprises a gas barrier resin, for example, meta-xylene adipamide (MXD-6), nylon 6, nylon 6,6, nylon 6 / nylon 6,6 copolymer, ethylene - vinyl acetate copolymer Weight coalescence (EVA), ethylene - vinyl alcohol copolymer (EVOH), polyglycolic acid (PGA), polyvinylidene chloride copolymer (PVDC), polyacrylonitrile, polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE) and styrene - isobutylene - styrene copolymer. Gas barrier layer may comprise a gas barrier resin mentioned above two or more.
[0036]
　The content of the gas barrier resin in the gas barrier layer is preferably at least 50 wt%, and more preferably 90 mass% or more. The content of the gas barrier resin is in the above range, it is possible to further improve the gas barrier properties of the composite container 10A.
[0037]
　Gas barrier layer, in a range that does not impair its characteristics, may contain a resin material other than the gas barrier resin. Other resins, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), a polyester resin such as polyethylene naphthalate (PEN), polyethylene (LDPE, MDPE, HDPE, LLDPE), polypropylene (PP), ethylene - propylene copolymer, poly-4-methylpentene, poly-1-polyolefin resins, such as butene, homopolymer of vinyl chloride, homopolymers of vinylidene chloride, vinyl chloride - vinyl acetate copolymer, vinyl chloride or vinylidene chloride If, vinyl resin such as a copolymer of maleic acid derivatives and higher alkyl vinyl ether, and ionomer resins.
[0038]
　In one embodiment, the gas barrier layer comprises a pro-oxidant. The oxidation-promoting agent, is not particularly limited as long as it promotes the reaction of oxygen absorbent and molecular oxygen which may be automatically oxidized by molecular oxygen, for example, radical generator, photooxidation catalyst, the transition such as metal salts. Of these, the transition metal salt is preferable because it is possible to exert a sufficient effect even in small quantities. Gas barrier layer, by comprising the pro-oxidant, oxidation of the oxygen absorber may be auto-oxidation is promoted by the molecular oxygen, the oxygen-absorbing ability is improved.
[0039]
　As metal salts, such as inorganic salts, organic salts and complex salts can be exemplified. As the inorganic salts, halide salts, oxy salt, oxy acid salts, and the like silicate. As the organic acid salts, carboxylates, sulfonates, such as phosphonate and the like. As the complex include complexes of β- diketone or β- keto ester.
[0040]
　Content of the oxidizing accelerator in the gas barrier layer is 0.001 mass% or more, preferably 3 wt% or less, 0.005 wt% or more, more preferably at most 2 mass%, 0.01 mass % or more, more preferably not more than 1.5 mass%. The content of the oxidizing accelerator to be in the above numerical range, while maintaining the transparency of the gas barrier layer, it is possible to improve the gas barrier properties.
[0041]
　Gas barrier layer may contain an oxygen absorber. As the oxygen absorbent, the iron based oxygen absorber and can include non-ferrous oxygen absorber, it is possible to maintain the transparency of the preform 10a, non-ferrous oxygen absorber is more preferable.
[0042]
　The iron-based oxygen absorbents, reduced iron powder, interfacial iron powder, atomized iron powder, iron grinding powder, electrolytic iron powder include iron powders such as pulverized iron.
[0043]
　As the non-ferrous oxygen absorber, and the like ethylenically unsaturated group-containing copolymer. Ethylenically unsaturated group-containing copolymer, for example, polybutadiene, polychloroprene, poly (2-ethyl-butadiene), poly (2-butyl-butadiene) which was polymerized by mainly 1,4 positions a polydiene, such as, polyoctenylene, polypentenylene, ring-opening metathesis polymer of a cycloolefin such as polynorbornene, styrene - isoprene block copolymer, styrene - butadiene copolymer, styrene - isoprene - styrene such as styrene block copolymer - diene block copolymerization and the like can be mentioned coalescence, among these, polybutadiene, polyoctenylene, styrene - isoprene - styrene block copolymer.
[0044]
　The content of oxygen absorbing agent in the gas barrier layer is 0.1 wt% or more, preferably 15 wt% or less, 0.5 mass% or more, more preferably at most 10 mass%, 1 mass% or more , still more preferably 7.5 mass% or less. The content of the oxygen absorber to be in the above numerical range, while maintaining the transparency of the gas barrier layer, it is possible to improve the gas barrier properties.
[0045]
　When the preform 10a has a multilayer structure, As a specific layer structure, for example, from the innermost layer, having a structure comprising a polyester resin layer / gas barrier layer / polyester resin layer, a polyester resin layer / gas barrier layer / configuration are mentioned with a polyester resin layer / gas barrier layer / polyester-based resin layer.
　More specific layer structure, having a structure comprising a layer comprising a layer / PET containing layers / MXD-6 containing PET, comprising a layer / PET containing layers / MXD-6 and pro-oxidants including PET having a structure comprising a layer, having a configuration comprising a layer containing a layer / PEN containing layer / MXD-6 containing PEN, a layer comprising a layer / PEN containing layer / MXD-6 and pro-oxidants including PEN having a structure comprising the like.
[0046]
　The preform 10a can be produced by injection molding using a conventionally known device such as a resin material.
　In one embodiment, the thermoplastic resin melt in an inert gas (nitrogen gas, argon gas) by mixing, molding the foamed preform having a foamed cell diameter of 0.5 ~ 100 [mu] m, the foamed preform by blow molding, it may be produced container body 10. Such container body 10, because a built-in foam cells, can increase the overall light-shielding container body 10.
[0047]
　 Heat-shrinkable plastic member 40a
　as shown in Figure 1, heat-shrinkable plastic member 40a without being bonded to the preform 10a, provided so as to surround the outer movement or relative preform 10a if it were in close contact to the extent not rotate, or is in close contact so as not to fall by its own weight.
　By plastic member 40a having a heat-shrinkable, during blow molding, or a shift with respect to the preform 10a, it is possible to prevent the bubble is formed between the container body 10 and the plastic member 40 can, the appearance can be obtained a good composite container 10A.
[0048]
　The heat shrinkable plastic member 40a is provided over the entire circumference to surround the preform 10a.
　Further, as shown as a shaded portion in FIG. 1, one end of the bottom portion 30a side of the heat shrinkable plastic member 40a of the preform 10a is thermocompression, thereby forming a bottom covering the bottom 30a of the preform 10a it is preferable.
　Usually, the heat-shrinkable plastic member 40a, it is difficult to cover the bottom 30a of the preform 10a. However, by adopting such a configuration, after the blow molding, the bottom of the container main body 10 makes it possible to cover with a plastic member 40 of the heat-shrinkable, such as gas barrier properties, a variety of functions in the bottom of the composite container 10A it can be imparted.
[0049]
　Thermocompression bonding is particularly preferably being carried out along the shape of the bottom portion 30a of the preform 10a. Thus, it is possible to prevent generation of bubbles between the container body 10 and the heat-shrinkable plastic member 40 after blow molding, is possible to improve the adhesion of the heat-shrinkable plastic member 40 relative to the container body 10 is possible, it is possible to improve the appearance of the composite container 10A.
[0050]
　In one embodiment, as shown in FIG. 2, the plastic member 40a has a margin 80a, the margin 80a is provided with a bent portion 44 which is formed along the shape of the preform 10a, the bent portion 44 It has first opposing face 46a projecting respectively and the second opposing face 46b. Moreover, it is integrated by heat bonding to each other and the first opposing face 46a and the second opposing face 46b. First opposing face 46a and the second opposing surface 46b are each viewed from the bottom direction, and extends in a substantially straight line along the radial direction of the body portion 20a of the preform 10a. In this case, the first opposing surface 46a and the second opposing face 46b is crimped over the radial entire region of the body portion 20a.
[0051]
　In one embodiment, heat-shrinkable plastic member 40a is thermally crimped portion is twisted, which may be provided with a torsion portion 80 (see FIG. 3).
　By providing a heat-shrinkable plastic member 40a is twisted portion 80, not only can be bottom forming, air bubbles between the container body 10 and the heat-shrinkable plastic member 40 after blow molding comprising the composite container 10A is it is possible to prevent the generated by the force applied during blow molding, etc. or worse peeling thermocompression bonding portions can be prevented from being damaged.
[0052]
　In one embodiment, heat-shrinkable plastic member 40a is an end of the body portion 41a, when attached to the preform 10a, the notch in at least one location on the side of the one end closer to the mouth portion 11a of the preform 10a a.
　To heat-shrinkable plastic member 40a, By providing such a cut, it is possible to easily separate and remove the plastic member 40 from the composite container 10A after blow molding.
[0053]
　The shape of the cut is not particularly limited, it may be a score line, such as any of a triangle or a quadrangle, or may be a notch form.
[0054]
　If the cut is the score line, the length is not limited in particular, as appropriate according to the shape of the container body 10 may be changed, for example, 0.5 mm or more in the plastic member 40a before the blow molding, it can be set to 5mm or less.
　The heat-shrinkable plastic member 40a having a cut line having such a length, the preform 10a, by blow molding, heat-shrinkable plastic member 40 after blow molding, 3 mm or more, cuts of 15mm or less will have a line, it can be easily separated from the container body 10 on the basis of the score line.
[0055]
　The shape of the notch is also not limited in particular, the size of the container body 10, such as a consideration of the shape, as appropriate, may be modified, for example, a triangular shape or a quadrangular shape, or a semicircular shape or fan such shape combining curves like shape, may be of various shapes.
　When the shape of the notch is triangular, for example, the vertical length of 0.5mm or more, 5 mm or less, the horizontal length of the 0.1mm or more, than what can be less 8mm limited thereto Absent.
　The heat-shrinkable plastic member 40a having a notch of such size with a preform 10a, by blow molding, heat-shrinkable plastic member 40 after blow molding, vertical length 1mm or more, 15mm or less, the horizontal length of the 0.5mm or more, and have a notch below the triangle 10 mm, can be easily separated from the container body 10 on the basis of the cut-outs.
[0056]
　Also, in one embodiment, heat-shrinkable plastic member 40a includes a knob portion for connecting the notch. The material constituting the knob portion is not limited in particular, it is of a resin material used in the manufacture of heat-shrinkable plastic member 40a may, be of paper or metal it may be.
[0057]
　NIR transmittance of a heat shrinkable plastic member 40a of the composite preform 70 is provided in the present invention is 50% or more, more preferably 60% or more and 100% or less, more preferably 70% or more, 100 % or less.
　By the near infrared transmittance of the heat-shrinkable plastic member 40a and above range, the near infrared heating blow molding process, only the heat-shrinkable plastic member 40a surrounding the preform 10a is warmed up, dissolved to put away, it is possible to prevent that the appearance is deteriorated. Moreover, since it is possible to heat the preform 10a can be efficiently enhanced production efficiency.
　NIR transmittance of a heat shrinkable plastic member 40a can be adjusted by changing the type and content of which will be described later resin material and a colorant.
　In the present invention, near infrared rays and a wavelength refers to a light beam of 800 nm ~ 2500 nm.
　Also, a near-infrared transmittance is 50% or more, measured the absorbance to heat shrinkable plastic member 40a using a known spectrophotometer (e.g., manufactured by Hamamatsu Photonics KK spectrometer) was time, the transmittance at 800 nm ~ 1500 nm is referred to be a 50% or more.
[0058]
　Heat-shrinkable plastic member 40a is preferably a specific gravity of less than 1, more preferably less than 0.97.
　The specific gravity of the heat-shrinkable plastic member 40a by the above, after milling the composite container 10A, when charged into the water, to be easily separated shrinkable plastic member 40 from the container body 10 it can.
　At this time, the specific gravity of the container body 10 is preferably 1 is greater, and more preferably greater than 1.2.
[0059]
　Heat-shrinkable plastic member 40a of the composite preform 70 is provided in the present invention, also have a single-layer structure, it may have a multilayer structure.
[0060]
　Heat-shrinkable plastic member 40a is provided with at least a colored layer containing a resin material and a colorant. By heat-shrinkable plastic member 40a comprises a coloring agent, it is possible to adjust the infrared transparent heat-shrinkable plastic member 40a. Further, it is possible to adjust the visible light transmittance of the composite container 10A after blow molding.
　Heat-shrinkable plastic member 40a is a colored layer may be provided more than two layers. Also, the type of materials constituting the respective colored layers, the content, the thickness of the coloring layer may be the same or may be different.
[0061]
　In one embodiment, the colored layer, as a resin material, comprises a polyolefin resin.
　As the polyolefin resin, for example, polyethylene (LDPE, MDPE, HDPE, LLDPE), polypropylene, polybutene, polybutadiene, polyisoprene and copolymers of monomers constituting these with (alkenes) and other monomer , for example, a copolymer of ethylene and carbon atoms and 4 or more α-olefins, ethylene - (meth) acrylic acid copolymer, ethylene - (meth) acrylate copolymer, ethylene - (meth) acrylate copolymers, ethylene - vinyl acetate copolymer, ethylene - vinyl alcohol copolymer, and the like ionomer resin.
　Heat-shrinkable plastic member 40a may comprise a polyolefin resin mentioned above one or more.
[0062]
　In one embodiment, the colored layer may comprise a resin other than the polyolefin resin, for example, PET, PEN, poly-4-methylpentene-1, polystyrene, AS resin, ABS Kimune, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, methyl diallyl phthalate resin, fluorine resin, polymethyl methacrylate, polyacrylic acid, polymethyl acrylate, polyacrylonitrile, polyacrylamide, polybutadiene, polybutene - 1, polyisoprene, polychloroprene, ethylene propylene rubber, butyl rubber, nitrile rubber, acrylic rubber, silicone rubber, fluorine rubber, nylon 6, nylon 6,6, MXD6, aromatic polyamides, polycarbonates, Porite Ethylene phthalate, polybutylene terephthalate, poly-naphthalene acid ethylene, U polymer, liquid crystal polymers, modified polyphenylene ether, polyether ketone, polyether ether ketone, unsaturated polyester, alkyd resin, polyimide, polysulfone, polyphenylene sulfide, polyether sulfone , silicone resins, polyurethane, phenol resins, urea resins, polyethylene oxide, polypropylene oxide, polyacetal, epoxy resins, and ionomer resins.
[0063]
　The content of the resin material in the colored layer is 70 mass% or more, preferably at most 95 mass%, 80 mass% or more, more preferably 90 mass% or less.
[0064]
　Colorant contained in the colored layer may be a pigment, it may be a dye, from the viewpoint of light resistance, pigments are preferred.
　There is no particular limitation on the color of the colorant may be used brown, black, green, white, a colorant such as blue or red. Incidentally, may be used a plurality of colors of colorants, for example, red, using a combination of colorants yellow and black, it may be brown.
　If the beer is filled into the composite container 10A as contents, the plastic member 40 after blow molding, it is necessary to cut the visible light wavelength 400 ~ 500 nm.
　In one embodiment, by incorporating a colorant brown heat-shrinkable plastic member 40a, it is possible to cut visible light with a wavelength 400 ~ 500 nm, bitter components in beer is degraded by sunlight, sunlight it is possible to prevent a problem which is the odor component 3-methyl-2-butene-1-thiol is generated.
　Article In the present invention, the term "beer", those stipulated in the Japanese Liquor Tax Law, ie "malt, those fermented hop and water as raw materials. And defining malt, hops, water and rice Cabinet Order what was fermented as a raw material (however, the sum of the weight of the goods to the provisions of raw materials in the ordinance is limited to those that do not exceed 5 to 10 minutes of weight of malt). "in addition, liquor Tax Law on the" low-malt beer "ie weight of malt in the raw material other than water of the raw material weight (1) over 67 100 minutes, (2) less than 67 100 min 50 100 minutes or more ones, (3) 100 minutes of less than 50 more than 25 100 min, and (4) 100 minutes of less than 25 ones and the so-called "third beer", "low-alcohol beer", and also includes "miscellaneous liquors".
[0065]
　Colored layer, the colorant may comprise one or more, the content is 0.1 mass% or more, preferably at most 30 mass%, 0.5 mass% or more, 10 mass % by more preferably less.
　The content of the colorant in the colored layer is in the above range, it is possible to favorably disperse the colorant in the heat-shrinkable plastic member 40a in. Further, it is possible to maintain the moldability, the heat-shrinkable plastic member 40a can be easily manufactured.
[0066]
　Within a range that does not impair the effects of the present invention, the colored layer may also contain other additives as described above.
[0067]
　The thickness of the colored layer prior to blow molding, 5 [mu] m or more, preferably 1000μm or less, 10 [mu] m or more, and more preferably 500μm or less. The thickness of the colored layer to be in the above numerical range, while maintaining the blow moldability, it is possible to improve the light shielding property.
　The thickness of the colored layer may be uniform, but after blow molding, considering locations covering the container body 10 may be appropriately changed.
[0068]
　In one embodiment, heat-shrinkable plastic member 40a may further comprise a gas barrier layer. Heat-shrinkable plastic member 40a may be provided with a gas barrier layer 2 or more layers. Also, the type of materials constituting the respective gas barrier layer, the content, the thickness of the coloring layer may be the same or may be different.
[0069]
　Gas barrier layer includes a gas barrier resin, for example, meta-xylene adipamide (MXD-6), nylon 6, nylon 6,6, nylon 6 / nylon 6,6 copolymer, ethylene - vinyl acetate copolymer ( EVA), ethylene - vinyl alcohol copolymer (EVOH), polyglycolic acid (PGA), polyvinylidene chloride copolymer (PVDC), polyacrylonitrile, polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE) and styrene - isobutylene - styrene copolymer. Gas barrier layer may comprise a gas barrier resin mentioned above two or more.
[0070]
　The content of the gas barrier resin in the gas barrier layer is preferably at least 50 wt%, and more preferably 90 mass% or more. Thus, it is possible to further improve the gas barrier properties of the composite container 10A.
[0071]
　Gas barrier layer may contain an oxygen absorber. The oxygen absorber is as described above.
[0072]
　The content of oxygen absorbing agent in the gas barrier layer is preferably 0.01 mass% or more, preferably at most 10 mass%, 0.05 mass% or more, more preferably at most 5 mass%, 0.1 mass % or more, more preferably 2 mass% or less. The content of the oxygen absorber to be in the above numerical range, while maintaining the transparency of the gas barrier layer, it is possible to improve the gas barrier properties.
