JP6531371B2 - Peeling container - Google Patents

Description

  The present invention relates to a peeling container in which the inner layer peels from the outer layer and shrinks as the contents decrease.

  DESCRIPTION OF RELATED ART Conventionally, the lamination | stacking peeling container which suppresses that air intrudes into the inside of a container is known by an inner layer peeling and shrinking | contracting from an outer layer with reduction of the content (for example, patent document 1). Such a laminate peeling container comprises an inner bag constituted by an inner layer and an outer shell constituted by an outer layer.

Patent No. 3563172 gazette

  As an outer layer of the lamination peeling container of patent document 1, in order to maintain the external appearance shape of a container, it is supposed that it is preferable to use a polyethylene resin.

  However, according to the method of use and the environment of the laminated peeling container, the present inventors conducted investigations, and the shape recovery of the outer shell was not sufficient depending on the usage and environment of the laminated peeling container, and in particular, lamination of a method of discharging contents by pressing the outer shell. In the peeling container, it is desired to improve the shape restoration of the outer shell. In addition, it is desirable that such a laminated peeling container is excellent in transparency and heat resistance, but the laminated peeling container of Patent Document 1 has insufficient transparency and heat resistance depending on the method of use and environment. It turned out that it might be.

  This invention is made in view of such a situation, and provides the lamination peeling container excellent in the shape restoration property, transparency, and heat resistance of an outer shell.

  According to the present invention, there is provided a laminated peeling container comprising an outer layer and an inner layer, wherein the inner layer peels and shrinks from the outer layer as the content decreases, and the outer layer is formed between propylene and another monomer. There is provided a laminated peeling container comprising a propylene copolymer layer consisting of a random copolymer.

  The inventors examined various materials constituting the outer shell to improve the shape restoration property, transparency and heat resistance of the outer shell, and as a result, propylene consisting of a random copolymer of propylene and another monomer When the outer shell was constituted by the copolymer layer, it was discovered that the shape restoration property, transparency and heat resistance of the outer shell can be improved, and the present invention was achieved.

Hereinafter, various embodiments of the present invention will be illustrated. The embodiments shown below can be combined with one another.
Preferably, the inner layer comprises an EVOH layer consisting of EVOH, and the melting point of the EVOH is higher than that of the random copolymer.
Preferably, the melting point of the EVOH is higher by at least 15 ° C. than the melting point of the random copolymer.
Preferably, the inner layer is provided with a polyethylene layer via an adhesive layer on the container inner surface side than the EVOH layer.

BRIEF DESCRIPTION OF THE DRAWINGS It is a perspective view which shows the structure of the lamination peeling container 1 of one Embodiment of this invention, (a) is a general view, (b) shows a bottom part. The lamination peeling container 1 of FIG. 1 is shown, (a) is a front view, (b) is a rear view, (c) is a top view, (d) is a bottom view. It is AA sectional drawing in FIG.2 (d). However, FIGS. 1 and 2 show a state before the bottom seal protrusion 27 is bent, and FIG. 3 shows a state after the bottom seal protrusion 27 is bent. It is an enlarged view of the area | region containing the opening 9 of FIG. The state which peeling of the inner layer 13 advanced from the state of FIG. 4 is shown. It is an enlarged view of a field including bottom 29 of Drawing 3, (a) shows the state before bottom seal projection 27 is bent, (b) shows the state after bottom seal projection 27 is bent. Show. FIG. 3 is a cross-sectional view showing a layer configuration of an inner layer 13; FIG. 5 is a perspective view showing various configurations of the valve member 5; The manufacturing process of the lamination peeling container 1 of FIG. 1 is shown. FIG. 10 shows a process subsequent to FIG. 9 of the delamination container 1 of FIG. 1. The other example of an inner layer preliminary | backup peeling and external air introduction hole formation process is shown. The usage method of the lamination peeling container 1 of FIG. 1 is shown.

  Hereinafter, embodiments of the present invention will be described. The various features shown in the embodiments described below can be combined with one another. In addition, the invention is established independently for each feature.

  As shown in FIGS. 1 and 2, the delamination container 1 according to the embodiment of the present invention includes a container body 3 and a valve member 5. The container main body 3 includes an accommodating portion 7 for accommodating the contents, and a port 9 for discharging the contents from the accommodating portion 7.

