TWI554442B - Layers peel the container - Google Patents

Description

Laminated peeling container

The present invention relates to a laminated peeling container which is peeled off and shrunk from the outer layer as the contents are reduced.

In the prior art, a laminated peeling container is known, which can suppress the problem that the inner layer peels and shrinks from the outer layer and the air enters the inside of the container as the content is reduced (for example, Patent Documents 1 and 2). Such a laminated peeling container has an inner bag composed of an inner layer and an outer casing composed of an outer layer.

[Background Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3563172

[Patent Document 2] Japanese Patent No. 3650175

(1st point of view)

As the outer layer of the build-up peeling container in Patent Document 1, in order to maintain the appearance of the container, a polyethylene resin is preferably used.

However, the inventors have found through research that the shape recovery performance of the outer casing is insufficient due to the use method and environment of the laminated peeling container, and in particular, in the laminated peeling container by discharging the contents by the outer casing, it is preferable to improve the shape recovery performance of the outer casing. . In addition, the laminated peeling container of the patent document 1 may have insufficient transparency and heat resistance due to the method of use and the environment.

The first aspect of the present invention is completed in view of such circumstances, and provides a shape recovery performance of the outer casing. Transparency. A laminated peeling container with good heat resistance.

(2nd point of view)

The laminated peeling container similar to the patent document 2 can be used as a container containing soy sauce or diced juice, and the content does not contact the air, and the deterioration of the content is suppressed. However, the inventors found in the evaluation of the laminated peeling container. When citrus seasonings such as diced juice are contained, it is easy to reduce the aroma of citrus.

The second aspect of the present invention has been made in view of such circumstances, and provides a laminated peeling container which makes it difficult to reduce the citrus flavor emitted from the citrus seasoning.

(1st point of view)

According to a first aspect of the present invention, there is provided a laminated peeling container having an outer layer and an inner layer, the outer layer being peeled off and shrunk from the outer layer as the content is reduced, the outer layer having a space between the propylene and the other monomer The random copolymer constitutes a layer of propylene copolymer.

The inventor has improved the shape recovery performance of the outer casing. Transparency. Heat resistance, various studies on the materials constituting the outer shell, and found that when the outer shell is composed of propylene copolymer, the shape recovery performance of the outer shell can be improved. Transparency. The heat resistance, the propylene copolymer layer is composed of a random copolymer of propylene and another monomer, and thus the present invention has been completed.

Examples of various embodiments of the first aspect of the present invention are shown below. The embodiments shown below can be combined with each other.

Preferably, the inner layer has an EVOH layer made of an EVOH resin, and the EVOH resin has a higher melting point than the random copolymer.

Preferably, the melting point of the EVOH resin is higher than the melting point of the random copolymer by 15 ° C or more.

Preferably, the inner layer has a polyethylene layer on the inner surface side of the container by the adhesive layer as compared with the inner layer side of the EVOH layer.

(2nd point of view)

According to a second aspect of the present invention, there is provided a build-up peeling container having an outer layer and an inner layer, the inner layer being peeled off and contracted from the outer layer as the content is reduced, and the inner layer is the innermost layer It has an inner EVOH layer composed of an EVOH resin.

The inventors of the present invention have studied the cause of the citrus flavor being easily reduced, and found that limonene, which is one of the substances constituting the citrus flavor, is easily adsorbed by the inner surface of the laminated peeling container. Based on the above findings, when the inventors searched for a material which is difficult to adsorb or absorb limonene, it was found that when the innermost layer of the inner layer is an EVOH layer composed of an EVOH resin, the citrus flavor emitted from the citrus seasoning is difficult to be lowered. The present invention has been completed.

Examples of various embodiments of the second aspect of the present invention are shown below. The embodiments shown below can be combined with each other.

Preferably, the inner EVOH layer has a thickness of 10 to 20 μm.

Preferably, the inner layer is an outermost layer and has an outer EVOH layer composed of an EVOH resin, and the outer EVOH layer is thicker than the inner EVOH layer.

Preferably, the EVOH resin constituting the inner EVOH layer and the outer EVOH layer has a tensile modulus of 2000 MPa or less.

Preferably, the inner EVOH layer is composed of an EVOH resin having a higher ethylene content than the outer EVOH layer.

Preferably, the inner layer has an adhesive layer between the inner EVOH layer and the outer EVOH layer.

Preferably, the thickness of the adhesive layer is greater than the inner EVOH layer and the outer EVOH layer The sum of the thicknesses is large.

Further, in the following embodiments, Experimental Example 1 relates to the shape of the valve member, Experimental Example 2 relates to the shape of the mounting portion of the valve member, Experimental Example 3 relates to the effect of using a random copolymer on the outer layer, and Experimental Example 4 relates to the inner layer. The innermost layer is the effect of the EVOH layer.

Experimental Example 3 relates to the first aspect of the present invention, and Experimental Example 4 relates to the second aspect of the present invention.

1‧‧‧Layered peeling container

3‧‧‧ container body

5‧‧‧Valve parts

7‧‧‧ Housing Department

7a‧‧‧ valve component mounting recess

7b‧‧‧Air flow trough

9‧‧‧ mouth

11‧‧‧ outer layer

12‧‧‧ Shell

13‧‧‧ inner layer

14‧‧‧ inner pocket

15‧‧‧ outside air introduction hole

17‧‧‧ Shoulder

19‧‧‧ Trunks

23‧‧‧ Cap

27‧‧‧Bottom seal protrusion

29‧‧‧ bottom

29a‧‧‧Central recessed area

29b‧‧‧ surrounding area

29c‧‧‧Apertured area

Fig. 1 is a perspective view showing a configuration of a laminated peeling container 1 according to a first embodiment of the present invention, wherein (a) is an overall view, (b) is a bottom portion, and (c) is an enlarged view showing a vicinity of a valve member mounting recess 7a. (c) shows a state in which the valve member 5 is removed.

Fig. 2 shows a laminated peeling container 1 of Fig. 1, (a) is a front view, (b) is a rear view, (c) is a plan view, and (d) is a bottom view.

Fig. 3 is a cross-sectional view taken along line A-A in Fig. 2(d). 1 to 2 show a state before the bottom seal protruding portion 27 is bent, and FIG. 3 shows a state after the bottom seal protruding portion 27 is bent.

Fig. 4 is an enlarged view showing a region of the mouth portion 9 in Fig. 3.

Fig. 5 is a view showing a state in which the inner layer 13 is peeled off from the state of Fig. 4 .

Fig. 6 is an enlarged view including a region of the bottom surface 29 in Fig. 3, wherein (a) shows a state before the bottom seal protruding portion 27 is bent, and (b) shows a state in which the bottom seal protruding portion 27 is bent.

Fig. 7 is a cross-sectional view showing the structure of the outer layer 11 and the inner layer 13 layer.

FIG. 8 is a perspective view showing various configurations of the valve member 5.

Fig. 9 is a view showing the manufacturing process of the laminated peeling container 1 of Fig. 1.

[Fig. 10] shows that the inner layer is ready to be peeled off. Another embodiment of a molding process of the external gas introduction hole.

[Fig. 11] shows that the inner layer is ready to be peeled off. Another embodiment of a molding process of the external gas introduction hole.

Fig. 12 is a cross-sectional view showing the shape of the tip end of the cylindrical blade, wherein (a) the tip end has a pointed shape, and the tip end of (b) has a circular shape.

Fig. 13 is a view showing a subsequent manufacturing process subsequent to Fig. 11 of the build-up peeling container 1 of Fig. 1.

Fig. 14 is a view showing a method of using the laminated peeling container 1 of Fig. 1.

Fig. 15 shows a configuration of a laminated peeling container 1 according to a second embodiment of the present invention, wherein (a) is a perspective view, (b) is an enlarged view of the vicinity of the valve member mounting recess 7a, and (c) is an AA in (b). Surface map.

(b) to (c) show the state after the valve member 5 is removed.

Fig. 16 shows a configuration example 1 of the valve member 5. (a) is a perspective view, and (b) is a front view.

Fig. 17 shows a configuration example 2 of the valve member 5. (a) is a perspective view, and (b) is a front view.

Fig. 18 shows a configuration example 3 of the valve member 5, (a) is a perspective view, and (b) is a front view.

Fig. 19 shows a configuration example 4 of the valve member 5, wherein (a) is a perspective view and (b) is a front view.

Fig. 20 shows a configuration example 1 of the valve member 5. (a) is a perspective view, (b) is a front view, and (c) is a perspective view as seen from the bottom surface side.

Fig. 21 is a perspective view showing a valve member 5 of the laminated peeling container 1 according to the third embodiment of the present invention, wherein (a) to (b) are perspective views of the valve member 5, and (c) is a front view of the valve member 5, and (d) ~(e) is a front view of the state in which the outer air introduction hole 15 is attached to the valve member 5 (the outer casing 12 is a sectional view).

