JPS6149341B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composite container with excellent storage stability consisting of a paper substrate and a flexible plastic cup, and a method for manufacturing the same. Paper containers have the ability to maintain their shape as containers and are easy to dispose of, such as by incineration, so they have come to be widely used as packaging containers for containing beverages and other liquid foods. In this case, since the paper substrate has extremely high gas permeability and water permeability, the paper substrate is combined with aluminum foil, etc., which has excellent gas barrier properties, and a thermoplastic resin film such as polyethylene is coated on the inner and outer surfaces of the paper substrate. Bonding is widely practiced. By adopting the above-described layer structure, the container wall has a structure that effectively suppresses gas permeation and water permeation, but there is still a serious drawback in the joint portion. In other words, paper containers have a side seam formed by overlapping and joining both edges of the sheets, but the cut edge of the paper sheet is always located inside this side seam, and this This results in gas and liquid permeation from the cut edges. In order to prevent this, it is necessary to take the troublesome measure of covering and protecting the cut edge located on the inside of the seam. According to the present invention, a composite container is provided which differs in structure and function from conventional paper-plastic composite containers. That is, the object of the present invention is to provide a paper-based outer member that provides shape retention and protection to the entire container, and a seamless flexible plastic inner member (hereinafter referred to as inner member) that has excellent gas barrier properties and pinhole resistance. To provide a functionally separated composite container consisting of a bag (sometimes referred to as a bag). Another object of the present invention is that the contents can be stored in a sealed state for a long period of time without any deterioration in quality without requiring special means such as refrigeration or freezing, and when the contents are filled hot. Another object of the present invention is to provide a paper-plastic composite container that is resistant to deformation under reduced pressure and does not cause deformation of the external appearance of the container. Still another object of the present invention is to provide a method for manufacturing a paper-plastic composite container which does not require coating and protecting the seams of paper sheets and which is extremely easy to operate. According to the invention, a cup-shaped outer member consisting of a paper substrate which is itself gas permeable;
Vinyl alcohol copolymer and polyamide 95:
Ethylene-vinyl ester copolymer containing in a weight ratio of 5 to 5:95, and having an ethylene content of 20 to 55 mol% and a saponification degree of 95% or more as the ethylene-vinyl alcohol copolymer. Saponified copolymer (A) and ethylene having an ethylene content of 25 to 60 mol%, a degree of saponification of 90% or more, and at least 3 mol% more than the saponified ethylene-vinyl ester copolymer (A). a flexible seamless cup-shaped inner member comprising a layer of a blend containing saponified ethylene-vinyl ester copolymer (B) having a content of 90:10 to 10:90; The cup-shaped inner member has a size that fits almost snugly into the inner surface of the outer member, and the inner member has an aperture ratio defined by H/D, where D is the opening dimension and H is the height. is 0.5
A composite container with excellent preservability is provided which is drawn and formed as described above and whose cup wall is molecularly oriented. The invention further provides that an ethylene-vinyl alcohol copolymer and a polyamide are applied in a weight ratio of 95:5 to 5:95 in the vicinity of the opening of the cup-shaped outer member, which is itself made of a gas-permeable paper substrate. A saponified ethylene-vinyl ester copolymer (A) containing, as the ethylene-vinyl alcohol copolymer, an ethylene content of 20 to 55 mol% and a saponification degree of 95% or more; is in the range of 25 to 60 mol%, the saponification degree is in the range of 90% or more, and the ethylene content is at least 3 mol% higher than that of the saponified ethylene-vinyl ester copolymer (A). A flexible film or sheet provided with a layer of a blend containing the combined saponified product (B) in a weight ratio of 90:10 to 10:90 is provided, and the outer member is used as a female mold, and the film or sheet is Provided is a method for manufacturing a composite container with excellent shelf life, characterized in that plug-assist molding is performed until a sheet is substantially snugly fitted to the inner surface of an outer member. The present invention will be described in detail below based on specific examples shown in the accompanying drawings. In FIG. 1 showing the overall structure of the composite container of the present invention, this composite container has a cup-shaped outer member 1 made of a paper substrate and a flexible seamless cup-shaped inner member made of gas barrier plastic. It consists of a member (inner bag) 2. This cup-shaped outer member 1 has a body part 3 formed by rolling up a paper base sheet and overlapping and joining both end edges thereof via an adhesive layer, and a body part 3 formed by joining the lower end of this body part 3. It consists of a bottom part 4 provided, and a curling part or flange part 5 formed by folding a paper substrate at the upper end opening of the body part 3, and the side surface of the body part 3 has the above-mentioned lap seam ) is formed. The cup-shaped outer member 1 is made of cup-shaped base paper which has been given water resistance by adding a sizing agent or acid resistance by adding an acid-resistant agent. In many cases, it is desirable, although not necessarily necessary, to coat the surface of the paper substrate with wax or resin from the standpoint of preserving the paper cup, retaining its shape when wet, etc. Furthermore, on the side of the paper substrate that is to become the inner surface of the cup, a metal foil such as aluminum foil is pasted or a paint containing a foil-like metal powder pigment such as aluminum flake is applied to enhance shape retention. A paint can also be provided. The curled portion or flange portion 5 of the cup-shaped outer member 1 and the opening periphery 8 of the cup-shaped inner member 2 are adhered via an adhesive layer 7 such as hot melt adhesive, and the inner member 2 is attached to the outer side of the cup-shaped outer member 1. Although it fits almost snugly into the inside of the member 1, the other portions other than the bonded portion are substantially not bonded. Returning again to FIG. 1, the opening of the composite container in which the outer cup 1 and the inner cup 2 are combined is provided with a lidding material generally indicated by 9. This lid material consists of a substrate 10 made of metal foil, plastic film, or a laminate thereof, and a heat sealant layer 11 applied to the surface of the substrate that is to be the container side. Sealing is effected by heat-sealing the opening end 8 of the inner cup on the flange 5. Incidentally, in order to easily discharge the air inside the outer cup 1 to the outside during the molding of the inner cup 2, at least a portion of the outer cup 1, preferably the bottom portion 4, is formed from a breathable paper sheet. is desirable. In the present invention, the seamless cup-shaped inner member 2 is made of ethylene-vinyl alcohol copolymer and polyamide in a ratio of 95:5 to 5:95, particularly 80:20 to 5:95.