  As shown in FIG. 3, the container body 3 includes the outer layer 11 and the inner layer 13 in the housing portion 7 and the opening 9, the outer layer 11 constitutes the outer shell 12, and the inner layer 13 constitutes the inner bag 14. Ru. As the inner layer 13 peels from the outer layer 11 as the content decreases, the inner bag 14 peels from the outer shell 12 and shrinks.

  As shown in FIG. 4, the mouth 9 is provided with a male screw 9d. A cap having an internal thread, a pump or the like is attached to the external thread 9 d. In FIG. 4, a part of the cap 23 having the inner ring 25 is illustrated. The outer diameter of the inner ring 25 is substantially the same as the inner diameter of the opening 9, and the outer surface of the inner ring 25 abuts on the contact surface 9a of the opening 9 to prevent the contents from leaking out. In the present embodiment, the enlarged diameter portion 9 b is provided at the tip of the opening 9, and the inner diameter at the enlarged diameter portion 9 b is larger than the inner diameter at the contact portion 9 e. The outer surface is not in contact with the enlarged diameter portion 9b. In the case where the opening 9 does not have the enlarged diameter portion 9b, the inner ring 25 may enter between the outer layer 11 and the inner layer 13 when the inner diameter of the opening 9 is slightly reduced due to manufacturing variations. In the case where the opening 9 has the enlarged diameter portion 9b, such a problem does not occur even if the inner diameter of the opening 9 is slightly dispersed.

  In addition, the mouth portion 9 includes an inner layer support portion 9c that suppresses the displacement of the inner layer 13 at a position closer to the housing portion 7 than the contact portion 9e. The inner layer support 9 c is formed by providing a neck in the mouth 9. Even when the enlarged diameter portion 9 b is provided in the opening 9, the inner layer 13 may be separated from the outer layer 11 due to the friction between the inner ring 25 and the inner layer 13. In this embodiment, even in such a case, the inner layer support portion 9 c suppresses the slippage of the inner layer 13, so that the inner bag 14 can be prevented from falling into the outer shell 12.

  As shown in FIGS. 3 to 5, the storage portion 7 has a body portion 19 whose cross-sectional shape is substantially constant in the longitudinal direction of the storage portion, and a shoulder portion 17 connecting the body portion 19 and the mouth portion 9. Equipped with The shoulder portion 17 is provided with a bent portion 21. The bent portion 21 is a portion where the bending angle α shown in FIG. 3 is 140 degrees or less and the radius of curvature on the container inner surface side is 4 mm or less. When the bent portion 21 is not present, peeling between the inner layer 13 and the outer layer 11 may spread from the body portion 19 to the mouth 9 and the inner layer 13 and the outer layer 11 may be peeled at the mouth 9 as well. However, since peeling of the inner layer 13 and the outer layer 11 in the mouth 9 causes the inner bag 14 to drop out into the outer shell 12, peeling of the inner layer 13 and the outer layer 11 at the mouth 9 is not desirable. In this embodiment, since the bent portion 21 is provided, when the peeling between the inner layer 13 and the outer layer 11 spreads from the trunk portion 19 to the bent portion 21, the inner layer 13 is bent at the bent portion 21 as shown in FIG. Therefore, the force for peeling the inner layer 13 from the outer layer 11 is not transmitted to the upper portion of the bent portion 21. As a result, the peeling between the inner layer 13 and the outer layer 11 at the portion above the bent portion 21 is suppressed. Ru. Although the bent portion 21 is provided in the shoulder portion 17 in FIGS. 3 to 5, the bent portion 21 may be provided at the boundary between the shoulder portion 17 and the trunk portion 19.

The lower limit of the bending angle α is not particularly defined, but is preferably 90 degrees or more in consideration of the easiness of manufacture. The lower limit of the curvature radius is also not particularly defined, but is preferably 0.2 mm or more in consideration of the easiness of production. The bending angle α is preferably 120 degrees or less, and the radius of curvature is preferably 2 mm or less, in order to more reliably prevent peeling of the inner layer 13 and the outer layer 11 at the mouth 9. Specifically, the bending angle α is, for example, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140 degrees, and a range between any two of the numerical values exemplified here. It may be Specifically, the radius of curvature is, for example, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2 mm, where It may be in the range between any two of the exemplified values.

