JPS58154755A - Composite container having excellent preservability and production thereof - Google Patents

Abstract

PURPOSE:To provide a composite container having excellent preservability for food cntained therein, consisting of an outer member composed of a paper substrate for shape retention and an inner member made of a flexible plastic having gas barrier properties. CONSTITUTION:A cup-shaped outer member 1 (numeral 3 represents a cup body, 4 is a cup bottom) composed of a paper substrate (gas-permeable) and a seamless cup-shaped inner member 2 having gas barrier properties provicted with a polymer blend layer composed of 95-5pts.wt. ethylene/vinyl alcohol copolymer and 5-95pts.wt. polyamide, having a draw ratio defined by H/D (wherein H is the height of an inner member and D is the opening size) of 0.5 or above, and having a cup wall molecular-orientated are joined to each other through an adhesive layer 7 between opening ends 5 and 8 to form a composite container (numeral 9 is a lid material provided with a heat sealant 11).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite container with excellent shelf life consisting of a paper substrate and a flexible plastic cup, and a method for manufacturing the same.

Paper containers have come to be widely used as packaging containers for containing beverages and other liquid foods because they retain their shape as containers and are easy to dispose of by incineration or other means. In this case, since the paper substrate 11 has relatively high gas permeability and water permeability, the paper substrate is combined with aluminum foil, etc., which has excellent gas barrier properties, and the inner and outer surfaces of the paper substrate are made of thermoplastic resin made of polyethylene. Bonding films is widely practiced.

By adopting the above-mentioned layer structure, the container has a structure that effectively suppresses gas permeation and water permeation, but there is still a serious drawback in the seam part, and in paper containers, the sheet It has a side seam formed by overlapping and joining both edges, but the cut edge of the paper sheet is always located inside this side seam, and gas permeation and liquid penetration from this cut edge is prevented. arise. In order to prevent this, it is necessary to take the troublesome means of covering and protecting the cut edge located on the inside of the KVi seam.

According to the present invention, a metal container is provided which has a different 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 that has excellent gas barrier properties and pinhole resistance. To provide a functionally separated composite container consisting of an inner bag (also referred to as an inner bag).

Another object of the present invention is to preserve the contents in a hermetically sealed state for a long period of time without deterioration of quality without requiring any special means such as refrigeration or freezing. Filled with heat
It is an object of the present invention to provide a vacuum-resistant paper-plastic composite container that does not cause deformation of the external appearance of the container even if the container is damaged.

Still another object of the present invention is to provide a method for manufacturing a paper-plastic bonded container that does not require coating or protecting the joints of paper sheets and is also extremely easy to manufacture.

According to the invention, a cup-shaped outer member consisting of a paper substrate, which is itself gas permeable, and a layer of a blend containing an ethylene-vinyl alcohol copolymer and a polyamide in a weight ratio of 95:5 to 5:95. a flexible seamless cup-shaped inner member having an opening dimension of D and a height of D, the inner cup-shaped member being sized to fit substantially snugly against the inner surface of the outer member; When S is H,
A composite container with excellent storage stability is provided, which is drawn so that the drawing ratio defined by H/D is [1.5 or more, and whose cup wall is molecularly oriented.

The invention further provides that an ethylene-vinyl alcohol copolymer and a polyamide 95
providing a flexible film or sheet with a layer of a blend containing a weight ratio of 5:95 to 5:95, with the outer member being a female mold, and applying the film or sheet approximately to the inner surface of the outer member; Provided is a method for manufacturing a composite container with excellent storage stability, which includes plug-assisted molding until the paper is folded and kneaded.

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 pot metal container of the present invention,
This composite container consists of a cup-shaped outer member 1 made of a paper substrate and a flexible seamless cup-shaped inner member (inner bag) 2 made of a gas-barrier plastic. This cup-shaped outer member IVi is provided by joining 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 joining the lower end of this body part 3. The bottom part 4 is separated from the curling part or flange part 5 formed by folding a paper substrate at the upper end opening of the body part, and the side surface of the body part 6 is covered with the overlapping joint described in [7] above. (lap seam) seam 6 is formed. The cup-shaped outer member 1 is made of a coppice 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 always necessary, to coat the surface of the paper substrate with wax or resin from the viewpoint of the paper cup's shelf life and shape retention when wet.

Furthermore, on the side of the paper substrate that is to become the inner surface of the cup, in order to enhance shape retention, a metal foil such as aluminum foil is pasted or a paint containing foil-like metal powder feed from Aluminum Flake is applied. You can also do it.

Curling portion or flange portion 5 of cup-shaped outer member 1
and the opening periphery 8 of the cup-shaped inner member 2 are bonded to each other via an adhesive layer 7 such as a hot melt adhesive, and the inner member 2 is bonded to the opening periphery 8 of the outer member 1. Although they fit together, other parts other than the bonded portion are substantially not bonded.

Returning again to FIG. 1, the outer cup 1 and the inner cup 2 are assembled, and a lidding material generally designated 9 is applied to the opening of the composite container. This lidding 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 become the container side. Sealing is achieved by heat-sealing the curling portion or the inner cup opening end 8 on the flange portion 5.

In addition, 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 4, should be formed from a breathable paper notebook. 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.
5:95 to 5:95, especially 80:20 to 5:95 by weight, and the inner member 2 has an opening dimension of D and a height of H. /
The aperture ratio defined by D is 0.5 or more, preferably 0.7
It is notable that it is drawn and formed as described above, that the cup wall is molecularly oriented, and that it has a size (dimensions) that almost exactly fits the inner surface of the inner member 2ii and the outer member 1. .

Ethylene-vinyl alcohol copolymer, i.e. saponified thiethylene-vinyl ester copolymer, is one of the most excellent oxygen barrier properties among various thermoplastic resins, but this copolymer has The drawback is that it has little elongation and poor workability, and under conditions where molecular orientation occurs in the resin layer, drawing forming such as plug assist forming is difficult, and if forced to form, pin poles and cracks may occur. This has the disadvantage that gas barrier properties are lost as a result. Moreover, in the case of a paper cup container, the drawing ratio expressed by 11/D is large, and therefore, it is extremely difficult to form the paper cup so that it fits perfectly 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 paper cup and whose wall surface is molecularly oriented.