The inner member 2 is provided with a layer of a blend containing a weight ratio of
0.5 or more, preferably 0.7 or more, and the cup wall is molecularly oriented, and this inner member 2 has a size (dimension) that fits almost snugly into the inner surface of the outer member 1. A notable feature is that Ethylene-vinyl alcohol copolymer, that is, saponified ethylene-vinyl ester copolymer, is
Among the various thermoplastic resins, this copolymer has one of the best oxygen barrier properties, but its drawbacks include low elongation and poor processability, and the problem of molecular orientation in the resin layer. Under such conditions, drawing forming such as plug-assist forming is difficult, and if forced to form, pinholes, cracks, etc. occur, and the long-awaited gas barrier properties are lost. Moreover, in the case of paper cup containers, the drawing ratio expressed by H/D is large, and therefore it is extremely difficult to form the paper cup so that it fits snugly inside the outer member of the paper cup. The present invention utilizes the fact that a blend containing an ethylene-vinyl alcohol copolymer and a polyamide in the above-mentioned ratio has an outstanding combination of stretch formability and oxygen barrier properties, It is characterized in that the layers are drawn at a high drawing ratio to form a seamless cup having a size that fits snugly into the outer member of the finger cup and whose wall surface is molecularly oriented. In the composite container of the present invention, the cup-shaped outer member 1 made of paper substrate and the cup-shaped inner member 2 made of gas barrier plastic are formed in the above-mentioned positional relationship, so that the inner member 2 may be Even in very thin cases such as plastic bags, the outer member 1 made of paper substrate provides sufficient shape retention and protection. 2
The advantage is that the blend has excellent gas barrier properties, and this gas barrier property is maintained even when the container wall is significantly thinned, thereby providing excellent storage stability of the contents. There is. Furthermore, since the cup-shaped inner member 2 made of plastic is formed by molding the cup-shaped outer member 1 made of paper substrate into a female die and drawing molding such as plug assist molding, the inner member 2 is tightly fitted into the outer member 1. Therefore, the internal volume of this composite container is almost equal to the internal volume of the outer cup, and the inner surface feels good when the lid is opened. Furthermore, in a preferred embodiment of the present invention, as shown in FIG. By keeping the outer peripheral wall surface in a substantially non-adhesive state, even if the volume of the contents decreases and further steam condenses after hot filling with the contents and then sealing with the lid, This flexible plastic inner member 2 acts as a layer that relieves the pressure difference between the inside and outside and prevents deformation of the outside of the container, so it does not reduce the appearance or commercial value of the packaging container, and also prevents lid peel-off. This eliminates the risk of the plastic inner member 2 being lifted upwards when the package is opened by peeling. As mentioned above, the present invention provides that a blend of an ethylene-vinyl alcohol copolymer (hereinafter also referred to as a saponified ethylene-vinyl acetate copolymer) and a polyamide impairs its excellent gas barrier properties. By taking advantage of the fact that deep drawing is possible without any problems, deep drawing is performed using the paper substrate cup 1 as a female die to a size that fits snugly therein. In the present invention, the above-mentioned ethylene-vinyl alcohol copolymer has an ethylene content of 20
55 mol% to 55 mol%, especially 25 to 50 mol%, saponification degree
Saponified ethylene-vinyl ester copolymer (A) with an ethylene content of 95% or more and an ethylene content of 25%
60 to 60 mol%, especially 30 to 55 mol%, saponification degree
A saponified ethylene-vinyl ester copolymer (B) having an ethylene content of at least 3 mol%, especially 5 mol% or more, in the range of 90% or more and more than the saponified ethylene-vinyl ester copolymer (A). ) in a weight ratio of 90:10 to 10:90, especially 80:20 to 20:80. Figures 2 and 3 of the accompanying drawings show the longitudinal direction (MD) and transverse direction of the film when the composition ratio of the saponified ethylene-vinyl acetate copolymer and the copolymerized nylon described in Example 1, which will be described later, is changed. Indicates the elongation at break in the direction (TD). Referring to these drawings, the saponified ethylene-vinyl acetate copolymer alone shows extremely small elongation, but when copolymerized nylon is blended with it,
It can be seen that the elongation at break increases to a maximum of 300-400%. This increasing tendency of elongation is observed even in the case of saponified ethylene-vinyl acetate copolymer (marked with ○) with an ethylene content of 30 mol% and a saponification degree of 99%. Even in the case of saponified ethylene-vinyl acetate copolymer (x mark), there is almost complete agreement. Furthermore, the above-mentioned low ethylene content ethylene-
Saponified vinyl acetate copolymer and saponified ethylene-vinyl acetate copolymer with high ethylene content.
When combined at a weight ratio of 50:50 and further blended with copolymerized nylon, the ● in Figures 2 and 3 is obtained.
As shown by the curved line, the elongation at break is approximately twice as high as when a single saponified ethylene-vinyl acetate copolymer is blended with copolymerized nylon. In the present invention, the reason why drawability is improved by blending the ethylene-vinyl alcohol copolymer and polyamide at a certain quantitative ratio,
The reason why elongation increases markedly when polyamide is blended with a combination of saponified ethylene-vinyl ester copolymers with different ethylene contents has not been completely elucidated. . However, in view of the fact that in such a combination, the miscibility between the polymers is extremely good, one of the reasons seems to be that plasticity is imparted to this blend during stretching. In the present invention, a saponified copolymer having an ethylene content of less than 20 mol % is not suitable for the purpose of the present invention because it has poor thermoformability, lacks thermal stability, and is sensitive to humidity. In addition, saponified copolymers with an ethylene content of more than 60 mol% have significantly poorer gas barrier properties against oxygen, etc. than those with an ethylene content within the range of the present invention, and also have lower miscibility with polyamides. . In a combination of saponified ethylene-vinyl ester copolymers with a difference in ethylene content of less than 3 mol %, even if polyamide is combined with the combination, a dramatic increase in elongation cannot be expected. The gas barrier properties of saponified ethylene-vinyl ester copolymers are significantly influenced by the degree of saponification. For saponified copolymers with low ethylene content (A), the degree of saponification should be at least 95%, while for saponified copolymers with high ethylene content (B), the degree of saponification should be up to 90%. Permissible. The molecular weight of this saponified ethylene-vinyl ester copolymer (ethylene-vinyl alcohol copolymer) is not particularly limited, and it is generally sufficient that it has a molecular weight sufficient to form a film. The intrinsic viscosity of ethylene-vinyl alcohol copolymer is [η]
is measured, for example, in a mixed solvent of 85% by weight of phenol and 15% of water at a temperature of 30°C, but in the present invention, the intrinsic viscosity [η] determined by the above-mentioned measurement method
It is preferable to use an ethylene-vinyl alcohol copolymer having a ratio of 0.07 to 0.17/g. In addition, this ethylene-vinyl alcohol copolymer may contain propylene, butene-1, or
Other olefins such as pentene-1 and 4-methylpentene-1 may be copolymerized. As the polyamide to be combined with the saponified ethylene-vinyl ester copolymer, a high molecular weight linear polyamide is used. The polyamide may be a homopolyamide, a copolyamide, or a blend thereof. Such polyamides include, for example, the following amide repeating units, ie, -CO-R-NH- ...(1) or CO-R ¹ -CONH-R ² -NH- ...(2) where R , R ¹ and R ² each represent a straight-chain alkylene group, homopolyamides, copolyamides or blends thereof having amide repeating units of: From the viewpoint of gas barrier properties against oxygen, carbon dioxide, etc., 100 carbon atoms in polyamide
The number of amide groups per unit is 4 to 30, especially 6 to 30.
