WO2019044678A1

WO2019044678A1 - Delamination container

Info

Publication number: WO2019044678A1
Application number: PCT/JP2018/031283
Authority: WO
Inventors: 真輔樽野
Original assignee: キョーラク株式会社
Priority date: 2017-08-31
Filing date: 2018-08-24
Publication date: 2019-03-07
Also published as: JP6912718B2; TW201934427A; JP2019043604A

Abstract

Provided is a delamination container in which damage from being dropped at a low temperature is suppressed. The present invention provides a delamination container comprising a container body having an outer shell and an inner bag, which contracts as the contents thereof decrease, wherein the outer shell has a mixed layer which includes a polypropylene and a polyethylene elastomer.

Description

Peeling container

The present invention relates to a laminated peeling container.

DESCRIPTION OF RELATED ART Conventionally, the lamination | stacking peeling container which suppresses that air intrudes into the inside of a container by shrinking | contracting an inner bag accompanying reduction of the content is known (for example, patent document 1).

JP, 2015-163531, A

When the inventor of the present invention conducted a test of repeatedly dropping at a low temperature with respect to the container of Patent Document 1, the container might be broken.

This invention is made in view of such a situation, and provides the lamination peeling container in which the damage at the time of the fall at low temperature is suppressed.

According to the present invention, there is provided a exfoliation container comprising a container body having an outer shell and an inner bag, and the inner bag shrinking as the content decreases, and the outer shell is made of polypropylene and a polyethylene elastomer. There is provided a delamination container having a mixed layer comprising

As a result of intensive studies, the present inventors have found that by providing a mixed layer containing polypropylene and a polyethylene-based elastomer in the outer shell, damage at the time of falling at low temperatures is suppressed, leading to the completion of the present invention. It was

Hereinafter, various embodiments of the present invention will be illustrated. The embodiments shown below can be combined with one another.
Preferably, the outer shell has an innermost layer facing the inner bag, and the mass ratio of the polyethylene-based elastomer in the resin component contained in the innermost layer is the polyethylene-based elastomer in the resin component contained in the mixed layer Less than mass fraction.
Preferably, the proportion of the polyethylene-based elastomer in the resin component contained in the mixed layer is 1 to 20% by mass.
Preferably, the mixed layer further comprises linear low density polyethylene.

It is a perspective view which shows the structure of the container main body 3 of the lamination peeling container 1 of 1st Embodiment of this invention. FIG. 2 is a cross-sectional view passing through the center of the outside air introduction hole 15 in FIG. 1; In FIG. 2, the valve member 5 is attached to the outside air introduction hole 15. 3A shows a bottom view, FIG. 3B is a front view, FIG. 3C is a cross-sectional view taken along the line AA in FIG. 3A, and FIG. 3D is a view in FIG. FIG. 7B is a cross-sectional view of FIG. In FIG. 3A, the grounding region 29f, which is grounded when the container body 3 is placed on a horizontal surface, is hatched. In FIG. 3D, the layer configuration is omitted and represented by hatching. It is a perspective view which shows the structure of the container main body 3 of the lamination peeling container 1 of 2nd Embodiment of this invention. 5A shows a bottom view, FIG. 5B is a front view, FIG. 5C is a cross-sectional view taken along the line AA in FIG. 5A, and FIG. 5D is a view in FIG. FIG. 7B is a cross-sectional view of FIG. In FIG. 5A, the grounding region 29f, which is grounded when the container body 3 is placed on a horizontal surface, is hatched. In FIG. 5D, the layer configuration is omitted and represented by hatching. It is a perspective view which shows the structure of the container main body 3 of the lamination peeling container 1 of 3rd Embodiment of this invention.

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.

1. First Embodiment As shown in FIGS. 1 to 3, a laminate peeling container 1 according to a first 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. 2, the container main body 3 includes an accommodating portion 7 which accommodates the contents, and a port 9 which discharges the contents from the accommodating portion 7. The container body 3 is provided with the outer shell 12 and the inner bag 14 in the housing portion 7 and the mouth portion 9, and the inner bag 14 separates from the outer shell 12 and contracts as the contents decrease.