Therefore, in the composite container of the present invention, the cup-shaped outer member 1 made of a paper substrate and the gas barrier glass I
Since the cup-shaped inner member 2 consisting of A protective eel effect is obtained,
Moreover, even though the outer side is made of a gas-permeable paper substrate, the excellent gas barrier properties and gas barrier properties of the blend constituting the inner member 2 are maintained even when the vessel wall is significantly thinned. Therefore, there is an advantage that excellent preservability of the contents can be obtained. In addition, since the cup-shaped inner member 2 made of plastic is formed by drawing molding such as plug assist molding using the cup-shaped outer member 1 made of paper substrate as a female mold, the inner member 2 is perfectly fitted to 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. Adhesive, the outer wall surface is virtually non-adhesive 1! By maintaining the IK, even if the volume of the contents decreases and further steam condensation occurs when the contents are hot-filled and then sealed with the lid, the usable plastic inner member 2 It acts as a layer to alleviate the pressure difference between the inside and outside, and prevents the outside of the container from deforming, so it does not reduce the appearance or commercial value of the packaging container. Moreover, when the lid is opened with beer-off (peel-off) K, the plastic inside The fear that the member 2 will be lifted upward can be eliminated.

As mentioned above, the present invention provides a blend of an ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as a saponified ethylene-vinyl acetate copolymer) and a polyamide,
Taking advantage of the fact that deep drawing is possible without sacrificing its excellent gas barrier properties, deep drawing 9 is used to form the paper substrate cup 1 into a female die to a size that fits snugly therein.
It performs molding.

In the present invention, the ethylene-vinyl alcohol copolymer has an ethylene content of 20 to 60 mol, particularly 25 to 50 mol, and a saponification degree of 90 or higher, particularly 9
A saponified product of 5 or more ethylene-vinyl ester copolymers is used. This ethylene-vinyl alcohol copolymer may contain propylene, butene-1, pentene-1, etc. within a range that does not impair its essence, that is, within a range of 5 moles or less per total.
Other olefins such as 1,4-methylpe/tene-1 may also be copolymerized.

In the present invention, the above-mentioned ethylene-vinyl alcohol copolymers can be used alone or in combination with a length of 2 m or more, but the ethylene content is 20 to -55 molt;
Saponified ethylene-vinyl ester copolymer (A) having a saponification degree of 95% or more and an ethylene content of 25 to 60 mol, especially 30 to 5 mol.
Ethylene-vinyl having an ethylene content in the range of 5 mole, and a degree of saponification of 90% or more, and the saponified ethylene-vinyl ester copolymer (4) has an ethylene content of at least 3 mole, especially 5 mole or more. saponified ester copolymer CB) at a ratio of 90:10 to 10:90, especially 80:
It is particularly desirable to use them in combination in a weight ratio of: 20:20 to 20:80.

The attached drawings, FIGS. 2 and 6, show the longitudinal direction (MD) and the 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 adjusted to the appropriate ratio. The elongation at break in the transverse direction (TD) is shown. Referring to these drawings, it can be seen that when saponified ethylene-vinyl acetate copolymer is used alone, only a very small elongation is expected, but when copolymerized nylon is blended with it, the elongation at break is at most 300 to 400 inches. It can be seen that the amount increases. 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 a saponified ethylene-vinyl acetate copolymer (x mark) with a saponification degree of 98 molar and 1 mol, there is almost complete agreement.

Furthermore, the above-mentioned saponified ethylene-vinyl acetate copolymer with a low ethylene content and ethylene-vinyl acetate copolymer with a high ethylene content are used.
When a saponified vinyl acetate copolymer is combined with saponified vinyl acetate copolymer at a weight ratio of 50:50 and copolymerized nylon is further blended into this composition, the elongation at one break increases as shown by the curves marked with in Figures 2 and 6. The improvement is about twice that of blending copolymerized nylon with a single saponified ethylene-vinyl acetate copolymer.

In the present invention, the reason why drawability is improved by blending an ethylene-vinyl alcohol copolymer and polyamide at a certain ratio, and why multiple types of ethylene-vinyl esters having different ethylene contents are used. The reason why elongation is significantly increased by blending polyamide into a saponified polymer combination has not been fully elucidated. However, in view of the extremely good miscibility of the polymers in such a combination, one of the reasons seems to be that plasticity is imparted to this blend during Fi stretching.

In the present invention, a saponified copolymer with an ethylene content of 4 less than 20 moles is not suitable for the purpose of the present invention because it has poor thermoformability, lacks thermal stability, and has humidity sensitivity. . In addition, saponified copolymers with an ethylene content of 60 moles or more have significantly poorer gas barrier properties against oxygen, etc. than those with an ethylene content within the range of the present invention, and have a lower miscibility with polyamides. do.

In a combination of saponified ethylene-vinyl ester copolymers with a difference in ethylene content of less than 3 molti, even if polyamide is combined therewith, there is a tendency that no dramatic increase in elongation can be expected.

The gas barrier properties of saponified ethylene-vinyl ester copolymers are greatly influenced by the degree of saponification. For saponified copolymers L4) with a low ethylene content, the degree of saponification should be greater than 95, while for saponified copolymers (B) with a high ethylene content, a degree of saponification up to 90 is permissible. be done.

The molecular weight of this saponified ethylene-vinyl ester copolymer (ethylene-vinyl alcohol copolymer) is not particularly limited, as long as it has a molecular weight sufficient to form a film. The intrinsic viscosity [η] of the ethylene-vinyl alcohol copolymer is measured, for example, in a mixed solvent of 85% by weight of phenol and 15 hours of water at a temperature of 3 Orr.
In the present invention, it is desirable to use an ethylene-vinyl alcohol copolymer having an intrinsic viscosity [η] in the range of 0.07 to 0 A7 t/f as determined by the above-mentioned measuring method.

