WO2021024984A1 - Delamination container - Google Patents

Delamination container Download PDF

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Publication number
WO2021024984A1
WO2021024984A1 PCT/JP2020/029671 JP2020029671W WO2021024984A1 WO 2021024984 A1 WO2021024984 A1 WO 2021024984A1 JP 2020029671 W JP2020029671 W JP 2020029671W WO 2021024984 A1 WO2021024984 A1 WO 2021024984A1
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WIPO (PCT)
Prior art keywords
container
inner bag
contents
particles
content
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PCT/JP2020/029671
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French (fr)
Japanese (ja)
Inventor
達郎 青木
敬能 細谷
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キョーラク株式会社
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Publication of WO2021024984A1 publication Critical patent/WO2021024984A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents

Definitions

  • the present invention relates to a laminated stripping container.
  • Patent Document 1 a laminated peeling container having an outer shell and an inner bag and having a container body in which the inner bag shrinks as the contents decrease is known (for example, Patent Document 1).
  • Patent Document 1 In a container such as Patent Document 1, it is desired that the contents can be used up to the end, but it is difficult to completely discharge the contents, and a certain amount of the contents remains.
  • the present invention has been made in view of such circumstances, and provides a laminated peeling container capable of reducing the residual amount of contents.
  • the present invention is a laminated peeling container having an outer shell and an inner bag and having a container body in which the inner bag shrinks as the contents decrease, and the inner bag is in contact with the contents.
  • a laminated peeling container provided with an innermost layer, the innermost layer being composed of a base resin and a resin composition containing filled particles, and having an uneven shape due to the presence of the filled particles on the inner surface of the innermost layer. Is provided.
  • the inner surface of the innermost layer is provided with an uneven shape, the friction between the inner surface of the innermost layer and the contents is reduced and the sliding property is improved. Therefore, the contents are smoothly discharged, and the residual amount of the contents is reduced.
  • the laminated stripping container described above wherein at least a part of the filled particles is exposed from the inner surface of the innermost layer.
  • the laminated stripping container described above, wherein the resin composition is a laminated stripping container having a content of the packed particles of 15 to 50% by mass.
  • the laminated stripping container is the above-mentioned laminated stripping container, in which the filling particles are made of an acrylic resin.
  • the base resin is a polyolefin, which is a laminated peeling container.
  • it is the laminated peeling container described above, wherein the liquid repellent is attached to the surface of the uneven shape.
  • FIG. 5 is a layer configuration diagram of an inner bag 14 in a state where the liquid repellent 8 is attached to the surface of the uneven shape 2c. It is a cross-sectional view of the same cross section as FIG. 2 in a state where the laminated peeling container 1 is tilted before the discharge of the content 18 is started. It is a cross-sectional view of the same cross section as FIG. 2 in a state where the laminated peeling container 1 is tilted at a time point after almost all of the contents 18 are discharged. It is a front view of the laminated peeling container 1 of the 2nd Embodiment of this invention.
  • the laminated peeling container 1 of the first embodiment of the present invention is a squeeze type and includes a container body 1a, a cap 16, and a valve member 17.
  • the container body 1a includes a housing portion 7 and a mouth portion 9.
  • the mouth portion 9 includes an engaging portion 9d to which the cap 16 can be attached.
  • the engaging portion 9d is a male screw portion in the case of a screw type cap, and is an annular protrusion protruding in the circumferential direction in the case of a stopper type cap.
  • the mouth portion 9 is provided so as to extend from the upper end 7b of the accommodating portion 7.
  • the mouth portion 9 has a cylindrical shape.
  • the accommodating portion 7 has a larger outer diameter than the mouth portion 9 (in the present specification, the “outer diameter” means the circumscribed circle diameter when the cross section is not circular).
  • the container body 1a has an outer shell 12 and an inner bag 14.
  • the inner bag 14 is arranged inside the outer shell 12.
  • the inner bag 14 is filled with the contents 18, and as the contents 18 decrease, the inner bag 14 contracts away from the outer shell 12.
  • the inner bag 14 usually contains about 1 to 10% of air 19 with respect to the capacity of the inner bag 14.
  • the air 19 is included in a so-called head space provided in the vicinity of the cap 16.
  • the outer shell 12 of the container body 1a is provided with an outside air introduction portion 15.
  • the outside air introduction portion 15 is a hole for introducing outside air into the intermediate space between the outer shell 12 and the inner bag 14.
  • the outside air introduction portion 15 can be equipped with a valve member 17 for adjusting the inflow and outflow of air into the intermediate space between the outer shell 12 and the inner bag 14.
  • the outside air introduction portion 15 is provided in the recess 7e provided in the accommodating portion 7.
  • the cap 16 includes a check valve 16a and a discharge port 16b.
  • the check valve 16a has a function of preventing air from entering the inner bag 14 from the outside while enabling the discharge of the content 18.
  • the content 18 is discharged through the discharge port 16b.
  • the outer shell 12 is formed thicker than the inner bag 14 so as to have high resilience.
  • the outer shell 12 is composed of, for example, polyolefins such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, ethylene-propylene copolymer and a mixture thereof.
  • the outer shell 12 may have a plurality of layers.
  • FIG. 3 is an example of the layer structure of the inner bag 14, and includes the innermost layer 2, the intermediate layer 3, the adhesive resin layer 4, and the barrier layer 5 in this order from the inner surface side of the inner bag 14.
  • the layer structure of the inner bag 14 may omit at least one of these layers, or may include yet another layer.
  • each layer will be described.
  • the barrier layer 5 is made of a resin having a high gas barrier property. Examples of such a resin include ethylene vinyl alcohol copolymer (EVOH: ethylene vinyl acetate copolymer saponified product and the like), aromatic polyamide and the like.
  • the intermediate layer 3 is composed of a resin composition containing a thermoplastic resin such as polyolefin.
  • the intermediate layer 3 can be omitted.
  • the intermediate layer 3 may be a repro layer obtained by recycling burrs generated during blow molding of the container 1.
  • the adhesive resin layer 4 is made of an adhesive resin.
  • the adhesive resin include acid-modified polyolefin resins (eg, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene) and the like.
  • the innermost layer 2 is a layer that comes into contact with the contents, and is composed of a resin composition containing a base resin 2a and packed particles 2b.
  • the inner surface of the innermost layer 2 (that is, the inner surface of the container 1) is provided with an uneven shape 2c due to the presence of the filled particles 2b. Since the uneven shape 2c is provided on the inner surface of the innermost layer 2, friction between the inner surface of the innermost layer 2 and the contents is reduced, and the sliding property is improved.
  • the uneven shape 2c preferably has a ten-point average roughness Rz of about 7 to 500 ⁇ m, more preferably 10 to 300 ⁇ m, and most preferably 10 to 100 ⁇ m. By setting within this range, the sliding property can be particularly improved.
  • the ten-point average roughness Rz is defined by JIS B0601 (-1982).
  • the base resin 2a is preferably a thermoplastic resin such as polyolefin.
  • the polyolefin include polyethylene and polypropylene.
  • the packed particles 2b are particles capable of imparting an uneven shape 2c, and packed particles containing at least one of an organic component and an inorganic component can be adopted.
  • the inorganic component examples include 1) metals such as aluminum, copper, iron, titanium, silver and calcium or alloys or intermetal compounds containing these, and 2) silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, iron oxide and the like. Oxides, 3) inorganic acid salts or organic acid salts such as calcium phosphate and calcium stearate, 4) glass, 5) ceramics such as aluminum nitride, boron nitride, silicon carbide and silicon nitride can be preferably used.
  • organic component examples include acrylic resin, urethane resin, melamine resin, amino resin, epoxy resin, polyethylene resin, polystyrene resin, polypropylene resin, polyester resin, cellulose resin, vinyl chloride resin, and polyvinyl.
  • Organic polymer components such as alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, polyacrylonitrile, and polyamide can be preferably used.
  • the filling particles 2b are acrylic resins. This is because the acrylic resin has high transparency, and the transparency is unlikely to decrease due to the addition of the filling particles 2b.