  As shown in FIG. 4, in the bending portion 21, the distance L2 from the container central axis C to the container inner surface at the bending portion 21 is 1.3 of the distance L1 from the container central axis C to the container inner surface at the opening 9. It is provided in the position which becomes twice or more. The laminated peeling container 1 of the present embodiment is formed by blow molding, and the blow ratio at the bent portion 21 becomes larger and the thickness becomes thinner as L2 / L1 becomes larger, so L2 / L1 ≧ 1. By setting it to 3, the thickness of the inner layer 13 at the bent portion 21 becomes sufficiently thin, the inner layer 13 is more easily bent at the bent portion 21, and the peeling between the inner layer 13 and the outer layer 11 at the opening 9 becomes more reliable. It is prevented. L2 / L1 is, for example, 1.3 to 3, and preferably 1.4 to 2. Specifically, L2 / L1 is, for example, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.5, 3 It may be in the range between any two of the numerical values exemplified in.

  In one example, the thickness at the mouth 9 is 0.45 to 0.50 mm, the thickness at the bent part 21 is 0.25 to 0.30 mm, and the thickness at the trunk 19 is 0. 15 to 0.20 mm. Thus, when the thickness of the bent portion 21 is sufficiently smaller than the thickness at the mouth portion 9, the bent portion 21 effectively exhibits its function.

  By the way, as shown in FIG. 4, the valve member 5 for adjusting the inflow and outflow of air between the intermediate space 21 between the outer shell 12 and the inner bag 14 and the outer space S of the container body 3 as shown in FIG. Is provided. The outer shell 12 is provided with an outside air introducing hole 15 which connects the intermediate space 21 and the outer space S in the housing portion 7. The outside air introduction hole 15 is a through hole provided only in the outer shell 12 and does not reach the inner bag 14. The valve member 5 is provided in the shaft portion 5a which is inserted into the outside air introducing hole 15 and can slide relative to the outside air introducing hole 15, and is provided on the intermediate space 21 side of the shaft portion 5a and has a larger cross-sectional area than the shaft portion 5a. A lid 5 c and a locking portion 5 b provided on the outer space S side of the shaft 5 a and preventing the valve member 5 from entering the intermediate space 21 are provided.

  The lid 5 c is configured to substantially close the outside air introduction hole 15 when the outer shell 12 is compressed, and has a shape in which the cross-sectional area decreases as it approaches the shaft 5 a. In addition, the locking portion 5b is configured such that air can be introduced into the intermediate space 21 when the outer shell 12 is restored after being compressed. When the shell 12 is compressed, the pressure in the intermediate space 21 becomes higher than the external pressure, and the air in the intermediate space 21 leaks from the outside air introduction hole 15 to the outside. The pressure difference and the flow of air move the lid 5 c toward the outside air introducing hole 15, and the lid 5 c closes the outside air introducing hole 15. Since the cross-sectional area of the lid 5c is smaller as it approaches the shaft 5a, the lid 5c easily fits into the outside air introducing hole 15 and closes the outside air introducing hole 15.

  When the outer shell 12 is further compressed in this state, the pressure in the intermediate space 21 increases, and as a result, the inner bag 14 is compressed and the contents in the inner bag 14 are discharged. Also, when the compressive force on the shell 12 is released, the shell 12 tries to be restored by its own elasticity. At this time, the lid 5 c is separated from the outside air introducing hole 15, the closing of the outside air introducing hole 15 is released, and the outside air is introduced into the intermediate space 21. Further, in order to prevent the locking portion 5 b from blocking the outside air introduction hole 15, the locking portion 5 b is provided with a protrusion 5 d at a portion in contact with the outer shell 12, and the protrusion 5 d is in contact with the outer shell 12. Thus, a gap is provided between the shell 12 and the locking portion 5b. It should be noted that instead of providing the protrusion 5d, the locking portion 5b may be prevented from blocking the outside air introduction hole 15 by providing a groove in the locking portion 5b. A specific example of the configuration of the valve member 5 is shown in FIG.

  The valve member 5 can be mounted on the container main body 3 by inserting the valve member 5 into the intermediate space 21 into the lid 5 c while the lid 5 c spreads the outside air introducing hole 15. Therefore, the end of the lid 5c is preferably tapered. Such a valve member 5 can be mounted simply by pushing the lid 5 c into the intermediate space 21 from the outside of the container main body 3, so that the productivity is excellent.