The mouth 9 is provided with an engagement portion 9 d that can be engaged with a cap with a check valve. The cap may be attached in a stopper type or may be attached in a screw type.

As shown in FIG. 1, the recess 7 a is provided in the housing portion 7, and the outside air introduction hole 15 is provided in the recess 7 a. The outside air introduction hole 15 is a through hole provided only in the outer shell 12 and communicates the intermediate space 21 between the outer shell 12 and the inner bag 14 with the outer space S of the container body 3.

As shown in FIG. 2, the valve member 5 is provided in the shaft portion 5 a which is inserted into the outside air introduction hole 15 and can slide relative to the outside air introduction hole 15, and is provided on the intermediate space 21 side of the shaft portion 5 a A lid 5c having a cross-sectional area larger than 5a, and a locking portion 5b provided on the outer space S side of the shaft 5a 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 pressing force on the outer shell 12 is released, the outer 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, the flow passage 5 d is provided in the locking portion 5 b so that the locking portion 5 b does not block the outside air introduction hole 15, and the flow is performed even in a state where the locking portion 5 b is in contact with the outer shell 12. Outside air can be introduced into the intermediate space 21 through the passage 5 d and the outside air introducing hole 15.

As shown in FIGS. 1 and 3, a recessed area 29 a and a peripheral area 29 b are provided on the bottom surface 29 of the housing portion 7. The peripheral area 29b is provided to surround the recessed area 29a. The recessed area 29a is an area recessed from the peripheral area 29b. A pinch off portion 27 is provided in the recessed area 29a. The pinch-off portion 27 is a seal portion of the laminated parison in blow molding using a tubular laminated parison. The pinch off portion 27 has an elongated shape. The peripheral region 29 b is provided with a groove 29 c on the extension of the pinch-off portion 27. The radius of curvature of the edge 29d of the groove 29c is preferably 4 mm or more. The radius of curvature is, for example, 4 to 20 mm, preferably 5 to 9 mm, and specifically, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 mm, and may be in the range between any two of the numerical values exemplified here. By setting the radius of curvature to 4 mm or more, breakage of the container at the edge 29d of the groove 29c is suppressed. In FIG. 3B, a circle 29e having the same radius as the radius of curvature of the edge 29d is indicated by a dotted line.

The peripheral region 29b is provided with a ground region 29f that is grounded when the container body 3 is placed on a horizontal surface. In FIG. 3A, the ground contact area 29f is hatched. Assuming that the radius of the outer edge 29g of the ground contact area 29f is R1 and the radius of the outer periphery of the container body 3 is R2, R1 / R2 is preferably 0.75 or more. This value is, for example, 0.75 to 0.90, preferably 0.77 to 0.85, and specifically, for example, 0.75, 0.76, 0.77, 0.78, 0.. 79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, where It may be in the range between any two of the exemplified values. By setting this value to 0.75 or more, the impact locally applied to the container main body 3 when the container main body 3 is dropped is alleviated and breakage of the container is suppressed.

Further, as shown in FIG. 3D, the groove 29c is shallow in depth toward the radially outer side, and the container main body 3 is less likely to tip over due to such a configuration.

Next, the layer configuration of the container body 3 will be described in more detail. The container body 3 comprises an outer shell 12 and an inner bag 14.

The outer shell 12 may have a single-layer structure or a multi-layer structure. The outer shell 12 has a mixed layer containing polypropylene and a polyethylene-based elastomer. The polypropylene may be a homopolymer of propylene or a copolymer of propylene and another monomer. The copolymer may be a block copolymer or a random copolymer, but is preferably a random copolymer from the viewpoint of transparency.

The proportion of polypropylene in the resin component contained in the mixed layer is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, and specifically, for example, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99% by mass, It may be in the range between any two of the numerical values exemplified here.