  • Tb—Ta is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and more preferably 50 ° C. or higher. More preferred. This is because if the packed particles 2b are melted when the container 1 is heated to melt the base resin 2a during production by blow molding, it becomes difficult to form the uneven shape 2c.
  • the shape of the packed particles 2b is not limited, and may be, for example, spherical, spheroidal, indefinite, teardrop-shaped, flat, hollow, porous, or the like.
  • the filled particles 2b may be buried in the base resin 2a, but it is preferable that at least a part of the filled particles 2b is exposed from the inner surface of the innermost layer 2. In this case, the uneven shape 2c is likely to be formed. Further, when the packed particles 2b have a property of being more excellent in sliding property than the base resin 2a, the sliding property can be further improved by exposing the packed particles 2b from the inner surface of the innermost layer 2. ..
  • the content of the packed particles 2b in the resin composition is preferably 15 to 50% by mass, more preferably 20 to 40% by mass. Specifically, this content is, for example, 15, 20, 25, 30, 35, 40, 45, 50% by mass, and may be within the range between any two of the numerical values exemplified here. .. If the content of the packed particles 2b is too small, the uneven shape 2c becomes insufficient, and if the content of the packed particles 2b is too large, the packed particles 2b are likely to fall off from the innermost layer 2.
  • a lubricant may be added to the resin composition constituting the innermost layer 2 in order to further improve the sliding property.
  • liquid repellent 8 As shown in FIG. 4, it is preferable that the liquid repellent 8 is attached to the surface of the uneven shape 2c.
  • the liquid repellent 8 is a substance having at least one (preferably both) of water repellency and oil repellency, and may be liquid or particulate. The sliding property can be further improved by adhering the liquid repellent 8 to the surface of the uneven shape 2c.
  • Examples of the liquid repellent having water repellency include hydrophobic oxide fine particles.
  • the average diameter of the primary particles of the hydrophobic oxide fine particles is usually 3 to 100 nm, preferably 5 to 50 nm, and more preferably 5 to 20 nm.
  • the hydrophobic oxide fine particles are in an appropriate aggregated state, and a gas such as air can be retained in the voids in the aggregate, resulting in excellent sliding property. be able to. That is, since this agglutinated state is maintained even after adhering to the surface of the uneven shape 2c, excellent sliding property can be exhibited.
  • the measurement of the average diameter of the primary particles can be carried out with a scanning electron microscope (FE-SEM), and when the resolution of the scanning electron microscope is low, other electrons such as a transmission electron microscope are used. It may be carried out in combination with an electron microscope. Specifically, when the particle shape is spherical, the diameter is regarded as the diameter, and when the particle shape is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the diameter, and 20 particles arbitrarily selected by observation with a scanning electron microscope or the like are considered. Let the average of the particle diameters of the above be the primary particle average diameter.
  • the hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be made hydrophobic by surface treatment.
  • the type of oxide is also not limited as long as it has hydrophobicity.
  • at least one of silica (silicon dioxide), alumina, titania and the like can be used.
  • the amount of hydrophobic oxide fine particles attached to the container body is not limited, but is usually preferably 0.01 to 10 g / m 2 and 0.2 to 1.5 g / m 2. It is more preferable, and 0.3 to 1 g / m 2 is most preferable. By setting it within the above range, more excellent sliding property can be obtained for a long period of time, and it is more advantageous in terms of suppression of falling off of hydrophobic oxide fine particles, cost and the like.
  • liquid repellent having water repellency and oil repellency examples include fluorine compounds.
  • fluorine-based compound examples include polyfluoroalkyl methacrylate resins.
  • the container body 1a can be formed by, for example, direct blow molding.
  • the container body 1a is a pair of split molds in which a molten tubular laminated parison extruded from an extrusion head is formed. It can be formed by blow molding using.
  • the laminated parison includes an outer layer and an inner layer corresponding to the outer shell 12 and the inner bag 14. The bottom of the container body 1a is closed at the sealing portion formed by welding the opposing surfaces of the laminated parison.
  • the laminated parison can be formed by coextrusion molding, multi-layer injection molding, etc.
  • the innermost layer of the laminated parison is formed of a resin composition (that is, a resin composition containing a base resin 2a and packed particles 2b) constituting the innermost layer 2 of the inner bag 14.
  • the liquid repellent 8 is sprayed as it is or in a state of being dispersed or dissolved in a medium (dispersion medium or solvent) to form an uneven shape 2c due to the presence of the filling particles 2b.
  • the liquid repellent 8 can be attached to the surface.
  • a drying step may be performed as appropriate.
  • the facing surfaces of the inner bag 14 are in a state of being substantially in contact with each other.
  • the air 19 remains in the inner bag 14, when the outer shell 12 is compressed, the facing surfaces of the inner bag 14 are separated from each other by the air 19, and a path for the contents 18 is formed.
  • the content 18 is easily moved toward the cap 16, and the content 18 is easily pushed out by the air 19. Therefore, the residual amount of the content 18 is reduced.
  • the air 19 does not remain in the inner bag 14 after almost the entire amount of the contents 18 in the inner bag 14 is discharged, the contents 18 are difficult to be discharged and the residual amount of the contents 18 is reduced. More.
  • the container 1 of the present embodiment has excellent sliding property of the content 18, when the container 1 is tilted as shown in FIG. 5, the content 18 quickly moves toward the cap 16. Therefore, it is difficult for the air 19 to be discharged, and the air 19 tends to remain in the inner bag 14 at a time after almost the entire amount of the contents 18 in the inner bag 14 is discharged, and the contents 18 remain. The amount is reduced.
  • the content 18 is a viscous material such as ketchup, mayonnaise, glycerin, sauce, or honey
  • the moving speed of the content 18 when the container 1 is tilted is low, and thus the significance of applying it to the present invention. Is particularly large.
  • the viscosity of the content 18 is preferably 0.1 Pa ⁇ s or more, for example, 0.1 to 15 Pa ⁇ s, and specifically, for example, for example, 0.1, 0.3, 0. It is 5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 Pa ⁇ s, and is within the range between any two of the numerical values exemplified here. It may be. Viscosity is measured at 25 ° C. in accordance with JIS Z8803.
  • the laminated peeling container 1 of the present embodiment is a pump type and includes a container body 1a and a pump 23.
  • the structure of the container body 1a is the same as that of the first embodiment except that the recess 7e is not provided and the outside air introduction portion 15 is provided at the bottom portion 1b of the container 1a.
  • the pump 23 is attached to the mouth portion 9.
  • the pump 23 includes a liquid guide tube 23a and a discharge port 23b that are inserted into the container body 1a.
  • the pump 23 has a built-in pump mechanism, and the contents 18 sucked up through the liquid guide pipe 23a can be discharged from the discharge port 23b by the action of the pump mechanism.
  • the outside air introduction portion 15 is a gap provided between the outer shell 12 and the inner bag 14 in the seal portion of the bottom portion 1b. With the discharge of the content 18, the outside air is introduced between the outer shell 12 and the inner bag 14 through the outside air introduction hole 15, and the inner bag 14 contracts.
  • the outside air introduction hole 15 may be a hole provided in the outer shell 12 as in the first embodiment.
  • the content 18 near the bottom 1b of the container 1 is sucked up. Therefore, the better the sliding property of the content 18, the easier it is to suck up the content 18, and the content 18 remains. The amount is reduced. Since the container 1 of the present embodiment has excellent sliding property of the content 18, the content 18 quickly moves toward the bottom 1b of the container 1, so that the residual amount of the content 18 is small.
  • a container 1 having a capacity of 200 cc and having the shape shown in FIG. 1 was produced by direct blow molding of a parison.
  • the innermost layer of the parison was formed of a resin composition containing a base resin 2a and packed particles 2b.
  • the base resin 2a is polyethylene (melting point 112 ° C.)
  • the packed particles 2b are acrylic resin (melting point 230 ° C.).
  • the content of the packed particles in the resin composition was 20% by mass.
  • the wall thicknesses of the outer shell 12 and the inner bag 14 at the center in the height direction of the container 1 were 0.58 mm and 0.14 mm, respectively.