  The housing portion 7 is covered with a shrink film after the valve member 5 is attached. At this time, the valve member 5 is mounted in the valve member mounting recess 7 a provided in the housing portion 7 so that the valve member 5 does not interfere with the shrink film. Further, an air flow groove 7b extending in the direction from the valve member mounting recess 7a to the port 9 is provided so that the valve member mounting recess 7a is not sealed by the shrink film.

  As shown in FIG. 1B, the bottom 29 of the housing 7 is provided with a central concave area 29a and a peripheral area 29b provided around the center 29a, and the central concave area 29a has a bottom projecting from the bottom 29 A seal projection 27 is provided. As shown in FIGS. 6A and 6B, the bottom seal protrusion 27 is a seal portion of a laminated parison in blow molding using a cylindrical laminated parison including the outer layer 11 and the inner layer 13. The bottom seal protrusion 27 includes a base portion 27 d, a thin portion 27 a, and a thick portion 27 b having a larger thickness than the thin portion 27 a from the bottom surface 29 side.

  Immediately after blow molding, the bottom seal projection 27 is in a state of standing substantially perpendicular to the plane P defined by the peripheral area 29b, as shown in FIG. 6 (a). When an impact is applied to the container, the inner layers 13 in the welded portion 27c are easily separated from each other, and the impact resistance is insufficient. Therefore, in the present embodiment, the thin portion 27a is softened by blowing hot air to the bottom seal protrusion 27 after blow molding, and the bottom seal protrusion 27 is bent in the thin portion 27a as shown in FIG. 6B. There is. Thus, the impact resistance of the bottom seal projection 27 is improved by the simple step of simply bending the bottom seal projection 27. Further, as shown in FIG. 6 (b), the bottom seal protrusion 27 does not protrude from the plane P defined by the peripheral area 29b in a bent state. By this, when standing up the lamination peeling container 1, it is prevented that the bottom seal | sticker protrusion part 27 protrudes from the surface P, and the lamination peeling container 1 is drawn.

  The base portion 27d is provided closer to the bottom surface 29 than the thin portion 27a and is a portion thicker than the thin portion 27a. The base portion 27d may be omitted, but the thin portion 27a is formed on the base portion 27d. The impact resistance of the bottom seal projection 27 can be further improved by providing

  Further, as shown in FIG. 1 (b), the recessed area of the bottom surface 29 is provided across the entire bottom surface 29 in the longitudinal direction of the bottom seal projection 27. That is, the central concave area 29a and the peripheral concave area 29c are connected. Such a configuration makes it easy to bend the bottom seal projection 27.

  Next, the layer configuration of the container body 3 will be described in more detail. The container body 3 includes an outer layer 11 and an inner layer 13.

  The outer layer 11 is made of, for example, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, an ethylene-propylene copolymer, and a mixture thereof. The outer layer 11 may have a multi-layer configuration. For example, both sides of the repro layer may be sandwiched by polypropylene layers. Here, the repro layer refers to a layer used by recycling the burrs formed at the time of forming the container. In addition, the outer layer 11 is formed thicker than the inner layer 13 so as to have high restorability.

  In the present embodiment, the outer layer 11 comprises a random copolymer layer consisting of a random copolymer between propylene and another monomer. The outer layer 11 may be a single layer of a random copolymer layer, or may be a multilayer structure. For example, both sides of the repro layer may be sandwiched by random copolymer layers. By forming the outer layer 11 with a random copolymer of a specific configuration, it is possible to improve the shape restorability, transparency and heat resistance of the outer shell 12.

  The random copolymer has a content of monomers other than propylene of less than 50 mol%, preferably 5 to 35 mol%. Specifically, this content is, for example, 5, 10, 15, 20, 25, 30 mol%, and may be in the range between any two of the numerical values exemplified here. As a monomer to be copolymerized with propylene, any monomer may be used as long as it improves the impact resistance of a random copolymer as compared to a homopolymer of polypropylene, and ethylene is particularly preferable. In the case of a random copolymer of propylene and ethylene, the content of ethylene is preferably 5 to 30 mol%, and specifically, for example, 5, 10, 15, 20, 25, 30 mol%, and the numerical values exemplified here It may be in the range between any two. The weight average molecular weight of the random copolymer is preferably 10 to 500,000, and more preferably 10 to 300,000. Specifically, this weight average molecular weight is, for example, 10, 15, 20, 25, 30, 35, 40, 45, 500,000, and is in the range between any two of the numerical values exemplified here. It is also good.