The proportion of the polyethylene-based elastomer in the resin component contained in the mixed layer is preferably 1 to 20% by mass, and more preferably 3 to 15% by mass. Specifically, this ratio is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 mass. %, And may be in the range between any two of the numerical values exemplified here. If the proportion of the polyethylene-based elastomer is too small, the container may not be sufficiently effective in suppressing breakage when falling at a low temperature, and if the proportion of the polyethylene-based elastomer is too large, the container may stick or the strength of the container may decrease. is there.

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 can improve the impact resistance of a random copolymer as compared to a homopolymer of propylene, 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%, the numerical values exemplified here It may be in the range between any two.

The polyethylene-based elastomer refers to an elastomer having polyethylene as a hard segment and a predetermined rubber component as a soft segment. For example, a C-4 polyethylene-based elastomer containing butene as a comonomer to ethylene, a C-6 polyethylene-based elastomer containing hexene, and a C-8 polyethylene-based elastomer containing octene can be mentioned.

The mixed layer may contain only polypropylene and a polyethylene-based elastomer as resin components, and may contain other resin components. Polyethylene etc. are mentioned as another resin component. The polyethylene may be any of low density polyethylene, linear low density polyethylene, and high density polyethylene, but linear low density polyethylene is preferable.

The proportion of the other resin component in the resin component contained in the mixed layer is preferably 1 to 20% by mass, and more preferably 3 to 15% by mass. Specifically, this ratio is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 mass. %, And may be in the range between any two of the numerical values exemplified here.

When the outer shell 12 has a multilayer structure, an innermost layer facing the inner bag 14 may be provided in addition to the above mixed layer. When the innermost layer contains a large amount of polyethylene elastomer, the releasability between the outer shell 12 and the inner bag 14 may be deteriorated. Therefore, the mass ratio of the polyethylene elastomer in the resin component contained in the innermost layer is P1, Assuming that the mass ratio of the polyethylene-based elastomer in the resin component contained in the mixed layer is P2, P1 / P2 is preferably smaller than 1 and more preferably 0.5 or less. Specifically, this value is, for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 It may be in the range between any two of the numerical values exemplified here.

The innermost layer may contain only polypropylene as a resin component, and may contain other resin components. Other resin components are the same as in the mixed layer. The innermost layer may also contain a lubricant such as a fatty acid amide (eg, oleic acid amide).

When the outer shell 12 has a multilayer structure, the mixed layer may be the outermost layer, or the outermost layer having another resin component may be provided. For example, as the outermost layer, a layer made of polyethylene (eg, low density polyethylene) may be provided. The shell 12 may also include a repro layer that is used by recycling the burrs that were present when the container was molded. The repro layer is preferably provided between the mixed layer and the innermost layer.

Assuming that the thickness of the entire outer shell 12 is T1, and the thickness of the mixed layer is T2, T2 / T1 is, for example, 0.1 to 1, and specifically, for example, 0.1, 0.2, 0.. 3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 and may be in the range between any two of the numerical values exemplified here. Assuming that the thickness of the innermost layer is T3, T3 / T1 is, for example, 0.05 to 0.5, and specifically, for example, 0.05, 0.1, 0.15, 0.2, 0. 25, 0.3, 0.35, 0.4, 0.45, 0.5, and may be in the range between any two of the numerical values exemplified here. T2 / T3 is, for example, 0.5 to 10, and specifically, for example, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, even within the range between any two of the numerical values exemplified here Good.

The inner bag 14 includes an EVOH layer provided on the container outer surface side, an inner surface layer provided on the container inner surface side of the EVOH layer, and an adhesive layer provided between the EVOH layer and the inner surface layer. By providing the EVOH layer, the gas barrier properties and the removability from the outer shell 12 can be improved. The adhesive layer may be omitted.

The EVOH layer is a layer composed 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 is easily reduced as the ethylene content is smaller, so 25 mol% or more is preferable.

The inner layer is a layer in contact with the contents, and is made of, for example, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, cycloolefin polymer, EVOH and a mixture thereof .

The adhesive layer is a layer having a function of adhering the EVOH layer to the inner surface layer, 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-mentioned polyolefin, or ethylene acetate It is a vinyl copolymer (EVA). An example of the adhesive layer is low density polyethylene or a mixture of linear low density polyethylene and acid-modified polyethylene.