  • Example 1 and Comparative Example 1 After filling the containers of Example 1 and Comparative Example 1 with the contents shown in Table 1, a cap with a check valve was attached, and the contents were discharged with the cap facing diagonally downward. The contents were repeatedly discharged until the contents were no longer discharged. The residual amount of the contents was measured after the contents were not discharged. A discharge test was performed on each of Example 1 and Comparative Example 1 using three samples (Nos. 1 to 3). The results are shown in Table 1.
  • a container 1 having a shape shown in FIG. 7 and having a capacity of 100 cc was produced by direct blow molding of a parison.
  • the innermost layer of the parison was formed of a resin composition containing a base resin 2a and packed particles 2b.
  • the base resin 2a is polyethylene (melting point 112 ° C.)
  • the packed particles 2b are acrylic resin (melting point 230 ° C.).
  • the content of the packed particles in the resin composition was 20% by mass.
  • the wall thicknesses of the outer shell 12 and the inner bag 14 at the center in the height direction of the container 1 were 0.59 mm and 0.17 mm, respectively.
  • Example 2 and Comparative Example 2 After filling the containers of Example 2 and Comparative Example 2 with the contents shown in Table 1, a pump was attached and the contents were discharged by the pump. The contents were repeatedly discharged until the contents were no longer discharged. The residual amount of the contents was measured after the contents were not discharged. A discharge test was performed on each of Example 2 and Comparative Example 2 using three samples (Nos. 1 to 3). The results are shown in Table 1.
  • Table 1 The details of the contents in Table 1 are as follows.
  • the viscosity value was measured at 25 ° C. with a tuning fork type vibration viscometer "SV10" manufactured by A & D Co., Ltd. in accordance with JIS Z8803.
  • Glycerin Japanese Pharmacopoeia Glycerin (glycerin content 84.0-87.0%) Viscosity 0.13 Pa ⁇ s
  • Source Otafuku Sauce of your choice Viscosity 0.84 Pa ⁇ s
  • Honey TOPVALUE Pure honey Viscosity 11Pa ⁇ s
  • 1 Laminated peeling container, 1a: Container body, 1b: Bottom, 2: Innermost layer, 2a: Base resin, 2b: Filled particles, 2c: Concavo-convex shape, 3: Intermediate layer, 4: Adhesive resin layer, 5: Barrier Layer, 7: Containment part, 7b: Upper end, 7e: Recessed part, 8: Liquid repellent, 9: Mouth part, 9d: Engaging part, 12: Outer shell, 14: Inner bag, 15: Outside air introduction part, 16: Cap , 16a: Check valve, 16b: Discharge port, 17: Valve member, 18: Contents, 19: Air, 23: Pump, 23a: Liquid guide tube, 23b: Discharge port

Abstract

Provided is a delamination container capable of reducing a remaining amount of a content. According to the present invention, there is provided a delamination container provided with a container body that has an outer shell and an inner bag and in which the inner bag contracts with a reduction in a content, wherein the inner bag is provided with an innermost layer that contacts the content, the innermost layer is made of a resin composition containing a base material resin and filling particles, and an inner surface of the innermost layer has an irregularity shape resulting from the existence of the filling particles.

Description

積層剥離容器Laminate peeling container
　本発明は、積層剥離容器に関する。 The present invention relates to a laminated stripping container.
　従来、外殻と内袋とを有し且つ内容物の減少に伴って内袋が収縮する容器本体を備える積層剥離容器が知られている（例えば、特許文献１）。 Conventionally, a laminated peeling container having an outer shell and an inner bag and having a container body in which the inner bag shrinks as the contents decrease is known (for example, Patent Document 1).
特開２０１５－２２７２０６号公報JP-A-2015-227206
　特許文献１のような容器では、内容物が最後まで使い切ることができることが望まれているが、内容物が完全に吐出させることは困難であり、ある程度の量の内容物が残留してしまう。 In a container such as Patent Document 1, it is desired that the contents can be used up to the end, but it is difficult to completely discharge the contents, and a certain amount of the contents remains.
　本発明はこのような事情に鑑みてなされたものであり、内容物の残留量を低減させることができる積層剥離容器を提供するものである。 The present invention has been made in view of such circumstances, and provides a laminated peeling container capable of reducing the residual amount of contents.
　本発明によれば、外殻と内袋とを有し且つ内容物の減少に伴って前記内袋が収縮する容器本体を備える積層剥離容器であって、前記内袋は、前記内容物と接する最内層を備え、前記最内層は、基材樹脂と充填粒子を含む樹脂組成物で構成され、前記最内層の内面に前記充填粒子の存在に起因する凹凸形状が設けられている、積層剥離容器が提供される。 According to the present invention, it is a laminated peeling container having an outer shell and an inner bag and having a container body in which the inner bag shrinks as the contents decrease, and the inner bag is in contact with the contents. A laminated peeling container provided with an innermost layer, the innermost layer being composed of a base resin and a resin composition containing filled particles, and having an uneven shape due to the presence of the filled particles on the inner surface of the innermost layer. Is provided.
　本発明の構成では、最内層の内面に凹凸形状が設けられているので、最内層の内面と内容物の摩擦が低減されて滑落性が向上する。このため、内容物がスムーズに吐出されて、内容物の残留量が低減される。 In the configuration of the present invention, since the inner surface of the innermost layer is provided with an uneven shape, the friction between the inner surface of the innermost layer and the contents is reduced and the sliding property is improved. Therefore, the contents are smoothly discharged, and the residual amount of the contents is reduced.
　以下、本発明の種々の実施形態を例示する。以下に示す実施形態は互いに組み合わせ可能である。
　好ましくは、前記記載の積層剥離容器であって、前記充填粒子の少なくとも一部が前記最内層の内面から露出している、積層剥離容器である。
　好ましくは、前記記載の積層剥離容器であって、前記樹脂組成物は、前記充填粒子の含有量が１５～５０質量％である、積層剥離容器である。
　好ましくは、前記記載の積層剥離容器であって、前記充填粒子は、アクリル系樹脂で構成されている、積層剥離容器である。
　好ましくは、前記記載の積層剥離容器であって、前記基材樹脂は、ポリオレフィンである、積層剥離容器である。
　好ましくは、前記記載の積層剥離容器であって、前記凹凸形状の表面に撥液剤が付着している、積層剥離容器である。 Hereinafter, various embodiments of the present invention will be illustrated. The embodiments shown below can be combined with each other.
Preferably, it is the laminated stripping container described above, wherein at least a part of the filled particles is exposed from the inner surface of the innermost layer.
Preferably, the laminated stripping container described above, wherein the resin composition is a laminated stripping container having a content of the packed particles of 15 to 50% by mass.
Preferably, the laminated stripping container is the above-mentioned laminated stripping container, in which the filling particles are made of an acrylic resin.
Preferably, it is the laminated peeling container described above, and the base resin is a polyolefin, which is a laminated peeling container.
Preferably, it is the laminated peeling container described above, wherein the liquid repellent is attached to the surface of the uneven shape.
本発明の第１実施形態の積層剥離容器１の正面図である。It is a front view of the laminated peeling container 1 of 1st Embodiment of this invention. 図１中のキャップ１６の蓋を開いた状態でのＡ－Ａ断面図である。It is sectional drawing of AA in the state which the lid of the cap 16 in FIG. 1 is opened. 内袋１４の層構成図である。It is a layer block diagram of the inner bag 14. 凹凸形状２ｃの表面に撥液剤８が付着した状態の内袋１４の層構成図である。FIG. 5 is a layer configuration diagram of an inner bag 14 in a state where the liquid repellent 8 is attached to the surface of the uneven shape 2c. 内容物１８の吐出開始前の時点で、積層剥離容器１を傾けた状態の図２と同じ断面の断面図である。It is a cross-sectional view of the same cross section as FIG. 2 in a state where the laminated peeling container 1 is tilted before the discharge of the content 18 is started. 内容物１８のほぼ全量が吐出された後の時点で、積層剥離容器１を傾けた状態の図２と同じ断面の断面図である。It is a cross-sectional view of the same cross section as FIG. 2 in a state where the laminated peeling container 1 is tilted at a time point after almost all of the contents 18 are discharged. 本発明の第２実施形態の積層剥離容器１の正面図である。It is a front view of the laminated peeling container 1 of the 2nd Embodiment of this invention.