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: -CO-R-NH- (1) or -CO-R1-CONE-RN-NH- ...
...(2) In the formula, each of R, R' and R represents a linear alkylene group, and a homopolyamide, copolyamide or a blend thereof having an amide repeating unit of the following can be mentioned, From the viewpoint of gas barrier properties against carbon dioxide, etc.,
Preference is given to using homopolyamides, copolyamides or blends thereof in which the number of amide groups per 100 carbon atoms in the polyamide ranges from 4 to 3o, in particular from 6 to 25. Examples of suitable homopolyamides are polycapramide (nylon 6), poly-ω-aminohebutanoic acid (nylon 7), poly-ω-
aminononanoic acid (nylon 9) polyundecaneamide (
Nylon 11) Polylaurinlactam (Nylon 12)
Polyethylenediamine adipamide (nylon 2.6) Polytetramethylene adipamide (nylon 4°6) Polyhexamethylene adipamide (nylon 6°6) Polyhexamethylene dodecamide (nylon 6°10) Polyhexa They include methylene dodecamide (nylon 6°12), polyoctamethylene adipamide (nylon 8°6), polydecamethylene adipamide (nylon 10°6), polydecamethylene adipamide (nylon 10.8), and the like.

Examples of suitable copolyamides include caprolactam/laurinlactam copolymer, caprolactam/hexamethylene diammonium a) copolymer, lauryl lactam/hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate. /hexamethylene diammonium sepagu 1 polymer, ethylene diammonium adipate/hexamethylene diammonium adipate copolymer, caprolactam/hexamethylene diammonium adipate/hexamethylene diammonium sebacate copolymer, and the like.

These homopolyamides and copolyamides can also be used in the form of so-called blends, for example blends of polycaprolactam and polyhexamethylene adipamide, blends of polycaprolactam and caprolactam/hexamethylene diammonium adipate copolymer; etc. can be used for the purpose of the present invention.

The real deal! [It is important from the viewpoint of drawability that the polyamide used has miscibility with the ethylene-vinyl alcohol copolymer. This miscibility is related to both the number of amide groups in the polyamide polymer chain and the melting point of the polyamide. That is, polyamides with extremely low amide group concentrations and polyamides with extremely high amide group concentrations have low compatibility with ethylene-vinyl alcohol copolymers.
Polyamides with the amide group concentrations mentioned above should be used. 1+, the melting point of polyamide is generally higher than that of ethylene-vinyl alcohol copolymer, but the difference in melting point between polyamide and ethylene-vinyl alcohol copolymer is
Polyamides with a temperature below 100C, especially below 65C 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, in particular 99:1 copolyamides of nylon 6 and nylon 6.6.
70:0 to 0, preferably 97:6 to 80:2 [10
It is a copolyamide containing in weight ratio.

The molecular weight of these polyamides is generally within the range that allows film forming ability, and they can be used without any particular restrictions.
, and the relative viscosity &(ηrgl) when measured at 2Or
It is generally desirable that the value be in the range of 1.2 to 6.0. Polyamides with a relative viscosity of less than 12 are
When combined with a saponified copolymer and subjected to drawing processing such as plug-assist molding, it is often difficult to provide a molded product with excellent mechanical strength, and polyamides whose relative viscosity is higher than the above range. seems to have generally inferior melt moldability.

In the present invention, it is also important from the point of view of stretch formability that the saponified copolymer and polyamide are used in a weight ratio of 95:5 to 5:95 4IK 80:20 to 5:95.
When the amount of polyamide exceeds the above range, and when the amount of saponified copolymer exceeds the above range, K also tends to have a lower stretch formability.

In a preferred embodiment of the present invention, the saponified copolymer (A) with a low ethylene content and the saponified copolymer with a high ethylene content <8) are combined in 1. It is also important to combine 4:B in a weight ratio of 90:10 to 10:90, especially 80:20 to 20:80; outside the above range, the stretchability of the final resin composition tends to deteriorate significantly. be. 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 best to use approximately equal amounts of both resins. preferable.

The method of blending the above-mentioned two-component or filter-component resins is not limited in percentage, and a resin composition for molding can be easily obtained by, for example, melt blending or triblending. From the point of view of preventing thermal deterioration, triblends are preferable, and triblends (compounds are fed to a molding extruder or injection machine, and mixing is carried out using a screw in the extruder or injection machine). The above-mentioned resin composition used may contain compounding agents known per se, such as antioxidants, antistatic agents, lubricants, ultraviolet absorbers, colorants, fillers, plasticizers, etc., according to known formulations.

The above-described blend of ethylene-vinyl alcohol copolymer and polyamide can be used in the form of a single layer to form the inner seamless member 2, but is generally used in the form of a laminate with other resin layers. It is best used for forming seamless cups.

In one preferred embodiment of the invention, the cup-shaped inner member 2 comprises at least one layer of said blend;
at least one layer consisting of polyolefin b
Formed as a laminate. In FIG. 4 showing a cross section of such an inner member 2, the inner member 2Fi is composed 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 and 15' are provided between the inner and outer surface layers, if desired.

That is, although the blend has the drawback that the gas barrier property is dependent on humidity and the barrier property decreases as the humidity increases, this drawback is overcome by forming the above-mentioned multilayer structure. Examples of the polyolefin include low-1 medium- or high-density polyethylene, tactical (crystalline) polypropylene, crystalline ethylene-propylene copolymer, ethylene-acetate 1/2 vinyl copolymer, ionically crosslinked olefin copolymer, or these. A blend of these is used. In the present invention, as the polyolefin, crystalline polypropylene and polyethylene are mixed in a ratio of 90:10 to 5:9.
It is particularly preferable to use a polyolefin blend containing 5, especially in a weight ratio of 75:25 to 20:80. That is, when polyolefin alone is drawn at a high surface drawing ratio as described above, it tends to cause defects such as pinholes and cracks, but by using the above-mentioned blend, pinholes and cracks are formed in the polyolefin layer. It is possible to effectively prevent the defects of the hall owner from entering.

If blend layer 14 is sufficiently thick, polyolefin outer surface layer 16 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, ethylene-vinyl acetate copolymers, acrylic acid, methacrylic acid, fumaric acid, 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 its anhydride is used.

This acid or acid anhydride-modified olefin resin can be used alone or diluted with unmodified olefin resin, so that the final carbonyl group concentration falls within the range of 10 to 800 mEquivalent/100f resin. It is better to

In another preferred embodiment of the present invention, the cup-shaped inner member is formed from a laminate consisting of the above-described blending material and a coating layer of vinylidene-based resin. In the fifth example showing this embodiment, a polyolefin layer 16 is provided on the outside of the blend 14 via a thermoplastic adhesive layer 15', and a vinylidene chloride resin coating is provided on the inside of the blend layer 14. A layer 16 is provided. This type of cup-shaped inner member 2 is particularly excellent in retaining the flavor and gas barrier properties of the contents, and retaining the taste and flavor of the contents.