[0073]
　Gas barrier layer may be comprise a pro-oxidant. The oxidation-promoting agent, is not particularly limited as long as it promotes the reaction of oxygen absorbent and molecular oxygen which may be automatically oxidized by molecular oxygen, for example, radical generator, photooxidation catalyst, the transition such as metal salts. Of these, the transition metal salt is preferable because it is possible to exert a sufficient effect even in small quantities. Gas barrier layer, by comprising the pro-oxidant, oxidation of the oxygen absorber may be auto-oxidation is promoted by the molecular oxygen, the oxygen-absorbing ability is improved.
[0074]
　As metal salts, such as inorganic salts, organic salts and complex salts can be exemplified. As the inorganic salts, halide salts, oxy salt, oxy acid salts, and the like silicate. As the organic acid salts, carboxylates, sulfonates, such as phosphonate and the like. As the complex include complexes of β- diketone or β- keto ester.
[0075]
　Content of the oxidizing accelerator in the gas barrier layer is 0.001 mass% or more, is preferably not more than 2 wt%, 0.005 wt% or more, more preferably at most 1 mass%, 0.01 mass % or more, more preferably not more than 0.5 mass%. The content of the oxidizing accelerator to be in the above numerical range, while maintaining the transparency of the gas barrier layer, it is possible to improve the gas barrier properties.
[0076]
　Gas barrier layer, to the extent that its properties are not impaired, may contain a resin material and additives as described above.
[0077]
　The thickness of the blow molding before the gas barrier layer, 10 [mu] m or more, preferably 300μm or less, 15 [mu] m or more, and more preferably 100μm or less. The thickness of the gas barrier layer is in the above range, it is possible to improve the gas barrier properties of the composite container 10A.
　The thickness of the gas barrier layer may be uniform, but after blow molding, considering locations covering the container body 10 may be appropriately changed.
[0078]
　Also, in one embodiment, heat-shrinkable plastic member 40a is provided with a colored layer may further include an adhesive layer between the gas barrier layer.
[0079]
　As the adhesive constituting the adhesive layer, for example, polyvinyl acetate based adhesives, polyacrylic ester-based adhesive, cyanoacrylate adhesive, an ethylene copolymer adhesive, cellulose-based adhesives, polyester-based adhesives, polyamide adhesives, polyimide adhesives, amino resin-based adhesives, phenolic resin adhesives, epoxy adhesives, polyurethane adhesives, rubber-based adhesives, and the like silicone adhesive.
[0080]
　The thickness of the adhesive layer before the blow molding, is not particularly limited, it can be 5μm or more, and 150μm or less.
[0081]
　When the heat shrinkable plastic member 40a has a multilayer structure, As a specific layer structure, for example, those from the innermost layer, the structure comprising a colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer, the colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer / adhesive layer / gas barrier layer / adhesive layer / colored layer structure comprising one, and the like.
[0082]
　In one embodiment, heat-shrinkable plastic member 40a can be prepared by a process comprising the extrusion process.
　More specifically, first, a resin composition comprising a resin material and a coloring agent as described above, and heated and melted in the extruder, continuously extruded from a ring die and molten resin material, by cooling, un shaping the extruded tube 1 of stretch (see Figure 4 (a)).
　By then welded or bonded to one end of the extruded tube in the unstretched, it closes one end of the extruded tube.
　Furthermore, the extruded tube 1 one end is closed, is placed in a mold 2 having an inner diameter larger than the outer diameter of the extruded tube 1 (see Figure 4 (b)).
　Then, placing the blowing device 3 to the other end of the extruded tube 1 (attached) (see FIG. 4 (c)). At this time, the blow device 3 includes a collapsible tube 1, it is preferable to contact so that air does not leak from between them.
　Subsequently, collapsible tube 1, a die 2 and blow device 3, while fed into the heating furnace 4 in this arrangement, is heated to 70 ~ 0.99 ° C. In the heating furnace 4 (see FIG. 4 (d)). As the heating furnace 4, in order to its internal a uniform temperature, it may be used hot air circulating furnace. Or extrusion tube 1, a die 2 and blow device 3, by passing a heated liquid may be heated them.
　Next, extruded tube 1, a die 2 and blow device 3, taken out of the heating furnace 4, by ejecting air into the extrusion tube 1 from the blowing device 3, to Shin pressure rolling the inner surface of the extruded tube 1. Thus, extruded tube 1 is expanded, it is expanded along the inner surface shape of the mold 2 (see FIG. 4 (e)).
　Thereafter, while the blow device 3 in a state of jetting air, the extruded tube 1 is cooled in cold water, taken out extruded tube from the mold 2 (see FIG. 4 (f)). Heat-shrinkable plastic member 40a is obtained by cutting it in desired size (see FIG. 4 (g)).
　The heat shrinkable plastic member 40a of the multilayer structure, together with the resin composition can be produced by co-extruding the resin composition including a gas barrier resin.
[0083]
　Furthermore, the heat-shrinkable plastic member 40a is printed, such as images and characters may be subjected. In this case, without imparting the separately etc. label to the container body 10 after blow molding, it is possible to display images and characters on the composite container 10A.
[0084]
　 The method of producing a composite preform 70
　manufacturing method of a composite preform 70 of the present invention,
　the preform 10a and preparing a heat-shrinkable plastic member 40a,
　the preform 10a of the heat-shrinkable plastic member 40a and the other end a step of fitting the,
　heating the preform 10a and the heat-shrinkable plastic member 40a, a heat-shrinkable plastic member 40a comprising a step of heat shrinking, the.
[0085]
　The method of producing a composite preform 70 of the present invention, the margin of the heat-shrinkable plastic member 40a may further comprise the step of thermocompression bonding.
　The method of producing a composite preform 70 of the present invention, twisting a blank portion which thermocompression bonding may further comprise the step of forming the twisted portion 80.
　The method of producing a composite preform 70 of the present invention may include the step of providing a notch in the heat-shrinkable plastic member 40a.
　The method of producing a composite preform 70 of the present invention may further comprise the step of sterilizing the preforms 10a and / or heat-shrinkable plastic member 40a.
　Furthermore, the manufacturing method of the composite preform 70 of the present invention, with respect to heat-shrinkable plastic member 40a, may include a step of performing printing of images and text.
[0086]
　 Step of preparing a preform 10a and the heat-shrinkable plastic member 40a
　preform 10a and the heat-shrinkable plastic member 40a may be used those produced by the method described above, using what is commercially available it may be.
[0087]
　Length X of the heat-shrinkable plastic member 40a, as shown in FIG. 5, it is preferable that the long, has a margin than the length of the sum Y of the body portion 20a and the bottom 30a of the preform 10a . Thus, before and after blow molding, it is possible to thermocompression bonding one end of the plastic member 40a (40).
　The length of the margin is preferably 3mm or more, 5 mm or more, and more preferably 20mm or less.
　The length of the margin is in the above range, it is possible to perform the thermocompression bonding of one end of the plastic member 40a (40) more easily. Moreover, excessively prevented be provided a margin portion, it is possible to reduce the material used, the cost can be reduced.
　In the present invention, the length of the heat shrinkable plastic member 40a, as shown in FIG. 6 refers to the length X of the pre-heat shrinkable. Further, the sum of the length of the body portion 20a and the bottom 30a of the preform 10a, refers to the length Y as shown in FIG.
[0088]
　 Fitting process
　method of manufacturing a composite preform 70 of the present invention comprises the steps of from one end of the heat shrinkable plastic member 40a fitted preform 10a.
[0089]
　In a preferred embodiment, prior to the fitting step, the preform 10a, it is preferable to preheat by using a near-infrared and hot air.
　Thus, it is possible to further improve the preform 10a, the adhesion between the heat-shrinkable plastic member 40a.
　Preheating temperature of the preform 10a surface, but are not particularly limited, 40 ° C. or higher, preferably it is heated to 90 ° C. or less, 50 ° C. or higher, and more preferably is heated to 70 ° C. or less. The heating temperature is in the above range, the preform 10a, it is possible to further improve the adhesion between the heat-shrinkable plastic member 40a.
[0090]
　 Heat shrinking step
　method for producing a composite preform 70 of the present invention, heating the preform 10a and the heat-shrinkable plastic member 40a, a heat-shrinkable plastic member 40a and heat-shrunk, the step of adhering to the preform 10a including.
[0091]
　Heating method of the preform 10a and the heat-shrinkable plastic member 40a is not particularly limited, can be appropriately performed using near-infrared or the like hot air. Heating temperature, 60 ° C. or higher, preferably at 250 ° C. or less, 80 ° C. or more, more preferably 0.99 ° C. or less. Note that the heating temperature is that the surface temperature of the heat shrinkable plastic member 40a at the time of heating, near infrared and, not that of the irradiation temperature, such as hot air.
[0092]
　 Thermocompression bonding
　method of manufacturing a composite preform 70 of the present invention, the one end of the heat-shrinkable plastic member 40a performing the fitting of the preform 10a opposite end (the other end) comprise the step of thermocompression bonding it may be.
[0093]
　Instruments used in thermocompression bonding of the heat-shrinkable plastic member 40a (hereinafter also referred to as "crimping tool") is near infrared and, after heating the bonding portion due to warm air, and the like sandwich, the said end as long as it can be crimped it is not particularly limited, for example, can utilize metal and heat resistance of the resin of the instrument may be a combination of these.
　Along the shape of the bottom portion 30a of the preform 10a, when performing thermal compression bonding of heat-shrinkable plastic member 40a, it can be carried out by sandwiching a pair of crimping device 90A having a shape as shown in FIG. 8, the B . The material of the bonding tool is not particularly limited, it is possible to use those made of metal or heat-resistant resin.
　The surface of the crimping tool may be one flat, may have an uneven shape in part or whole.
　Moreover, crimping tool may have a heating mechanism on the surface thereof. Thus, it is possible to further increase the bonding strength. The heating temperature of the bonding tool surface, for example, 100 ° C. or higher, it is preferable to 250 ° C. or less.
[0094]
　Pressure during crimping, 50 N / cm 2 or more, 1000 N / cm 2 preferably less, 100 N / cm 2 or more, 500 N / cm 2 or less being more preferred.
[0095]
　Temperature of the heat shrinkable plastic member 40a at the time of bonding, it is preferable to appropriately changed according to the configuration of the heat-shrinkable plastic member 40a, for example, 80 ° C. or higher, can be 200 ° C. or less.
[0096]
　One end of the heat-shrinkable plastic member 40a after the thermocompression bonding may be cut into a desired by suitable length. Thus, it becomes a good appearance of the bottom at the time of a composite container.
　Cut crimp portion, as shown in FIG. 1 may be performed in a straight line (not shown) which may be performed in a shape along the shape of the bottom portion of the preform 10a.
[0097]
　 Twisting portion forming step
　method of the present invention, the torsion thermocompression portion may include a step of forming the twisted portion 80 shown in FIG.
　The method of the present invention, in addition to the thermal bonding step, by including a twisted portion forming step, in addition to being able to form a bottom portion of the heat-shrinkable plastic member 40 after blow molding, the container body 10 composite container 10A is provided bubbles between the heat shrinkable plastic member 40 can be prevented from being generated with. At the time of blow molding, peeling or thermocompression bonding portion of the heat-shrinkable plastic member 40a, it is possible to prevent breakage.
[0098]
　The method of forming the twisted portion 80 is not limited in particular, it can be performed by twisting the portion crimped by hand using a tool such as pliers.
　Further, it is possible to mechanically performed by using a rotation device including a holding section and the rotation part for holding the preforms 10a and heat-shrinkable plastic member 40a.
　Also, may be performed by a combination of these methods, specifically, sandwiched thermocompression portion using an instrument such as a pliers, by rotating the rotating portion the preform 10a and the heat-shrinkable plastic member 40a also it makes it possible to form a twist portion 80.
[0099]
　In one embodiment, formation of the twisted portion 80 can be carried out thermocompression bonding at the same time. Thus, it is possible to reduce the working process, it is possible to increase the productivity.
　Specifically, the rotary mechanism provided in the crimping tool, the preforms 10a and heat-shrinkable plastic member 40a is fixed to the holding part, it can be performed by rotating the crimping tool. Further, by using the crimping tool as holding unit, it can be carried out by rotating the preform 10a and the heat-shrinkable plastic member 40a by the rotation unit.
[0100]
　The degree of twisting of margin, is not particularly limited, it may be enough to from 0.25 to 30 rotation may be carried out until the threading, but can be the appearance better ones and the heat bonding portions can be more effectively prevented from being damaged by blow molding is preferably carried out until the threading.
[0101]
　 Step provided cut
　method of the present invention may include the step of providing a notch in the heat-shrinkable plastic member 40a.
　By providing a notch in the heat-shrinkable plastic member 40a, made of a composite container 10A after blow molding the heat-shrinkable plastic member 40 to be able to easily separated and removed from the incision.
[0102]
　The position where the cut, is not particularly limited, a one end of the barrel portion 41a of the heat-shrinkable plastic member 40a, when attached to the preform 10a, close to the mouth portion 11a of the preform 10a It is provided on one end side from the viewpoint of ease of separation. Further, not limited to the number of cuts may have cut in two or more places.
[0103]
　The method of forming the notches is not particularly limited, for example, if it is before fitting the preform 10a, by the use of scissors or a knife, it is possible to form a notch in the heat-shrinkable plastic member 40a it can. Moreover, even after fitting of the preform 10a, by using a laser beam, it is possible to form a notch.
　Laser beam used is not particularly limited, for example, the He-Ne laser, Ar laser, a carbon dioxide gas laser, excimer laser, a metal vapor laser, a fiber laser, Nd: YAG lasers such including YAG lasers, and their including harmonic laser.
　The formation of the cuts may be may be subjected to composite preform 70 to the composite container 10A described blow molding, by using a laser beam to form a heat-shrinkable plastic member 40.
[0104]
　The method of the present invention, in order to separate the heat-shrinkable plastic member 40 easier ones, may include a step of providing a knob portion which connects the notch.
　Knob portion can be by conventional known adhesive bonding to the heat shrinkable plastic member 40a. For example, polyvinyl acetate based adhesives, polyacrylic ester-based adhesive, cyanoacrylate adhesive, an ethylene copolymer adhesive, cellulose-based adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives, phenolic resin adhesives, epoxy adhesives, polyurethane adhesives, rubber-based adhesive, may be used an adhesive such as silicone adhesive.
[0105]
　Knob portion may be performed on the pre-blow molding the heat-shrinkable plastic member 40a, may be performed on the heat-shrinkable plastic member 40 after blow molding.
[0106]
　 Sterilization step
　method of the present invention, the inner and outer surfaces and / or heat-shrinkable plastic member 40a inner and outer surfaces of the preform 10a may include a step of sterilization.
　The sterilization process is carried out preform 10a prior to the fitting may be performed on the heat-shrinkable plastic member 40a, the preform 10a after the fitting, to heat-shrinkable plastic member 40a at best, it may be carried out at both time points.
　Furthermore, sterilization may be performed with respect to the container body 10 and heat-shrinkable plastic member 40 provided in the composite container 10A after blow molding.
[0107]
　The sterilization method, for example, drug sterilized, light sterilization, radiation sterilization, hot water sterilization, and hot fill sterilization and Pasto Rising sterilization and the like, may be used in combination.
[0108]
　Next the sterilization process will be described below.
[0109]
as one (1) drug sterilization, hydrogen peroxide (H 2 O 2 ) sterilization treatment. Mist of hydrogen peroxide sterilization process including the hydrogen peroxide component to generate a gas or a mixture thereof, the mist of the hydrogen peroxide gas, or a mixture thereof preforms 10a, heat-shrinkable plastic member 40a, the composite flop and performs sterilization treatment by injecting against reform 70 or composite container 10A. Further, the preform 10a, heat-shrinkable plastic member 40a, is the composite preform 70 is dipped in hydrogen peroxide solution may be performed sterilization by blowing hot air.
　Contacting hydrogen peroxide, by adhering microorganisms adhering to the preform 10a surface is sterilized, or scratched.
　Incidentally, the mist of the preform 10a, immediately before and / or after spraying of gas or a mixture thereof, by blowing hot air against the preform 10a, able to activate the attached hydrogen peroxide, more sterilized it can be carried out effectively. Also, the hot air treatment, it is possible to remove excess hydrogen peroxide.
[0110]
(2) as a drug sterilization, peracetic acid (CH 3 COOH) can also be mentioned sterilization treatment.
The peracetic acid sterilization process, and performs the preform 10a, heat-shrinkable plastic member 40a, sterilized by spraying a peracetic acid solution in a liquid or gaseous to the composite preform 70 or the composite container 10A .
[0111]
(3) as a drug sterilization treatment include chlorine sterilization treatment. The chlorination process, for example using an acidic cleaning liquid, such as chlorite solution, the preform 10a by such an acidic cleaning liquid, heat-shrinkable plastic member 40a, by washing the composite preform 70 or the composite container 10A sterilization and performs the processing.
[0112]
(4) as an agent sterilization process, it is possible to use an aqueous alkali solution sterilization treatment using an alkaline aqueous solution. Alkaline aqueous solution sterilization treatment, for example aqueous sodium hydroxide, aqueous potassium hydroxide, the preform 10a by an aqueous alkaline solution consisting of a sodium carbonate aqueous solution, heat-shrinkable plastic member 40a, by washing the composite preform 70 or the composite container 10A and performs the sterilization process.
[0113]
(5) as an agent sterilization, ozone (O 3 can be used ozone sterilization process using). Ozone sterilization is to perform ozone preforms 10a, heat-shrinkable plastic member 40a, sterilized and injected into the composite preform 70 or the composite container 10A.
[0114]