2. Second Embodiment A peeling container 1 according to a second embodiment of the present invention will be described with reference to FIGS. 4 to 5. The container main body 3 of the layered peeling container 1 of the present embodiment has the same layer configuration as that of the first embodiment, but the shape of the bottom surface 29 is different.

The shape of the bottom surface of this embodiment is the same as that of Patent Document 1, and the radius of curvature of the edge 29 d of the groove 29 c is 3 mm. When the radius of the outer edge 29g of the ground contact area 29f is R1 and the radius of the outer periphery of the container body 3 is R2, R1 / R2 is 0.72.

Also in the container of the present embodiment, by providing the mixed layer on the outer shell 12, the container is less likely to be damaged when dropped at a low temperature, but the radius of curvature of the edge 29d is less than 4 mm, and R1 / R2 is 0.75. Because of being less than, the container may be more likely to be damaged when dropped at a lower temperature than in the first embodiment.

3. Third Embodiment A delamination container 1 according to a third embodiment of the present invention will be described with reference to FIG. The container main body 3 of the layered peeling container 1 of the present embodiment has the same layer configuration and bottom shape as the first embodiment, but the shape of the housing portion 7 is different. Also in the container having the shape as in this embodiment, the same function and effect as the first embodiment can be obtained.

[Test Example 1]
1. Preparation of sample Outer shell [mixed layer (15.5%) / repro layer (58.0%) / innermost layer (10.0%)] / inner bag [EVOH layer (5.5%) in order from the outside of the container A container body 3 having a layer structure constituted of: / adhesive layer (4.5%) / inner surface layer (6.5%) was produced by blow molding. The numbers in parenthesis in the layer construction indicate the ratio of the thickness of each layer to the total wall thickness of the container. The wall thickness of the container was about 0.7 mm. The container main body 3 has the shape shown in the first embodiment, and the container 7 has a diameter of 50 mm. An outside air introduction hole 15 was formed in the outer shell 12 of the container body 3 and the inner bag 14 was preliminarily peeled from the outer shell 12 to prepare a sample.

The following were used as resin which comprises each layer.
<Mixed layer of outer shell>
A mixed resin containing 83.7% by mass, 9.3% by mass, and 7% by mass of the following random polypropylene, linear low density polyethylene, and polyethylene-based elastomer, respectively.
Random polypropylene (density: 0.890 g / cm ³ , MFR (230 ° C., 2.16 kg): 1.20 g / 10 min, melting point: 135 ° C.)
Polyethylene elastomer (Comonomer: 1-butene, density: 0.860 g / cm ³ , MFR (190 ° C., 2.16 kg): 0.50 g / 10 min, melting point: 50 ° C.)
Linear low density polyethylene (density: 0.898 g / cm ³ , MFR (190 ° C., 2.16 kg): 2.00 g / 10 min, melting point: 94 ° C.)

<Repro layer of outer shell>
Resin obtained by recycling burrs when molding containers

<The innermost layer of the outer shell>
A mixed resin (containing 0.35% by mass of oleic acid amide) containing 90.7% by mass and 9.3% by mass of the above-mentioned random polypropylene and linear low density polyethylene, respectively.

<EVOH layer of inner bag>
EVOH (Model: Soarnol SF7503B, Nippon Synthetic Chemical Industry Co., Ltd.)

<Adhesive layer of inner bag>
Acid-modified polyolefin (Model: Modic L522, manufactured by Mitsubishi Chemical Corporation)

<The innermost layer of the inner bag>
Low density polyethylene (Model: Suntec-LD, grade: F2206, manufactured by Asahi Kasei Corporation)

2. Cold Drop Test A container body 3 was filled with a saline solution having a specific gravity of 1.16 g / ml, and five samples were prepared. For each sample, vertical falling and horizontal falling were alternately repeated 5 times against a concrete floor from a height of 1 m in a 5 ° C. environment. If a crack was found in the container along the way, the drop test for that sample was ended at that point. In the case of vertical drop, the container cap was dropped with the top and bottom facing down. In side-to-side falling, the container was turned sideways and dropped with the pinch-off portion directed vertically.
In Test Example 1, no cracks were observed in the container in five drop tests for all the samples.