Hereinafter, embodiments of the present invention will be described. The various features shown in the following embodiments may be combined with each other. Moreover, each feature independently establishes the invention.

1. First embodiment

As shown in FIG. 1 to FIG. 2, the laminated peeling container 1 according to the first embodiment of the present invention includes a container body 3 and a valve member 5. The container body 3 has a housing portion 7 that accommodates the contents and a mouth portion 9 that ejects the contents from the housing portion 7.

As shown in Fig. 3, the container body 3 has an outer layer 11 and an inner layer 13 in the housing portion 7 and the mouth portion 9, the outer casing 12 is composed of an outer layer 11, and the inner bag 14 is composed of an inner layer 13. As the contents are reduced, the inner layer 13 is peeled off from the outer layer 11, and the inner bag 14 is peeled off and shrunk from the outer casing 12.

As shown in Fig. 4, the mouth portion 9 is provided with an external thread portion 9d. A cap, a pump, or the like having an internal thread is attached to the male screw portion 9d. In Figure 4, a portion of the cap 23 having the inner ring 25 is shown. The outer diameter of the inner ring 25 is substantially the same as the inner diameter of the mouth portion 9, and the outer surface of the inner ring 25 is connected to the joint surface 9a of the mouth portion 9 to prevent leakage of contents. In the present embodiment, the front end of the mouth portion 9 is provided with the enlarged diameter portion 9b. Since the inner diameter of the enlarged diameter portion 9b is larger than the inner diameter of the connecting portion portion 9e, the outer surface of the inner ring 25 does not contact the enlarged diameter portion 9b. . When the mouth portion 9 has no diameter-enlarged portion 9b, even if there is a slight manufacturing variation in the inner diameter of the mouth portion 9, a manufacturing defect occurs in which the inner ring 25 enters between the outer layer 11 and the inner layer 13, but the mouth portion 9 has When the diameter portion 9b is enlarged, the inner diameter of the mouth portion 9 does not change even if it is slightly changed. I have such a bad situation.

Further, the mouth portion 9 has an inner layer supporting portion 9c portion that suppresses the falling of the inner layer 13 at a position where the connecting portion 9e approaches the housing portion 7. The inner layer supporting portion 9c is formed by providing a constriction at the mouth portion 9. Even if the enlarged diameter portion 9b is provided in the mouth portion 9, the inner layer 13 is peeled off from the outer layer 11 due to the friction between the inner ring 25 and the inner layer 13. In the present embodiment, even in such a case, since the inner layer supporting portion 9c suppresses the inner layer 13 from falling off, the inner bag 14 can be prevented from falling off inside the outer casing 12.

As shown in FIGS. 3 to 5, the accommodating portion 7 has a trunk portion 19 that is substantially constant in longitudinal cross-sectional shape toward the accommodating portion, and a shoulder portion 17 that connects the trunk portion 19 and the mouth portion 9. A bent portion 22 is provided on the shoulder portion 17. The bent portion 22 is a portion in which the bending angle α is 140 degrees or less and the radius of curvature of the inner surface side of the container is 4 mm or less as shown in FIG. When the bent portion 22 is not provided, the peeling between the inner layer 13 and the outer layer 11 is expanded from the trunk portion 19 to the mouth portion 9, and the inner layer 13 is also peeled off from the outer layer 11 at the mouth portion 9. When the inner layer 13 of the mouth portion 9 is peeled off from the outer layer 11, the inner bag 14 is detached from the inner casing 12, so that the inner layer 13 of the mouth portion 9 is peeled off from the outer layer 11, which is not preferable. In the present embodiment, since the bent portion 22 is provided, the peeling between the inner layer 13 and the outer layer 11 is expanded from the trunk portion 19 to the bent portion 22, as shown in Fig. 5, the inner layer 13 is bent at the bent portion 22. When the bending of the inner layer 13 from the outer layer 11 is not transmitted to the upper side portion of the bent portion 22, the portion on the upper side of the bent portion 22 suppresses the peeling of the inner layer 13 from the outer layer 11. Further, although the bent portion 22 is provided at the shoulder portion 17 in FIGS. 3 to 5, the bent portion 22 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 specified, but it is easy to manufacture. In the case of consideration, it is preferably 90 degrees or more. The lower limit of the radius of curvature is not particularly limited, but is preferably 0.2 mm or more in terms of ease of manufacture. Further, in order to more reliably prevent the inner layer 13 of the mouth portion 9 from being peeled off from the outer layer 11, the bending angle α is preferably 120 degrees or less, and the radius of curvature is preferably 2 mm or less. The bending angle α may specifically be, for example, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140 degrees, or may be a value between any two numbers shown here. The radius of curvature may specifically be, for example, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2 mm, or may be in the range between any two values shown herein.

As shown in Fig. 4, for the bent portion 22, the distance L2 from the container central axis C to the inner surface of the container at the bent portion 22 is 1.3 times or more the distance L1 from the container central axis C to the inner surface of the container at the mouth portion 9. . In the present embodiment, the laminated peeling container 1 is blow-molded, because the larger the L2/L1 is, the larger the inflation ratio of the bent portion 22 is, the thinner the wall thickness is, so that L2/L1 In the case of 1.3, the wall thickness of the inner layer 13 at the bent portion 22 becomes very thin, and the inner layer 13 is easily bent at the bent portion 22, and the inner layer 13 can be more reliably prevented from the outer layer 13 at the mouth portion 9. 11 peeling. L2/L1 is preferably, for example, 1.3 to 3, 1.4 to 2. L2/L1 may in particular be, for example, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.5, 3, and may be a value between any two numbers shown here.

In one example, the wall thickness at the mouth portion 9 is 0.45 to 0.50 mm, the wall thickness at the bent portion 22 is 0.25 to 0.30 mm, and the wall thickness at the trunk portion 19 is 0.15 to 0.20 mm. Thus, the thickness of the bent portion 22 is extremely small compared to the thickness of the mouth portion 9, whereby the bent portion 22 effectively exerts its function.

As shown in FIG. 4, a valve member 5 is provided at the accommodating portion 7 to regulate air in and out between the intermediate space 21 between the outer casing 12 and the inner bag 14 and the outer space S of the container body 3. An external air introduction hole 15 that communicates the intermediate space 21 and the external space S is provided at the housing portion 7 of the outer casing 12. The external gas introduction hole 15 is a through hole provided only at the outer casing 12 and does not contact the inner bag 14. The valve member 5 has a cover portion 5c that is inserted into the outer air introduction hole 15 shaft portion 5a, is provided on the central portion 21 side of the shaft portion 5a and has a larger cross-sectional area than the shaft portion 5a, and is provided on the shaft portion 5a. The outer space S is on one side and prevents the valve member 5 from entering the engaging portion 5b of the intermediate space 21. In the present embodiment, the shaft portion 5a is slidable relative to the outside air introduction hole 15.

The lid portion 5c has a structure in which the outer air introduction hole 15 is substantially blocked when the outer casing 12 is compressed, and has a shape having a small cross section as approaching the shaft portion 5a. Further, the structure of the engaging portion 5b can introduce air into the intermediate space 21 when the outer casing 12 is restored after being compressed. When the outer casing 12 is compressed, the pressure inside the central space 21 becomes higher than the pressure outside, and the air in the central space 21 is discharged from the outer gas introduction hole 15 to the outside. The lid portion 5c moves to the outside air introduction hole 15 due to the pressure difference and the air flow, and the lid portion 5c blocks the outside air introduction hole 15. In the lid portion 5c, the lid portion 5c is easily fitted into the outside air introducing hole 15 to block the outside air introducing hole 15 as the shaft portion 5a has a small cross-sectional shape.

When the outer casing 12 is further compressed in this state, the pressure inside the intermediate space 21 rises, and as a result, the inner bag 14 is compressed to discharge the contents inside the inner bag 14. Further, when the pressure applied to the outer casing 12 is released, the elastic outer casing 12 is restored. At this time, the lid portion 5c is separated from the outside air introduction hole 15, the blockage of the outside air introduction hole 15 is released, and the outside gas enters the middle space 21 in. Further, in order to prevent the engaging portion 5b from blocking the external air introducing hole 15, a projection 5d is provided at a portion where the engaging portion 5b is in contact with the outer casing 12, and the projection 5d is in contact with the outer casing 12 between the outer casing 12 and the engaging portion 5b. There is a gap in the setting. Further, instead of providing the projection 5d, the engagement portion 5b may be prevented from blocking the external air introduction hole 15 by providing a groove in the engagement portion 5b. The specific configuration of the valve member 5 is shown in Fig. 8 and Figs. 16 to 20 .

In the valve member 5, the cover portion 5c pushes the outside air introduction hole 15 and is inserted into the intermediate space 21 of the cover portion 5c, whereby it can be attached to the container body 3. For this reason, the front end of the lid portion 5c is preferably tapered. Thus, the valve member 5 can be attached only by pressing the lid portion 5c from the outside of the container body 3 into the intermediate space 21, so that the productivity is excellent.