as (1) light disinfection treatment, mention may be made of UV sterilization processing and light pulse sterilization process. The sterilization process, the preform 10a, heat-shrinkable plastic member 40a, is intended to perform a sterilization process by irradiating light to the composite preform 70 or the composite container 10A. Such light can be used, for example light emitted from the ultraviolet or xenon lamps of a wavelength 0.99 ~ 2000 nm.
[0115]
(2) can be cited plasma sterilization as light sterilization treatment. Plasma sterilization treatment generates a low-temperature plasma in a vacuum chamber, the plasma preform 10a, heat-shrinkable plastic member 40a, those subjected to sterilization treatment by irradiating the composite preform 70 or the composite container 10A.
[0116]

　as one of the radiation sterilization, it is possible to use an EB sterilizing treatment. The EB sterilizing treatment, and performs preform 10a, heat-shrinkable plastic member 40a, sterilized by irradiating an electron beam (EB) to the composite preform 70 or the composite container 10A.
[0117]
(1) hot water sterilization prepares warm water, for example 70 ° C. ~ 95 ° C., injects the hot water preform 10a, heat-shrinkable plastic member 40a, the composite preform 70 or the composite container 10A those subjected to sterilization treatment by.
[0118]

(1) Hot fill sterilization prepares a content liquid, for example 60 ° C. ~ 80 ° C. in medium temperature, by filling the liquid content of the medium temperature in the composite container 10A, to the composite container 10A those subjected to sterilization processing Te. The hot filling sterilization may be carried out a work of filling the content liquid in the composite container 10A, sterilized simultaneously.
[0119]
(2) In addition, preparing a hot liquid contents, for example 80 ° C. ~ 95 ° C., can be hot-filled sterilized the composite container 10A by filling and tipping the hot liquid contents in the composite container 10A.
[0120]
(3) In addition, the water vapor preforms 10a, heat-shrinkable plastic member 40a, after depositing the composite preform 70 can also be sterilized by heating the preform.
[0121]