Preferably, homopolyamides, copolyamides or blends thereof in the range of 25 are used. Examples of suitable homopolyamides are: polycapramide (nylon 6) poly-ω-aminoheptanoic acid (nylon 7) poly-ω-aminononanoic acid (nylon 9) polyundecaneamide (nylon 11) polylaurinlactam (nylon 12) polyethylene diamine Adipamide (nylon 2,6) Polytetramethylene adipamide (nylon 4,
6) Polyhexamethylene adipamide (nylon 6,
6) Polyhexamethylene sebamide (nylon 6,
10) Polyhexamethylene dodecamide (nylon 6,
12) Polyoctamethylene adipamide (nylon 8,
6) Polydecamethylene adipamide (nylon 10,
6) Polydodecamethylene sebamide (nylon 10,
8) etc. Examples of suitable copolyamides include caprolactam/laurinlactam copolymer, caprolactam/hexamethylene diammonium adipate copolymer, lauryl lactam/hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate/hexamethylene diammonium Sebacate copolymer, ethylene diammonium adipate/hexamethylene diammonium adipate copolymer, caprolactam/hexamethylene diammonium adipate/hexamethylene diammonium sebacate copolymer, and the like. These homopolyamides and copolyamides are
It can also be used in the form of a so-called blend; for example, a blend of polycaprolactam and polyhexamethylene adipamide, a blend of polycaprolactam and a caprolactam/hexamethylene diammonium adipate copolymer, etc. can all be used for the purpose of the present invention. It is possible. It is important for the polyamide used in the present invention to be miscible with the ethylene-vinyl alcohol copolymer from the viewpoint of drawability. This miscibility is related both to the number of amide groups in the polyamide polymer chain and to the melting point of the polyamide. That is, a polyamide with an extremely low amide group concentration or a polyamide with an extremely high amide group concentration has low compatibility with the ethylene-vinyl alcohol copolymer, so a polyamide with the above-mentioned amide group concentration should be used. In addition, the melting point of polyamide is generally higher than that of ethylene-vinyl alcohol copolymer, but polyamides in which the difference in melting point between polyamide and ethylene-vinyl alcohol copolymer is 100°C or less, particularly 65% or less, Should be used. From this point of view, particularly desirable polyamides for the purposes of the present invention are copolyamides consisting of nylon 6 and nylon 6,6, particularly nylon 6 and nylon 6,6 in a ratio of 99:1 to 70:30, preferably 97:3. The copolyamide contains a weight ratio of 3 to 80:20. Generally speaking, the molecular weight of these polyamides can be used without any particular restriction as long as they are within the range that allows film forming. It is generally desirable that the relative viscosity (ηrel) is in the range of 1.2 to 6.0. When polyamides with a relative viscosity of less than 1.2 are combined with a saponified copolymer and subjected to drawing processing such as plug assist molding,
It is often difficult to provide molded articles with excellent mechanical strength, and polyamides whose relative viscosity is higher than the above range generally appear to have poor melt moldability. In the present invention, it is also important to use the saponified copolymer and polyamide in a weight ratio of 95:5 to 5:95, particularly 80:20 to 5:95, from the viewpoint of stretch formability. Even when there are more than the range,
Furthermore, when the content of the saponified copolymer is greater than the above range, the stretch formability tends to decrease. In a preferred embodiment of the present invention, the saponified copolymer (A) with a low ethylene content and the saponified copolymer (B) with a high ethylene content are mixed in the following manner: A:B=90:10 to 10: 90 It is particularly important to combine them at a weight ratio of 80:20 to 20:80; outside of the above range, the stretchability of the final resin composition tends to decrease significantly. Furthermore, as the amount of high ethylene content increases, gas barrier properties tend to decrease, so in order to obtain the optimal combination of stretch formability and gas barrier properties, it is most preferable to use approximately the same amount of both resins. . There are no particular restrictions on the method of blending the above-mentioned two-component or three-component resins, and a resin composition for molding can be easily obtained by, for example, melt blending or dry blending. Dry blending is preferred from the viewpoint of preventing thermal deterioration, and the dry blend (compound) is supplied to a molding extruder or after injection, and kneaded by a screw in the extruder or injection machine. The above-mentioned resin composition used in the present invention includes additives known per se, such as antioxidants, antistatic agents,
A lubricant, an ultraviolet absorber, a coloring agent, a filler, a plasticizer, etc. can be blended according to known formulations. The blend of ethylene-vinyl alcohol copolymer and polyamide described above can be used in the form of a single layer to form the inner seamless member 2;
Generally, it is preferable to use it in the form of a laminate with other resin layers for molding a seamless cup. In one preferred embodiment of the invention, the cup-shaped inner member 2 is formed from a laminate having at least one layer of the blend and at least one layer of polyolefin. In FIG. 4 showing a cross section of such an inner member 2,
The inner member 2 consists of an inner surface layer 12 made of polyolefin, an outer surface layer 13 made of polyolefin, and an intermediate layer 14 made of the blend layer,
Thermoplastic adhesive layers 15, 15' are provided between the intermediate layer and the inner and outer surface layers, if desired. That is, the blend has the disadvantage that its gas barrier properties depend on humidity, and as the humidity increases, the barrier properties decrease; however, by forming the above-mentioned multilayer structure, this disadvantage can be overcome. Examples of the polyfin include low-, medium-, or high-density polyethylene, isotactic (crystalline) polypropylene, crystalline ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionically crosslinked olefin copolymer, or these. Blends are used. In the present invention, as polyolefin,
90:10 crystalline polypropylene and polyethylene
It is particularly desirable to use polyolefin blends containing a weight ratio of between 5:95 and especially between 75:25 and 20:80. That is, when polyolefin alone is drawn at a high drawing ratio as described above, it tends to produce defects such as pinholes and cracks, but by using the blend described above, pinholes and cracks are formed in the polyolefin layer. Defects such as holes can be effectively prevented from forming. If blend layer 14 is sufficiently thick, polyolefin outer surface layer 13 and thermoplastic adhesive layer 15' can be omitted. Thermoplastic adhesives include acid- or acid anhydride-modified olefin resins, such as polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, and ethylene-vinyl acetate copolymers, as well as acrylic acid, methacrylic acid, fumaric acid, and maleic acid. An acid or acid anhydride-modified olefin resin obtained by graft copolymerizing an ethylenically unsaturated carboxylic acid such as , maleic anhydride, itaconic acid, citraconic acid, or citraconic anhydride or an anhydride thereof is used. This acid or acid anhydride-modified olefin resin can be used alone or diluted with unmodified olefin resin, and the final carbonyl group concentration can be