Moreover, 400-1600 MPa is preferable and, as for the tensile elasticity modulus of a random copolymer, 1000-1600 MPa is preferable. When the tensile modulus is in such a range, the shape recovery is particularly good. Specifically, the tensile modulus of elasticity is, for example, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 Mpa, and any of the numerical values exemplified herein may be between two It may be in the range of
If the container is too hard, the feeling of use of the container may be deteriorated, so that the outer layer 11 may be formed by mixing a soft copolymer such as linear low density polyethylene with the random copolymer. However, materials to be mixed with the random copolymer are preferably mixed to be less than 50% by weight with respect to the entire mixture so as not to significantly inhibit the effective properties of the random copolymer. For example, the outer layer 11 can be made of a material in which a random copolymer and linear low density polyethylene are mixed at a weight ratio of 85:15.

  As shown in FIG. 7, the inner layer 13 is provided between the EVOH layer 13a provided on the container outer surface side, the inner surface layer 13b provided on the container inner surface side of the EVOH layer 13a, and the EVOH layer 13a and the inner surface layer 13b. And the adhesive layer 13c. By providing the EVOH layer 13a, the gas barrier properties and the removability from the outer layer 11 can be improved.

  The EVOH layer 13a is a layer made of an ethylene-vinyl alcohol copolymer (EVOH) resin, and is obtained by hydrolysis of ethylene and a vinyl acetate copolymer. The ethylene content of the EVOH resin is, for example, 25 to 50 mol%, and preferably 32 mol% or less from the viewpoint of oxygen barrier properties. The lower limit of the ethylene content is not particularly limited, but the flexibility of the EVOH layer 13a is likely to decrease as the ethylene content decreases, so 25 mol% or more is preferable. Further, the EVOH layer 13a preferably contains an oxygen absorbent. By including the oxygen absorber in the EVOH layer 13a, the oxygen barrier property of the EVOH layer 13a can be further improved. The flexural modulus of the EVOH resin is preferably 2350 MPa or less, and more preferably 2250 MPa or less. The lower limit of the flexural modulus of the EVOH resin is not particularly defined, but is, for example, 1800, 1900 or 2000 MPa. Flexural modulus can be measured by a test method in accordance with ISO178. The test speed is 2 mm / min.

  The melting point of the EVOH resin is preferably higher than the melting point of the random copolymer constituting the outer layer 11. The external air introduction hole 15 is preferably formed in the outer layer 11 using a heating type piercing device, but the external air introduction hole 15 is formed in the outer layer 11 by making the melting point of the EVOH resin higher than the melting point of the random copolymer. When forming, the holes are prevented from reaching the inner layer 13. From this viewpoint, the difference between (the melting point of EVOH)-(the melting point of the random copolymer layer) is preferably as large as possible, preferably 15 ° C. or more, and particularly preferably 30 ° C. or more. The difference between the melting points is, for example, 5 to 50 ° C., and specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 ° C., any of the numerical values exemplified here It may be in the range between or two.

  The inner surface layer 13b is a layer in contact with the contents of the laminated peeling container 1, and is, for example, a polyolefin such as low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer and a mixture thereof It is preferably made of low density polyethylene or linear low density polyethylene. 50-300 Mpa is preferable and, as for the tensile elasticity modulus of resin which comprises the inner surface layer 13b, 70-200 Mpa is preferable. This is because the inner surface layer 13b is particularly flexible when the tensile modulus is in such a range. The tensile modulus is specifically, for example, specifically, for example, 50, 100, 150, 200, 250, 300 Mpa, and may be in the range between any two of the numerical values exemplified here. .

  The adhesive layer 13c is a layer having a function of adhering the EVOH layer 13a and the inner surface layer 13b, and, for example, one obtained by adding an acid-modified polyolefin (eg, maleic anhydride-modified polyethylene) in which a carboxyl group is introduced to the above-described polyolefin Ethylene vinyl acetate copolymer (EVA). An example of the adhesive layer 13c is a mixture of low density polyethylene or linear low density polyethylene and acid-modified polyethylene.