The vinylidene chloride resin includes 99 to 70% by weight of vinylidene chloride, 1 to 60% by weight of at least one of acrylic or methacrylic monomers, and 0 parts by weight based on 100 parts by weight of the total amount of the monomers. 100 parts by weight of at least one other ethylenically unsaturated monomer, and 20 tons? , the oxygen permeability coefficient at 100SRH is 9 x 10-”head/-fist/cm
B, below q and water vapor permeability coefficient (JIS Z-02
08) is 3X10-sf/-cm/rr? A coating layer mainly composed of a copolymer having a
As the polyolefin layer and the adhesive layer, those already mentioned above are used.

Of course, the blends mentioned above are not limited to the above-mentioned laminates, but include, for example, laminates with polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, methacrylic resin, poly-4=methylpentene-1, etc. It can be used for the inner member 2 in a shape.

In the composite container of the present invention, the paper substrate of the cup-shaped outer member 10 has a basis weight of 50 to 400 f/d in terms of shape retention.
It is preferable to use a base paper with a diameter in the range of O, OO1 to 0.
It is desirable to have a basis weight of 5r/wsl. especially,
According to the present invention, even when the basis weight is set to a relatively small amount such as o, ooi to 0.1r/-, excellent shape retention and preservation of the contents can be obtained, and the container is lightweight and Significant benefits are also achieved in terms of reduced manufacturing costs and ease of disposal.

The composite container of the present invention is manufactured by the method illustrated in Fig. 6-A and Fig. 1)-B. First, in Figure 6-A,
An auxiliary female mold 17 holds the 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. Then, in FIG. 6-B, the film or sheet 18 is pressed with the plug 19 to twist the film or sheet almost snugly inside the outer member 1. Plug assist molding is performed to form a seamless cup 2 of the same size. At this time, the plastic film or sheet 18 is preheated to a temperature at which it can be drawn and formed, and has an H/D of 0.5,
% or higher drawing forming becomes possible.

In the present invention, generally mp-2
Drawing forming is possible in a temperature range of 0°C to mp+4 [1c, and more preferably, drawing is carried out at a temperature of 165°C to 160°C with good workability. 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 drawing at a high speed is possible. For this purpose, the bottom 4 of the outer cup 1 is made breathable so that the air between the outer cup 1 and the inner cup 2 escapes to the outside through the bottom 4 and the ventilation hole 20 of the auxiliary female mold 17. It is better to do so. Of course, plug-assisted vacuum forming can also be performed by reducing the pressure through the vent hole 20.

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 10 in advance, the opening of the inner cup 2 and the outer cup 1 can be formed at the same time as the molding. The curling portion or the flange portion 5 can also be bonded via the adhesive layer 7.

According to the present invention, it is possible to easily form a deep-drawn cup 2 having a size that fits almost perfectly inside the hole or paper cup 1 described in detail above. Since this inner cup member is subjected to a high-level drawing process, its wall portion has molecular orientation, and its five-dimensional birefringence ΔX, Δy, and Δ2 is particularly oriented at a distance of 1 to 2α from the mouth of the container. The absolute value of at least one book is 0. It has the characteristic that it is 1×10−” 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 briefly explained with reference to the following examples.

Example 1 Relative viscosity is 3.3, caprolactam concentration is 91 molar,
Caprolactam with a melting point of 193C by the previous FDTA method/
Hexamethylene diammonium adipate copolymer (6
, 66 copolymerized nylon (vl)), the ethylene content is 30 mol, the degree of saponification is 99 mol, the vinyl alcohol content is 69 mol, and the intrinsic viscosity is 0.12 t/? , heating rate l1110C/m (differential thermal analysis method (DTA method) of 74 degrees)
Ethylene-vinyl alcohol copolymer with a melting point of 182C, ethylene content of 41 molar, saponification degree of 98%, vinyl alcohol content of 57 molar, and intrinsic viscosity of 0.10 t/f. , the melting point according to differential thermal analysis (DTA method) is 164 when the heating rate is 10C/star.
The mixing ratio (weight ratio) of t: with the ethylene vinyl alcohol copolymer (B1) is 50:50 and the triblend product is 20:80 to 90:10 (20/
8 (1 to 90/10) using a Henschel type dry blender at room temperature for 10 minutes.

For comparison, two-component mixtures of the copolymerized nylon (N1), the ethylene-vinyl alcohol copolymer (,4), and the copolymerized nylon and the ethylene-vinyl alcohol copolymer (B1) were prepared. were prepared by the method described above, each in a weight ratio ranging from 20/80 to 80/20.

Each of these mixtures and the above-mentioned copolymerized nylon (N1
), ethylene-vinyl alcohol copolymer (3) and (B1) each with a diameter of 50 m and an effective length of 1 l10
Using a 0sa extruder, a sheet with a width of 150 mm and a wall thickness of 0.5 wm was formed using a T-die.

Next, the longitudinal direction (extrusion direction) of each sheet obtained.

MD) and its elongation to break in the transverse direction (TD) ((elongation at break/initial length) xloo.

unit (ch) using a tensile tester (manufactured by Toyo Baldwin Co., Ltd.,
A tensile test was carried out at room temperature and at a tensile rate of 200 cm/piece using a Tensilon UTM-1 model.

The initial length of each sample was 5.0 cm''r in the longitudinal direction of the sheet (extrusion direction).

The relationship between the fracture elongation of MD) and the mixing ratio of each mixture is shown in FIG. Additionally, FIG. 6 shows the same measurement results in the transverse direction (TD) of the sheet. Here, each result is an arithmetic average value of data obtained by measuring 5 points of the same type of notebook, and the relative error was within 5 points for each of the same samples.