　以下、本発明の実施形態について説明する。以下に示す実施形態中で示した各種特徴事項は、互いに組み合わせ可能である。また、各特徴事項について独立して発明が成立する。 Hereinafter, embodiments of the present invention will be described. The various features shown in the embodiments shown below can be combined with each other. In addition, the invention is independently established for each feature.
１．第１実施形態
１－１．積層剥離容器１の構成
　図１に示すように、本発明の第１実施形態の積層剥離容器１は、スクイズ式であり、容器本体１ａと、キャップ１６と、弁部材１７を備える。 1. 1. First Embodiment 1-1. Configuration of Laminated Peeling Container 1 As shown in FIG. 1, the laminated peeling container 1 of the first embodiment of the present invention is a squeeze type and includes a container body 1a, a cap 16, and a valve member 17.
　図２に示すように、容器本体１ａは、収容部７と、口部９を備える。口部９は、キャップ１６を装着可能な係合部９ｄを備える。係合部９ｄは、ネジ式キャップの場合は雄ねじ部であり、打栓式キャップの場合は周方向に突出する環状突起である。口部９は、収容部７の上端７ｂから延びるように設けられている。口部９は、円筒形である。収容部７は、口部９よりも外径（本明細書において、「外径」は、断面が円形でない場合は、外接円径を意味する。）が大きい。 As shown in FIG. 2, the container body 1a includes a housing portion 7 and a mouth portion 9. The mouth portion 9 includes an engaging portion 9d to which the cap 16 can be attached. The engaging portion 9d is a male screw portion in the case of a screw type cap, and is an annular protrusion protruding in the circumferential direction in the case of a stopper type cap. The mouth portion 9 is provided so as to extend from the upper end 7b of the accommodating portion 7. The mouth portion 9 has a cylindrical shape. The accommodating portion 7 has a larger outer diameter than the mouth portion 9 (in the present specification, the “outer diameter” means the circumscribed circle diameter when the cross section is not circular).
　図２に示すように、容器本体１ａは、外殻１２と内袋１４とを有する。内袋１４は、外殻１２の内側に配置されている。内袋１４内には、内容物１８が充填されており、内容物１８の減少に伴って内袋１４が外殻１２から離れて収縮する。このような容器では、内袋１４内に外気が侵入しにくいので、内容物の劣化が抑制される。内袋１４内には、通常、内袋１４の容量に対して１～１０％程度のエアー１９が含まれる。エアー１９は、キャップ１６近傍に設けられた、いわゆるヘッドスペースに含まれる。 As shown in FIG. 2, the container body 1a has an outer shell 12 and an inner bag 14. The inner bag 14 is arranged inside the outer shell 12. The inner bag 14 is filled with the contents 18, and as the contents 18 decrease, the inner bag 14 contracts away from the outer shell 12. In such a container, since it is difficult for outside air to enter the inner bag 14, deterioration of the contents is suppressed. The inner bag 14 usually contains about 1 to 10% of air 19 with respect to the capacity of the inner bag 14. The air 19 is included in a so-called head space provided in the vicinity of the cap 16.
　図２に示すように、容器本体１ａの外殻１２には、外気導入部１５が設けられている。外気導入部１５は、外殻１２と内袋１４の間の中間空間に外気を導入するための孔である。外気導入部１５には、外殻１２と内袋１４の間の中間空間への空気の出入りを調整するための弁部材１７を装着することができる。外気導入部１５は、収容部７に設けられた凹部７ｅ内に設けられている。 As shown in FIG. 2, the outer shell 12 of the container body 1a is provided with an outside air introduction portion 15. The outside air introduction portion 15 is a hole for introducing outside air into the intermediate space between the outer shell 12 and the inner bag 14. The outside air introduction portion 15 can be equipped with a valve member 17 for adjusting the inflow and outflow of air into the intermediate space between the outer shell 12 and the inner bag 14. The outside air introduction portion 15 is provided in the recess 7e provided in the accommodating portion 7.
　キャップ１６は、逆止弁１６ａと、吐出口１６ｂを備える。逆止弁１６ａは、内容物１８の吐出を可能にしつつ、外部から空気が内袋１４内に侵入することを防ぐ機能を有する。内容物１８は、吐出口１６ｂを通じて吐出される。 The cap 16 includes a check valve 16a and a discharge port 16b. The check valve 16a has a function of preventing air from entering the inner bag 14 from the outside while enabling the discharge of the content 18. The content 18 is discharged through the discharge port 16b.
　外殻１２は、復元性が高くなるように、内袋１４よりも肉厚に形成される。外殻１２は、例えば、低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体及びその混合物などのポリオレフィンで構成される。外殻１２は、複数層構成であってもよい。 The outer shell 12 is formed thicker than the inner bag 14 so as to have high resilience. The outer shell 12 is composed of, for example, polyolefins such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, ethylene-propylene copolymer and a mixture thereof. The outer shell 12 may have a plurality of layers.
　図３は、内袋１４の層構成の一例であり、内袋１４の内面側から順に、最内層２と、中間層３と、接着樹脂層４と、バリア層５を備える。内袋１４の層構成は、これらの層のうちの少なくとも１つを省いたものであってもよく、さらに別の層を備えるものであってもよい。以下、各層について説明する。
（バリア層５）
　バリア層５は、ガスバリア性が高い樹脂で構成される。このような樹脂としては、エチレンビニルアルコール共重合体（ＥＶＯＨ：エチレン酢酸ビニル共重合体ケン化物等を指す。）や芳香族ポリアミド等が挙げられる。バリア層５を設けることによって、酸素透過による内容物の酸化劣化を有効に抑制することができる。 FIG. 3 is an example of the layer structure of the inner bag 14, and includes the innermost layer 2, the intermediate layer 3, the adhesive resin layer 4, and the barrier layer 5 in this order from the inner surface side of the inner bag 14. The layer structure of the inner bag 14 may omit at least one of these layers, or may include yet another layer. Hereinafter, each layer will be described.
(Barrier layer 5)
The barrier layer 5 is made of a resin having a high gas barrier property. Examples of such a resin include ethylene vinyl alcohol copolymer (EVOH: ethylene vinyl acetate copolymer saponified product and the like), aromatic polyamide and the like. By providing the barrier layer 5, oxidative deterioration of the contents due to oxygen permeation can be effectively suppressed.
（中間層３）
　中間層３は、ポリオレフィン等の熱可塑性樹脂を含む樹脂組成物で構成される。中間層３は、省略可能である。中間層３は、容器１のブロー成形時にでたバリをリサイクルして使用したリプロ層であってもよい。 (Intermediate layer 3)
The intermediate layer 3 is composed of a resin composition containing a thermoplastic resin such as polyolefin. The intermediate layer 3 can be omitted. The intermediate layer 3 may be a repro layer obtained by recycling burrs generated during blow molding of the container 1.
（接着樹脂層４）
　接着樹脂層４は、接着性樹脂で構成される。接着性樹脂としては、酸変性ポリオレフィン樹脂（例：無水マレイン酸変性ポリエチレン、無水マレイン酸変性ポリプロピレン）等が挙げられる。接着樹脂層４を設けることによってバリア層５と、中間層３又は最内層２との接着性が向上する。 (Adhesive resin layer 4)
The adhesive resin layer 4 is made of an adhesive resin. Examples of the adhesive resin include acid-modified polyolefin resins (eg, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene) and the like. By providing the adhesive resin layer 4, the adhesiveness between the barrier layer 5 and the intermediate layer 3 or the innermost layer 2 is improved.