[Test Example 2]
1. Preparation of Sample A sample was prepared in the same manner as in Test Example 1. However, the layer configuration is, in order from the outside of the container, outer shell [outer layer (15.0%) / repro layer (57.0%) / innermost layer (10.0%)] / inner bag [EVOH layer (6. 0%) / adhesive layer (5.0%) / inner layer (7.0%)].

The following were used as resin which comprises each layer. The outer repro layer and the inner bag were made of the same resin as in Test Example 1.
<The outermost layer of the outer shell>
A mixed resin containing 85% by mass and 15% by mass of the above random polypropylene and linear low density polyethylene, respectively.

<The innermost layer of the outer shell>
The above-mentioned random polypropylene (containing 0.35% by mass of oleic acid amide).

2. Low Temperature Drop Test A low temperature drop test was conducted in the same manner as in Test Example 1. In each of the five samples, cracks were observed in the first longitudinal fall, the third longitudinal fall, the third longitudinal fall, the third transverse fall, and the fourth longitudinal fall.

[Test Example 3]
1. Preparation of Sample A sample was prepared in the same manner as in Test Example 1. However, the layer configuration is, in order from the outside of the container, outer shell [outer layer (15.5%) / repro layer (59.0%) / innermost layer (10.5%)] / inner bag [EVOH layer (5. 0%) / adhesive layer (4.5%) / inner layer (5.5%)].

The outermost layer of the shell was composed of the above low density polyethylene. The outer repro layer, the innermost layer and the inner bag were made of the same resin as in Test Example 2.

2. Low Temperature Drop Test A low temperature drop test was conducted in the same manner as in Test Example 1. In the two samples, cracks were observed in the third and fourth lateral drops, respectively. The three samples did not show any cracks even after five drop tests.

[Test Example 4]
1. Sample Preparation A sample having the bottom shape shown in the second embodiment was prepared in the same layer configuration and method as in Test Example 2.

2. Low Temperature Drop Test A low temperature drop test was conducted in the same manner as in Test Example 1. In each of the five samples, cracks were observed in the first longitudinal fall, the first longitudinal fall, the first longitudinal fall, the first transverse fall, and the first transverse fall.

[Discussion]
In Test Example 1, no cracks were observed in all the samples, and it was demonstrated that the structure of the present invention suppresses breakage at a low temperature drop. Comparison of Test Example 2 and Test Example 4 demonstrates that the bottom surface shaped container shown in the first embodiment suppresses breakage at a low temperature drop more than the bottom surface shaped container shown in the second embodiment. .

1: laminated peeling container, 3: container body, 5: valve member, 5a: shaft portion, 5b: locking portion, 5c: lid portion, 5d: flow passage, 7: storage portion, 7a: recessed portion, 9: mouth portion , 9d: engaging portion, 12: outer shell, 14: inner bag, 15: outside air introducing hole, 21: intermediate space, 27: pinch-off portion, 29: bottom surface, 29a: concave region, 29b: peripheral region, 29c: groove , 29d: edge, 29e: circle, 29f: contact area, 29g: outer edge, S: external space

Claims

A laminated peeling container comprising: a container body having an outer shell and an inner bag, and the inner bag shrinks as the content decreases.
The exfoliation container, wherein the outer shell has a mixed layer containing polypropylene and a polyethylene-based elastomer.
The outer shell comprises an innermost layer facing the inner bag,
The lamination peeling container of Claim 1 in which the mass ratio of the polyethylene-type elastomer in the resin component contained in the said innermost layer is lower than the mass ratio of the polyethylene-type elastomer in the resin component contained in the said mixed layer.
The laminate peeling container according to claim 1 or 2, wherein the proportion of the polyethylene-based elastomer in the resin component contained in the mixed layer is 1 to 20% by mass.
The laminated peeling container according to any one of claims 1 to 3, wherein the mixed layer further comprises linear low density polyethylene.