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

The valve member mounting recess 7a is provided at the shoulder 17 of the outer casing 12. The shoulder portion 17 is a sloped surface, and a flat region FR is provided in the valve member mounting recess portion 7a. Since the flat region FR is disposed substantially parallel to the slope of the shoulder portion 17, the flat region FR is also a sloped surface. Since the external air introduction hole 15 is provided in the flat region FR in the valve member mounting recess 7a, the external air introduction hole 15 is provided on the inclined surface. When the external air introduction hole 15 is provided, for example, on the vertical surface of the trunk portion 19, once the peeled inner bag 14 contacts the valve member 5, the valve member 5 may be hindered from moving, in the present embodiment, Since the external air introduction hole 15 is provided on the inclined surface, there is no such influence, and the smooth movement of the valve member 5 is ensured. Further, the inclination angle of the inclined surface is not particularly limited, but is preferably 45 to 89 degrees, more preferably 55 to 85 degrees, still more preferably 60 to 80 degrees.

Further, as shown in FIG. 1(c), the flat region FR in the valve member mounting recess 7a is provided so that the outer air introducing hole 15 extends to a width W of 3 mm or more (preferably 3.5 mm or more). For example, when the external air introduction hole 15 is φ4 mm and the external air introduction hole 15 is at the center of the flat region FR, the valve member mounting recess 7a is φ10 mm or more. The upper limit of the width W of the flat region FR is not particularly limited. However, as the width W of the flat region FR increases, the area of the valve member mounting recess 7a becomes large, and as a result, the gap area between the outer casing 12 and the shrink film becomes large, so that the gap area is also large. The width W is preferably not too large, for example, the upper limit is 10 mm. Therefore, the amplitude W can be 3 to 10 mm, specifically, for example, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10 mm, and can also be a value between any two numbers shown here. .

Further, the inventors found by experiment (Experimental Example 2) that if the flat area FR on the outer surface side of the outer casing 12 is wider, the radius of curvature of the inner surface of the outer casing 12 is larger, and the flat area FR is set on the outer surface side of the outer casing. When the gas introduction hole 15 extends to the periphery by 3 mm or more, the radius of curvature of the inner surface of the outer casing 12 becomes extremely large, and as a result, the adhesion between the outer casing 12 and the valve member 5 is improved. The radius of curvature of the inner surface of the outer casing 12 is preferably 200 mm or more, more preferably 250 mm or more, or 300 mm or more in the range of 2 mm around the outer gas introduction hole 15. When the radius of curvature is these values, the inner surface of the outer casing 12 is substantially flat because the adhesion between the outer casing 12 and the valve member 5 is good.

As shown in Fig. 1(b), at the bottom surface 29 of the accommodating portion 7, a central concave portion 29a and a peripheral portion 29b provided around it are provided, and at the central concave portion 29a, a bottom portion projecting from the bottom surface 29 is provided. The projection 27 is sealed. As shown in FIGS. 6(a) to 6(b), the bottom seal protruding portion 27 is a laminated parison sealing portion which is blow molded using a cylindrical laminated parison having an outer layer 11 and an inner layer 13. The bottom seal protruding portion 27 has a base portion 27d, a thin portion 27a, and a thick portion 27b which is thicker than the thin portion 27a in this order from the bottom surface 29 side.

After the blow molding, the bottom seal projection 27 is substantially perpendicular to the plane P defined by the peripheral region 29b as shown in Fig. 6(a), and the impact resistance in this state is insufficient, and when the container is subjected to impact, the welded portion 27c is The inner layer 13 is easily detached. On the other hand, in the present embodiment, as shown in FIG. 6(b), after the blow molding, hot air is blown to the bottom seal protruding portion 27 to soften the thin portion 27a, and the bottom seal protruding portion 27 is bent at the thin portion 27a. Thus, the impact resistance of the bottom seal projecting portion 27 can be improved only by a simple process of bending the bottom seal projection portion 27. Further, as shown in FIG. 6(b), the bent bottom seal projection 27 does not protrude from the plane P defined by the peripheral region 29b. When the laminated peeling container 1 is stood up as described above, the laminated peeling container 1 can be prevented from being shaken by the bottom sealing protruding portion 27 protruding from the flat surface P.

Further, the base portion 27d is a portion closer to the bottom surface 29 than the thin portion 27a and thicker than the thin portion 27a, and the thin portion 27a may be provided on the base portion 27d without the base portion 27d. The impact resistance of the bottom seal projection 27 can be improved.

Further, as shown in FIG. 1(b), the concave portion of the bottom surface 29 is in the longitudinal direction of the bottom sealing projection 27. The upper side traverses the entire bottom surface 29. That is, the central recessed area 29a and the peripheral recessed area 29c are connected. In such a configuration, the bottom seal projection 27 is easily bent.

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

The outer layer 11 is composed of, for example, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, and mixtures thereof. The outer layer 11 may be a multilayer structure. For example, the structure may be a polypropylene layer sandwiched on both sides of the regeneration layer. Here, the reproduction layer is a layer that reuses burrs generated when the container is formed. Moreover, the outer layer 11 is thicker than the inner layer 13 to improve the recovery performance.

In this embodiment, the outer layer 11 has a random copolymer layer made of a random copolymer between propylene and another monomer. The outer layer 11 may be a single layer of a random copolymer layer or a multilayer structure. For example, the structure may be sandwiched by a random copolymer layer on both sides of the reproduction layer. Since the outer layer 11 is composed of a specific random copolymer, the shape recovery property of the outer casing 12 can be improved. Transparency. Heat resistance.

The content of the monomer other than propylene in the random copolymer is less than 50 mol%, preferably 5 to 35 mol%. This content may specifically be, for example, 5, 10, 15, 20, 25, 30 mol%, or may be a value between any two of the numbers shown herein. As the monomer copolymerizing with propylene, the impact resistance of the random copolymer can be improved as compared with the homogeneous polymer of polypropylene, and ethylene is particularly preferable. Regarding the random copolymer of propylene and ethylene, the content of ethylene is preferably 5 to 30 mol%. Specifically, it may be, for example, 5, 10, 15, 20, 25, 30 mol%, or may be a numerical value between any two numbers shown here. The weight average molecular weight of the random copolymer is preferably from 100,000 to 500,000, more preferably from 100,000 to 300,000. The weight average molecular weight may specifically be, for example, 10, 15, 20, 25, 30, 35, 40, 45, 500,000, or may be a value between any two of the numbers shown herein.

Further, the tensile modulus of the random copolymer is preferably 400 to 1600 MPa and 1000 to 1600 MPa. When the tensile modulus is in this range, the shape resilience (i.e., shape recovery property) is particularly good. The tensile modulus of elasticity may specifically be, for example, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 MPa, or may be between any two numbers shown here. The value. Further, if the container is too hard, the use of the container is not good, so that a random copolymer and a soft material such as linear low-density polyethylene can be used in combination. However, in order not to substantially impede the effectiveness of the random copolymer, the weight of the mixed material is preferably less than 50% by weight based on the total weight of the mixture. For example, a mixed material of a random copolymer having a weight ratio of 85:15 and a linear low-density polyethylene can be used.

As shown in Fig. 7 (a), the inner layer 13 has an EVOH layer 13a provided on the outer surface side of the container, an inner surface layer 13b provided on the inner surface side of the container of the EVOH layer 13a, and an EVOH layer 13a and an inner surface layer 13b. The adhesive layer 13c is between. The provision of the EVOH layer 13a improves the gas barrier properties and the peelability from the outer layer 11.

The EVOH layer 13a is an ethylene-vinyl alcohol copolymer (EVOH) resin layer obtained by hydrolyzing a copolymer of ethylene and vinyl acetate. The ethylene content of the EVOH resin may be 25 to 50 mol%. In view of oxygen barrier property, it is preferably 32 mol% or less. The lower limit of the ethylene content is not particularly limited. However, the softening of the EVOH layer 13a is more likely to decrease in view of the lower ethylene content, and is preferably 25 mol% or more. Further, the EVOH layer 13a preferably contains an oxygen absorbent. When the EVOH layer 13a contains an oxygen absorbent, the oxygen barrier property of the EVOH layer 13a can be improved. The flexural modulus of the EVOH resin is preferably 2,350 MPa or less, and more preferably 2,250 MPa or less. The lower limit of the bending elastic modulus of the EVOH resin is not particularly specified and may be, for example, 1800, 1900 or 2000 MPa. The flexural modulus can be measured according to the test method of ISO178. The test speed was 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 outer gas introduction hole 15 is preferably processed on the outer layer 11 by a heating type perforating means. Since the melting point of the EVOH resin is higher than the melting point of the random copolymer, when the outer gas introduction hole 15 is processed on the outer layer 11, the hole can be prevented from reaching the inner layer 13. From this point of view, the difference between (the melting point of the EVOH resin) - (the melting point of the random copolymer) is preferably as large as possible, and is preferably 15 ° C or more, and particularly preferably 30 ° C or more. This melting point difference may be, for example, 5 to 50 ° C, specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 ° C, or any two numbers shown here. The value between.