（最内層２） (Innermost layer 2)
　最内層２は、内容物と接触する層であり、基材樹脂２ａと充填粒子２ｂを含む樹脂組成物で構成される。最内層２の内面（すなわち、容器１の内面）に充填粒子２ｂの存在に起因する凹凸形状２ｃが設けられている。最内層２の内面に凹凸形状２ｃが設けられているので、最内層２の内面と内容物の摩擦が低減されて滑落性が向上する。 The innermost layer 2 is a layer that comes into contact with the contents, and is composed of a resin composition containing a base resin 2a and packed particles 2b. The inner surface of the innermost layer 2 (that is, the inner surface of the container 1) is provided with an uneven shape 2c due to the presence of the filled particles 2b. Since the uneven shape 2c is provided on the inner surface of the innermost layer 2, friction between the inner surface of the innermost layer 2 and the contents is reduced, and the sliding property is improved.
　凹凸形状２ｃは、十点平均粗さＲｚを７～５００μｍ程度とするのが好ましく、特に１０～３００μｍとするのがより好ましく、１０～１００μｍとするのが最も好ましい。この範囲内に設定することによって、滑落性を特に向上させることができる。十点平均粗さＲｚはＪＩＳ  Ｂ０６０１（－１９８２）で定義される。 The uneven shape 2c preferably has a ten-point average roughness Rz of about 7 to 500 μm, more preferably 10 to 300 μm, and most preferably 10 to 100 μm. By setting within this range, the sliding property can be particularly improved. The ten-point average roughness Rz is defined by JIS B0601 (-1982).
　基材樹脂２ａは、ポリオレフィン等の熱可塑性樹脂が好ましい。ポリオレフィンとしては、ポリエチレンやポリプロピレンが挙げられる。 The base resin 2a is preferably a thermoplastic resin such as polyolefin. Examples of the polyolefin include polyethylene and polypropylene.
　充填粒子２ｂは、凹凸形状２ｃを付与可能な粒子であり、有機成分及び無機成分の少なくとも１種を含む充填粒子を採用することができる。 The packed particles 2b are particles capable of imparting an uneven shape 2c, and packed particles containing at least one of an organic component and an inorganic component can be adopted.
　無機成分としては、例えば１）アルミニウム、銅、鉄、チタン、銀、カルシウム等の金属又はこれらを含む合金又は金属間化合物、２）酸化珪素、酸化アルミニウム、酸化ジルコニウム、酸化チタン、酸化鉄等の酸化物、３）リン酸カルシウム、ステアリン酸カルシウム等の無機酸塩又は有機酸塩、４）ガラス、５）窒化アルミニウム、窒化硼素、炭化珪素、窒化珪素等のセラミック等を好適に用いることができる。 Examples of the inorganic component include 1) metals such as aluminum, copper, iron, titanium, silver and calcium or alloys or intermetal compounds containing these, and 2) silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, iron oxide and the like. Oxides, 3) inorganic acid salts or organic acid salts such as calcium phosphate and calcium stearate, 4) glass, 5) ceramics such as aluminum nitride, boron nitride, silicon carbide and silicon nitride can be preferably used.
　有機成分としては、例えばアクリル系樹脂、ウレタン系樹脂、メラミン系樹脂、アミノ樹脂、エポキシ樹脂、ポリエチレン系樹脂、ポリスチレン系樹脂、ポリプロピレン系樹脂、ポリエステル系樹脂、セルロース系樹脂、塩化ビニル系樹脂、ポリビニルアルコール、エチレン－酢酸ビニル共重合体、エチレン－ビニルアルコール共重合体、エチレン－アクリル酸エチル共重合体、ポリアクリロニトリル、ポリアミド等の有機高分子成分（又は樹脂成分）を好適に用いることができる。 Examples of the organic component include acrylic resin, urethane resin, melamine resin, amino resin, epoxy resin, polyethylene resin, polystyrene resin, polypropylene resin, polyester resin, cellulose resin, vinyl chloride resin, and polyvinyl. Organic polymer components (or resin components) such as alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, polyacrylonitrile, and polyamide can be preferably used.
　充填粒子２ｂがアクリル系樹脂であることが好ましい。アクリル系樹脂は、透明性が高く、充填粒子２ｂの添加による透明性の低下が生じにくいからである。 It is preferable that the filling particles 2b are acrylic resins. This is because the acrylic resin has high transparency, and the transparency is unlikely to decrease due to the addition of the filling particles 2b.
　基材樹脂２ａの融点をＴａとし、充填粒子２ｂの融点Ｔｂとすると、Ｔｂ－Ｔａは、１０℃以上であることが好ましく、３０℃以上であることがさらに好ましく、５０℃以上であることがさらに好ましい。容器１をブロー成形によって製造時に基材樹脂２ａを溶融するために加熱したときに充填粒子２ｂが溶融されてしまうと、凹凸形状２ｃが形成されにくくなるからである。 Assuming that the melting point of the base resin 2a is Ta and the melting point of the packed particles 2b is Tb, Tb—Ta is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and more preferably 50 ° C. or higher. More preferred. This is because if the packed particles 2b are melted when the container 1 is heated to melt the base resin 2a during production by blow molding, it becomes difficult to form the uneven shape 2c.
　充填粒子２ｂの形状は限定的でなく、例えば球状、回転楕円体状、不定形状、涙滴状、扁平状、中空状、多孔質状等のいずれであっても良い。 The shape of the packed particles 2b is not limited, and may be, for example, spherical, spheroidal, indefinite, teardrop-shaped, flat, hollow, porous, or the like.
　充填粒子２ｂは、基材樹脂２ａに埋没している状態であってもよいが、少なくとも一部が最内層２の内面から露出していることが好ましい。この場合、凹凸形状２ｃが形成されやすいからである。また、充填粒子２ｂが基材樹脂２ａよりも滑落性に優れた性質を有するものである場合には、充填粒子２ｂを最内層２の内面から露出させることによって滑落性をさらに向上させることができる。 The filled particles 2b may be buried in the base resin 2a, but it is preferable that at least a part of the filled particles 2b is exposed from the inner surface of the innermost layer 2. In this case, the uneven shape 2c is likely to be formed. Further, when the packed particles 2b have a property of being more excellent in sliding property than the base resin 2a, the sliding property can be further improved by exposing the packed particles 2b from the inner surface of the innermost layer 2. ..
　樹脂組成物中の充填粒子２ｂの含有量は、１５～５０質量％であることが好ましく、２０～４０質量％であることがさらに好ましい。この含有量は、具体的には例えば、１５、２０、２５、３０、３５、４０、４５、５０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。充填粒子２ｂの含有量が少なすぎると凹凸形状２ｃが不十分になり、充填粒子２ｂの含有量が多すぎると、充填粒子２ｂが最内層２から脱落しやすくなる。 The content of the packed particles 2b in the resin composition is preferably 15 to 50% by mass, more preferably 20 to 40% by mass. Specifically, this content is, for example, 15, 20, 25, 30, 35, 40, 45, 50% by mass, and may be within the range between any two of the numerical values exemplified here. .. If the content of the packed particles 2b is too small, the uneven shape 2c becomes insufficient, and if the content of the packed particles 2b is too large, the packed particles 2b are likely to fall off from the innermost layer 2.
　最内層２を構成する樹脂組成物には、滑落性をさらに向上させるべく、滑剤を添加してもよい。 A lubricant may be added to the resin composition constituting the innermost layer 2 in order to further improve the sliding property.
（撥液剤）
　図４に示すように、凹凸形状２ｃの表面に、撥液剤８が付着していることが好ましい。撥液剤８は、撥水性と撥油性の少なくとも一方（好ましくは両方）を有する物質であり、液状であっても粒子状であってもよい。凹凸形状２ｃの表面に撥液剤８を付着させることによって滑落性をさらに向上させることができる。 (Liquid repellent)
As shown in FIG. 4, it is preferable that the liquid repellent 8 is attached to the surface of the uneven shape 2c. The liquid repellent 8 is a substance having at least one (preferably both) of water repellency and oil repellency, and may be liquid or particulate. The sliding property can be further improved by adhering the liquid repellent 8 to the surface of the uneven shape 2c.