The (1) Other sterilization, filling the liquid content into the composite container 10A, then Past Rising sterilized performing sterilizing treatment on the content liquid filled composite container 10A to the like.
[0122]
　Printing process
　printing to heat-shrinkable plastic member 40a can be carried out, for example, an ink jet method, silk printing, a gravure printing method, offset printing method, flexo printing method, thermal transfer method, a printing method such as hot stamping (stamping) .
　For example, when using an ink jet method, by applying a UV curable ink to a heat-shrinkable plastic member 40a, this performs UV irradiation, by curing, printing such as images and characters on a heat-shrinkable plastic member 40a it can be subjected.
　This printing may be subjected to heat-shrinkable plastic member 40a before fitting the preform 10a, be subjected in a state in which a heat-shrinkable plastic member 40a on the outside of the preform 10a good. Furthermore, the printing on the heat-shrinkable plastic member 40 provided in the composite container 10A after blow molding may be subjected.
[0123]
　 Composite container 10A
　composite container 10A of the present invention is a blow-molded article of the composite preform 70 as described above, as shown in FIG. 9, a container body 10 located inside, provided in close contact with the outside of the container body 10 It was a heat-shrinkable plastic member 40, and a. Also, in one embodiment, composite container 10A of the present invention comprises a deposition film 21 formed on the inner surface of the container body 10.
[0124]
　Heat-shrinkable plastic member 40, because they are not welded or bonded to the container body 10 can be separated from the container body 10 (peeling) was removed and collected.
　As a method for separation (peeling) from the container body 10 of the heat-shrinkable plastic member 40, for example, or excised heat-shrinkable plastic member 40 with a blade, pre-cut to the heat-shrinkable plastic member 40 provided a cut line or above, it can be peeled off the heat-shrinkable plastic member 40 along these.
　In another embodiment, after pulverizing the composite container 10A, immersed in hot water, and heat-shrinkable plastic member 40, by utilizing a difference in specific gravity between the container body 10, the separation and recovery of heat shrinkable plastic member 40 can do. The heat shrinkable plastic member 40 in hot water because of having heat shrinkability can be easily peeled from the container body 10.
　The method as described above, since the heat-shrinkable plastic member 40 can be separated and removed from the container body 10, can be recycled colorless transparent container main body 10 as in the prior art.
[0125]
　Oxygen permeability of the composite container 10A is, 0.5 cc / m 2 is preferably not more than day · 0.21 atm ·, 0.3 cc / m 2 and more preferably less · day · 0.21 atm.
　In the present invention, oxygen permeability, in compliance with pressure method such as JIS K 7126, an oxygen permeability measurement apparatus (e.g., MOCON Co., Ltd., trade name: OX-TRAN 2/20) 23 ℃ , humidity 90% RH is a value measured by the conditions, the mouth was measured in the whole container composite container 10A which closes in the jig, which is a value obtained by dividing by the surface area of the entire container except for the mouth.
[0126]
　 The container body 10
　the container body 10 includes a mouth portion 11, a neck portion 11 neck portion 13 provided below, a shoulder 12 provided on the neck portion 13 downwards, the body portion 20 provided on the shoulder portion 12 downwardly, and a bottom portion 30 provided on the barrel 20 downward. In the present specification, the "up" and "down" refers to the upper and lower in each state a composite container 10A was erected (Fig. 9).
[0127]
　Mouth 11 includes a threaded portion 14 which is attached to the cap (not shown), and a flange portion 17 provided on the threaded portion 14 downward. The shape of the mouth portion 11 may be a conventionally known shape, mouth or capping type, may be a mouth shape capable of mounting the crown.
[0128]
　Neck 13 is located between the flange portion 17 and the shoulder 12 has a generally cylindrical shape with a substantially uniform diameter. Also, the shoulder portion 12 is positioned between the neck portion 13 and the body 20 has a shape whose diameter gradually expands toward the barrel portion 20 from the neck 13 side.
[0129]
　In one embodiment, the body portion 20 has a cylindrical shape having a substantially uniform diameter as a whole. However, not limited to this, the body portion 20 may have a polygonal tubular shape such as a square tube shape or octagonal tubular shape. Also, in one embodiment, the body portion 20 has a cylindrical shape with a horizontal section is not uniform direction from top to bottom.
　Further, the body portion 20 may be provided with a relief structure such as a panel or a groove.
　Contents are, for beer or carbonated beverages carbonated water, etc., barrel 20 is preferably not provided with the uneven structure. Thus, based on the rise of the container body 10 pressure, it is possible to prevent deformation.
[0130]
　Bottom 30 includes a recess 31 located in the center, and a ground portion 32 provided around the recess 31. Incidentally, there is no particular limitation on the shape of the bottom portion 30 may have a conventional bottom shape (e.g. petaloid bottom shape or round shape, etc.). Beer and the content, when filling carbonated beverages such as carbonated water to the composite container 10A, the shape of the bottom 30 is preferably petaloid shape.
[0131]
　Container body 10 composite container 10A is provided with the present invention, also have a single-layer structure, it may have a multilayer structure.
　In one embodiment, the container body comprises a gas barrier layer. For such the type and content of the resin material contained in the gas barrier layer is as described above.
[0132]
　The average thickness excluding the mouth portion 11 of the container body 10, 200 [mu] m or more, preferably 1000μm or less, 250 [mu] m or more, and more preferably less 750 [mu] m. Thus, filled with beer and carbonated water, it is possible to effectively prevent deformation of the container body 10 when the storage.
[0133]
　 Plastic member 40
　heat shrinkable plastic member 40 is in close contact with a thin extended state to the outer surface of the container body 10 is attached in a state of not easily move or rotate relative to the container body 10. Further, as shown in FIG. 10, the heat-shrinkable plastic member 40 is provided over the entire circumference so as to surround the container body 10 has a substantially circular horizontal cross section.
　One end of the bottom portion 30 side plastic member 40 of the container body 10 is crimped to form a bottom that covers the bottom 30 of the container body 10.
[0134]
　One end of the heat-shrinkable plastic member 40 which composite container 10A is provided with the present invention is forming a bottom is crimped, among the container body 10, except for the mouth portion 11 and neck portion 13, shoulder portion 12, body portion 20 and the bottom 30 it can be provided so as to cover. With such a configuration, the shoulder portion 12 of the container body 10, it is possible to impart the desired features and characteristics for the body portion 20 and a bottom 30.
　Further, as described above, the crimped portion may be twisted.
[0135]
　Heat-shrinkable plastic member 40 provided in the composite container 10A of the present invention comprises at least a colored layer.
　Also, in one embodiment, heat-shrinkable plastic member 40 is provided with a gas barrier layer.
　For such the type and content of the resin material contained in the layers included in the heat-shrinkable plastic member 40 is as described above.
[0136]
　The thickness of the heat-shrinkable plastic member 40 is in a state of being attached to the container body 10, 5 [mu] m or more, preferably 200μm or less, 10 [mu] m or more, and more preferably 100μm or less. The thickness of the heat-shrinkable plastic member 40 may be uniform as a whole, may have appropriate different thicknesses depending on the position covering the container body 10.
　The thickness of the colored layer in the composite container 10A is, 5 [mu] m or more, preferably 100μm or less, 5 [mu] m or more, more preferably 50μm or less.
　The thickness of the gas barrier layer in the composite container 10A is, 1 [mu] m or more, preferably 100μm or less, 1 [mu] m or more, more preferably 20μm or less.
[0137]
　Heat-shrinkable plastic member 40 is provided so as to surround the outside of the preform 10a, as described later, the heat-shrinkable plastic member 40a which is brought into close contact with the outer side of the preform 10a, 2 axes drawn along the preform 10a it is obtained by being blown.
[0138]
　As described above, as the content, when filling beer, the heat-shrinkable plastic member 40 is required to have a function to cut visible light with a wavelength 400 ~ 500 nm.
　Transmittance of visible light of wavelengths 400 ~ 500 nm of the composite container 10A having a heat-shrinkable plastic member 40 is more preferably 15% or less, more preferable to be 5% or less, if it is less than 1% preferable.
　Transmittance of visible light can be adjusted by adjusting the type and content of the coloring agent contained in the heat-shrinkable plastic member 40.
　Further, the transmittance of visible light spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer) was used to measure at 0.5nm intervals, it can be determined light transmittance of visible light wavelengths .
[0139]
　Heat-shrinkable plastic member 40 may have a notch. This cut may be a score line, such as any of a triangle or a quadrangle, or may be a notch form.
　For example, if you have a score line provided on the heat-shrinkable plastic member 40a before the blow molding, the score lines by stretching the heat-shrinkable plastic member 40a by blow molding, the tensile shape from the left and right.
　The heat shrinkable plastic member 40 may have a knob portion which connects the notch.
　For more information on cuts and knob portion of the omitted here because of the above.
[0140]
　 Deposited film 21
　in one embodiment, composite container 10A of the present invention, the inner surface of the container body 10, comprises a deposited film 21.
　In this case, the deposition film 21, a substantially uniform thickness is formed over the entire inner surface of the container body 10. By composite container 10A of the present invention is provided with a vapor-deposited film 21, it is possible to improve the oxygen, carbon dioxide and water vapor barrier properties.
[0141]
　In one embodiment, the deposition film 21, the gas barrier properties such as oxygen and water vapor, as well as from the viewpoint of transparency, is preferably made of an inorganic oxide.
　Examples of such an inorganic oxide, can be used aluminum oxide, silicon oxide, Magushiumu, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, such as barium oxide. From the viewpoint of gas barrier properties and production efficiency among these, silicon oxide is particularly preferred.
　Also, in one embodiment, it may be used carbon doped silicon oxide (SiOC).
[0142]
　When the deposited film 21 is intended to include silicon oxide, silicon oxide of the general formula SiO X (where, X is a number from 0 to 2) is represented by, from the viewpoint of gas barrier properties and transparency, X is 1 preferably represents the number of .3 to 1.9.
　Further, the deposited film 21 including silicon oxide, silicon oxide as a main component, further carbon, hydrogen, silicon, and at least one of the one or compound of two or more of the elements oxygen contained by such chemical bonding good. For example, compounds having C-H bonds, a compound having a Si-H bond, if the carbon units is graphitic, diamond-like, has become fullerenic like, further, chemically bonding the organic silicon compound or derivatives thereof of the raw material it may contain such. Specific examples, CH 3 hydrocarbons with site, SiH 3 silyl, SiH 2 Hydro silica such silylene, SiH 2 and the like hydroxyl group derivatives such as OH silanol.
[0143]
　In other embodiments, the deposition film 21 is, for example, DLC may be a hard carbon film made of (Diamond Like Carbon) film. The hard carbon film made of DLC film, i carbon film or hydrogenated amorphous carbon film (a-C: H) and is also of the hard carbon film called, SP 3 is that the amorphous carbon film was mainly bond.
[0144]
　The thickness of the deposited film 21, 0.002 .mu.m or more, preferably 0.4μm or less, more 0.005 .mu.m, and more preferably 0.1μm or less.
　The thickness of the deposited film 21, to be in the above numerical range, while maintaining a gas barrier property, it is possible to prevent the occurrence of cracks in the deposited film 21. Note that in FIG. 9 and 10 depict the deposition film 21 is exaggerated in the thickness direction.
[0145]
　The composite container 10A of the present invention may be labeled is attached to the container body 10 and / or heat-shrinkable plastic member 40. The label may be one which is provided so as to cover the entire container body 10, or may be one which is provided so as to cover a part.
[0146]
　The label, for example, shrink labels, stretch labels, roll label, tack labels, paper labels, or suspended label like strap from the neck portion 13 of the composite container 10A (hereinafter, optionally referred to as "swing label".) and the like. Among these, the shrink label because of high productivity, it is preferable to use a stretch label or roll label.
　Moreover, and shrink labels imparted with conventional known light shielding property may be further improved light-shielding properties using a paper label.
[0147]
　Shrink label can be wound so as to cover the steel member 40 the entire or part container body 10 and / or heat-shrinkable plastic. Shrink label can be obtained by mounting on the container body 10 and / or heat-shrinkable plastic member 40, shrink processing at a temperature of 80 ° to 90 °.
[0148]
　Shrink labels, polylactic acid film, polystyrene film, polyester film, low density polyethylene film, medium-density polyethylene film, high density polyethylene film, low density linear polyethylene film, a cyclic polyolefin film, a polypropylene film, an ethylene - propylene copolymers, ethylene - vinyl acetate copolymer, ionomer resin, ethylene - acrylic acid copolymer, ethylene - centrifugal polyolefin film formed as a film of a resin such as methyl acrylate copolymer, polyester - polystyrene multilayer film, a nonwoven fabric a laminate film comprising a shrink film, polyester - polystyrene co-extruded film, 6-nylon film, a polyamide film such as 6,6-nylon film, chlorinated polyethylene , Modified polyolefin film formed as a film of a resin such as chlorinated polypropylene, vinyl chloride - is film formation of a resin-vinyl acetate copolymer film can be produced by using a resin film such as an acrylic resin film.
[0149]
　The film uses one or more resin constituting the extrusion method, a cast molding method, T-die method, a cutting method, an inflation method, a single layer using a film of method such as by which was formed, or two or more resins obtained by multi-layer film forming or the like co-extrusion using, or two or more resins mixed film using a uniaxial or the like tenter method or tubular method It may be used various resin film obtained by stretching biaxially. Among these, a stretched film, uniaxially stretched film flow direction is preferred. Further, as the resin film, it may be used foamed resin film.
[0150]
　In the present invention, from the viewpoint of high heat insulating property, oriented polyester film, oriented polystyrene-based film, stretched polyolefin film, polylactic acid film, foamed polyolefin film, oriented polyester - polystyrene co-extruded film or foamed polystyrene film, polyester - can be preferably used such as polystyrene multilayer film. It is also possible to use a laminated film between the film and the nonwoven fabric.
　Incidentally, the stretched film may be a uniaxially stretched may be a biaxial stretching, in the case of uniaxially oriented film, even longitudinal uniaxial stretching may be transverse uniaxial stretching.
[0151]
　The thickness of the shrink label, but are not limited to, it can be a state of being attached to the composite container 10A for example 10 [mu] m ~ 80 [mu] m approximately.
[0152]
　Stretch labels, shrink label similar, it can be wound so as to cover the steel member 40 the entire or part container body 10 and / or heat-shrinkable plastic. Stretch label is fitted to a composite container 10A in a state of being pulled in the circumferential direction, then, contracted by removing tensile force, it is possible to follow the composite container 10A, to produce by wound.
[0153]
　Stretch labels, thermoplastic resin film having suitable flexibility, for example, low density polyethylene, medium density polyethylene, high density polyethylene, low density linear polyethylene, a monolayer comprising a polyolefin resin such as polypropylene or a multilayer resin film it can be produced using. Among them, it is preferable to produce by using a multilayer film comprising a single layer film made of low density linear polyethylene, a layer made of low-density linear polyethylene. These films can be produced by the aforementioned method.
[0154]
　The thickness of the stretch label, but are not limited to, can be a state of being attached to the composite container 10A for example 5 [mu] m ~ 50 [mu] m approximately.
[0155]
　Roll labels and tack labels also shrink label similar, it can be wound so as to cover the steel member 40 the entire or part container body 10 and / or heat-shrinkable plastic. Roll label wrapped resin film in the composite container can be produced by bonding or fusing the end portion of the resin film.
　Tack label via an adhesive resin film in the composite container can be produced by sticking directly.
　As the adhesive, for example, polyvinyl acetate based adhesives, polyacrylic ester-based adhesive, cyanoacrylate adhesive, an ethylene copolymer adhesive, cellulose-based adhesives, polyester adhesives, polyamide adhesives, polyimide-based adhesives, amino resin-based adhesives, phenolic resin adhesives, epoxy adhesives, polyurethane adhesives, rubber-based adhesives, and the like silicone adhesive.
[0156]
　The thickness of the roll labels and tack labels include, but are not limited to, can be a state of being attached to the composite container 10A for example 5 [mu] m ~ 100 [mu] m approximately.
[0157]