The inner surface layer 13b is a contact layer for laminating the contents of the peeling container 1, and is composed of polyolefin such as low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, and the like. It is preferably composed of low density polyethylene or linear low density polyethylene. The tensile modulus of the resin constituting the inner surface layer 13b is preferably 50 to 300 MPa, preferably 70 to 200 MPa. Since the tensile modulus is in this range, the inner surface layer 13b is particularly soft. The tensile modulus of elasticity may specifically be, for example, 50, 100, 150, 200, 250, 300 MPa, or may be shown here. The value between any two numbers.

The adhesive layer 13c may be obtained by adding an acid-modified polyolefin (for example, maleic anhydride-modified polyethylene) having a carboxyl group introduced into the above polyolefin, or an ethylene vinyl acetate copolymer (EVA) having a viscosity. The function of the EVOH layer 13a and the inner surface layer 13b. An example of the adhesive layer 13c is a mixture of low density polyethylene or linear low density polyethylene and acid modified polyethylene.

As shown in Fig. 7(b), the inner layer 13 is formed to have an inner EVOH layer 13d as the innermost layer, an outer EVOH layer 13e as the outermost layer, and an adhesive layer 13c provided therebetween.

The inner EVOH layer 13d is made of an ethylene-vinyl alcohol copolymer (EVOH) resin. According to the experiment of the present inventors (Experimental Example 4), it was found that when the innermost layer of the inner layer 13 is used as the inner EVOH layer 13d, the adsorption or absorption of limonene in the container is suppressed, and as a result, the citrus flavor is emitted from the citrus seasoning. The reduction in the scent is suppressed.

Since the rigidity of the EVOH resin is relatively high, when the EVOH resin is used as the material of the inner layer 13, a softener is usually added to the EVOH resin to improve the flexibility. However, if a softener is added to the EVOH resin constituting the inner EVOH layer 13d which is the innermost layer of the inner layer 13, the softener may be eluted in the content, so that the EVOH resin constituting the inner EVOH layer 13d has to be used without containing a softener. s material. Since the EVOH resin not containing a softening agent is large in rigidity and the inner EVOH layer 13d is too thick, there is a possibility that the inner bag 14 is difficult to smoothly shrink when the contents are ejected. And if the inner EVOH layer 13d is too thin, the inner EVOH layer 13d is not formed. The uniform adhesive layer 13c is exposed from the inner surface of the container, and pinholes are easily formed in the inner EVOH layer 13d. From such a viewpoint, the thickness of the inner EVOH layer 13d is preferably 10 to 20 μm.

The ethylene content of the EVOH resin constituting the inner EVOH layer 13d is, for example, 25 to 50 mol%, because the higher the ethylene content, the better the flexibility of the inner EVOH layer 13d, and the ethylene content is preferably higher than the EVOH resin constituting the outer EVOH layer 13e. It is preferably 35 mol% or more. Further, in other words, the ethylene content of the EVOH resin constituting the inner EVOH layer 13d is preferably such that the tensile modulus of the EVOH resin is 2,000 MPa or less.

The outer EVOH layer 13e is composed of an ethylene-vinyl alcohol copolymer (EVOH) resin like the inner EVOH layer 13d. However, since the outer EVOH layer 13e is not in contact with the contents, the addition of a softening agent can improve the flexibility, and for this reason, the thickness of the outer EVOH layer 13e can be made thicker than that of the inner EVOH layer. The thickness of the outer EVOH layer 13e is not particularly limited and may be, for example, 20 to 30 μm. When the outer EVOH layer 13e is too thin, the gas barrier property of the inner layer 13 is insufficient, and when the outer EVOH layer 13e is too thick, the flexibility of the inner layer 13 is insufficient, and the inner bag 14 is difficult to smoothly shrink when the contents are ejected. The thickness ratio of the outer EVOH layer 13e/inner EVOH layer 13d is not particularly limited, and is preferably, for example, 1.1 to 4, 1.2 to 2.0. This ratio may specifically be, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 3, 4, which may also be shown here. The value in the range between any two values. Further, the outermost layer of the inner layer 13 is provided as the outer EVOH layer 13e, and the peeling property of the inner layer 13 from the outer layer 11 can be improved.

The ethylene content of the EVOH resin constituting the outer EVOH layer 13e is, for example, 25~ 50 mol% is preferably 32 mol% or less from the viewpoint of oxygen barrier properties. The lower limit of the ethylene content is not particularly limited, and the smaller the ethylene content, the more easily the flexibility of the outer EVOH layer 13e is lowered. Therefore, it is preferably 25 mol% or more.

The amount of the softener added to the EVOH resin constituting the outer EVOH layer 13e and the ethylene content of the EVOH resin are preferably set such that the tensile modulus of the EVOH resin is 2000 MPa or less. Since both the inner EVOH layer 13d and the outer EVOH layer 13e are composed of an EVOH resin having a tensile modulus of 2000 MPa or less, the inner bag 14 can be smoothly shrunk. Further, the outer EVOH layer 13e preferably contains an oxygen absorbent. Since the outer EVOH layer 13e contains an oxygen absorbent, the oxygen barrier property of the outer EVOH layer 13e can be improved.

The melting point of the EVOH resin constituting the outer EVOH layer 13e is preferably higher than the melting point of the resin constituting the outer layer 11. The outer gas introduction hole 15 is preferably processed by the heating type perforating means on the outer layer 11, because the melting point of the EVOH resin is higher than the melting point of the resin constituting the outer layer 11, and when the outer gas introduction hole 15 is processed on the outer layer 11, the hole can be prevented from reaching the inner layer. 13. From this point of view, the difference between (the melting point of EVOH) - (the melting point of the resin constituting the outer layer 11) is preferably as large as possible, and is preferably 15 ° C or higher, and particularly preferably 30 ° C or higher. This melting point difference may be, for example, 5 to 50 ° C, specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 ° C, or any two numbers shown here. The value between.

The adhesive layer 13c is a layer disposed between the inner EVOH layer and the outer EVOH layer 13e of the 13d, and may be an acid-modified polyolefin to which a carboxyl group is introduced to the above polyolefin (for example, maleic anhydride modified poly The ethylene, or ethylene vinyl acetate copolymer (EVA) obtained has the function of bonding the EVOH layer 13a and the inner surface layer 13b. An example of the adhesive layer 13c is a mixture of low density polyethylene or linear low density polyethylene and acid modified polyethylene. The adhesive layer 13c may directly bond the inner EVOH layer 13d and the outer EVOH layer 13e, or may be indirectly by the adhesive layer 13c and the inner EVOH layer 13d, or an additional layer provided between the adhesive layer 13c and the outer EVOH layer 13e. Bonding.

The rigidity of the adhesive layer 13c per unit thickness is smaller than that of either the inner EVOH layer 13d and the outer EVOH layer 13e, that is, the flexibility is good. For this reason, the thick adhesive layer 13 increases the ratio of the thickness of the adhesive layer 13c to the entire thickness of the inner layer 13, so that the flexibility is improved, and the inner bag 14 is easily shrunk smoothly when the contents are ejected. Specifically, the thickness of the adhesive layer 13c is preferably larger than the sum of the thickness of the inner EVOH layer 13d and the thickness of the outer EVOH layer 13e. The thickness ratio of the adhesive layer 13c/(inner EVOH layer 13d+outer EVOH layer 13e) is, for example, 1.1 to 8, specifically, for example, 1.1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 7, 8, can also be a numerical value between any two numbers shown here.

Next, an example of a method of manufacturing the laminated peeling container 1 of the present embodiment will be described.

First, as shown in Fig. 9(a), the laminated structure corresponding to the container body 3 to be produced is extruded (one example is PE layer/adhesive layer/EVOH layer/PP layer in order from the inner surface side of the container/ In the molten state laminated parison of the laminated structure of the regenerated layer/PP layer, the laminated parison in the molten state is placed on the split mold for blow molding, and the split mold is closed. Next, as shown in FIG. 9(b), a blow nozzle is inserted into the opening of the container body 3 on the side of the mouth portion 9, and the mold cavity is blown into the cavity of the split mold.

Next, as shown in FIG. 9(c), the split mold is opened, and the blow molded article is taken out. The split mold includes a cavity shape of 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. Further, in the split mold, a pinch portion is provided below the bottom seal protruding portion 27 to remove the burr formed on the lower side of the bottom seal projecting portion 27.

Next, as shown in Fig. 9 (d), the blow molded articles taken out are arranged in a row.