It is preferable to have a range of 10 to 800 mm equivalent/100 g resin. In another preferred embodiment of the present invention, the cup-shaped inner member is formed of a laminate comprising the blend layer described above and a vinylidene chloride resin coating layer. In FIG. 5 showing this embodiment, a polyolefin layer 13 is provided on the outside of the blend 14 via a thermoplastic adhesive layer 15', and a coating layer of vinylidene chloride resin is provided on the inside of the blend layer 14. 16 are provided. This type of cup-shaped inner member 2 is particularly excellent in preserving the flavor and gas barrier properties of the contents, and preserving the taste and flavor of the contents. The vinylidene chloride resin includes 99 to 70% by weight of vinylidene chloride, 1 to 30% by weight of at least one acrylic or methacrylic monomer, and 0 parts by weight based on 100 parts by weight of the total amount of the monomers. ~
It is substantially composed of 100 parts by weight of at least one other ethylenically unsaturated monomer other than ethylene, and has an oxygen permeability coefficient of 9 x 10 ^-14 cc cm/cm ² at 20°C and 100% RH.・Sec・cmHg or less and water vapor permeability coefficient (JISZ-0208) of 3×10 ^-3 g・
A coating layer mainly composed of a copolymer having a particle diameter of cm/m ² ·day or less is preferably used, and as the polyolefin layer and the adhesive layer, those already mentioned above are used. Of course, the above-mentioned blends are not limited to the above-mentioned laminates, but can be used in the form of laminates with, for example, polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, methacrylic resin, poly-4-methylpentene-1, etc. It can be used for member 2. In the composite container of the present invention, the cup-shaped outer member 1
In terms of shape retention, paper substrates with a basis weight of 50 to
A cup base paper having a weight in the range of 400 g/m ² is suitable, while the cup-shaped inner member 2 preferably has a basis weight of 0.001 to 0.5 g/ml based on the internal volume. In particular, the present invention provides excellent shape retention and content preservation even when the basis weight is extremely small, such as 0.001 to 0.1 g, resulting in lighter containers and reduced manufacturing costs. Remarkable effects are also achieved in terms of ease of disposal and disposal. The composite container of the present invention is shown in Figures 6-A and 6-B.
It is manufactured by the method illustrated in the figure. First, 6-A
In the figure, an auxiliary female die 17 holds a cup-shaped outer member 1 made of paper, which is manufactured in a manner known per se. A film or sheet 18 consisting of a single layer or a laminate of the aforementioned blend is supplied to the opening of the cup-shaped outer member 1. Next, 6th-B
In the figure, the film or sheet 18 is inserted into the plug 1.
9 to plug assist form the film or sheet into a seamless cup 2 of a size that fits substantially snugly inside the outer member 1. At this time, the plastic film or sheet 18
is preheated in advance to a temperature that allows drawing, and enables high-level drawing with H/D of 0.5, especially 0.7 or higher. In the present invention, based on the melting point (mp) of the component with the lowest melting point in the blend described above,
In general, drawing is possible in the temperature range of mp - 20°C to mp + 40°C, and a more suitable temperature range is specifically 135 to 160°C, where drawing can be performed with good workability. be exposed.
The above-mentioned preferred temperature range is higher than the melting point of polyethylene but lower than the melting point of polypropylene, and thus the use of the above-mentioned polyolefin blend provides particularly good workability in plug-assisted molding. advantages are also achieved. Although it is not particularly necessary when plug-assisted forming is performed at a relatively low speed, the blend or laminate thereof used in the present invention has excellent pinhole resistance, so it can be drawn at a high speed. For this purpose, the bottom 4 of the outer cup 1 is made breathable,
Preferably, the air between the outer cup 1 and the inner cup 2 is allowed to escape to the outside through the bottom part 4 and the vent hole 20 of the auxiliary female mold 17. Of course, it is also possible to reduce the pressure through the vent hole 20 and perform plug-assisted vacuum forming. Furthermore, if an adhesive layer 7 such as a hot melt adhesive is applied to the curling portion or flange portion 5 of the cup-shaped outer member 1 in advance, the molding can be carried out at the same time as the molding.
The opening of the inner cup 2 and the curling interior or flange 5 of the outer cup 1 can also be bonded together via an adhesive layer 7. According to the present invention, as described in detail above, it is possible to easily form the deep-drawn cup 2 inside the paper cup 1 with a size that fits it almost exactly. Since this inner cup member undergoes a high degree of drawing processing, its walls are molecularly oriented, and its three-dimensional birefringence △x, △y, and △z is reduced, especially in the area 1 to 2 cm from the mouth of the container. It has the characteristic that the absolute value of at least one of them is 0.1×10 ⁻³ or more. The composite container of the present invention is particularly useful as a container for hot filling or external sterilization of various contents. The present invention will be explained with reference to the following examples. Example 1 A caprolactam/hexamethylene diammonium adipate copolymer (6.66 copolymer nylon (N1)) with a relative viscosity of 3.3, a caprolactam concentration of 91 mol%, and a melting point of 193°C by the DTA method, and an ethylene content of 30 mol%, saponification degree 99%, vinyl alcohol content 69 mol%, intrinsic viscosity 0.12
/g, ethylene-vinyl alcohol copolymer (A) with a melting point of 182°C as measured by differential thermal analysis (DTA method) at a temperature increase rate of 10°C/mm, an ethylene content of 41 mol%, and a degree of saponification. is 98%, vinyl alcohol content is 57 mol%, intrinsic viscosity is 0.10/g,
A dry blend with a mixing ratio (weight ratio) of 50:50 with ethylene vinyl alcohol copolymer (B1) whose melting point is 164°C as measured by differential thermal analysis (DTA method) at a heating rate of 10°C/mm. The mixture was mixed for 10 minutes at room temperature using a Henschel type dry blender at a mixing ratio (weight ratio) of 20:80 to 90:10 (20/80 to 90/10). For comparison, the copolymerized nylon (N1) and
The ethylene-vinyl alcohol copolymer (A) and the two-component mixture of the copolymerized nylon and the ethylene-vinyl alcohol copolymer (B1) were prepared in a weight ratio of 20/80 to 80/2, respectively.