From FIG. 2 and FIG. 6, the elongation at break of the two-component and six-component mixtures is clearly larger than the elongation at break of each of the oil-removal products alone. In addition, it is clear that the elongation at break in the three-component mixture is significantly larger than the results for the two-component mixtures described above.On the other hand, when the basis weight is 222 r/ze and the thickness is 0.275- It is made of kelp base paper, has an inner diameter (D) of 701m, and a total height (H).
) is 50 degrees (11/D=0.71) and has a curling part at the mouth part. After setting the cylindrical tip-shaped outer member in the mold, apply an applicator manufactured by Nordson Corporation in the United States only to the curling part. Using this, Nisudyne #8909 (hot-melt adhesive type adhesive) manufactured by Tanezu Nisdyne ■ was melt-extruded at 18 DC and applied as an adhesive to the curled portion.

Next, among the two-component mixture sheets, two types of sheets with a mixing ratio (weight ratio) of N1:81 of 50:50, N1
: Weight ratio of (A+B'I) is 50:(25+25)
6-component mixture sheet and B1 and N for comparison
Each single sheet of 1, and a commercially available unstretched single layer sheet of polyethylene terephthalate group (thickness 0.5cm, hereinafter pE
After heating a total of six types of sheets (denoted as T) for 10 seconds at a thermolabel temperature of 146 to 148C using an infrared heater, the sheets were placed into a mold in which the pot-shaped outer member (female m) was set, and placed in a plug assist vacuum. Each of the six types of sheets is adhered to each of the sheets using a pressing adhesive using a pressure forming method, and the outer member is the above-mentioned Kotsu base paper, the inner member is each of the six types of inner bags, and the curling part at the opening. Composite tip that is only glued (basis weight:
0.016F/-) was obtained.

Next, 185% of commercially available 1st can of soybean oil was filled into each of these six types of jointed pots, and as a lid material, ethylene-based oil with a vinyl acetate content of 20% and a melting point of 92'C was used.
A heat sealant layer (
A film with a six-layer structure consisting of a 15-μ thick low-density polyethylene as the middle layer and a 30-μ thick aluminum foil as the outer layer was used.
After heat-sealing the mouth of each composite pot of the 6811 class at 50° C., it was stored indoors (in a bright place) at 25° C. for 2 months. After two months, each of the six types of pots showed excellent shape retention with no deformation, but the two types of composite pots whose inner member was composed of an inner bag made of each of N1 and B1 did not have the same shape. Leakage of soybean oil was observed due to pinholes that occurred when each sheet was plug-assisted molded into an inner bag using the above-mentioned molding method, so it was determined that the sheet was not rated as -4. On the other hand, when we opened the lid material heat-sealed to the mouth of each of these six types of composite pots, we found that the seal images of each of the six types of pots opened very smoothly, and no dusting occurred when opening the crucian carp. After opening, no sealing material remained at the opening of the cap, and IIJ opening was achieved.

Furthermore, in the remaining 4S class composite pots excluding the 28 class composite pots in which the inner member is composed of N1 and B1 alone, soybean oil stored under 25C conditions for 12 months was tested using the Standard Oil and Fat Analysis Test Method (Nippon Oil Chemical Co., Ltd.). The peroxide value of each soybean oil was measured according to the Japanese Association of Japan.

The results are shown in Table 1. All values are average values of 5.

As is clear from Table 1, the inner bag (inner member) is commercially available
The peroxide value of soybean oil stored in a composite pot molded from an ET sheet is determined by two types of composite pots, one in which the two-component mixture is used as the inner bag (inner bag) and the other in which the three-component mixture is used as the inner bag (inner bag). The peroxide value of pET is clearly higher than that of soybean oil stored in each composite container.
The oxidative deterioration of soybean oil is clearly progressing in the composite pot made from the three-component mixture. It is known from Table 1 that the small composite cup having the six-component mixture as the inner member has the best storage stability.

Table 1 100: (0+0) Not measured due to leakage Comparative example 50: (,50+0) 2. [11 Example 50: (25+25) 1.04
Example 50: (0+50) 2.21
Example 0: (0+100) Not measured due to leakage Comparative example PET 10.
29 Comparative example) Initial peroxide value: 1.0
3mgqA Example 2゜In place of the 6.66 copolymerized nylon described in Example 1, polycapramide (6 nylon<N2)) with a relative viscosity of 1.9 and a melting point of 219C according to the DTA method was used, and ethylene-acetic acid was used. The saponified vinyl copolymer was A in Example 1.
and B1, the mixing ratio (weight ratio) of #2:(,4+81) is 50:(50+0) and 50. :(
0+50) and 50:(4
0+10), 50: (25+25), 50: (10
+40) and a total of 6 sheets of 100 sheets of nylon were obtained using the same method and equipment as in Example 1 (the thicknesses were 4 and 0.5 respectively).
ms).

On the other hand, Example 1
In the same manner as above, the inner bag was made of the above-mentioned six types of mixture, the outer member was made of the above-mentioned paper kelp, and only the curling part of the mouth part was glued with the hot-melt adhesive type adhesive described in Example 1 (17). We obtained six types of composite tips.

Next, these six types of composite pots were filled with commercially available soybean oil according to the method described in Example 1, and the mouths were sealed, and then stored indoors at 25C for 2 months to determine 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 2 100: (0+O) 50 or more Note 1) Comparative example 50: (50+O) 3.91
Example 50: (40+10) 1.82
Example 50: (25+25)゛ 1.26
Example 50: (10+40) 1.79
Example: Leakage from a container of soybean oil was detected.

Note 2) Initial peroxide: 1. [13mgqAg Example 3゜Internal and external layer extruder with a built-in full-flight screw with a diameter of 65 mm and an effective length of 1430 m, and a melt channel branched into 2 flow paths, with a diameter of 505 m and an effective length. Intermediate layer extruder with 1100m full-flight screw and same <a diameter 5C1w, effective length 1
Built-in 100-inch full-flight screw, and 2
A five-layer sheet with a width of 200 fins and a wall thickness (total thickness) of 0.5 wam is extruded using a combination of an adhesive layer extruder with nine melt channels branched into flow paths and a multilayer five-layer T die. Molded. The resin used for molding has density (,4,
q TMD -1505) is 0.910? /cc
, melt index (ASTMD-1238) is 1.
69/10m, said tactical polypropylene with a melting point of 165C and a density of 0.942 r/CC.