Next, as shown in Fig. 9(e), only the outer layer 11 is opened at the upper cylindrical portion 31 provided on the upper side of the mouth portion 9, and the air blower 33 is blown between the outer layer 11 and the inner layer 13 in the housing portion. The portion (the valve member mounting recess 7a) on which the valve member 5 is attached is prepared to peel off the inner layer 13 from the outer layer 11. The preliminary peeling can make the process of processing the external air introduction hole 15 and the process of attaching the valve member 5 easier. Further, in order to prevent the blown air from leaking from the distal end side of the upper tubular portion 31, the distal end side of the upper tubular portion 31 can be covered with a lid member. Further, since the outer layer 11 is opened only by pressing the upper cylindrical portion 31 before the opening, the inner layer 13 can be peeled off from the outer layer 11 at the upper cylindrical portion 31. Further, the preliminary peeling may be performed on the entire housing portion 7, or may be performed on a part of the housing portion 7.

Next, as shown in Fig. 9 (f), the outer air introduction hole 15 is processed in the outer casing 12 by the opening device. The external gas introduction hole 15 is preferably a circular hole, and may have another shape.

The inner layer preliminary peeling and the outer gas introduction hole opening step may be carried out in the following manner. First, as shown in Fig. 10 (a), the air inside the inner bag 14 is sucked from the mouth portion 9, and the air pressure inside the inner bag 14 is lowered. In this state, the outer layer 11 is slowly pressurized by a perforating means in the form of a heat pipe or a pipe cutter. This perforating device has a cylindrical knife that sucks air from the inside of the cylinder. Not open on outer layer 11 At the time of the hole, air is not entered between the outer layer 11 and the inner layer 13, and the inner layer 13 is not peeled off from the outer layer 11.

When the outer blade 11 is opened by the cylindrical blade, as shown in Fig. 11 (b), the cut piece that has been cut off is removed from the cylindrical blade to form the outer air introduction hole 15.

At this instant, 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 Figs. 10(c) to (d), the outer gas introduction hole 15 is expanded in diameter by the opening device. Further, if a sufficiently large external gas introduction hole 15 into which the valve member 5 is inserted is formed in the steps of Figs. 10(a) to (b), the expansion of Figs. 10(c) to (d) is not required. Path process.

The step of opening the inner layer and the opening of the outer air introduction hole can be carried out according to the following method. Here, the outer air introduction hole 15 is opened in the outer casing 12 of the build-up peeling container 1 by the heating type perforating device 2 with reference to Figs. 11 (a) to (f), and a method of preliminary peeling will be described.

First, as shown in Fig. 11 (a), the laminated peeling container 1 is placed at a position close to the punching device 2. The perforating device 2 has a cylindrical blade 2a, and a motor 2c that drives the blade 2a to rotate by the conveyor 2b, and heats the heating device 2d of the blade 2a. The punching device 2 is movable in the direction of the arrow X1 in FIG. 11(c) and the direction of the arrow X2 in FIG. 11(e), and is supported by a servo cylinder (not shown) that uniaxially moves the punching device 2 by the rotation of the servo motor. With such a configuration, the heated blade 2a is rotated, and the tip end thereof can be pressed against the outer casing 12 of the laminated peeling container 1. Moreover, by controlling the position and moving speed of the punching device 2 by the servo motor, the production tact can be shortened.

A vent pipe 2e that communicates with a cavity in the blade 2a is connected to the blade 2a, and the vent pipe 2e is connected to an intake and exhaust device not shown. According to this, air can be sucked from the inside of the blade 2a and air can be blown into the inside of the blade 2a. The heating device 2d has a coil 2e formed by a wire, and the coil 2e is supplied with an alternating current to heat the blade 2a according to the principle of electromagnetic induction. The heating device 2d is disposed close to the blow molded article 1a and is different from the blade 2a.

Due to such a configuration, the wiring of the heating device 2d is simplified, and the tip end of the blade 2a can be efficiently heated.

Next, as shown in Fig. 11 (b), the piercing device 2 is placed close to the laminated peeling container 1, and the blade 2a is made to enter the coil 2f. In this state, the blade 2a is heated by applying an alternating current to the coil 2f.

Next, as shown in Fig. 11(c), the punching device 2 is moved at a high speed in the direction of the arrow X1 until the leading end of the blade 2a reaches a position before the delamination layer peeling container 1 is reached.

Next, as shown in Fig. 11(d), the air inside the blade 2a is sucked so that the suction force acts on the tip end of the blade 2a, and the piercing device 2 approaches the laminated peeling container 1 at a slight speed, and the tip end of the blade 2a intrudes into the laminated peeling container. 1 outer casing 12. Thus, the production tempo can be shortened by the combination of high speed movement and low speed movement. Further, in the present embodiment, the entire punching device 2 is moved. In the other embodiment, the air cylinder mechanism moves the blade 2a alone and moves at a high speed until the tip end of the blade 2a reaches the position before the delamination layer peeling container 1 is reached, and the blade edge 2a intrudes. It is also possible to move the blade 2a at a slight speed when the outer casing 12 is used.

When the front end of the blade 2a reaches the boundary between the outer casing 12 and the inner bag 14, the outer casing 12 is opened to form the outer air introduction hole 15 in the shape of the front end of the blade 2a. When the outer casing 12 is opened, the cut piece 15a is sucked into the cavity of the blade 2a. When the front end of the blade edge 2a reaches the boundary between the outer casing 12 and the inner bag 14, the movement can be stopped. In order to form the outer air introduction hole 15 more reliably, the front end of the blade 2a can be moved until the interface of the outer casing 12 and the inner bag 14 is pressed by the inner bag 14. . At this time, in order to suppress damage of the inner bag 14 by the blade 2a, the shape of the tip end of the blade 2a is preferably a circular shape as shown in Fig. 12(b) as compared with the sharp shape shown in Fig. 12(a). When the tip end of the blade 2a is rounded, it is difficult to process the external air introduction hole 15 in the outer casing 12. In the present embodiment, the outer air introduction hole 15 is easily processed in the outer casing 12 in accordance with the rotation of the heated blade 2a. Further, in order to melt the inner bag 14 without causing heat of the blade 2a, the melting point of the resin constituting the outermost layer of the inner bag 14 is preferably higher than the melting point of the resin constituting the innermost layer of the outer casing 12.

Next, as shown in Fig. 11(e), the punching device 2 is retracted in the direction of the arrow X2, and air is blown into the cavity of the blade 2a, and the cut piece 15a is discharged from the tip end of the blade 2a.

In the above steps, the outer air introduction hole 15 in the outer casing 12 is molded.

Next, as shown in Fig. 11 (f), air is introduced into the outer casing 12 and the inner bag 14 through the outer air introduction hole 15 by the air blower 33, and the outer casing 12 is preliminarily peeled off from the inner bag 14. Further, the outside air introducing hole 15 is blown with a predetermined amount of air without leaking air, and the control of the preliminary peeling of the inner bag 14 is facilitated. The preliminary peeling may be performed on the entire accommodating portion 7, or may be performed on a part of the accommodating portion 7, because the portion where the preliminary peeling is not performed cannot detect whether or not the inner bag 14 has a pinhole, and it is preferable that the accommodating portion 7 is substantially The inner bag 14 is preliminarily peeled off from the outer casing 12.

Next, as shown in FIG. 13(a), hot air is blown to the bottom seal protruding portion 27 to soften the thin portion 27a, and the bottom seal protruding portion 27 is bent.

Next, as shown in Fig. 13 (b), the pinhole inspection of the inner bag 14 is performed. Specifically, first, the adapter 35 is attached to the mouth portion 9, and the inspection gas containing a specific type of gas is injected into the inner bag 14 through the mouth portion 9. When a pinhole is present in the inner bag 14, a specific type of gas leaks from the intermediate space 21 through the pinhole, and is discharged from the intermediate space 21 through the external air introduction hole 15 to the outside of the container. A sensing portion (detector) 37 for a specific gas is provided at a position close to the outside air introducing hole 15 outside the container, and leakage of a specific type of gas can be sensed. When the concentration of the specific type gas detected by the sensing unit 37 is equal to or less than the threshold value, it is determined that there is no pinhole in the inner bag 14, and the laminated peeling container 1 is a good product. On the other hand, when the concentration of the specific type of gas sensed by the sensing unit 37 exceeds the threshold value, it is determined that there is a pinhole in the inner bag 14, and the laminated peeling container 1 is a defective product. The laminated peeling container 1 judged to be a defective product is removed from the production line.

As the specific type of gas, a gas having a small amount in the air (preferably a gas of 1% or less) such as hydrogen, carbon dioxide, helium, argon, helium or the like is preferably selected. The concentration of the specific type of gas in the gas is not particularly limited, and the test gas may be composed of only a specific type of gas, or may be a mixed gas of air and a specific gas.

The injection pressure of the inspection gas is not particularly limited, and is, for example, 1.5 to 4.0 kPa. If the injection pressure is too low, the leakage of a specific type of gas becomes too small, and it may be perceived regardless of the presence or absence of pinholes. If the injection pressure is too high for a specific gas, the inspection of the gas is followed by the expansion of the inner bag 14 against the outer casing 12, which is related to the reduction of the accuracy of the pinhole inspection in the inner bag 14.