A range of 20 was prepared using the method described above. Using an extruder with a diameter of 50 mm and an effective length of 1100 mm, each of these mixtures and each of the above-mentioned copolymerized nylon (N1), ethylene-vinyl alcohol copolymers (A) and (B1) was A sheet with a width of 150 mm and a wall thickness of 0.5 mm was formed using a die. Next, the elongation ((elongation at break (/initial length) x
100, unit %) was subjected to a tensile test using a tensile testing machine (manufactured by Toyo Baldwin Co., Ltd., Tensilon UTM-I type) at room temperature and at a tensile speed of 200 mm/mm. The initial length of each sample was 5.0 cm. Figure 2 shows the relationship between the elongation of fracture in the longitudinal direction (extrusion direction, MD) of the sheet and the mixing ratio of each mixture. In addition, Figure 3 shows the same measurement results in the transverse cross-sectional direction (TD) of the sheet. Here, each result is the arithmetic average value of the data obtained by measuring the same type of sheet at 5 points, and the relative error is were within 5% for each same sample. From Figures 2 and 3, it can be seen that the two components and the three components
The elongation at break of the component mixture is clearly larger than the elongation at break of each of the resins alone. Furthermore, it is clear that the rupture elongation of the three-component mixture is significantly greater than the results of the two-component mixtures described above. On the other hand, it is made of coppice base paper with a basis weight of 222 g/m ² and a thickness of 0.275 mm, with an inner diameter (D) of 70 mm, an overall height (H) of 50 mm (H/D=0.71), and a curling part at the mouth. After setting the cylindrical tip-shaped outer member having a shape in the mold, apply Esdine #8909 (hot melt adhesive type adhesive) manufactured by Sekisui Esdine Co., Ltd. only to the curling part using an applicator manufactured by Nordson Corporation in the United States. was melt-extruded at 180°C and applied as an adhesive to the curled part. Next, among the two-component mixture sheets, N1:
Two types of sheets with a mixing ratio (weight ratio) of B1 of 50:50, a weight ratio of N1: (A + B1) of 50: (25 + 25)
A 3-component mixture sheet, individual sheets of B1 and N1 for comparison, and a commercially available unstretched monolayer sheet of polyethylene terephthalate (thickness
A total of six types of sheets (0.5mm, hereinafter referred to as PET) were heated to a thermolabel temperature using an infrared heater.
After heating at 143 to 148°C for 10 seconds, each of the six types of sheets was press-molded into the mold in which the socket-shaped outer member (female mold) was set, using a plug-assisted vacuum-pressure forming method. The curling part is adhered to each of the child sheets by the adhesive applied to the curling part, the outer member is the coppice base paper, the inner member is each of the six types of inner bags, and only the curling part at the mouth part is glued. A composite pot (area weight: 0.016 g/ml) was obtained. Next, each of these six types of composite pots was filled with 185 ml of commercially available 18 cans of soybean oil, and as a lid material, 90 weight ethylene-vinyl acetate copolymer with a vinyl acetate content of 20% and a melting point of 92°C was used. % and 10% by weight of a vinyl aromatic polymer with a hydrogenation rate of 100% (trade name: Alcon P, manufactured by Arakawa Chemical Industry Co., Ltd.) was used as a heat sealant layer (thickness 30μ), and as an intermediate layer 15μ thick. Using a three-layer film consisting of low-density polyethylene and 30μ aluminum foil as the outer layer, heat-seal the openings of each of the six types of composite tips using an iron at 150℃, and then heat-seal at 25℃ for 2 months. Stored indoors (in bright light). 2
After several months, each of the six types of tips did not deform and had excellent shape retention, but the inner member
In two types of composite cots, each consisting of an inner bag made of N1 and B1, soybean oil leaks due to pinholes that occur when the sheets are plug-assisted molded into the inner bag using the above-mentioned molding method. Since this was observed, it was determined that the product could not be used as a container. On the other hand, when we opened the lid material heat-sealed to the opening of each of these six types of composite cups, we found that the sealed lids of each of the six types opened very smoothly, and no dusting occurred during opening. No residual sealant was found in the opening of the top, and the seal was easy to open. Furthermore, in the remaining four types of composite pots, excluding the two types of composite pots in which the inner member is composed of N1 and B1, soybean oil stored at 25°C for 2 months was tested using the standard fat and oil analysis method ( The peroxide value of each soybean oil was measured according to the Japanese Oil Chemists' Association). The results are shown in Table 1. All values are average values of n=3. As is clear from Table 1, the peroxide value of soybean oil stored in a composite pot whose inner bag (inner member) is formed from a commercially available PET sheet is higher than that of the two-component mixture. It is clearly higher than the peroxide value of soybean oil stored in the two types of composite pots containing the above-described three-component mixture as the inner member, and the peroxide value of the soybean oil stored in the composite pot with the above three-component mixture as the inner member. It's clearly progressing. In addition, the peroxide value of soybean oil in the composite pot made from the above-mentioned ternary mixture is smaller than the result from the above-mentioned composite pot made from the binary mixture, and the storage stability of the composite pot made from the above-mentioned ternary mixture as the inner member is It is known from Table 1 that this is the best.

[Table] Example 2 Instead of the 6,66 copolymerized nylon described in Example 1, a material with a relative viscosity of 1.9 and a melting point according to the DTA method was used.
Using polycapramide (6 nylon (N2)) at 219°C, the saponified ethylene-vinyl acetate copolymer was A and B1 in Example 1, and N2:
The mixing ratio (weight ratio) of (A + B1) is 50:
(50+0), 50:(0+50) and 50:(40+10), 50:(25+25), 50:
Three types of ternary mixtures of (10+40) and a total of six types of 6 types of 100% nylon sheets were obtained using the same method and equipment as in Example 1 (all thicknesses were 0.5 mm). On the other hand, using the same cot-shaped base paper as in Example 1 and using the cot-shaped outer member having the same shape and dimensions as in Example 1, the inner member was fabricated by the same method as in Example 1.
Six types of composite tips were obtained, in which the inner bag was made of a mixture of different types, the outer member was made of the above-mentioned paper tip, and only the curled part of the opening was adhered with the hot melt adhesive type adhesive described in Example 1. Next, Example 1 was applied to these six types of composite tips.
After filling with commercially available soybean oil according to the method described in Example 1, the mouth was sealed and stored indoors at 25°C for 2 months, and the peroxide value in the soybean oil was measured in the same manner as in Example 1. The results are shown in Table 2.

[Table] Example 3 An inner and outer layer extruder with a built-in full-flight screw with a diameter of 62 mm and an effective length of 1430 mm, and a melt channel branched into two flow paths, with a diameter of 50 mm.
Interlayer extruder with full-flight screw with an effective length of 1100 mm and also a diameter of 50 mm
A combination of an adhesive layer extruder equipped with a full-flight screw with an effective length of 1100 mm and a melt channel branched into two channels, and a multi-layer five-layer T die, the width is 200 mm and the wall thickness is 200 mm. (total thickness) is 0.5
A five-layer sheet of mm was extruded. The resin used for molding has a density (ASTMD-1505) of 0.91 for the inner and outer layers.
g/cc, melt index (ASTMD-1238)
isotactic polypropylene with a melting point of 165°C and a density of 0.942g/cc, a melt index of 0.3g/10mm and a melting point of 135°C.