　Paper labels are also shrink label similar, it can be wound so as to cover the steel member 40 the entire or part container body 10 and / or heat-shrinkable plastic. Paper labels, tack labels Similarly, via an adhesive resin film in the composite container can be produced by sticking directly.
[0158]
　Paper label is preferably produced by using paper with excellent polyisocyanate compounds such as water resistance impregnated.
[0159]
　The thickness of the paper labels, but are not limited to, it can be a state of being attached to the composite container 10A for example 50 [mu] m ~ 300 [mu] m approximately.
[0160]
　Suspension labels can be produced by suspending the like string a resin film made of, or paper labels from the neck portion 13 of the composite container 10A. The like size and thickness of the label is not particularly limited, may be used labels of any size and thickness.
[0161]
　The label, the print may have been subjected to. Printing, for example ink-jet method, a gravure printing method, offset printing method, flexo printing method, thermal transfer method, a hot stamping (stamping), silk screen printing method, can be carried out by a printing method, such as pad printing. As a matter to be displayed, in addition, such as design and product names, contents liquid name of the manufacturer, may be a character information, such as raw materials name. Label, part or entire region, red, blue, yellow, green, brown, black, may be colored to the color such as white, may be even further transparent or opaque.
[0162]
　 Method of manufacturing a composite container 10A
　method of manufacturing a composite container 10A of the present invention,
　the steps of inserting into the blow mold while heating the composite preform 70,
　subjected to blow molding the composite preform 70 after heating by the steps of inflating the preform 10a and the heat-shrinkable plastic member 40a integrally,
comprising.
　Also, in one embodiment, method of manufacturing a composite container 10A of the present invention further comprises a step of forming a deposited film 21 on the inner surface of the container body 10.
　Further, as described above, with respect to composite container 10A, it may include a step of performing sterilization.
[0163]
　The FIG. 11 (a) ~ (d), will be described in detail blow molding process of the composite preform 70 of the present invention.
[0164]
　In one embodiment, the composite preform 70 is heated by near infrared irradiation device 51 (see FIG. 11 (a)). It is not limited to this, warm or microwave may be heated by a laser.
　In this case, the composite preform 70, while rotating in a state in which the mouth portion 11a facing downward, is heated like evenly in the circumferential direction by the heating device 51.
　The heating temperature of the preform 10a and the plastic member 40a in the heating step, for example, be a 90 ℃ ~ 130 ℃.
[0165]
　Subsequently, the composite preform 70 which is heated by the near-infrared irradiation device 51 is sent to the blow mold 50 (see FIG. 11 (b)).
[0166]
　Composite container 10A is molded by using the blow molding die 50.
　In one embodiment, the blow molding mold 50 is composed of mutually split pair of barrel die 50a, and 50b, a bottom mold 50c (see FIG. 11 (b)). In FIG. 11 (b), a pair of barrel die 50a, 50b between is open to each other, the bottom mold 50c is raised upward. A pair of barrel die 50a in this state, between 50b, the composite preform 70 is inserted.
[0167]
　Next, as shown in FIG. 11 (c), a pair of barrel die 50a in After lowered bottom mold 50c, 50b are closed, the pair of barrel die 50a, by 50b and bottom mold 50c closed blow mold 50 is configured with. Then contact with the bottom portion of the preform inside surface rod enters the mouth direction for performing stretching in the longitudinal direction, as it is stretched, is then pressed air into the preform 10a, 2 the composite preform 70 axial stretch blow molding is performed.
[0168]
　During this time, the barrel mold 50a, 50b is heated to 30 ° C. ~ 80 ° C., the bottom mold 50c is cooled to 5 ℃ ~ 25 ℃. In this case, the blow mold 50 within preform 10a and the heat-shrinkable plastic member 40a of the composite preform 70 is inflated as a unit. Thus, the preform 10a and the heat-shrinkable plastic member 40a is shaped into a shape corresponding to the inner surface of the blow mold 50 together.
[0169]
　Next, as shown in FIG. 11 (d), a pair of barrel die 50a, 50b and a bottom mold 50c is separated from each other, from the blow molding mold 50 inside, composite container 10A before deposition film formed is taken out .
[0170]
　Is not limited to the above method, the composite container 10A may be manufactured by blow molding in two stages.
　Specifically, first, the composite preform 70, and blow molding to be larger than the composite container 10A of the capacitor to be produced, then, by heating the composite container 10A, is free shrink. Then, by blowing a composite container 10A obtained by this contraction, it is possible to obtain a composite container 10A of desired capacity. By producing a composite container 10A Such blow molding, it is possible to improve the strength and heat resistance of the composite container 10A.
[0171]
　An embodiment of the apparatus used in the blow molding will be described below with reference to FIG. 12.
　Manufacturing apparatus 100 shown in FIG. 12 is an apparatus for manufacturing a composite container 10A described above. Manufacturing apparatus 100 of the composite container 10A includes a molding unit 101, a plastic member mounting unit 102, the heating unit 103, and a blow molding unit 104.
　These molding unit 101, a plastic member mounting unit 102, the heating unit 103, the blow molding unit 104 are integrated with each other in the manufacturing apparatus 100.
　By using the present apparatus can be carried out in the same apparatus the production of composite preform 70 and the composite container 10A.
[0172]
　The manufacturing apparatus 100 of the composite container, the molding unit 101, a plastic member mounting unit 102 further includes a control unit 105 for controlling the heating unit 103 and the blow molding unit 104,. In the present specification, the term "is integrated", or a plurality of elements are integrated are physically connected, or is controlled integrally by one control unit (e.g., controller 105) It refers to are.
[0173]
　Incidentally, the molding unit 101, a plastic member mounting unit 102, the heating unit 103 and the blow molding unit 104, is a manufacturing apparatus 100, and from the upstream side are disposed in this order toward the downstream side. 11, these units are disposed in a straight line, not limited to this, it may be arranged annularly.
[0174]
　Molding unit 101 is for molding the plastics material of the preform 10a. The molding unit 101 is an injection molding unit for performing, for example, injection molding, in this case, the molding unit 101 is closed and the injection unit 106 for injecting to melt the resin pellets, and a mold 107 for molding the preform 10a is doing. Incidentally, the molding unit 101, a compression molding unit to produce a preform 10a by compression molding or by injection-compression molding may be injection compression molding unit for producing a preform 10a,.
[0175]
　Plastic member fitting unit 102 is intended to provide a plastic member 40a on the outside of the preform 10a which is molded in the molding unit 101. The plastic member fitting unit 102 includes a holding portion 108 for holding the preforms 10a, with gripping the plastic member 40a, and a mounting portion 109 for mounting the plastic member 40a to the preform 10a .
　Plastic member fitting unit 102 is attached to one of the plastic member 40a to one preform 10a, not limited to this, overlapping a plurality of plastic members 40a to one preform 10a mounted it may be one that.
[0176]
　Note that after the mounting portion 109 was loosely inserted plastic member 40a with respect to the preform 10a, may be a plastic member 40a is thermally contracted by heating mechanism (not shown).
[0177]
　Heating unit 103, by heating the preform 10a and the plastic member 40a, is intended to heat the preform 10a and the plastic member 40a to a temperature suitable for blow molding, for example, a near-infrared heater heating device 51 have.
[0178]
　Blow molding unit 104, by performing blow-molded to the preform 10a and the plastic member 40a, is intended to expand the preform 10a and the plastic member 40a integrally includes a blow mold 50, preform the 10a and plastic member 40a and a stretching rod 110 which is stretched.
[0179]
　Control unit 105, as described above, controls the molding unit 101, a plastic member mounting unit 102, the heating unit 103 and the blow molding unit 104,. In this case, one controller 105 is controlling all of the units is not limited thereto. A plurality of controller 105 is provided to control the respective control units 105 are each one or more units, each control unit 105 to each other or each unit to each other, may be performed signal interact with each other.
[0180]
　Although not shown, the manufacturing apparatus 100 of the composite container, the cooling unit for cooling the preform 10a (composite preform 70), the temperature control unit for adjusting the temperature of the preform 10a (composite preform 70), blow preform 10a before being molded may have a like standby unit to be on standby (the composite preform 70).
[0181]
　Further, on the downstream side of the blow molding unit 104, a printing unit for performing printing on plastic member 40 after it has been blow molded (not shown) may be provided. In this case, the printing unit, the molding unit 101, a plastic member mounting unit 102, the heating unit 103, and may be integrated with the blow molding unit 104.
[0182]
　Deposited film 21, plasma CVD method, PVD method (the ion plating method, etc.), a sputtering method, can be formed by a conventionally known method.
　Hereinafter, with reference to FIG. 13, a method for forming a deposited film 21 by the plasma CVD method.
[0183]
　First, the configuration of a high-frequency plasma CVD apparatus 200. High-frequency plasma CVD apparatus 200 includes a base 201, and an external electrode 203 which is supported on base 201 via an insulating plate 202.
　In one embodiment, the external electrodes 203, so as to allow loading and unloading of the composite container 10A, and a plurality of members that can be separated from each other. The external electrode 203 includes a reaction chamber 204 which is slightly larger space than the composite container 10A.
　Also, in one embodiment, the reaction chamber 204, internal electrodes 205 are disposed. Internal electrode 205 is made of a hollow body, and and having a plurality of raw material gas blow openings 206. Source gas supply pipe 207 made of a conductive material is continuously provided on the internal electrode 205. Further, the reaction chamber 204, a vacuum source via the exhaust pipe 208 (not shown) is connected.
[0184]
　High-frequency power supply 210 is connected via a matching box 209 to the external electrodes 203. On the other hand, the internal electrode 205 is grounded via the source gas supply pipe 207. A plurality of magnets 211 for generating a magnetic field in the reaction chamber 204 around the external electrodes 203 are disposed.
[0185]
　The raw material gas supply pipe 207 provided continuously to the inner electrode 105, arrow P 2 as indicated by, deposition monomer gas such as an organic silicon compound, oxygen gas, an inert gas, for deposition prepared using other feed gas composition gas is supplied. Also the deposition material gas composition through the raw material gas supply pipe 207 to the inner electrode 205 is supplied, deposition raw material gas composition from the source gas blow openings 206 provided in the internal electrode 205 is blown out.
[0186]
　Further, through the exhaust pipe 208, the arrow P 1 as shown in, the air in the reaction chamber 204 is configured to be evacuated by the vacuum source (vacuum pump).
[0187]
　Formation of the deposited film 21, first, to accommodate the composite container 10A into the reaction chamber 204 of the external electrodes 203. Then, by a vacuum pump connected to the exhaust pipe 208 (not shown), the reaction chamber 204 was evacuated to a plasma can generate pressure, raising the degree of vacuum.
[0188]
　Then, the container body 10, argon (Ar), an inert gas such as helium (He) was supplied from the raw material gas supply pipe 207 blown from the source gas blow openings 206, the external electrodes 203 and internal electrodes 205 at the same time applying a high frequency voltage between the. Together to generate a high-frequency glow discharge in the reaction chamber 204 by which to generate a magnetic field in the reaction chamber 204 by the magnet 211. Inert gas is ejected from the source gas blow openings 206 are plasma in the reaction chamber 204, are caused to collide with the acceleration on the inner surface of the container body 10, fine irregularities are formed on the inner surface of the container body 10. Then, by generating a magnetic field by the magnet 211 into the reaction chamber 204 not only becomes possible to generate plasma of the inert gas dense quality, and plasma to the inner surface of the container body 10 the inert gas collide with the acceleration, the inner surface of efficiently container body 10 can be formed with fine irregularities.
[0189]
　Then, again, by a vacuum pump connected to the exhaust pipe 208, and evacuated to the reaction chamber 204 to the plasma can generate pressure, said the raising the vacuum degree in the reaction chamber 204 as well.
[0190]
　Then, the reaction chamber 204 through the raw material gas supply pipe 207, a deposition monomer gas such as an organic silicon compound, oxygen gas, an inert gas, the other a deposition material gas compositions prepared using suitable It is supplied at a flow rate. Further, a high frequency voltage is applied between the external electrodes 203 and internal electrodes 205, which both generates a high-frequency glow discharge in the reaction chamber 204, to generate a magnetic field in the reaction chamber 204 by the magnet 211. At this time, by a high-frequency glow discharge, vapor deposition raw material gas composition is supplied into the reaction chamber 204, it is reacted gas phase in the reaction chamber 204, mainly composed of inorganic oxides, such as plasma and silicon oxide reaction the product is produced. The reaction product is deposited on the entire inner surface of the container body 10 with the acceleration. Then, by generating a magnetic field by the magnet 211 into the reaction chamber 204 not only becomes possible to generate a reaction product plasma high-density high-quality, plasma on the inner surface of the container body 10 the reaction product was a collision with the acceleration, it is possible to depositing the vapor deposited on the inner surface film 21 efficiently container body 10.
[0191]
　After a sufficient time to form the deposition film 21, to supply the deposition material gas composition through the raw material gas supply pipe 207 into the reaction chamber 204 is stopped, then, the atmosphere in the reaction chamber 204 Introduce. In this way, the composite container 10A is obtained over the entire surface deposited film 21 of the inner surface of the container body 10 is formed.
[0192]
　 Products using the composite container 10A
　product of the present invention, which contents is filled in a composite container 10A as described above,
　characterized in that the cap 18 to the mouth 11 of the container body 10 is attached ( see FIG. 14).
[0193]
　Cap 18 product comprising the present invention may be made of a overcap covering the flange portion of the mouth portion 11 of the container body. Cap 18 product comprising the present invention, by an over cap having a light shielding property, it is possible to improve the light shielding property, it is possible to further improve the storage stability of the contents.
[0194]
　In one embodiment, the mouth portion 11 includes a threaded portion 14 which the cap 18 is attached, and a flange portion 17 provided on the threaded portion 14 downward. Below the flange 17 the neck 13 is provided as described above, heat-shrinkable plastic member 40 has reached to the lower surface of the flange portion 17 (see FIG. 15).
[0195]
　In one embodiment, the cap 18 includes a generally cylindrical side wall portion 18a, is connected to the upper end of the side wall portion 18a, and a top surface 18b of the flat, substantially circular. The inner surface of the side wall portion 18a, and is formed with a screw portion 18c that engages the threaded portion 14 of the mouth 11, an annular inner peripheral projection 18d located below the threaded portion 18c is. The upper end of the inner peripheral projection 18d are weakening line 18e is formed, weakening line 18e when loosened cap 18 has become breakable. The lower part of the side wall portion 18a, and the support ring 18f, from the lower end of the support ring 18f and the engaging projection 18g of the annular inwardly extending are formed. Engaging protrusion 18g engages the lower surface of the flange portion 17. Accordingly, loosening the cap 18, when the weakening line 18e is broken, since the engaging protrusion 18g is engaged with the flange portion 17, the support ring 18f is adapted to remain in the mouth portion 11 side. Incidentally, if the inner peripheral projection 18d is provided, the engaging projection 18g is also weakened line 18e not in engagement is breakable in the flange portion 17, the engaging projection 18g is a flange portion 17 It may not engage, may not be engaged (see Figure 15).
[0196]
　Also, in one embodiment, the cap 18 and / or flange portion 17, becomes covered by the light shielding film. By such a configuration, it is possible to further improve the light blocking property of the composite container 10A, it is possible to further improve the storage stability of the contents.
　The light-shielding film, those opaque having a light-shielding property is used. As the material of the light-shielding film, such as polyethylene terephthalate (PET), polystyrene (PS), polypropylene (PP), include polyethylene (PE) it is. The light shielding film is preferably a cylindrical film of heat-shrinkable.
[0197]
　Contents to be filled in the products of the present invention is not limited in particular, in addition to the beer as described above, to fill alcohols such as sake and wine, soft drinks and sports drinks, such as vegetable juices and smoothies a be able to. In addition, but this invention is not limited to beverages, shampoo, rinse, cosmetics, or the like may be filled with drugs.
Example
[0198]
　Following examples, the present invention will be described in further detail, the present invention is not limited to these examples.
[0199]