In the present embodiment, the sensing unit 37 is provided outside the laminated peeling container 1 so as to be close to the outside air introducing hole 15. As a modified example, the sensing portion 37 is inserted into the intermediate space 21 through the external air introducing hole 15, so that it can be placed in the intermediate space 21 A specific gas is detected inside. At this time, the specific gas passing through the pinhole of the inner bag 14 can be sensed before being diffused, whereby the sensing accuracy of the specific gas can be improved. As another modification, the test gas containing the specific gas is injected into the intermediate space 21 from the outside air introduction hole 15, and the specific gas leaking into the inner bag 14 through the pinhole of the inner bag 14 is sensed.

At this time, the sensing portion 37 can be provided at a position close to the mouth portion 9 outside the container, and the sensing portion 37 can be inserted into the inner bag 14 from the mouth portion 9.

The laminated peeling container 1 after the pinhole inspection can be directly sent to the next step, and as a modification, the step of inflating the inner bag 14 by blowing air into the inner bag 14 may be carried out to the next step. In the latter case, the step of blowing air in Fig. 13(e) may be omitted.

Next, as shown in FIG. 13(c), the valve member 5 is inserted into the external air introduction hole 15.

Next, as shown in Fig. 13 (d), the upper cylindrical portion 31 is cut away.

Next, as shown in Fig. 13 (e), the inner bag 14 is blown to bulge the inner bag 14.

Next, as shown in Fig. 13 (f), the contents are filled in the inner bag 14.

Next, as shown in Fig. 13 (g), the cap 23 is attached to the mouth portion 9.

Next, as shown in Fig. 13 (h), the accommodating portion 7 is packed with a shrink film, and the product is completed.

The order of the various processes shown here can be appropriately changed. For example, the hot air bending step may be performed before the external gas introduction hole process or before the inner layer preliminary peeling process. Further, the step of cutting the upper tubular portion 31 can be performed before the valve member 5 is inserted into the external gas introduction hole 15.

Next, explain how the product works when it is used. As shown in Figs. 14(a) to (c), the product containing the contents is tilted, and the side of the outer casing 12 is held and pressed to eject the contents. At the beginning of use, there is substantially no gap between the inner bag 14 and the outer casing 12, pressure is applied to the outer casing 12, and the pressure of the inner bag 14 is converted, and the inner bag 14 is compressed to eject the contents.

The cap 23 is provided with a check valve (not shown) to allow the contents of the inner bag 14 to be ejected, and the outside air does not enter the inner bag 14. For this reason, if the pressure applied to the outer casing 12 is removed after the contents are ejected, the outer casing 12 is restored to its original shape by its own resilience, the inner bag 14 is reduced, and the outer casing 12 is expanded. Further, as shown in Fig. 14 (d), the intermediate space 21 between the inner bag 14 and the outer casing 12 is in a low pressure state, and the outside air enters the intermediate space 21 through the external air introduction hole 15 on the outer casing 12. When the middle space 21 is in a low pressure state, the lid portion 5c does not block the external air introduction hole 15 and does not hinder the introduction of external air. Further, even when the engaging portion 5b is in contact with the outer casing 12, the engaging portion 5b does not interfere with the introduction of the outside air, and the engaging portion 5b has a projection 5d or a groove to ensure the air passage is smooth.

Next, as shown in Fig. 14(e), the side surface of the outer casing 12 is gripped and compressed again, and since the lid portion 5c blocks the outer gas introduction hole 15, the pressure inside the intermediate space 21 rises and is applied to the outer casing 12. The pressure is transmitted to the inner bag 14 by the central space 21, and the inner bag 14 is compressed by this force to eject the contents.

Next, as shown in Fig. 14 (f), when the pressure applied to the outer casing 12 is removed after the contents are ejected, the outside air enters the intermediate space 21 from the external air introduction hole 15, and the outer casing 12 returns to its original shape due to its own resilience. .

2. Second embodiment

Hereinafter, a laminated peeling container according to a second embodiment of the present invention will be described with reference to Fig. 15 . The layered peeling container in the present embodiment has the same layer configuration and function as those of the first embodiment, but differs in specific shapes. The configuration of the build-up peeling container 1 of the present embodiment in the vicinity of the valve member mounting recess is different from that of the first embodiment. Hereinafter, the description will be centered on this point.

As shown in Fig. 15 (a), in the laminated peeling container 1 of the present embodiment, the mouth portion 9 and the trunk portion 19 are connected to the shoulder portion 17. In the first embodiment, the shoulder portion 17 is provided with the bent portion 22. In the present embodiment, the bent portion 22 is not provided in the shoulder portion 17, and the boundary 20 between the shoulder portion 17 and the trunk portion 19 is the same as that of the bent portion 22. The function of suppressing the inner bag 14 from peeling off to the mouth portion 9.

The valve member mounting recess 7a is provided in the trunk portion 19 which is formed by a substantially vertical wall, and the valve member mounting recess 7a is provided with a flat region. The FR flat region FR has a slope of about 70 degrees, and becomes a valve member mounting recess 7a of about 70 degrees. The aspect of the tilt. The outer air introduction hole 15 is provided in the flat region FR, and the width W of the flat region FR around the outer air introduction hole 15 is 3 mm or more as in the first embodiment. The side wall 7c of the valve member mounting recess 7a expands to a tapered surface toward the outside, and is formed The valve member is easily drafted when the recess 7a is mounted. Further, as shown in FIG. 15(c), the inner bag 14 is easily peeled off from the upper edge 7d of the flat region FR as a starting point.

3. Third embodiment

Next, the laminated peeling container 1 according to the third embodiment of the present invention will be described with reference to Fig. 21 . The laminated peeling container 1 of the present embodiment has the same layer configuration and function as the first to second embodiments, but the configuration of the valve member 5 is different.

Specifically, in the present embodiment, the engaging portion 5b of the valve member 5 has a pair of base portions 5b1 and a bridge portion 5b2 provided between the base portions 5b1. The shaft portion 5a is provided at the bridge portion 5b2.

The lid portion 5c has a structure in which the outer gas introduction hole 15 is substantially blocked when the outer casing 12 is compressed, and has a tapered surface which becomes smaller as the cross section of the shaft portion 5a becomes smaller. The inclination angle β of the tapered surface 5d shown in Fig. 21(c) is preferably 15 to 45 degrees, more preferably 20 to 35 degrees, with respect to the extending direction D of the shaft portion 5a. When the inclination angle β is too large, air leakage is likely to occur, and when the inclination angle β is too small, the valve member 5 becomes long.

Further, as shown in FIG. 21(d), the engaging portion 5b is attached to the outside air introducing hole 15, and the base portion 5b1 is connected to the outer casing 12 via the connecting surface 5e, and the bridge portion 5b2 is curved. According to this configuration, the restoring force in the direction away from the container is generated in the direction indicated by the arrow FO of the bridge portion 5b2, whereby the force in the same direction is applied to the lid portion 5c, and the lid portion 5c is pressed against the outer casing 12.

In this state, the cover portion 5c is simply pressed against the outer casing 12, and if the outer casing 12 is compressed, The pressure in the space 21 is higher than the external pressure. According to this pressure difference, the lid portion 5c is pressed against the outside air introduction hole 15 by a larger force, and the lid portion 5c blocks the outside air introduction hole 15. Since the lid portion 5c is provided with the tapered surface 5d, the lid portion 5c is easily fitted into the external gas introduction hole 15 to block the external gas introduction hole 15.

When the outer casing 12 is further compressed in this state, the pressure inside the intermediate space 21 rises, and as a result, the inner bag 14 is compressed to discharge the contents inside the inner bag 14. Further, when the pressure applied to the outer casing 12 is released, the elastic outer casing 12 is restored. As the outer casing 12 returns to the lower air pressure in the intermediate space 21, a force F1 is applied to the inner side of the lid portion 5c as shown in Fig. 21(e). Thereby, the bridge portion 5b2 is bent while forming a gap z between the lid portion 5c and the outer casing 12, and the outside air is introduced into the middle space 21 through the passage 5f between the bridge portion 5b2 and the outer casing 12, the outer air introduction hole, and the gap z. .

In the present embodiment, the valve member 5 can be injection-molded by a simple split mold, and the productivity is good, and the mold is divided in the arrow X direction along the parting line L shown in Fig. 21 (a).

[Embodiment]

1. Experimental Example 1

In the following experimental examples, a laminated peeling container having an outer layer 11 and an inner layer 13 was blow-molded, and an outer air introducing hole 15 of φ 4 mm was processed only on the outer layer 11 having a thickness of 0.7 mm by a heating type punching device. Further, the valve members 5 of the configuration examples 1 to 5 shown in FIGS. 16 to 20 and Table 1 are injection-molded, and the lid portion 5c of the valve member 5 is pressed into the intermediate space 21 through the external air introduction hole 15.