Next, an example of the manufacturing method of the lamination peeling container 1 of this embodiment is demonstrated.
First, as shown in FIG. 9 (a), a laminated structure corresponding to the container main body 3 to be manufactured (an example is shown in FIG. 9 (a) sequentially from the inner surface side of the container, PE layer / adhesion layer / EVOH layer) The laminated parison in the molten state is extruded, and the laminated parison in the molten state is set in a blow molding mold and the divided mold is closed.
Next, as shown in FIG. 9B, a blow nozzle is inserted into the opening on the mouth 9 side of the container main body 3 and air is blown into the cavity of the split mold in a state where the mold is clamped.

  Next, as shown in FIG. 9C, the split mold is opened to take out the blow molded product. The split mold has a cavity shape such that various shapes of the container body 3 such as the valve member mounting recess 7a, the air flow groove 7b, and the bottom seal protrusion 27 are formed in a blow molded product. Further, in the split mold, a pinch-off portion is provided on the lower side of the bottom seal protrusion 27, and a lower burr is formed on the lower portion of the bottom seal protrusion 27, and this is removed.

Next, as shown in FIG. 9 (d), the taken out blow molded articles are aligned.
Next, as shown in FIG. 9E, in the upper cylindrical portion 31 provided on the upper side of the mouth portion 9, only the outer layer 11 is pierced and a blower 33 is used between the outer layer 11 and the inner layer 13 By blowing in air, the inner layer 13 is preliminarily peeled off from the outer layer 11 at a portion (valve member mounting recess 7 a) of the housing portion 7 to which the valve member 5 is attached. By this preliminary peeling, the process of forming the outside air introduction hole 15 and the process of mounting the valve member 5 are facilitated. The tip end side of the upper cylindrical portion 31 may be covered with a cover member so that the blown air does not leak from the tip end side of the upper cylindrical portion 31. Further, in order to make it easy to make a hole only in the outer layer 11, the inner layer 13 may be separated from the outer layer 11 in the upper cylindrical portion 31 by crushing the upper cylindrical portion 31 before making the hole. Well, the preliminary peeling may be performed on the entire container 7 or a part of the container 7.
Next, as shown in FIG. 9 (f), an external air introduction hole 15 is formed in the outer shell 12 using a drilling device. The outside air introducing hole 15 is preferably a round hole, but may have another shape.
Next, as shown in FIG. 10A, hot air is applied to the bottom seal protrusion 27 to soften the thin portion 27a, and the bottom seal protrusion 27 is bent.
Next, as shown in FIG. 10 (b), the valve member 5 is inserted into the outside air introduction hole 15.
Next, as shown in FIG. 10C, the upper cylindrical portion 31 is cut.
Next, as shown in FIG. 10 (d), the inner bag 14 is inflated by blowing air into the inner bag 14.
Next, as shown in FIG. 10E, the contents are filled in the inner bag 14.
Next, as shown in FIG. 10F, the cap 23 is attached to the mouth 9.
Next, as shown in FIG. 10 (g), the container 7 is covered with a shrink film to complete the product.

  The order of the various steps shown here can be changed as appropriate. For example, the hot air bending process may be performed before the external air introduction hole opening process or before the inner layer preliminary peeling process. Further, the step of cutting the upper cylindrical portion 31 may be performed before inserting the valve member 5 into the outside air introduction hole 15.

Furthermore, the inner layer preliminary peeling and the outside air introducing hole opening step can also be performed by the following method.
First, as shown in FIG. 11A, the air in the inner bag 14 is sucked from the mouth 9 to decompress the inside of the inner bag 14. In that state, a piercing device such as a heat pipe or pipe cutter is slowly pressed against the outer layer 11. This perforation device has a cylindrical cutter, and the air inside the cylinder is sucked. When no hole is formed in the outer layer 11, air does not enter between the outer layer 11 and the inner layer 13, so the inner layer 13 is not peeled off from the outer layer 11.

  When the cylindrical cutter penetrates the outer layer 11, as shown in FIG. 11B, the cut-out cut piece is removed through the cylindrical cutter to form the outside air introduction hole 15. At this moment, air enters between the outer layer 11 and the inner layer 13 and the inner layer 13 is peeled off from the outer layer 11.