(Step of preparing a preform 10a)
　using an injection molding machine, shown in Figure 7, has a single-layer structure was produced a PET preform 10a. The weight of the preform 10a is 30.0 g, the length Y was 90 mm.
[0200]
(Step of preparing a heat-shrinkable plastic member 40a)
　a resin composition comprising a polyethylene and brown colorant heated and melted as the polyolefin resin, extruded from a ring die. Then, the extruded tube inner surface pressure or the tube outer surface subjected to enlarged the negative pressure from the inner surface, to produce a heat-shrinkable plastic member 40a having a single layer structure. The content of brown colorant in the heat-shrinkable plastic member 40a is set to 1.5 mass%.
　Was the near-infrared transmittance of the heat-shrinkable plastic member 40a is measured using a Hamamatsu spectrometer, was 64%.
　Length X of the heat-shrinkable plastic member 40a was 100 mm.
[0201]
(Fitting step)
　Then, manually, the preform 10a, is fitted from one end of the heat shrinkable plastic member 40a.
[0202]
(Thermal shrinkage and thermal compression bonding step)
　after fitting, using a hot air dryer to heat the preform 10a and the heat-shrinkable plastic member 40a to 100 ° C., a heat-shrinkable plastic member 40a was thermally shrink. Then, the margin portion 80a of a metal plate heated to 100 ° C. 300N / cm 2 was sandwiched heat pressed at a pressure of, to obtain a composite preform 70.
[0203]
(Combined production of containers)
　the composite preform 70 obtained as described above using near infrared heater, and heated to 100 ° C., was conveyed to the blow molding mold, represented in Figure 9b. Within this blow molding mold, the composite preform 70 is blow molded, full delivery volume to obtain a composite container 10A of 500 mL.
[0204]
　Then, using a high frequency plasma CVD apparatus 100 shown in FIG. 11, to form a deposited film 21 made of silicon oxide on the container main body 10 inner surface. The thickness of the deposited film was 150 nm.
[0205]
　The body portion and the bottom portion of the composite container 10A, where the transmittance of visible light of wavelengths 400 ~ 500 nm, was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer), both 0.5 %Met.
　Also, in compliance with JIS K 7126, an oxygen gas permeability measurement apparatus (MOCON Co., Ltd., trade name: OX-TRAN2 / 20) using, 23 ° C., the oxygen permeability of the composite container 10A according to the conditions of humidity of 90% RH When the rate was measured, 0.12Cc / M 2 was · day · 0.21atm.
[0206]