℃ blended material with a weight ratio of 30:70 with high-density polyethylene, the adhesive layer has a density of 0.925 g/cc, a melt index of 3.0 g/10 mm, and a maleic anhydride modified wire with a melting point of 120 ℃ by the above-mentioned DTA method. low-density polyethylene (manufactured by Teruwa Denko Co., Ltd., grade name: Shorex ER603N), and the 6.66 copolymerized nylon (N1) and ethylene-vinyl alcohol copolymer (A), (B1) described in Example 1 in the intermediate layer. ), a ternary mixture with N1:A:B1=50:25:25, and a ternary mixture with N1:A:50:50, N1:
Two types of binary mixtures with B1 = 50:50, and for comparison, straight resins with N1 = 100%, A = 100%, and B1 = 100%. Therefore, the molded symmetric five-layer sheet is a total of 6 The layer composition ratio of each sheet is: outer layer:adhesive layer:intermediate layer:adhesive layer:
The thickness ratio of the inner layers was 45:2.5:5:2.5:45. Furthermore, for comparison, a single-layer sheet (0.5 mm thick, hereinafter referred to as PO) of a blend of the polypropylene and the high-density polyethylene was also molded using only the extruder for the inner and outer layers. On the other hand, it is made of coppice base paper with a basis weight of 300 g/m ² and a thickness of 0.323 mm, and has an inner diameter (D) of 65 mm, an overall height (H) of 70 mm (H/D=1.08), and a curling part at the mouth. After setting the cylindrical tip-shaped outer member in the mold, apply high-density polyethylene (melting point, An aqueous emulsion (solid content concentration 30% by weight) at a temperature of 133°C was applied as an adhesive. Next, the seven types of laminated sheets were heated to a thermolabel temperature of 143 to 148°C using an infrared heater.
(138℃ to 143℃ only for P single sheet)
After heating for 10 seconds, the two-layer sheet and the above-mentioned two-layer sheet were pressed into the mold in which the tip-shaped outer member (female mold) was set, using a plug-assisted vacuum-pressure forming method, and at the same time, the emulsion moyon applied to the curling part was formed. is dried and adhered to the sheet, and the outer member is the above-mentioned Kotsu base paper, the inner member is the above-mentioned six types of laminated (five-layer) inner bag and P inner bag, and only the curling part of the mouth part is bonded. A kosupu (fabric weight: 0.038 g/ml) was obtained. The average thickness of the entire inner member was 0.15 mm. The composite cup (hereinafter referred to as "A") having an inner bag made of a laminated sheet in which the middle layer is made of a three-component mixture among the five-layer sheets was tested using a tensile tester (room temperature,
The adhesive strength between the outer member and the inner member at the curled part of the mouth and the body wall part was measured at room temperature using a tensile speed of 200 mm/mm). The results are shown in Table 3. For comparison, the aqueous emulsion of the maleic anhydride-grafted high-density polyethylene was applied to the mouth curling part and the entire inner surface of the above-mentioned spout-shaped outer member set in a mold, and then
Using the above-described molding method and conditions, the material composition, thickness, etc. are the same as all of the above, and the outer member (the paper tip) and the inner member (among the five-layer sheets, the middle layer is a laminated sheet consisting of a ternary mixture) A composite cup (wet weight: 0.039 g/ml) was obtained, in which the contact surface with the molded inner bag was adhered over the entire area of the cup. Hereinafter, this composite tip will be referred to as "B". Then, the adhesive strength of the curled part of the mouth part and the body wall part was measured according to the method described above. The results are also shown in Table 3. Next, there are a total of 8 composite chips, including both composite chips A and B, the other five types of composite chips with a five-layer inner bag, and for comparison, a composite chip whose inner member is a single layer (PO) of only the polyolefin mixture. Regarding the type, heat-fill each 230 ml of orange juice with an orange concentration of 50% at 82°C, and immediately after filling, heat the lid material described in Example 1 at 150°C using an iron.
After heat sealing and air cooling at 25℃, it was kept for 2 months.
It was stored at 25°C (indoors in a bright place). When the deformation state of each cup was observed after two months, it was found that there was a composite cup A in which the outer member and the inner member were bonded together at the curling part of the mouth, five other types of composite cups with a five-layer inner bag, and the above-mentioned composite cup. In contrast, no deformation was observed in the composite tip with P as the inner bag, whereas extreme dents and deformation occurred in the composite tip (B) in which the outer and inner members were bonded over the entire contact surface. Ta. In addition, the b value of each orange juice stored in each of these 8 types of composite pots and stored at 25° C. for one month was determined using a color difference meter. The results are shown in Table 4. Table 4 also shows the results for the orange juice stored in a glass bottle used as a control. Because the blended resin layer of the ethylene-vinyl alcohol copolymer and the 6,66 copolymerized nylon in the inner member acted effectively as an oxygen barrier layer, the orange youth's discoloration was slight, especially in the A and B composite chips. On the other hand, in the case of a composite cup in which the intermediate layer contains the above-mentioned blend as a barrier material or P, which does not exist, as an inner member, the color of the bottle has clearly faded, and the inner member is Five-layer structure with middle layers of N1, A, and B1 (each 100
Table 4 shows that when these five-layer sheets are formed into an inner bag using the method described above, the color of the youth material is significantly faded due to the occurrence of pinholes or cracks in each of the intermediate layers. known. Furthermore, regarding the inner member of the A composite tip, the three-dimensional birefringence △ of the inner member corresponding to the extrusion direction (MD) of the sheet and the direction perpendicular to it (TD) is found in the 1 to 2 cm below the mouth (curling part).
x, △y, and △z were observed using a polarizing microscope (manufactured by Nippon Kogaku Kogyo Co., Ltd., POH type). The results are △x=2.94×10 ^-3 and △y=2.53 for MD.
×10 ^-3 , △z=0.412×10 ^-3 and for TD, △x=2.34×10 ^-3 , △y=2.46×10 ^-3 , △z=
-0.122×10 ^-3 and it is known that the inner member has many molecules oriented in the axial direction (height direction) of the inner bag. In addition, here, when nz is the refractive index in the inner bag axis direction (height direction), ny is the refractive index in the circumferential direction, and nx is the refractive index in the thickness direction, the three-dimensional birefringence △x + △
y, △z are △x=nz−ny, △y=nz−, respectively
It is defined as x, △z=nx−ny.