  Next, as shown in FIG. 11 (c), the diameter of the outside air introduction hole 15 is expanded using a drilling device. When the outside air introducing hole 15 of a size sufficient for the insertion of the valve member 5 is formed in the steps of FIGS. 11 (a) and 11 (b), the diameter increasing step of FIG. 11 (c) is unnecessary.

Next, the operation principle when using the manufactured product will be described.
As shown in FIGS. 12 (a) to 12 (c), the side of the shell 12 is gripped and compressed in a state where the product filled with contents is inclined, and the contents are discharged. At the start of use, since there is substantially no gap between the inner bag 14 and the outer shell 12, the compressive force applied to the outer shell 12 directly becomes the compressive force of the inner bag 14 and the inner bag 14 is compressed. The contents are discharged.

  The cap 23 incorporates a check valve (not shown) and can discharge the contents in the inner bag 14 but can not take in the outside air into the inner bag 14. Therefore, when the compressive force applied to the shell 12 after discharging the contents is removed, the shell 12 tries to return to its original shape by its own restoring force, but the inner bag 14 remains deflated and only the shell 12 It will expand. Then, as shown in FIG. 12 (d), the inside of the intermediate space 21 between the inner bag 14 and the outer shell 12 is in a decompressed state, and the outside air is in the intermediate space 21 through the outdoor air introducing hole 15 formed in the outer shell 12. be introduced. When the intermediate space 21 is in a depressurized state, the lid 5 c is not pressed against the outside air introducing hole 15, so the introduction of the outside air is not hindered. Further, the securing portion 5b is provided with an airway securing means such as a protrusion 5d or a groove so that the securing portion 5b does not prevent the introduction of the outside air even when the securing portion 5b contacts the outer shell 12.

  Next, as shown in FIG. 12 (e), when the side surface of the outer shell 12 is gripped and compressed again, the pressure in the intermediate space 21 is increased by the lid 5c closing the outside air introduction hole 15. The compression force applied to the outer shell 12 is transmitted to the inner bag 14 through the intermediate space 21. The inner bag 14 is compressed by this force and the contents are discharged.

  Next, as shown in FIG. 12 (f), when the compression force applied to the shell 12 is removed after the content is discharged, the shell 12 introduces outside air from the outside air introducing hole 15 into the intermediate space 21. , It is restored to its original shape by its own resilience.

  In the following examples and comparative examples, various peeling containers having different layer configurations are manufactured by blow molding, and the restorability, rigidity, impact resistance, heat resistance, transparency, gas barrier property, moldability, outer layer processability, etc. The various evaluations of In addition, outer-layer processability shows the easiness of the process of processing which forms an external air introduction hole only in an outer layer using a heating type piercing device.

Example 1
In Example 1, layer constitution was made into a random copolymer layer / EVOH layer / adhesion layer / LLDPE layer in order from the container outer side. For the random copolymer layer, a random copolymer of propylene and ethylene (type: Novatec EG7FTB, manufactured by Nippon Polypropylene Corp., melting point 150 ° C.) was used. For the EVOH layer, a high melting point EVOH (type: Soarol SF7503B, manufactured by Japan Synthetic Chemical Co., Ltd., melting point 188 ° C., flexural modulus 2190 MPa) was used. When the above various evaluations were performed, excellent results were obtained in all the evaluation items.

Example 2
In Example 2, layer constitution was made into a random copolymer layer / repro layer / random copolymer layer / EVOH layer / adhesion layer / LLDPE layer in order from the container outer side. The repro layer is made of a material by recycling the burrs generated when the container was molded, but the composition is very close to the random copolymer layer. The random copolymer layer and the EVOH layer were formed of the same materials as in Example 1. When the above various evaluations were performed, excellent results were obtained in all the evaluation items.

Example 3
The layer configuration of Example 3 is the same as that of Example 1, but a low melting point EVOH (type: Soarnol A4412, manufactured by Japan Synthetic Chemical Co., Ltd., melting point 164 ° C.) was used for the EVOH layer. When the above various evaluations were performed, excellent results were obtained with all the evaluation items other than the outer layer processability, but the outer layer processability was slightly inferior to that of Example 1. This result demonstrates that the difference of (melting point of EVOH)-(melting point of random copolymer layer) is preferably 15 ° C. or more.