　撥水性を有する撥液剤としては、疎水性酸化物微粒子が挙げられる。疎水性酸化物微粒子は、一次粒子平均径が通常３～１００ｎｍであり、好ましくは５～５０ｎｍであり、より好ましくは５～２０ｎｍである。一次粒子平均径を上記範囲とすることにより、疎水性酸化物微粒子が適度な凝集状態となり、その凝集体中にある空隙に空気等の気体を保持することができる結果、優れた滑落性を得ることができる。すなわち、この凝集状態は、凹凸形状２ｃの表面に付着した後も維持されるので、優れた滑落性を発揮することができる。 Examples of the liquid repellent having water repellency include hydrophobic oxide fine particles. The average diameter of the primary particles of the hydrophobic oxide fine particles is usually 3 to 100 nm, preferably 5 to 50 nm, and more preferably 5 to 20 nm. By setting the average diameter of the primary particles in the above range, the hydrophobic oxide fine particles are in an appropriate aggregated state, and a gas such as air can be retained in the voids in the aggregate, resulting in excellent sliding property. be able to. That is, since this agglutinated state is maintained even after adhering to the surface of the uneven shape 2c, excellent sliding property can be exhibited.
　なお、本発明において、一次粒子平均径の測定は、走査型電子顕微鏡（ＦＥ－ＳＥＭ）で実施することができ、走査型電子顕微鏡の分解能が低い場合には透過型電子顕微鏡等の他の電子顕微鏡を併用して実施しても良い。具体的には、粒子形状が球状の場合はその直径、非球状の場合はその最長径と最短径との平均値を直径とみなし、走査型電子顕微鏡等による観察により任意に選んだ２０個分の粒子の直径の平均を一次粒子平均径とする。 In the present invention, the measurement of the average diameter of the primary particles can be carried out with a scanning electron microscope (FE-SEM), and when the resolution of the scanning electron microscope is low, other electrons such as a transmission electron microscope are used. It may be carried out in combination with an electron microscope. Specifically, when the particle shape is spherical, the diameter is regarded as the diameter, and when the particle shape is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the diameter, and 20 particles arbitrarily selected by observation with a scanning electron microscope or the like are considered. Let the average of the particle diameters of the above be the primary particle average diameter.
　疎水性酸化物微粒子としては、疎水性を有するものであれば特に限定されず、表面処理により疎水化されたものであっても良い。例えば、親水性酸化物微粒子をシランカップリング剤等で表面処理を施し、表面状態を疎水性とした微粒子を用いることもできる。酸化物の種類も、疎水性を有するものであれば限定されない。例えばシリカ（二酸化ケイ素）、アルミナ、チタニア等の少なくとも１種を用いることができる。 The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be made hydrophobic by surface treatment. For example, it is also possible to use fine particles in which hydrophilic oxide fine particles are surface-treated with a silane coupling agent or the like to make the surface state hydrophobic. The type of oxide is also not limited as long as it has hydrophobicity. For example, at least one of silica (silicon dioxide), alumina, titania and the like can be used.
　容器本体に付着させる疎水性酸化物微粒子の付着量（乾燥後重量）は限定的ではないが、通常０．０１～１０ｇ／ｍ２とするのが好ましく、０．２～１．５ｇ／ｍ２とするのがより好ましく、０．３～１ｇ／ｍ２とするのが最も好ましい。上記範囲内に設定することによって、より優れた滑落性が長期にわたって得ることができる上、疎水性酸化物微粒子の脱落抑制、コスト等の点でもいっそう有利となる。 The amount of hydrophobic oxide fine particles attached to the container body (weight after drying) is not limited, but is usually preferably 0.01 to 10 g / m 2 and 0.2 to 1.5 g / m 2. It is more preferable, and 0.3 to 1 g / m 2 is most preferable. By setting it within the above range, more excellent sliding property can be obtained for a long period of time, and it is more advantageous in terms of suppression of falling off of hydrophobic oxide fine particles, cost and the like.
　撥水性及び撥油性を有する撥液剤としては、フッ素系化合物が挙げられる。フッ素系化合物としては、ポリフルオロアルキルメタアクリレート樹脂が挙げられる。フッ素系化合物を凹凸形状２ｃの表面に付着させることによって、マヨネーズのような油性の内容物についても、優れた滑落性が発揮される。 Examples of the liquid repellent having water repellency and oil repellency include fluorine compounds. Examples of the fluorine-based compound include polyfluoroalkyl methacrylate resins. By adhering the fluorine-based compound to the surface of the concave-convex shape 2c, excellent sliding property is exhibited even for oil-based contents such as mayonnaise.
１－２．容器本体１ａの製造方法
　容器本体１ａは、例えば、ダイレクトブロー成形によって形成可能であり、この場合、容器本体１ａは、押出ヘッドから押し出された溶融状態の筒状の積層パリソンを一対の分割金型を用いてブロー成形することによって形成することができる。積層パリソンは、外殻１２及び内袋１４に対応する外層及び内層を備える。積層パリソンの対向する面同士が溶着されて形成されたシール部において容器本体１ａの底が閉じられる 1-2. Manufacturing Method of Container Body 1a The container body 1a can be formed by, for example, direct blow molding. In this case, the container body 1a is a pair of split molds in which a molten tubular laminated parison extruded from an extrusion head is formed. It can be formed by blow molding using. The laminated parison includes an outer layer and an inner layer corresponding to the outer shell 12 and the inner bag 14. The bottom of the container body 1a is closed at the sealing portion formed by welding the opposing surfaces of the laminated parison.
　積層パリソンは、共押出成形や多層射出成形等によって形成可能である。積層パリソンの最内層は、内袋１４の最内層２を構成する樹脂組成物（つまり、基材樹脂２ａと充填粒子２ｂを含む樹脂組成物）によって形成される。 The laminated parison can be formed by coextrusion molding, multi-layer injection molding, etc. The innermost layer of the laminated parison is formed of a resin composition (that is, a resin composition containing a base resin 2a and packed particles 2b) constituting the innermost layer 2 of the inner bag 14.
　容器本体１ａをブロー成形によって形成した後に、撥液剤８をそのまま、又は媒体（分散媒又は溶媒）に分散若しくは溶解させた状態でスプレーすることによって、充填粒子２ｂの存在に起因する凹凸形状２ｃの表面に撥液剤８を付着させることができる。媒体を用いた場合には、適宜、乾燥工程を行ってもよい。 After the container body 1a is formed by blow molding, the liquid repellent 8 is sprayed as it is or in a state of being dispersed or dissolved in a medium (dispersion medium or solvent) to form an uneven shape 2c due to the presence of the filling particles 2b. The liquid repellent 8 can be attached to the surface. When a medium is used, a drying step may be performed as appropriate.
１－３．内容物１８の吐出
　図５に示すように、キャップ１６が斜め下方に向くように容器１を傾けると内容物１８がキャップ１６の方向に移動すると共にエアー１９が容器１の底部１ｂに向かって移動する。エアー１９が底部１ｂに移動した後に外殻１２を圧縮すると、吐出口１６ｂから内容物１８が吐出されて、エアー１９は内袋１４内に残留する。一方、エアー１９がキャップ１６に近傍に存在している状態で外殻１２を圧縮すると、吐出口１６ｂからエアー１９が吐出されて、内袋１４内のエアー１９が減少する。 1-3. Discharge of content 18 As shown in FIG. 5, when the container 1 is tilted so that the cap 16 faces diagonally downward, the content 18 moves in the direction of the cap 16 and the air 19 moves toward the bottom 1b of the container 1. To do. When the outer shell 12 is compressed after the air 19 has moved to the bottom 1b, the content 18 is discharged from the discharge port 16b, and the air 19 remains in the inner bag 14. On the other hand, when the outer shell 12 is compressed while the air 19 is present in the vicinity of the cap 16, the air 19 is discharged from the discharge port 16b, and the air 19 in the inner bag 14 is reduced.