The melt index is 0.31/10m, the melting point is 1
The weight ratio of 65C high-density polyethylene is 30 near 0, and the adhesive layer has a density of 0.925? /cr:,,
Maleic anhydride-modified linear low-density polyethylene (manufactured by Showa Denko ■, grade name: Niayourex ER605N) with a melt index of 'Off/10m and a melting point of 12DC determined by the above-mentioned DTA method and Example 1 in the intermediate layer.
Among the mixtures consisting of 6,66 copolymerized nylon (N1) and ethylene-vinyl alcohol copolymers (A) and (B1) described in , N1:, 4:1 = 50:25:25
a six-component mixture, and N1:, 4=50:50, N
1 Two types of binary mixtures with IN = 50:50, for comparison, N1 = 100%, A = 100ch, B1 = 100
- Each of the resins is straight, so there are a total of 6 types of molded symmetrical five-layer sheets, and the layer composition ratio of each of these sheets, that is, the thickness ratio of outer layer: adhesive layer: intermediate layer: adhesive layer: inner layer is 45. :2.5:5:.

It was 2.5:45. Furthermore, for comparison, using only the extruder for the inner and outer layers, a blend of the polypropylene and the high-density polyethylene (Kusaba Sea) (0,5
5wm thick (hereinafter referred to as PO)) On the other hand, the basis weight was 300. f/W? , is made of 0.323m thick paper, with an inner diameter of 65 mm (CD) and an overall height (H
) is 70■ (#/D=1.08) and has a curling part at the mouth part.A cylindrical tip-shaped outer member is set in the mold, and then only the curling part is filled with a mold made by Nordson, USA. Using an applicator, apply high-density polyethylene (melting point, 1
An aqueous emulsion (solid content: 30% by weight) of 33C) was applied as an adhesive.

Next, the seven types of laminated sheets were heated using an infrared heater r (P
10 for υ single sheet (138C to 143C)
After heating for seconds, the two-layer sheet and the two-layer sheet are pressed into a mold in which the female mold has been inserted by plug-assisted vacuum-pressure forming, and at the same time the emulsion applied to the curling part is applied to the mold. Dry and adhere to the sheet, the outer member is the above-mentioned Kotop base paper and the inner member is the above-mentioned six types of laminated (five layers) inner layer and P6 inner bag,
A composite cup (fabric weight: 6,0389/d) was obtained in which only 9 parts of the curling part were bonded. The average thickness of the entire inner member was 0.15 mm. Of the five-layer sheet, the middle layer has an inner bag made from a laminated sheet made of a six-component mixture (hereinafter referred to as "A"), and was tested in a tensile tester (1 temperature, tensile speed f 20057M). 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 6.

For comparison, the aqueous emulsion of the maleic anhydride-grafted high-density polyethylene was applied to the curled mouth part and the entire inner surface of the tip-shaped outer member set in a mold, and then the molding method and the molding method described above were applied. Under the conditions, the material composition and thickness are the same as all of the above, and the outer member (the paper tip) and the inner member (the inner member formed from a laminated sheet in which the middle layer of the five-layer sheet is made of a three-component mixture) A composite cup (fabric weight: 0.039 f/d) was obtained in which the contact surface with the bag was adhered over the entire area of the cup. Hereinafter, this composite tip will be referred to as IBM. 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 H, 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, orange juice with an orange concentration of 50-230 was heated at 82C, and immediately after filling, the lid material described in Example 1 was heat-sealed at 150 r' with an iron, air-cooled at 25 r, and then kept for 2 months. It was stored at 25C (indoor bright place). When we observed the state of deformation of each cup after 2 months, we found that the outer and inner members were bonded only at the girl/gu part of the mouth, the A composite cup, and the other five types of composite cups with a five-layer inner bag. While no deformation was observed in the composite cup with the Pb inner bag, extreme denting deformation occurred in the composite cup CB) in which the outer and inner members were bonded over the entire contact surface. .

In addition, 25 pieces are stored in each of these 8 types of composite cups.
The b value of each orange juice stored at C for one month was determined using a color difference meter. The results are shown in Table 4. Table 4
Also shown are the results for the orange juice stored in a glass bottle used as a control. Because the blend resin layer of IIJ ethylene-vinyl alcohol copolymer and the 6.66 copolymerized nylon in the inner member acted effectively as an oxygen barrier layer, the orange juice had only a slight discoloration, especially in both A and B composites. The cotsup exhibits a storage stability similar to that of a glass bottle; on the other hand, the juice clearly fades in color in a composite cotup whose inner member is p6, in which the blend as a barrier material is not present in the middle layer;
In a composite cup where the inner member has a five-layer structure and the intermediate layer consists of each of #i, , 4 and B1 (each 1001), when these five-layer sheets are formed into an inner bag by the method described above, It is known from Table 4 that the color of the juice is significantly faded due to the occurrence of pinholes or cracks in each intermediate layer.

Furthermore, regarding the inner member of the A composite tip, in a part 1 to 2 cm below the mouth (curling part), the three-dimensional birefringence ΔX of the inner member corresponding to the extrusion direction (MD) of the sheet and the perpendicular direction (TD) thereof, Δy and Δ2 were observed using a polarizing microscope (manufactured by Nippon Kogaku Kogyo ■, POHfji&). The result is Δ for MDK, r=2,94x
1Q', △y=2.53X 10", △!: Q, 41
Extract at 2X 104, ΔX=2.54 for TD
X 10', △y=2.46×104, △Z=-〇,
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 sz is the refractive index in the inner bag axis direction (height direction), the depth is the same in the circumferential direction, and the nail is the refractive index in the thickness direction, the five-dimensional birefringence △X, △y, and Δ2 are respectively ΔX =Turtle-
y, Δy=3z-x, Δz= ~-rLy.