【table】

[Table] Example 4 As a polyolefin, melt index (ASTM D-1238) is 0.3 g/10 mm, density (AST
D-1505) is 0.95g/cc, the melting point is 141℃ high density polyethylene and the melt index is 5.0
/10mm, density 0.91g/cc, melting point 160℃
Blend with isotactic polypropylene at a mixing ratio (weight ratio) of 30:70, maleic anhydride-modified high-density polyethylene (manufactured by Mitsubishi Yuka Co., Ltd.; H-
31B) as an adhesive and the following 12 types of barrier resins: (i) 6,66 copolymer nylon (N1) in Example 1, (ii) ethylene-vinyl alcohol copolymer (A) in Example 1. ) (iii) Ethylene-vinyl alcohol copolymer (B1) in Example 1 (iv) Two-component blend with a weight ratio of N1 and A of 80:20 (v) Weight of N1 and A A two-component blend with a weight ratio of 50:50 (vi) A two-component blend with a weight ratio of N1 and A of 20:80 (vii) A two-component blend with a weight ratio of N1 and B1 of 80:20 Blend (viii) A two-component blend in which the weight ratio of N1 and B1 is 50:50 (ix) A two-component blend in which the weight ratio of N1 and B1 is 80:20 (x) N1: (A + B1) is 80: (10 + 10) [weight ratio] 3-component blend () The above N1: (A + B1) is 50: (25 + 25)
[Weight ratio] Three-component blend () The above N1: (A + B1) is 20: (40 + 40)
A polyolefin outer layer extruder with a built-in full-flight screw with a diameter of 65 mm and an effective length of 1430 mm is used to extrude 12 types of three-layer laminated sheets consisting of a three-component blend of [weight ratio]. A combination of an intermediate layer (adhesive layer) extruder with a full-flight screw with a diameter of 1100 mm and a barrier layer extruder with a built-in full-flight screw with a diameter of 50 mm and an effective length of 1100 mm, and a multi-layer extruder Obtained using layer T dice. Each of the three-layer sheets obtained had a width of 200 mm and a wall thickness (total thickness) of 0.3 mm, and the composition ratio of each layer was polyolefin layer:barrier layer=20:0.5:1 (thickness ratio). Next, on the barrier layer side of each of these sheets, 83% by weight of vinylidene chloride, 14% by weight of methoxyethyl methyl acrylate, and 3% by weight of methyl acrylate were added.
40 parts by weight of ethylene trichloride per 100 parts by weight of the total amount of
A polyvinylidene chloride resin latex (dispersion medium: water, solid content concentration: 47% by weight) having a composition ratio of parts by weight was coated by a known bar coater method, and a perfect oven (air circulation type) was used. 70℃
After heating for 5 minutes, heat to 80℃ in an air thermostat.
Aging (heat treatment) was performed for 4 minutes. The average thickness of the polyvinylidene chloride resin layer after drying and aging was 5.2 μm. (Oxygen permeability coefficient: 1.5×10 ^-14 cc・cm/cm ²・sec・cmH
g 620℃, 100%RH), water vapor permeability coefficient: 0.96×
10 ^-3 g・cm/m ²・day (JISZ-0208) On the other hand, it is made of Kotsupu base paper with a basis weight of 300 g/m ² and a thickness of 0.323 mm, and the internal dimensions (D) are 65 x 65 mm.
After the mold (H) is 90 mm (H/D = 1.38) and a square tip-shaped outer member with a flange at the mouth is set in the mold, an applicator manufactured by Nordson Corporation in the United States is applied only to the flange part. An aqueous emulsion (solid content concentration: 30% by weight) of high-density polyethylene (melting point, 133° C.) grafted with 3% by weight of maleic anhydride was applied as an adhesive using a vacuum cleaner. Next, the 12 types of laminated sheets were heated by infrared heat for 10 minutes at a thermolabel temperature of 148 to 153℃.
After heating for seconds, each of the laminated sheets is pressed into the mold in which the pot-shaped outer member (female mold) is set, by plug-assisted vacuum-pressure forming, and at the same time, the emulsion applied to the flange is dried. Then, a composite cot tip (wet weight: 0.022 g/
ml) was obtained. Here, the inner member has the polyolefin mixture layer on the paper substrate (cop-shaped base paper) side and the polyvinylidene chloride resin layer on the inner side,
The average thickness of the entire inner member was 0.1 mm. Among the laminated sheets, a composite cup (hereinafter referred to as "C") having an inner bag formed from a laminated sheet using the above () as a barrier layer was tested using a tensile tester (room temperature, tensile speed 200 mm/mm).
The adhesive strength between the outer member and the inner member at the curling part of the mouth and the body wall part was measured at room temperature. The results are shown in Table 5. For comparison, the aqueous emulsion of maleic anhydride-grafted high-density polyethylene was applied to the mouth flange and the entire inner surface of the above-mentioned chip-shaped outer member set in a mold, and then the above-mentioned molding method and conditions were applied. The material composition and thickness are the same as all of the above, and the outer member (the paper tip)
A composite cup (wet weight: 0.023 g/ml) was obtained in which the contact surface between the inner bag and the inner member (the same type of inner bag as the "C" composite cup) was adhered over the entire area of the cup. Hereinafter, this composite tip will be referred to as "D". Then, the adhesive strength of the curled part of the mouth part and the body wall part was measured according to the method described above. The results are also shown in Table 5. Pour 20℃ tap water into these C and D composite cups.
It was filled with 350 ml of ethylene-vinyl acetate copolymer with a vinyl acetate content of 20% by weight and a melting point of 92°C (90% by weight) as in Example 1, and a vinyl aromatic polymer with a hydrogenation stream of 100%. A heat sealant layer (30μ thick, consisting of a 15μ thick low-density polyethylene as the middle layer and a 30μ thick aluminum foil as the outer layer) was prepared by combining 10% by weight of the mixture (trade name: Alcon P, manufactured by Arakawa Chemical Industry Co., Ltd.). Using a three-layer film, heat the above C at 170°C with an iron.
After heat-sealing the mouth of each of the composite cups of and D, they were stored at 25°C for 6 months. After 6 months, no deformation occurred in both the C and D tips, and the shape retention was excellent. In addition, when we opened the lid material that was heat-sealed to the openings of both C and D cups, we found that the sealed lids of both C and D cups opened very smoothly, and no dusting occurred during opening. No residual sealant was observed in the opening of the cap, and the seal was easy to open. Next, both the above C and D composite tips and other
Composite tip with 11 types of inner bags (inner members),
and an inner member for comparison consists of a single layer of only the polyolefin mixture, and the contact surface between the inner member and the outer member is bonded over the entire area with the maleic anhydride-modified high-density polyethylene. Composite tip (Weight: 0.022g/
ml (hereinafter referred to as "E"), an orange thickening machine hot-fills 380 ml of 50% orange juice at 82℃, and immediately after filling, iron the lid material to 170℃. Heat seal at 25
After air cooling at ℃, it was stored at 25℃ (indoors in a bright place) for 2 months. When we observed the state of deformation of each cup after two months, we found that no deformation was observed in the C composite cup, in which the outer and inner members were bonded only at the curled part of the mouth, and in the other 11 types of composite cups, which had inner bags. On the other hand, extreme concave deformation occurred in the composite tips (D and E) where the outer and inner members were bonded at the contact area.