Comparative Example 1
In Comparative Example 1, the layer configuration was LDPE layer / EVOH layer / adhesive layer / LLDPE layer sequentially from the outside of the container. When the above-mentioned various evaluations were performed, at least rigidity and heat resistance were low.

Comparative Example 2
In Comparative Example 2, the layer configuration was HDPE layer / EVOH layer / adhesive layer / LLDPE layer sequentially from the container outer side. When the above-mentioned various evaluations were performed, at least restorability and transparency were low.

Comparative Example 3
In Comparative Example 3, the layer configuration was, in order from the outside of the container, polypropylene layer / EVOH layer / adhesive layer / LLDPE layer. A homopolymer of propylene having a melting point of 160 ° C. was used as the material of the polypropylene layer. The same material as in Example 1 was used for the EVOH layer. When the above various evaluations were performed, at least the impact resistance was low. Moreover, outer layer processability was inferior to Example 1.

Comparative Example 4
In Comparative Example 4, the layer configuration was set as block copolymer layer / EVOH layer / adhesive layer / LLDPE layer sequentially from the container outer side. When the above-mentioned various evaluations were performed, at least transparency and impact resistance were low.

Comparative Example 5
In Comparative Example 5, the layer configuration was PET layer / EVOH layer / adhesive layer / LLDPE layer in order from the outside of the container. When the above various evaluations were performed, at least the moldability and the heat resistance were low.

Comparative Example 6
In Comparative Example 6, the layer configuration was, in order from the outside of the container, polyamide layer / EVOH layer / adhesive layer / LLDPE layer. When the above various evaluations were performed, at least the formability was low.

Comparative Example 7
In Comparative Example 6, the layer configuration was polypropylene layer / polyamide layer / adhesive layer / LLDPE layer in order from the outside of the container. When the above various evaluations were performed, at least the gas barrier properties and the formability were low.

<Flexibility test>
The EVOH resin used as the EVOH layer was subjected to a flex resistance test using a Gelvo Flex Tester (manufactured by Brugger, KFT-C-Flex Durability Tester) in accordance with ASTM F392. The test environment was 23 ° C. and 50% RH.
First, a sample consisting of a 28 cm × 19 cm × 30 μm single layer film was prepared.
Next, both ends of the sample were fixed to the pair of mandrels A and B by winding the long side of the sample around a pair of mandrels (90 mm in diameter) spaced 180 mm apart.
Next, with the mandrel A fixed, the mandrel B was gradually brought close while twisting, and the twisting was stopped when the twisting angle reached 440 degrees and the horizontal movement distance became 9.98 cm. Thereafter, the horizontal movement of the mandrel B was continued, and the horizontal movement was stopped when the horizontal movement distance after stopping the twisting became 6.35 cm. Thereafter, the mandrel B was returned to the initial state by the reverse operation to the above. After performing such an operation 100 times, the presence or absence of a pinhole was investigated. The results are shown in Table 1.

SF7503B in Table 1 is the EVOH resin used as the EVOH layer of Example 1. On the other hand, D2908 in Table 1 is a SOARNOL D2908 (manufactured by Japan Synthetic Chemical Co., Ltd.), a common EVOH resin. Two tests were performed for each EVOH resin.

  As shown in Table 1, while the D2908 produced a large number of pinholes by the above test, SF7503B did not have any pinholes and had better flexibility than general EVOH resins. I found that.

1: laminated peeling container, 3: container body, 5: valve member, 7: accommodation portion, 9: mouth, 11: outer layer, 12: outer shell, 13: inner layer, 14: inner bag, 15: outside air introduction hole, 23: Cap, 27: Bottom seal projection

Claims (4)

A laminated peeling container comprising an outer layer and an inner layer, wherein the inner layer peels and shrinks from the outer layer as the content decreases.
The outer layer comprises a propylene copolymer layer consisting of a random copolymer between propylene and another monomer,
The inner layer, as the outermost layer, Ru comprises an EVOH layer made of the EVOH resin, delamination container. The lamination peeling container according to claim 1, wherein the melting point of the EVOH resin is higher than that of the random copolymer. The lamination peeling container according to claim 2, wherein the melting point of the EVOH resin is higher by 15 ° C or more than the melting point of the random copolymer. The peeling container according to claim 2 or 3, wherein the inner layer comprises a polyethylene layer via an adhesive layer on the inner surface side of the container than the EVOH layer.