Table 6 Sample name Adhesive strength (Kf/1511II
Width) Curling part of mouth Body wall part A composite tip 0.9 0B composite tip 0.8 0.7 Example 4 Melt index (Asruo) as polyolefin
-1238) is 0.3f/101111. Density (AST
MD-1505) is 0.95f/CL, the melting point is 14
1C high density polyethylene and melt index is 5.
0r/10111m, density 0.91 f/cc, blend with isotactic polypropylene having a melting point of 160C (weight ratio) of 30N0, maleic anhydride-modified high-density polyethylene (Mitsubishi Oil Co., Ltd.) Nia 7-31B) manufactured by Kasha was used as the adhesive, and the following 12 types were used as the barrier resin: (1) 6 and 66 in Example 1;
Copolymerized nylon (N1) (11) Ethylene-vinyl alcohol copolymer CA in Example 1) (IiD Ethylene-vinyl alcohol copolymer (B1) in Example 1 (1v) Weight ratio of the above N1 and the above A is 80:20 2
Component blend (V) The weight ratio of the N1 and the A is 50:5
0 two-component blend (■1) 2 in which the weight ratio of the N1 and the A is 20:80.
Component blend (vlp) Weight specific force of N1 and B1: 80:2
0 binary blend (viii) The weight ratio of the N1 and the B1 is 50
:50 two-component blend (IX) A two-component blend (IX) in which the weight ratio of N1 and B1 is 80:20.
10) [Weight ratio] of the six-component blend (xD N1:CA+B1) is 50:(25+2
5) [Weight ratio] to the six-component blend IO /l/1: (A + B' () is 20: (40
+40) [weight ratio] 12 types of three-layer laminated sheets made of a three-component blend with a diameter of 6
Polyolefin outer layer extruder equipped with a full-flight screw with a diameter of 5 mm and an effective length of 1430 m, and an extruder for the middle layer (for adhesive layer) equipped with a full-flight screw with a diameter of 5 mm and an effective length of 1100 m. Also, a combination of a barrier single phase extruder with a built-in full-flight screw with a diameter of 50mm and an effective length of 1100mm, and a three-layer T for multilayers.
Get nine using the dice.

Each of the obtained three-layer sheets had a width of 200M and a wall thickness (total thickness) of 0.3 wl, and the composition ratio of each layer was polyolefin layer:adhesive layer:one barrier layer=20=0.5:1 ( thickness ratio).

Next, on the barrier layer side of each of these sheets, 83 parts by weight of vinylidene chloride and 14 parts by weight of methoxyethyl methyl acrylate were added.
Polyvinylidene chloride resin latex (dispersion medium: water, solid content concentration: 47% by weight) having a composition ratio of 40 parts by weight of ethylene trichloride to 100 parts by weight of the total amount of 6% by weight of methyl acrylate. It was coated by a known bar coater method, heated for 5 minutes at 70υ using a Perfect Oven (air circulation type), and then aged (heat treated) at 80C for 4 minutes in an air constant temperature bath.

The average thickness of the polyvinylidene chloride resin layer after drying and aging was 52 μm. (Oxygen permeability coefficient: 1.5xjQ cc・(7)/ad-w・cmH
'J 620C1100ToRH), water vapor permeability coefficient: 0.96 X 10' t-cm/rr?・dll
V (JISZ-0208) On the other hand, the basis weight is 5001/rr? , thickness is 0623Ill
It is made of I Kotsup base paper, and the internal dimensions CD) are 65 x 65.
As the saying goes, after setting a square, pot-shaped outer member with a total height (H) of 90 am (H/D = 1.38) and a flange at the mouth in a mold, only the flange part is placed.
Using an applicator manufactured by Nordso/USA, an aqueous emulsion (solid content [
30% by weight) was applied as an adhesive.

Next, the 12 types of laminated sheets are heated with an infrared heater for 10 seconds at a thermolabel temperature of 148 to 153C, and then plug-assisted vacuum pressure is applied into the mold in which the pot-shaped outer member (female mold) is set. At the same time as each of the laminated sheets is press-molded by a molding method, the emulsion applied to the flange portion is dried and adhered to the sheet, and the outer member is the coppice base paper and the inner member is each of the 12 types of laminated inner bags, Composite tip with only the mouth flange glued (fabric weight: 0.022
f/d) was obtained. Here, the inner member had the above-mentioned polyolefin mixture layer on the paper substrate (cop-shaped base paper) side and the above-mentioned polyvinylidene chloride-based resin layer on the inner side, and the average thickness of the entire inner member was 0.1 ws. Then, one layer of the laminated sheet is a barrier layer, and the composite tip (hereinafter referred to as "
C#), 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 using a tensile tester (room temperature, tensile speed 200 f/f). The results are shown in Table 5.

For comparison, the aqueous emulsion of the maleic anhydride-grafted high-density polyethylene was applied to the mouth flange and the entire inner surface of the tip-shaped outer member set in a mold, and then the molding method and conditions described above were applied. The material composition and thickness are the same as all of the above, and the outer member (
Composite tip (fabric weight: 0.023) in which the contact surface between the paper tip) and the inner member (inner bag of the same type as the # C1l 41 cup tip) is glued over the entire tip.
t/d) was obtained. Hereinafter, this composite tip will be referred to as "DI".

Then, the adhesive strength of the curling 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 tl' of tap water into these C and D composite cups.
As in Example 1, ethylene with a vinyl acetate content of 20% by weight and a melting point of 92C was used as a lid material.
A heat sealant layer (
A 6-layer film consisting of a 15μ thick low-density polyethylene as the middle layer and a 60μ thick aluminum foil as the outer layer was used.
After heat-sealing the mouth of each of the composite cups C and D at 70C, they were stored at 25C for 6 months. After 6 months, no deformation occurred in both the C and D chips, 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 found in the opening of the cup, and the seal was easy to open.

Next, we will introduce both the above-mentioned composite tips C and D and other composite tips having 11 types of inner bags (inner members), and for comparison, the inner members are made of a single layer of only the above-mentioned polyolefin mixture, and the above-mentioned inner members and Composite tip (fabric weight: 0
．． 022f/-9 or below, this tip is written as 1E'') No. 6
As for the type, 380wt of orange juice with an orange concentration of 50-30% was heated at 82R, and immediately after filling, the lid material was heat-sealed with an iron at 17DC.
After air cooling at 5C, it was stored at 25C (indoors in a bright place) for 2 months. of each cup after 2 months! When we observed the shape, 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 with inner pouches. Extreme concave deformation occurred in the composite chips (D and E) where the outer and inner members were bonded over the entire contact surface, demonstrating the excellent decompression deformation resistance of the C composite chips and 11 other composite chips. I was taken into consideration.

In addition, 2 pieces are stored in each of the 14 types of composite cups mentioned above.
The b value of each orange juice stored at 5C for one month is
Each was determined using a color difference meter.