　When the appearance of the composite container 10A after manufacture were evaluated by visual observation, the bubble between the container body 10 and the plastic member 40 is absent, also, did not show peeling or breakage of the crimp portion, bottom 30 of the container body 10 by plastic member 40 has been completely covered.
[0207]

　except for not using the brown colorant in the production of heat-shrinkable plastic member 40a is to produce a composite container 10A in the same manner as in Example 1-1.
　Transmittance of visible light in the barrel and bottom of the composite container 10A is 88%, the oxygen permeability 0.12 cc / m 2 was · day · 0.21 atm.
　We have also measured by visual observation of the appearance, bubbles between the container body 10 and the plastic member 40 is absent, also peeling or breakage of the crimp portion is not observed, the container body 10 by plastic member 40 the bottom 30 has been completely covered.
[0208]

　except that was not carried out thermocompression bonding of the margin portion to produce a composite container 10A in the same manner as in Example 1-1.
　Transmittance of visible light in the body of the composite container 10A is 0.5%, the visible light transmittance of the bottom portion which is not covered with the plastic member is 88%, the oxygen permeability 0.12 cc / m 2 was · day · 0.21atm.
　We have also measured by visual observation of the appearance, the bottom 30 of the container body 10 is not covered with the plastic member 40.
[0209]

(Step of preparing a preform 10a)
　using an injection molding machine, shown in Figure 7, has a single-layer structure was produced a PET preform 10a. The weight of the preform 10a is 30.0 g, the length Y was 90 mm.
[0212]
(Prepare step of heat-shrinkable plastic member 40a)
　colored layer resin composition comprising a polyethylene and brown colorant as the polyolefin resin, extruded co EVOH and the adhesive from the ring-shaped die. Then, pressing the extruded tube inner surface or the tube outer surface subjected to enlarged the negative pressure from the inner surface, the colored layer / adhesive layer / gas barrier layer (EVOH) / adhesive layer / heat-shrinkable plastic having a structure of the colored layer, the manufacturing members 40a were prepared.
　Was measured near-infrared transmittance of the heat-shrinkable plastic member 40a using a Hamamatsu spectrometers, near infrared transmittance of 800nm was 70%.
　Length X of the heat-shrinkable plastic member 40a produced was 100 mm.
　The content of the colorant in the colored layer was 5 wt%.
[0213]
(Fitting step)
　Then, manually, the preform 10a, is fitted from one end of the heat shrinkable plastic member 40a.
[0214]
(Thermal shrinkage and thermal compression bonding step)
　after fitting, using a hot air dryer to heat the preform 10a and the heat-shrinkable plastic member 40a to 100 ° C., a heat-shrinkable plastic member 40a was thermally shrink. Then, the margin portion of a metal plate heated to 100 ° C. 300N / cm 2 was sandwiched heat pressed at a pressure of, to obtain a composite preform 70.
[0215]
(Combined production of containers)
　the composite preform 70 obtained as described above using near infrared heater, and heated to 100 ° C., was conveyed to the blow molding mold, represented in Figure 9b. Within this blow molding mold, the composite preform 70 is blow molded, full delivery volume to obtain a composite container 10A of 500 mL.
　Then, using a high frequency plasma CVD apparatus 100 shown in FIG. 11, to form a deposited film 21 made of silicon oxide on the container main body 10 inner surface. The thickness of the deposited film was 150 nm.
　Further, the barrel and bottom of the composite container 10A, where the transmittance of visible light of wavelengths 400 ~ 500 nm, was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer), both 0 It was .5%.
　Furthermore, conforming to JIS K 7126, an oxygen gas permeability measurement apparatus (MOCON Co., Ltd., trade name: OX-TRAN2 / 20) using, 23 ° C., the oxygen permeability of the composite container 10A according to the conditions of humidity of 90% RH was measured, 0.060Cc / M 2 was · day · 0.21atm.
[0216]

　When the appearance of the composite container 10A after manufacture were evaluated by visual observation, the bubble between the container body 10 and the plastic member 40 is absent, also, did not show peeling or breakage of the crimp portion, bottom 30 of the container body 10 by plastic member 40 has been completely covered.
[0217]

　except that did not contain a brown colorant in the colored layer resin composition was prepared composite container 10A in the same manner as in Example 2-1.
　Transmittance of visible light in the barrel and bottom of the composite container 10A is 88%, the oxygen permeability 0.060Cc / m 2 was · day · 0.21 atm.
　We have also measured by visual observation of the appearance, bubbles between the container body 10 and the plastic member 40 is absent, also peeling or breakage of the crimp portion is not observed, the container body 10 by plastic member 40 the bottom 30 has been completely covered.
[0218]

　except that was not carried out thermocompression bonding of the margin portion to produce a composite container 10A in the same manner as in Example 2-1.
　Transmittance of visible light in the body of the composite container 10A is 0.5%, the visible light transmittance of the bottom portion which is not covered with the plastic member is 88%, the oxygen permeability 0.060cc / m 2 was · day · 0.21atm.
　We have also measured by visual observation of the appearance, the bottom 30 of the container body 10 is not covered with the plastic member 40.
[0219]

　except that no provided a deposition film on the inner surface of the container body 10, to produce a composite container 10A in the same manner as in Example 2-1.
　Transmittance of visible light of the barrel and bottom is 0.5%, the oxygen permeability 0.650Cc / m 2 was · day · 0.21 atm.
　We have also measured by visual observation of the appearance, bubbles between the container body 10 and the plastic member 40 is absent, also peeling or breakage of the crimp portion is not observed, the container body 10 by plastic member 40 the bottom 30 has been completely covered.
[0220]
[Table 2]

[0221]

(Step of preparing a preform 10a)
　using an injection molding machine, has the shape shown in FIG. 7, the innermost layer, a layer / MXD-6 and pro-oxidant made of PET the preform 10a having a layer consisting of consisting layer / PE was produced. The content of the oxidation promoting agent was 1 mass%.
　The weight of the preform 10a is 30.0 g, the length Y was 90 mm.
[0222]
(Prepare step of heat-shrinkable plastic member 40a)
　colored layer resin composition comprising a polyethylene and brown colorant as the polyolefin resin, extruded co EVOH and the adhesive from the ring-shaped die. Next, by expanded and extruded pressurizing the tube inner surface or negative pressure tube outer surface than the inner surface, the heat-shrinkable with a colored layer / adhesive layer / gas barrier layer (EVOH) / adhesive layer / colored layer from the innermost layer It was produced plastic member 40a. The content of the brown colorant in the colored layer was 5 wt%.
　Was the near-infrared transmittance of the heat-shrinkable plastic member 40a is measured using a Hamamatsu spectrometer, was 70%.
　Length X of the heat-shrinkable plastic member 40a produced was 100 mm.
[0223]
(Fitting step)
　Then, manually, the preform 10a, is fitted from one end of the heat shrinkable plastic member 40a.
[0224]
(Thermal shrinkage and thermal compression bonding step)
　after fitting, using a hot air dryer to heat the preform 10a and the heat-shrinkable plastic member 40a to 100 ° C., a heat-shrinkable plastic member 40a was thermally shrink. Then, the margin portion 80a of a metal plate heated to 100 ° C. 300N / cm 2 was sandwiched heat pressed at a pressure of, to obtain a composite preform 70.
[0225]
(Combined production of containers)
　the composite preform 70 obtained as described above using near infrared heater, and heated to 100 ° C., was conveyed to the blow molding mold, represented in Figure 9b. Within this blow molding mold, the composite preform 70 is blow molded, full delivery volume to obtain a composite container 10A of 500 mL.
　Incidentally, in the container main body 10, the thickness of the gas barrier layer is 10 [mu] m, the thickness of the other layers (polyester resin layer) were both 120 [mu] m.
　Further, the plastic member 40, the thickness of the colored layers are both 10 [mu] m, the thickness of the adhesive layer are both 2 [mu] m, the thickness of the gas barrier layer was 5 [mu] m.
[0226]
　The body portion and the bottom portion of the composite container 10A, where the transmittance of visible light of wavelengths 400 ~ 500 nm, was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer), both 0.5 %Met.
　Furthermore, conforming to JIS K 7126, an oxygen gas permeability measurement apparatus (MOCON Co., Ltd., trade name: OX-TRAN2 / 20) using, 23 ° C., the oxygen permeability of the composite container 10A according to the conditions of humidity of 90% RH was measured, 0.075Cc / M 2 was · day · 0.21atm.
[0227]