　図６に示すように、内袋１４内の内容物１８のほぼ全量が吐出された後の時点では、内袋１４の対向する面同士がほぼ接触した状態となる。この時点で、エアー１９が内袋１４内に残留していると、外殻１２が圧縮されたときにエアー１９によって内袋１４の対向する面同士が離されて内容物１８の通り道が形成されて、内容物１８がキャップ１６に向かって移動しやすくなると共に、内容物１８がエアー１９によって押し出されやすくなる。このため、内容物１８の残留量が低減される。一方、内袋１４内の内容物１８のほぼ全量が吐出された後の時点でエアー１９が内袋１４内に残留していない場合、内容物１８が吐出されにくく、内容物１８の残留量が多くなる。 As shown in FIG. 6, after almost the entire amount of the contents 18 in the inner bag 14 has been discharged, the facing surfaces of the inner bag 14 are in a state of being substantially in contact with each other. At this point, if the air 19 remains in the inner bag 14, when the outer shell 12 is compressed, the facing surfaces of the inner bag 14 are separated from each other by the air 19, and a path for the contents 18 is formed. As a result, the content 18 is easily moved toward the cap 16, and the content 18 is easily pushed out by the air 19. Therefore, the residual amount of the content 18 is reduced. On the other hand, if the air 19 does not remain in the inner bag 14 after almost the entire amount of the contents 18 in the inner bag 14 is discharged, the contents 18 are difficult to be discharged and the residual amount of the contents 18 is reduced. More.
　本実施形態の容器１は内容物１８の滑落性が優れているので、図５に示すように容器１を傾けたときに、内容物１８が速やかにキャップ１６に向かって移動する。このため、エアー１９が吐出されにくく、内袋１４内の内容物１８のほぼ全量が吐出された後の時点において内袋１４内にエアー１９が残留された状態になりやすく、内容物１８の残留量が低減される。なお、内容物１８がケチャップ、マヨネーズ、グリセリン、ソース、はちみつのような粘稠体である場合には、容器１を傾けたときの内容物１８の移動速度が低いので、本発明と適用する意義が特に大きい。内容物１８の粘度は、０．１Ｐａ・ｓ以上が好ましく、例えば、０．１～１５Ｐａ・ｓであり、具体的には例えば、具体的には例えば、０．１、０．３、０．５、１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５Ｐａ・ｓであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。粘度は、２５℃でＪＩＳ　Ｚ８８０３に準拠して測定する。 Since the container 1 of the present embodiment has excellent sliding property of the content 18, when the container 1 is tilted as shown in FIG. 5, the content 18 quickly moves toward the cap 16. Therefore, it is difficult for the air 19 to be discharged, and the air 19 tends to remain in the inner bag 14 at a time after almost the entire amount of the contents 18 in the inner bag 14 is discharged, and the contents 18 remain. The amount is reduced. When the content 18 is a viscous material such as ketchup, mayonnaise, glycerin, sauce, or honey, the moving speed of the content 18 when the container 1 is tilted is low, and thus the significance of applying it to the present invention. Is particularly large. The viscosity of the content 18 is preferably 0.1 Pa · s or more, for example, 0.1 to 15 Pa · s, and specifically, for example, for example, 0.1, 0.3, 0. It is 5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 Pa · s, and is within the range between any two of the numerical values exemplified here. It may be. Viscosity is measured at 25 ° C. in accordance with JIS Z8803.
２．第２実施形態
　図７を用いて、本発明の第２実施形態について説明する。本実施形態の積層剥離容器１は、ポンプ式であり、容器本体１ａと、ポンプ２３を備える。容器本体１ａの構成は、凹部７ｅが設けられておらず、且つ外気導入部１５が容器１ａの底部１ｂに設けられている点以外は第１実施形態と同様である。 2. 2. Second Embodiment The second embodiment of the present invention will be described with reference to FIG. 7. The laminated peeling container 1 of the present embodiment is a pump type and includes a container body 1a and a pump 23. The structure of the container body 1a is the same as that of the first embodiment except that the recess 7e is not provided and the outside air introduction portion 15 is provided at the bottom portion 1b of the container 1a.
　ポンプ２３は、口部９に装着される。ポンプ２３は、容器本体１ａ内に挿入される導液管２３ａと吐出口２３ｂを備える。ポンプ２３は、ポンプ機構を内蔵しており、ポンプ機構の作用によって導液管２３ａを通じて吸い上げた内容物１８を吐出口２３ｂから吐出可能になっている。 The pump 23 is attached to the mouth portion 9. The pump 23 includes a liquid guide tube 23a and a discharge port 23b that are inserted into the container body 1a. The pump 23 has a built-in pump mechanism, and the contents 18 sucked up through the liquid guide pipe 23a can be discharged from the discharge port 23b by the action of the pump mechanism.
　本実施形態では、外気導入部１５は、底部１ｂのシール部において外殻１２と内袋１４の間に設けられた隙間である。内容物１８の吐出に伴って、外気導入孔１５を通じて、外殻１２と内袋１４の間に外気が導入されて、内袋１４が収縮する。なお、外気導入孔１５は、第１実施形態と同様に、外殻１２に設けられた孔であってもよい。 In the present embodiment, the outside air introduction portion 15 is a gap provided between the outer shell 12 and the inner bag 14 in the seal portion of the bottom portion 1b. With the discharge of the content 18, the outside air is introduced between the outer shell 12 and the inner bag 14 through the outside air introduction hole 15, and the inner bag 14 contracts. The outside air introduction hole 15 may be a hole provided in the outer shell 12 as in the first embodiment.
　ポンプ式の容器１では、容器１の底部１ｂ近傍の内容物１８が吸い上げられるので、内容物１８の滑落性が優れているほど、内容物１８の吸い上げが容易になって、内容物１８の残留量が低減される。そして、本実施形態の容器１は内容物１８の滑落性が優れているので、内容物１８が速やかに容器１の底部１ｂに向かって移動するので、内容物１８の残留量が少ない。 In the pump-type container 1, the content 18 near the bottom 1b of the container 1 is sucked up. Therefore, the better the sliding property of the content 18, the easier it is to suck up the content 18, and the content 18 remains. The amount is reduced. Since the container 1 of the present embodiment has excellent sliding property of the content 18, the content 18 quickly moves toward the bottom 1b of the container 1, so that the residual amount of the content 18 is small.
１．スクイズ式容器
１－１．サンプルの作製
＜実施例１＞
　パリソンのダイレクトブロー成形によって図１に示す形状の容量２００ｃｃの容器１を作製した。パリソンの最内層は、基材樹脂２ａと充填粒子２ｂを含む樹脂組成物で形成した。基材樹脂２ａは、ポリエチレン（融点１１２℃）であり、充填粒子２ｂは、アクリル系樹脂（融点２３０℃）である。樹脂組成物中の充填粒子の含有量は、２０質量％であった。容器１の高さ方向の中央での外殻１２及び内袋１４の肉厚は、それぞれ、０．５８ｍｍ、０．１４ｍｍであった。 1. 1. Squeeze container 1-1. Preparation of sample <Example 1>
A container 1 having a capacity of 200 cc and having the shape shown in FIG. 1 was produced by direct blow molding of a parison. The innermost layer of the parison was formed of a resin composition containing a base resin 2a and packed particles 2b. The base resin 2a is polyethylene (melting point 112 ° C.), and the packed particles 2b are acrylic resin (melting point 230 ° C.). The content of the packed particles in the resin composition was 20% by mass. The wall thicknesses of the outer shell 12 and the inner bag 14 at the center in the height direction of the container 1 were 0.58 mm and 0.14 mm, respectively.
＜比較例１＞
　充填粒子２ｂを添加しない以外は、実施例１と同様の条件で容器１を作製した。 <Comparative example 1>
A container 1 was prepared under the same conditions as in Example 1 except that the packed particles 2b were not added.
１－２．吐出試験
　実施例１及び比較例１の容器に表１に示す内容物を充填した後、逆止弁付きのキャップを装着し、キャップを斜め下方に向けた状態で内容物の吐出を行った。内容物の吐出は、内容物が吐出されなくなるまで、繰り返し行った。内容物が吐出されなくなった後に内容物の残留量を測定した。実施例１及び比較例１のそれぞれについて３つのサンプル（Ｎｏ．１～３）で吐出試験を行った。その結果を表１に示す。 1-2. Discharge test After filling the containers of Example 1 and Comparative Example 1 with the contents shown in Table 1, a cap with a check valve was attached, and the contents were discharged with the cap facing diagonally downward. The contents were repeatedly discharged until the contents were no longer discharged. The residual amount of the contents was measured after the contents were not discharged. A discharge test was performed on each of Example 1 and Comparative Example 1 using three samples (Nos. 1 to 3). The results are shown in Table 1.