The C-composite tip and 11 other types of composite tips were recognized for their excellent deformation resistance under reduced pressure. In addition, each of the 14 types of composite pots mentioned above was stored at 25° C. for one month, and the b value of each orange juice was determined using a color difference meter. The results are shown in Table 6. Table 6 also shows the results of the orange juice stored in the glass bottle used as a control. Because the blend resin layer of the ethylene/vinyl alcohol copolymer and the 6,66 copolymerized nylon and the polyvinylidene chloride resin layer in the inner member acted effectively as an oxygen barrier layer, the orange youth's discoloration was slight. In particular, it is known from Table 6 that both C and D composite pots exhibit a shelf life comparable to that of glass bottles, whereas in the E composite pot, where the barrier resin layer is not present, the color of the di-use is clearly faded. . In addition, the barrier layer of the inner member is a composite chip composed of each of () the above-mentioned 6,66 copolymerized nylon (N1), (ii), (iii) the above-mentioned ethylene-vinyl alcohol copolymer (A and B1). So, these (i), (ii), (iii)
When forming each laminated sheet using the above-mentioned method into an inner bag using the method described above, pinholes or cracks may occur in the layers (i), (ii), and (iii), resulting in large discoloration of the youth product. It is known from Table 6. Furthermore, each of the composite cups C, D, and E was filled with 280 ml of refined sake (first class) at 50°C, and immediately after filling, the mouth of each cup was sealed in the same way as above.
The deformation state of each composite tip after time was observed. C
While no deformation occurred in the composite tip, clear concave deformation occurred in both composite tips D and E. After leaving both the C and E composite cups filled with the above-mentioned sake at room temperature (25°C) for 3 weeks, a panel of 21 people tasted each of the sake filled in the above-mentioned two composite cups. The participants were asked to judge the taste, flavor, and flavor. 18 out of 21 received C
One person answered that the sake filled in the composite cup was better, one person judged that the sake filled in the E compound cup was better, and the remaining two judged that there was no difference.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a partially sectional front view of the composite container of the present invention;
Figures 2 and 3 show the time at which the film breaks in the longitudinal direction (MD) and transverse direction (TD), respectively, when the composition ratio of saponified ethylene-vinyl acetate copolymer and copolymerized nylon is changed. Diagrams showing elongation, FIGS. 4 and 5 are cross-sectional views showing two examples of layer configurations of the cup-shaped inner member, and FIGS. 6-A and 6
-B is a layout diagram illustrating the molding operation of the seamless cup-shaped inner member. 1 is a cup-shaped outer member, 2 is a seamless cup-shaped inner member, 3 is a cup body, 4 is a bottom of the cup, 5 is a curling part or a flange part of the cup, 6 is a seam, 7 is an adhesive layer, and 8 is an inner side In the open end of the member, 9 is a lidding material, 10 is a lidding material substrate, 11 is a heat sealant layer, 12 and 13 are surface layers made of polyolefin, and 14 is a layer made of a blend, respectively.

Claims (1)

[Scope of Claims] 1. A cup-shaped outer member made of a paper substrate that is itself gas permeable, and containing an ethylene-vinyl alcohol copolymer and a polyamide in a weight ratio of 95:5 to 5:95, and As an ethylene-vinyl alcohol copolymer, the ethylene content is between 20 and 20.
A saponified ethylene-vinyl ester copolymer (A) with an ethylene content of 55 mol% and a saponification degree of 95% or more, and a saponified ethylene-vinyl ester copolymer (A) with an ethylene content of 25 to 60 mol% and a saponification degree of 95% or more.
90 mol of saponified ethylene-vinyl ester copolymer (B) having an ethylene content of 90% or more and at least 3 mol% more than the saponified ethylene-vinyl ester copolymer (A): 10 a flexible, seamless, cup-shaped inner member having a layer of a blend containing the blend in a weight ratio of 10:90 to 10:90, the cup-shaped inner member being sized to fit substantially snugly against the inner surface of the outer member. and the inner member has an opening size of D and a height of H,
A composite container with excellent preservability characterized by being drawn so that the draw ratio defined by H/D is 0.5 or more and having a cup wall with molecular orientation. 2 The saponified product (A) is a saponified ethylene-vinyl ester copolymer having an ethylene content of 25 to 50 mol%, and the saponified product (B) is a saponified product of ethylene-vinyl ester copolymer having an ethylene content of 25 to 50 mol%.
Claim 1, which is a saponified ethylene-vinyl ester copolymer having an ethylene content of 55 mol% to 55 mol% and having an ethylene content at least 5 mol% higher than the saponified product (A). Composite container. 3 The polyamide is a carbon atom in the polyamide.
2. The composite container according to claim 1, which is a homopolyamide, a copolyamide, or a blend thereof, in which the number of amide groups per 100 is in the range of 4 to 30. 4 The polyamide is nylon 6 and nylon 6,
6. The composite container according to claim 1, which is a copolyamide containing 6 and 6 in a weight ratio of 99:1 to 70:30. 5. The composite container according to claim 1, which contains the saponified product (A) and the saponified product (B) in a weight ratio of 80:20 to 20:80. 6. The composite container according to claim 1, wherein the total amount of the ethylene-vinyl alcohol copolymer and polyamide are contained in a weight ratio of 80:20 to 5:95. 7. The cup-shaped inner member comprises a laminate having at least one layer of a blend of ethylene-vinyl alcohol copolymer and polyamide and at least one layer of polyolefin. Composite container as described. 8. The composite container according to claim 7, wherein the laminate has inner and outer surface areas made of polyolefin and an intermediate layer made of the blend. 9 The cup-shaped inner member includes a layer made of a blend of ethylene-vinyl alcohol copolymer and polyamide, a polyolefin layer applied to the outside of the blend layer, and a vinylidene chloride-based layer applied to the inside of the blend. The composite container according to claim 1, which is a laminate made of resin layers. 10. The composite container according to claim 7, 8 or 9, wherein the polyolefin is a polyolefin blend containing crystalline polypropylene and polyethylene in a weight ratio of 90:10 to 5:95. 11 An ethylene-vinyl alcohol copolymer and a polyamide are placed in the vicinity of the opening of the cup-shaped outer member made of a paper substrate that is itself gas permeable.
Ethylene-vinyl ester containing in a weight ratio of 95:5 to 5:95 and having an ethylene content of 20 to 55 mol% and a saponification degree of 95% or more as the ethylene-vinyl alcohol copolymer. The saponified polymer (A) has an ethylene content of 25 to 60 mol%, a degree of saponification of 90% or more, and is at least 3 mol% higher than the saponified ethylene-vinyl ester copolymer (A). Supplying a flexible film or sheet comprising a layer of a blend containing a saponified ethylene-vinyl ester copolymer (B) having an ethylene content in a weight ratio of 90:10 to 10:90, A method for manufacturing a composite container with excellent storage stability, characterized in that the outer member is a female mold, and plug assist molding is performed until the film or sheet is fitted almost tightly onto the inner surface of the outer member.