The workability, moldability, inclination resistance, and conveyance of the valve member 5 in the configuration examples 1 to 5 were evaluated. The results are shown in Table 1 below. In the evaluation items in Table 1, ×, △, and ○ are relative evaluation results, Δ indicates better than × evaluation results, and ○ indicates better results than △ evaluation.

The workability is an evaluation as to whether or not the valve member 5 can smoothly open and close the outside air introduction hole 15. In the configuration example 1 in which the length of the shaft portion 5a is shorter than the thickness of the outer layer 11, the sliding possible length is 0, and the outer air introducing hole 15 is in a closed state. In the second configuration example, the valve member 5 can open and close the outside air introduction hole 15, but the operation may not be smooth. In the configuration examples 3 to 5, the valve member 5 can smoothly open and close the outside air introduction hole 15. For example, the reason why the valve member 5 in the configuration example 2 is not smooth is the length of the sliding (the length of the shaft portion 5a - outside) The thickness of the layer 11 is 0.7 mm, the length is insufficient, and the gap corresponding to the outer air introduction hole 15 (the diameter of the outer air introduction hole 15 - the diameter of the shaft portion 5a) is 0.2 mm, which is not large enough. In the configuration examples 3 to 5, the sliding length may be 1 mm or more, and the length is sufficient, and the gap corresponding to the outside air introducing hole 15 is 0.3 mm or more. Since the valve member 5 is sufficiently large, the valve member 5 operates smoothly. In addition

When the sliding length exceeds 2 mm, the valve member 5 easily interferes with the shrink film and the inner layer 13, and thus the sliding length of the valve member 5 is preferably 1 to 2 mm.

Moldability is an evaluation of the ease of injection molding the valve member 5. The surface of the engaging portion 5b on the side of the shaft portion 5a is provided with a projection 5d as in the first embodiment, and when four grooves 5e having a circumferential direction at equal intervals are provided as in the second embodiment, the molded portion is formed. Since the valve member 5 is unreasonably pulled out from the split mold, or a mold having a special structure needs to be prepared, the formability is poor. When the two grooves 5e are provided at equal intervals in the circumferential direction as in the configuration examples 3 to 5, the valve member 5 is easily taken out from the split mold, and the moldability is good.

The inclination resistance is an evaluation of whether or not a gap is likely to occur at the air introduction hole 15 when the valve member 5 is tilted in a state where the lid portion 5c is pressed against the outside air introduction hole 15. When the shape of the boundary 5f of the lid portion 5c and the shaft portion 5a is recessed inwardly in the same manner as in the configuration examples 1 and 2, when the valve member 5 is inclined, a gap is easily formed in the air introduction hole 15. On the other hand, when the shape of the boundary 5f of the lid portion 5c and the shaft portion 5a is expanded outward into the R shape as in the configuration examples 3 to 5, when the valve member 5 is inclined, it is difficult to form a gap in the outside air introduction hole 15. Further, in the configuration example 3, the gap corresponding to the outside air introduction hole 15 is 0.7 mm, and if the valve member 5 is too large, the gap is relatively easy to form. In the configuration examples 4 to 5, the gap corresponding to the outside air introduction hole 15 is 0.6 mm or less, and the valve member 5 is excessively inclined because of the moderate size. It was suppressed. The space corresponding to the external air introduction hole 15 is preferably 0.2 to 0.7 mm, more preferably 0.3 to 0.6 mm, in view of workability and inclination resistance.

The conveyance property is easy to convey the component feeder of the evaluation holding valve member 5 in two parallel rails which are slightly larger than the diameter of the lid portion 5c. The valve member 5, the cover portion 5c passes downward between the two rails, and the engaging portion 5b is hung on the parallel rails to be held. It can be further classified into transportability, overlap resistance and peeling resistance.

The overlap resistance is a difficulty in evaluating the overlap between the engaging portions 5b of the valve member 5. In the configuration examples 1 to 4, the thickness of the engaging portion 5b is 1 mm, which is not sufficiently thick, and the engaging portions 5b are likely to overlap each other. In the configuration example 5, the thickness of the engaging portion 5b is 1.2 mm or more, and the thickness is sufficient, and it is difficult for the engaging portions 5b to overlap each other.

The drop resistance is such that the evaluation valve member 5 is not detached from the parallel track and can be properly held by the parallel track. In the configuration examples 1 to 4, the amount of protrusion of the engaging portion 5b (the diameter of the engaging portion 5b - the diameter of the lid portion 5c) is 1.5 mm or less, and the valve member 5 is easily separated from the parallel rail because it is too small.

On the other hand, in the configuration example 5, the amount of protrusion of the engaging portion 5b is 2 mm or more, and the valve member 5 is not separated from the parallel rail, and is easily conveyed by the parallel rail.

In the valve member 5 of the fifth embodiment, as shown in FIG. 20(c), the outer surface of the engaging portion 5b is provided with a recess 5g. When the molded valve member 5 is injected, burrs are generated at the position where the gate is ejected, and the position at which the gate is ejected is in the concave portion 5g, so that the burr can be prevented from interfering with the Shrink film.

2. Experimental Example 2

In the following experimental examples, a laminated peeling container having an outer layer 11 and an inner layer 13 was blow-molded, and an outer air introducing hole 15 of φ 4 mm was processed only on the outer layer 11 having a thickness of 0.7 mm by a heating type punching device. The sample No. 1 to No. 5 laminated peeling container samples were produced by changing the content of the build-up peeling container, the size of the outside air introducing hole 15, and the width W of the flat region FR in the valve member mounting recess 7a around the outside air introducing hole 15. Then, the valve member 5 having the shape shown in Fig. 20 is produced by injection molding, and the lid portion 5c of the valve member 5 is pressed into the intermediate space 21 through the external air introduction hole 15. After filling the contents (water) in the obtained laminated peeling container, the side surface of the laminated peeling container was pressed to eject the contents from the laminated peeling container. The discharge performance when the content of the content of 80% of the content was discharged (the discharge performance when the content was small) was evaluated. The contents were smoothly ejected and evaluated as "○", and it was difficult for the contents to be ejected as "X". The results are shown in Table 2.

As shown in Table 2, samples Nos. 1 to 3 had low ejection performance when the content was small, and samples 1 to 5 had high ejection performance when the content was small. In order to verify the reason for this result, regarding each sample, The radius of curvature of the inner surface of the outer casing 12 was measured within a range of 2 mm around the outer air introduction hole 15, and the results shown in Table 2 were obtained. It is found that as shown in Table 2, if the width W of the flat region FR of the outer surface of the outer casing 12 is 3 mm or more, the radius of curvature of the inner surface of the outer casing 12 is remarkably large, and the inner surface of the outer casing 12 is substantially flat. On the other hand, when the width W of the flat region FR of the outer surface of the outer casing 12 is found to be less than 3 mm, the inner surface of the outer casing 12 is not flat but curved. Then, it was found that this curved surface could not be properly fitted to the valve member 5 because air was leaked from the outside air introduction hole 15 and it was found that the discharge performance was low when the contents were small.

3. Experimental Example 3

In the following experimental examples, a laminate peeling container having various layer structures was produced by blow molding, and the restoring performance, rigidity, impact resistance, heat resistance, transparency, gas barrier property, moldability, and outer layer processability were evaluated. Further, the outer layer workability indicates the ease with which the processed air introduction hole is formed only in the outer layer by the heating type perforating device.

<Configuration Example 1>

In Composition Example 1, the layer constitution was a random copolymer layer/EVOH layer/adhesive layer/LLDPE layer in this order from the outside of the container. A random copolymer of propylene and ethylene (type: novaTecEG7FTB, manufactured by Japan Polypur Co., Ltd., melting point: 150 ° C) was used as the random copolymer layer.

As the EVOH layer, EVOH having a high melting point (type: soanoru SF7503B, manufactured by Nippon Synthetic Chemical Co., Ltd., melting point: 188 ° C, bending elastic modulus: 2,190 MPa) was used. After the above various evaluations, excellent results were obtained on all evaluation projects.

<Configuration Example 2>

In Composition Example 2, the layer constitution was a random copolymer layer/regeneration layer/random copolymer layer/EVOH layer/adhesion layer/LLDPE layer in this order from the outside of the container. The regeneration layer reuses the burrs generated during the formation of the container to form a material that is very close in composition to the random copolymer layer. The random copolymer layer and the EVOH layer were formed of the same material as in Composition 1. After the above various evaluations, excellent results were obtained on all evaluation projects.

<Configuration Example 3>

In the configuration example 3, the layer configuration is the same as that of the configuration example 1. However, the EVOH layer is made of a low melting point EVOH (type: soanoru A4412, manufactured by Nippon Synthetic Chemical Co., Ltd., melting point: 164 ° C). After the above-mentioned various evaluations, excellent results were obtained in all the evaluation items, and all the evaluation items other than the outer layer workability were excellent, but the outer layer workability was slightly worse than the configuration example 1. As a result of this, the difference between (the melting point of the EVOH resin) - (the melting point of the random copolymer layer) was confirmed to be preferably 15 ° C or more.