　When the appearance of the composite container 10A after manufacture were evaluated by visual observation, the bubble between the container body 10 and the plastic member 40 is absent, also, did not show peeling or breakage of the crimp portion, bottom 30 of the container body 10 by plastic member 40 has been completely covered.
[0228]

　except that did not contain a brown colorant in the colored layer resin composition was prepared composite container 10A in the same manner as in Example 3-1.
　Transmittance of visible light in the barrel and bottom of the composite container 10A is 88%, the oxygen permeability 0.075Cc / m 2 was · day · 0.21 atm.
　We have also measured by visual observation of the appearance, bubbles between the container body 10 and the plastic member 40 is absent, also peeling or breakage of the crimp portion is not observed, the container body 10 by plastic member 40 the bottom 30 has been completely covered.
[0229]

　except that was not carried out thermocompression bonding of the margin portion to produce a composite container 10A in the same manner as in Example 3-1.
　Transmittance of visible light in the body of the composite container 10A is 0.5%, the visible light transmittance of the bottom portion which is not covered with the plastic member is 88%, the oxygen permeability 0.075cc / m 2 was · day · 0.21atm.
　We have also measured by visual observation of the appearance, the bottom 30 of the container body 10 is not covered with the plastic member 40.
[0230]
[table 3]

[0231]

(Step of preparing a preform 10a)
　using an injection molding machine, has the shape shown in FIG. 7, consisting of PET layer / MXD-6 and an oxide promoter layer / PET the preform 10a having a layer comprising a produced. The content of the oxidation promoting agent was 1 mass%.
　The weight of the preform 10a is 30.0 g, the length Y was 90 mm.
[0232]
(Prepare step of heat-shrinkable plastic member 40a)
　was extruded a mixture comprising polyethylene and brown colorant as the polyolefin resin from a ring-shaped die. Then, the extruded tube inner surface pressure or the tube outer surface subjected to enlarged the negative pressure from the inner surface, it has a single-layer structure was prepared heat-shrinkable plastic member 40a.
　The content of the brown colorant in the colored layer was 5 wt%.
　Was the near-infrared transmittance of the heat-shrinkable plastic member 40a is measured using a Hamamatsu spectrometer, was 70%.
　Length X of the heat-shrinkable plastic member 40a produced was 100 mm.
[0233]
(Fitting step)
　Then, manually, the preform 10a, is fitted from one end of the heat shrinkable plastic member 40a.
[0234]
(Thermal shrinkage and thermal compression bonding step)
　after fitting, using a hot air dryer to heat the preform 10a and the heat-shrinkable plastic member 40a to 100 ° C., a heat-shrinkable plastic member 40a was thermally shrink. Then, the margin portion 80a of a metal plate heated to 100 ° C. 300N / cm 2 was sandwiched heat pressed at a pressure of, to obtain a composite preform 70.
[0235]
(Combined production of containers)
　the composite preform 70 obtained as described above using near infrared heater, and heated to 100 ° C., was conveyed to the blow molding mold, represented in Figure 9b. Within this blow molding mold, the composite preform 70 is blow molded, full delivery volume to obtain a composite container 10A of 500 mL.
　Incidentally, in the container main body 10, the thickness of the gas barrier layer is 30 [mu] m, the thickness of the other layers (polyester resin layer) were both 120 [mu] m.
　The thickness of the plastic member 40 was 50 [mu] m.
[0236]
　The body portion and the bottom portion of the composite container 10A, where the transmittance of visible light of wavelengths 400 ~ 500 nm, was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer), both 0.5 %Met.
　Furthermore, conforming to JIS K 7126, an oxygen gas permeability measurement apparatus (MOCON Co., Ltd., trade name: OX-TRAN2 / 20) using, 23 ° C., the oxygen permeability of the composite container 10A according to the conditions of humidity of 90% RH was measured, 0.51Cc / M 2 was · day · 0.21atm.
[0237]

　When the appearance of the composite container 10A after manufacture were evaluated by visual observation, the bubble between the container body 10 and the plastic member 40 is absent, also, did not show peeling or breakage of the crimp portion, bottom 30 of the container body 10 by plastic member 40 has been completely covered.
[0238]

　except for not using the brown colorant in the production of heat-shrinkable plastic member 40a is to produce a composite container 10A in the same manner as in Example 4-1.
　Transmittance of visible light in the barrel and bottom of the composite container 10A is 88%, the oxygen permeability 0.51Cc / m 2 was · day · 0.21 atm.
　We have also measured by visual observation of the appearance, bubbles between the container body 10 and the plastic member 40 is absent, also peeling or breakage of the crimp portion is not observed, the container body 10 by plastic member 40 the bottom 30 has been completely covered.
[0239]

　except that was not carried out thermocompression bonding of the margin portion to produce a composite container 10A in the same manner as in Example 4-1.
　Transmittance of visible light in the body of the composite container 10A is 0.5%, the visible light transmittance of the bottom portion which is not covered with the plastic member is 88%, the oxygen permeability 0.51cc / m 2 was · day · 0.21atm.
　We have also measured by visual observation of the appearance, the bottom 30 of the container body 10 is not covered with the plastic member 40.
[0240]
[Table 4]

[0241]

(Step of preparing a preform 10a)
　using an injection molding machine, shown in Figure 7, has a single-layer structure was produced a PET preform 10a. The weight of the preform 10a is 30.0 g, the length Y was 90 mm.
[0242]
(Step of preparing a heat-shrinkable plastic member 40a)
　by heating and melting a mixture comprising polyethylene and brown colorant as the polyolefin resin, extruded from a ring die. Then, the extruded tube inner surface pressure or the tube outer surface subjected to enlarged the negative pressure from the inner surface, to produce a heat-shrinkable plastic member 40a.
　The content of the brown colorant in the heat-shrinkable plastic member 40a is set to 1.5 mass%.
　Was the near-infrared transmittance of the heat-shrinkable plastic member 40a is measured using a Hamamatsu spectrometer, was 64%.
　Length X of the heat-shrinkable plastic member 40a produced was 100 mm.
[0243]
(Fitting step)
　Then, manually, the preform 10a, is fitted from one end of the heat shrinkable plastic member 40a.
[0244]
(Thermal shrinkage and thermal compression bonding step)
　after fitting, using a hot air dryer to heat the preform 10a and the heat-shrinkable plastic member 40a to 100 ° C., a heat-shrinkable plastic member 40a was thermally shrink. Then, the margin portion of a metal plate heated to 100 ° C. 300N / cm 2 was sandwiched heat pressed at a pressure of, to obtain a composite preform 70.
[0245]
(Composite container manufacturing)
　the composite preform 70 obtained as described above using near infrared heater, and heated to 100 ° C., was conveyed to the blow molding mold, represented in Figure 12 (b). Within this blow molding mold, the composite preform 70 is blow molded, full delivery volume to obtain a composite container 10A of 500 mL.
　Further, the barrel and bottom of the composite container 10A, where the transmittance of visible light of wavelengths 400 ~ 500 nm, was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer), both 0 It was .5%.
[0246]

　When the appearance of the composite container 10A after manufacture were evaluated by visual observation, the bubble between the container body 10 and the plastic member 40 is absent, also peeling or breakage of the thermocompression bonded portions is not observed , the bottom 30 of the container body 10 by plastic member 40 has been completely covered.
[0247]

　except for not using the brown colorant in the production of heat-shrinkable plastic member 40a is to produce a composite container 10A in the same manner as in Example 5-1.
　Transmittance of visible light in the barrel and bottom of the composite container 10A was 88%.
　We have also measured by visual observation of the appearance, bubbles between the container body 10 and the plastic member 40 is absent, also peeling or breakage of the thermocompression bonded portions is not observed, the container body by a plastic member 40 bottom 30 of the 10 had been completely covered.
[0248]

　except that was not carried out thermocompression bonding of the margin portion to produce a composite container 10A in the same manner as in Example 5-1.
　Transmittance of visible light in the body of the composite container 10A was 0.5%.
　We have also measured by visual observation of the appearance, the bottom 30 of the container body 10 is not covered with the plastic member 40.
[0249]
[table 5]

The scope of the claims
[Requested item 1]A mouth, a linked body portion to the mouth portion, and the preform comprising a bottom part connected to the body portion,
　the provided so as to surround the outer preform, a colored layer containing a resin material and a colorant the and at least comprises heat-shrinkable plastic member,
　and wherein the near infrared transmittance of the heat-shrinkable plastic member is 50% or more, the composite preform.
[Requested item 2]
　The heat-shrinkable plastic member further comprises a gas barrier layer, the composite preform as claimed in claim 1.
[Requested item 3]
　The colored layer comprises a polyolefin resin, a composite preform as claimed in claim 1 or 2.
[Requested item 4]
　The colorant is a brown pigment, the content is 0.1 mass% or more and 30 mass% or less, the composite preform as claimed in any one of claims 1-3.
[Requested item 5]
　The preform has a multilayer structure comprising at least a gas barrier layer, the composite preform as claimed in any one of claims 1-4.
[Requested item 6]
　The one end of the plastic member on the bottom side of the preform has been crimped, the composite preform as claimed in any one of claims 1 to 5
[Requested item 7]
　Crimping portions of the heat shrinkable plastic member, twisted to form a twisted portion, the composite preform as claimed in claim 6.
[Requested item 8]
　A composite container is blow-molded article of the composite preform as claimed in any one of claims 1 to 7,
　and the mouth portion, and the mouth neck part provided in subordinate side, provided on the neck downwards and the shoulder, and the shoulder body portion disposed below a bottom portion provided in the body portion downward, and the container body with a,
　provided in close contact with the outer side of the container main body, a resin material and a colorant and a heat-shrinkable plastic member at least including a colored layer containing,
　the one end of the plastic member on the bottom side of the container body is crimped, characterized in that it forms the bottom, the composite container.
[Requested item 9]
　Visible light transmittance at a wavelength of 400 ~ 500 nm is 20% or less, composite container according to claim 8.
[Requested item 10]
　The inner surface of the container main body, further comprising a deposited film, composite container according to claim 8 or 9.
[Requested item 11]
　Oxygen permeability, 0.5 cc / m 2 or less · day · 0.21 atm, composite container according to any one of claims 8-10.
[Requested item 12]
　A method of manufacturing a composite preform as claimed in any one of claims 1 to 7,
　a step of preparing a preform and heat shrinkable plastic member,
　said heat-shrinkable plastic member said preform a step of fitting the one end of
　the step of the margin thermocompression bonding with said heat-shrinkable plastic member,
　thermal heating said preform and said heat-shrinkable plastic member, said heat-shrinkable plastic member a step of shrinking,
　characterized in that it comprises a method of producing a composite preform.
[Requested item 13]
　Twisting the margin mentioned above thermocompression bonding, further comprising the step of forming the twisted portion, the method according to claim 12.
[Requested item 14]
　The prior fitting step, further comprising the step of preheating the preform, method of claim 12 or 13.
[Requested item 15]
　A method of manufacturing a composite container according to any one of claims 8 to 10,
　inserted into the blow mold while heating the composite preform as claimed in any one of claims 1 to 7 process and,
　by performing blow molding to the composite preform after heating, characterized by comprising a step of inflating integrally preforms and plastic member, the manufacturing method of the composite container.
[Requested item 16]A product beer is filled into the composite container of any one of claims 8 to 10, wherein the cap to the mouth portion of the container body is mounted, the product.