The results are shown in Table 6. Table 6 also shows the results for the orange juice stored in a glass bottle used as a control. The blend resin layer of the ethylene-vinyl alcohol copolymer and the 6,66 copolymerized nylon and the polyvinyl chloride IJ-based resin layer in the inner member act effectively as an oxygen barrier layer, so that the orange juice The discoloration is slight, and the C and D composite pots in particular exhibit a shelf life comparable to that of a glass bottle.In contrast, the presence of the barrier resin layer 1. It can be seen from Table 6 that the color of the juice is clearly faded in the E-composite cup.

In addition, the barrier layer of the inner member is (1) the 6.66 copolymerized nylon (N1), (11), (i) the ethylene-
In a composite copolymer composed of vinyl alcohol copolymers (A and l), these (1) and (It).

When each laminated sheet using (l11) is formed into an inner bag by the method described above, pinholes or cracks occur in the layers (i), (It), and (Iij), resulting in large discoloration of the juice. This is known from Table 6.

Furthermore, each of the composite cups of C, D, and H was filled with 280 units of 500 pieces of sake (-grade), and immediately after filling, the mouth of each cup was sealed in the same manner as above, and after 5 hours, each composite cup was The state of deformation was observed.While no deformation occurred at all in the C composite tap, clear denting deformation occurred in both the D and H composite taps.

Then, both of the composite cups C and E filled with the above-mentioned sake were left at room temperature (25R) for 6 weeks, and each of the filled sake was tasted, and the one with better taste, flavor, and flavor was judged. 18 out of 21 people answered that the sake filled in the C compound cup was better, 1 person judged that the sake filled in the E compound cup was better, and 2 people judged that there was no difference. .

Table 5 D compound tip 1, 10.8E compound tip
1. O0,7

[Brief explanation of drawings]

FIG. 1 is a partially sectional front view of the composite container of the present invention, and FIGS. 2 and 3 show the results of films obtained by changing the composition ratio of saponified ethylene-vinyl acetate copolymer and copolymerized nylon. Diagrams showing the elongation at break in the longitudinal direction (MD) and transverse direction (TD), respectively; FIGS. 4 and 5 are cross-sectional views showing two sides of the layered structure of the cup-shaped inner member; FIG. 75-A and FIGS. 6-8 are layout diagrams illustrating the forming operation of the seamless cup-shaped inner member. 1 is a cup-shaped outer member, 2 is a seamless cup-shaped inner member,
6 is a cup body, 4 is a cup bottom, 5 is a curling part or flange of the cup, 6 is a seam, 7 is an adhesive layer, 8 is an open end of the inner member, 9 is a lid material, 10 is a lid material substrate, 11 is a heat sealant layer, 12 and 16 are surface layers made of polyolefin, and 14 is a layer made of a blend, respectively. Fig. 1 Fig. 2 Fig. 1 ((Toy) Nairou//Engineer 4 Ren Self-developed Chen Hi = 11 mm φ Tori N North J Ka 411 week U (divided into 2 laps N) H
Total Iro7/lL Now/Rare 1111 Bi'/11. #I-Hoko 9 Annification Isu/Ikai'I 餞し (3 secret sequence 1) 3 figures

Claims (1)

[Scope of Claims] (1) A cup-shaped outer member made of a paper substrate that is itself gas permeable, and a blend containing an ethylene-vinyl alcohol copolymer and a polyamide in a weight ratio of 95:5 to 5:95. a flexible, seamless, cup-shaped inner member having a layer of material thereon, the cup-shaped inner member being sized to substantially snugly fit within the inner surface of the outer member, and the inner member having an opening dimension. D, when the height is B, H/D
1. A composite container with excellent preservability, characterized in that the container is drawn so that the drawing ratio defined by 9 is 0.5 or more, and the cup wall is molecularly oriented. (2) The saponified ethylene-vinyl ester copolymer (A) in which the ethylene-vinyl alcohol copolymer has an ethylene content of 20 to 55 moles and a saponification degree of 95 or more, and the ethylene content 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 more than that of the saponified ethylene-vinyl ester copolymer (,4).
The composite container according to claim 1, comprising a blend containing saponified vinyl ester copolymer (B) in a weight ratio of 90:10 to 10:90. (3) The saponified product (A) is a saponified ethylene-vinyl ester copolymer having an ethylene content of 25 to 50 moles, and the saponified product (B) has an ethylene content of 30 to 55 moles. The composite container according to claim 2, which is a saponified ethylene-vinyl ester copolymer having an ethylene content that is at least 5 moles higher than that of the saponified product CA). (4) The polyamide has 10C of carbon atoms in the polyamide.
The composite container 0 (5) according to claim 1 or 2, wherein the polyamide is a homopolyamide, a copolyamide, or a blend thereof, in which the number of amide groups in HIfi ranges from 4 to 60. nylon 6 and nylon 6
The composite container according to claim 1 or 2, which is a copolyamide containing D.D.6 and D.D.6 in a weight ratio of 99:1 to 7D:0. (6) The saponified product (A) and the saponified product CB) are
The composite container according to claim 2, containing the components in a weight ratio of 0:20 to 20:80. (7) A special film containing the total amount of the ethylene-vinyl alcohol copolymer and polyamide in a weight ratio of 80:20 to 5:95. I! ! The composite container according to item 1. (8) 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 according to item X1. (9) A composite container in which the laminate includes inner and outer surface layers made of polyolefin and an intermediate layer made of the blend. C11 The cup-shaped inner member has 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 layer applied to the inside of the blend. The composite container according to claim 1, which is a laminate comprising resin layers. α force The composite container according to claim 8, 9 or 10, wherein the polyolefin is a polyolefin blend containing crystalline polypropylene and polyethylene in a weight ratio of 90:10 to 5:95. alpha force: 95:5 to 5:95 of ethylene-vinyl alcohol copolymer and polyamide are applied near the opening of a cup-shaped outer member made of a paper substrate that is itself gas permeable.
providing a flexible film or sheet with a layer of a blend containing a weight ratio of 7, with the outer member being a female mold, and with the film or sheet substantially snug against the inner surface of the outer member. A manufacturing method for composite containers with excellent shelf life that requires plug assist molding until they are combined.