<Comparative composition example 1>

In Comparative Example 1, the layer constitution was LDPE layer/EVOH layer/adhesion layer/LLDPE layer in this order from the outside of the container. After performing the above various evaluations, at least rigidity and heat resistance are low.

<Comparative Example 2>

In Comparative Example 2, the layer constitution was sequentially HDP layer/EVOH layer/adhesive layer/LLDPE layer from the outside of the container. After performing the above various evaluations, at least the recovery performance and transparency are low.

<Comparative Example 3>

In Comparative Example 3, the layer constitution was a polypropylene layer/EVOH layer/adhesive layer/LLDPE layer in this order from the outside of the container. As the material of the polypropylene layer, a homogeneous polymer of propylene having a melting point of 160 ° C was used. In the EVOH layer, the same material as in Structural Example 1 was used. After performing the above various evaluations, at least the impact resistance is low. Further, the outer layer workability was inferior to that of the configuration example 1.

<Comparative composition example 4>

In Comparative Example 4, the layer constitution was sequentially a block copolymer layer/EVOH layer/adhesive layer/LLDPE layer from the outside of the container. After performing the above various evaluations, at least transparency and impact resistance are low.

<Comparative composition example 5>

In Comparative Example 5, the layer constitution was a PET layer/EVOH layer/adhesive layer/LLDPE layer in this order from the outside of the container. After performing the above various evaluations, at least moldability and heat resistance are low.

<Comparative composition example 6>

In Comparative Example 6, the layer constitution was a polyamine layer/EVOH layer/adhesion layer/LLDPE layer in this order from the outside of the container. After performing the above various evaluations, at least the moldability is low.

<Comparative Example 7>

In Comparative Example 6, the layer constitution was a polypropylene layer/polyimine layer/adhesive layer/LLDPE layer in this order from the outside of the container. After performing the above various evaluations, at least gas barrier properties and moldability are low.

<Flexibility test>

The EVOH resin used as the EVOH layer was subjected to a flexural resistance test using a bending tester (manufactured by Brugger, KFT-C-Flex Durability Tester) based on the ASTM standard. The test environment was 23 ° C, 50% RH.

First, a sample formed of a single layer film of 28 cm × 19 cm × 30 μm was produced.

Next, a pair of mandrels (90 mm in diameter) provided at intervals of 180 mm were wrapped around the long sides of the above samples, whereby a pair of mandrels A and B were fixed to both ends of the sample.

Next, while keeping the mandrel A fixed, the mandrel B is twisted while being twisted, and the torsion is stopped when the torsion angle is 440 degrees and the moving distance is 9.98 cm. Thereafter, the mandrel B is continued to continue the leveling movement, and the leveling movement is stopped when the level moving distance is 6.35 cm after the torsion is stopped.

Thereafter, the mandrel B is returned to the original state by the reverse action described above.

After 100 such operations, check for pinholes. The results are shown in Table 3.

SF7503B in Table 3 is an EVOH resin used as the EVOH layer of the configuration example 1. On the other hand, D2908 in Table 3 is a general EVOH resin soanoru D2908 (type: soanoru SF7503B, manufactured by Nippon Synthetic Chemical Co., Ltd.). Two tests were performed on each EVOH resin.

As shown in Table 3, it was found from the above test that there were many pinholes relative to D2908, and SF7503B had no pinhole at all, and the flexural resistance was good compared to the general EVOH resin.

4. Experimental Example 4

In the following experimental examples, various layers of peeling containers having different layer structures were produced by blow molding, and after filling the container with the mustard juice, after standing for one week, all the willow juice in the container was ejected, and the film was ejected. The citrus flavor of the willow juice was evaluated sensory. Further, when the willow juice was sprayed, the shape of the inner bag of the container was visually evaluated.

<Configuration Example 1>

The layer constitution of Composition Example 1 was sequentially a random copolymer layer/outer EVOH layer (thickness 25 μm)/adhesive layer (thickness 150 μm)/inside EVOH layer (thickness 15 μm) from the outside of the container. The outer EVOH layer is formed of an EVOH resin to which a softener is added, and the inner EVOH layer is formed of an EVOH resin to which no softener is added. The adhesive layer was formed by mixing a linear low-density polyethylene and an acid-modified polyethylene at a mass ratio of 50:50. At the time of the above evaluation, the intensity of the citrus flavor emitted by the sprayed diced juice was almost the same as that of the filling. And as the willow juice is sprayed out of the inner bag, the inner bag does not bend and shrinks smoothly.

<Configuration Example 2>

The layer configuration of the configuration example 2 was the same as that of the configuration example 1 except that the thickness of the side EVOH layer was 5 μm. After the above evaluation, the intensity ratio of the citrus flavor emitted by the sprayed willow juice The case 1 is slightly worse. And as the willow juice is sprayed out of the inner bag, the inner bag does not bend and shrinks smoothly.

<Configuration Example 3>

The layer configuration of the configuration example 3 was the same as that of the configuration example 1 except that the thickness of the inner EVOH layer was 25 μm. After the above evaluation, the intensity of the citrus flavor emitted from the sprayed willow juice was the same as in the configuration example 1. Further, as the diced juice was squished out of the inner bag, the inner bag of the constitution example 1 was easily bent.

<Configuration Example 4>

The layer configuration of the configuration example 4 was the same as that of the configuration example 1 except that the thickness of the outer EVOH layer was 75 μm and the thickness of the pressure-sensitive adhesive layer was 80 μm. After the above evaluation, the intensity of the citrus flavor emitted from the sprayed willow juice was the same as in the configuration example 1. Further, as the diced juice was squished out of the inner bag, the inner bag of the constitution example 1 was easily bent.

<Comparative composition example 1>

The layer configuration of Comparative Example 1 was the same as in Structural Example 1 except that the inner EVOH layer was replaced with a linear low-density polyethylene layer (50 μm). After the above evaluation, the intensity ratio of the citrus flavor emitted from the sprayed willow juice was slightly inferior to that of the configuration example 1. And as the willow juice is sprayed out of the inner bag, the inner bag does not bend and shrinks smoothly.

<Comparative Example 2>

The layer constitution of Comparative Example 2 was the same as that of Structural Example 1 except that the inner EVOH layer was replaced with a polyimide layer (50 μm). After the above evaluation, the citrus flavor of the sprayed willow juice The intensity ratio was slightly inferior to that of the configuration example 1. And as the willow juice is sprayed out of the inner bag, the inner bag does not bend and shrinks smoothly.

1‧‧‧Layered peeling container

3‧‧‧ container body

5‧‧‧Valve parts

7‧‧‧ Housing Department

7a‧‧‧ valve component mounting recess

7b‧‧‧Air flow trough

9‧‧‧ mouth

15‧‧‧ outside air introduction hole

17‧‧‧ Shoulder

19‧‧‧ Trunks

27‧‧‧Bottom seal protrusion

29‧‧‧ bottom

29a‧‧‧Central recessed area

29b‧‧‧ surrounding area

29c‧‧‧Apertured area

Claims (11)

A laminate peeling container having an outer layer and an inner layer, and the inner layer peeling and shrinking from the outer layer as the content is reduced, characterized in that the outer layer has a random copolymerization between propylene and another monomer A propylene copolymer layer made of the material, wherein the inner layer has an EVOH layer as an outermost layer and made of an EVOH resin. The laminate peeling container according to claim 1, wherein the EVOH resin has a higher melting point than the random copolymer. The laminate peeling container according to claim 1, wherein the EVOH resin has a melting point higher than a melting point of the random copolymer by 15 ° C or more. The laminated peeling container according to claim 1, wherein the inner layer has a polyethylene layer via the adhesive layer on the inner surface side of the inner surface of the EVOH layer. A peeling container having an outer layer and an inner layer, and the inner layer peeling and shrinking from the outer layer as the content is reduced, characterized in that the inner layer has: as the innermost layer and is made of EVOH resin An inner EVOH layer; and an outer EVOH layer as the outermost layer and made of EVOH resin. The laminate peeling container according to claim 5, wherein the inner EVOH layer has a thickness of 10 to 20 μm. The laminate peeling container of claim 5 or 6, wherein the outer EVOH layer is thicker than the inner EVOH layer. The laminated peeling container according to claim 5, wherein the EVOH resin constituting one of the inner EVOH layer and the outer EVOH layer has a tensile modulus of 2,000 MPa or less. The laminate peeling container according to claim 5, wherein the inner EVOH layer is made of an EVOH resin having a high ethylene content as compared with the outer EVOH layer. The laminate peeling container according to claim 5, wherein the inner layer has an adhesive layer between the inner EVOH layer and the outer EVOH layer. The laminate peeling container according to claim 10, wherein the thickness of the adhesive layer is greater than a sum of a thickness of the inner EVOH layer and a thickness of the outer EVOH layer.