２．ポンプ式容器
２－１．サンプルの作製
＜実施例２＞
　パリソンのダイレクトブロー成形によって図７に示す形状の容量１００ｃｃの容器１を作製した。パリソンの最内層は、基材樹脂２ａと充填粒子２ｂを含む樹脂組成物で形成した。基材樹脂２ａは、ポリエチレン（融点１１２℃）であり、充填粒子２ｂは、アクリル系樹脂（融点２３０℃）である。樹脂組成物中の充填粒子の含有量は、２０質量％であった。容器１の高さ方向の中央での外殻１２及び内袋１４の肉厚は、それぞれ、０．５９ｍｍ、０．１７ｍｍであった。 2. 2. Pump type container 2-1. Preparation of sample <Example 2>
A container 1 having a shape shown in FIG. 7 and having a capacity of 100 cc was produced by direct blow molding of a parison. The innermost layer of the parison was formed of a resin composition containing a base resin 2a and packed particles 2b. The base resin 2a is polyethylene (melting point 112 ° C.), and the packed particles 2b are acrylic resin (melting point 230 ° C.). The content of the packed particles in the resin composition was 20% by mass. The wall thicknesses of the outer shell 12 and the inner bag 14 at the center in the height direction of the container 1 were 0.59 mm and 0.17 mm, respectively.
＜比較例２＞
　充填粒子２ｂを添加しない以外は、実施例２と同様の条件で容器１を作製した。 <Comparative example 2>
A container 1 was prepared under the same conditions as in Example 2 except that the packed particles 2b were not added.
２－２．吐出試験
　実施例２及び比較例２の容器に表１に示す内容物を充填した後、ポンプを装着し、ポンプによる内容物の吐出を行った。内容物の吐出は、内容物が吐出されなくなるまで、繰り返し行った。内容物が吐出されなくなった後に内容物の残留量を測定した。実施例２及び比較例２のそれぞれについて３つのサンプル（Ｎｏ．１～３）で吐出試験を行った。その結果を表１に示す。 2-2. Discharge test After filling the containers of Example 2 and Comparative Example 2 with the contents shown in Table 1, a pump was attached and the contents were discharged by the pump. The contents were repeatedly discharged until the contents were no longer discharged. The residual amount of the contents was measured after the contents were not discharged. A discharge test was performed on each of Example 2 and Comparative Example 2 using three samples (Nos. 1 to 3). The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１中の内容物の詳細は、以下の通りである。粘度の値は、２５℃で株式会社エー・アンド・デイ製の音叉型振動式粘度計　「ＳＶ１０」にて、ＪＩＳ　Ｚ８８０３に準拠して測定したものである。
　グリセリン：日本薬局方グリセリン（グリセリン含有率８４．０－８７．０％）　粘度０．１３Ｐａ・ｓ
　ソース：オタフク　お好みソース　粘度０．８４ Ｐａ・ｓ
　はちみつ：ＴＯＰ　ＶＡＬＵＥ　純粋ハチミツ　粘度１１Ｐａ・ｓ The details of the contents in Table 1 are as follows. The viscosity value was measured at 25 ° C. with a tuning fork type vibration viscometer "SV10" manufactured by A & D Co., Ltd. in accordance with JIS Z8803.
Glycerin: Japanese Pharmacopoeia Glycerin (glycerin content 84.0-87.0%) Viscosity 0.13 Pa · s
Source: Otafuku Sauce of your choice Viscosity 0.84 Pa · s
Honey: TOPVALUE Pure honey Viscosity 11Pa · s
３．考察
　表１に示すように、スクイズ式とポンプ式の何れにおいても、実施例の容器では、内容物の残留量が大きく低減された。 3. 3. Discussion As shown in Table 1, in both the squeeze type and the pump type, the residual amount of the contents was greatly reduced in the container of the example.
１：積層剥離容器、１ａ：容器本体、１ｂ：底部、２：最内層、２ａ：基材樹脂、２ｂ：充填粒子、２ｃ：凹凸形状、３：中間層、４：接着樹脂層、５：バリア層、７：収容部、７ｂ：上端、７ｅ：凹部、８：撥液剤、９：口部、９ｄ：係合部、１２：外殻、１４：内袋、１５：外気導入部、１６：キャップ、１６ａ：逆止弁、１６ｂ：吐出口、１７：弁部材、１８：内容物、１９：エアー、２３：ポンプ、２３ａ：導液管、２３ｂ：吐出口 1: Laminated peeling container, 1a: Container body, 1b: Bottom, 2: Innermost layer, 2a: Base resin, 2b: Filled particles, 2c: Concavo-convex shape, 3: Intermediate layer, 4: Adhesive resin layer, 5: Barrier Layer, 7: Containment part, 7b: Upper end, 7e: Recessed part, 8: Liquid repellent, 9: Mouth part, 9d: Engaging part, 12: Outer shell, 14: Inner bag, 15: Outside air introduction part, 16: Cap , 16a: Check valve, 16b: Discharge port, 17: Valve member, 18: Contents, 19: Air, 23: Pump, 23a: Liquid guide tube, 23b: Discharge port

Claims (6)

  1. 　外殻と内袋とを有し且つ内容物の減少に伴って前記内袋が収縮する容器本体を備える積層剥離容器であって、
    　前記内袋は、前記内容物と接する最内層を備え、
    　前記最内層は、基材樹脂と充填粒子を含む樹脂組成物で構成され、
    　前記最内層の内面に前記充填粒子の存在に起因する凹凸形状が設けられている、積層剥離容器。     A laminated peeling container having an outer shell and an inner bag and having a container body in which the inner bag shrinks as the contents decrease.
    The inner bag includes an innermost layer in contact with the contents.
    The innermost layer is composed of a resin composition containing a base resin and packed particles.
    A laminated peeling container in which an uneven shape due to the presence of the filled particles is provided on the inner surface of the innermost layer.
  2. 　請求項１に記載の積層剥離容器であって、
    　前記充填粒子の少なくとも一部が前記最内層の内面から露出している、積層剥離容器。     The laminated peeling container according to claim 1.
    A laminated stripping container in which at least a part of the filled particles is exposed from the inner surface of the innermost layer.
  3. 　請求項１又は請求項２に記載の積層剥離容器であって、
    　前記樹脂組成物は、前記充填粒子の含有量が１５～５０質量％である、積層剥離容器。     The laminated peeling container according to claim 1 or 2.
    The resin composition is a laminated peeling container in which the content of the packed particles is 15 to 50% by mass.
  4. 　請求項１～請求項３の何れか１つに記載の積層剥離容器であって、
    　前記充填粒子は、アクリル系樹脂で構成されている、積層剥離容器。     The laminated peeling container according to any one of claims 1 to 3.
    The packed particles are a laminated peeling container made of an acrylic resin.
  5. 　請求項１～請求項４の何れか１つに記載の積層剥離容器であって、
    　前記基材樹脂は、ポリオレフィンである、積層剥離容器。     The laminated peeling container according to any one of claims 1 to 4.
    A laminated stripping container in which the base resin is polyolefin.
  6. 　請求項１～請求項５の何れか１つに記載の積層剥離容器であって、
    　前記凹凸形状の表面に撥液剤が付着している、積層剥離容器。     The laminated peeling container according to any one of claims 1 to 5.
    A laminated peeling container in which a liquid repellent is attached to the surface of the uneven shape.
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JP2015042481A (en) * 2013-07-26 2015-03-05 東洋製罐グループホールディングス株式会社 Resin structure having liquid layer on surface
JP2015229496A (en) * 2014-06-03 2015-12-21 東洋製罐グループホールディングス株式会社 Package
JP2016185702A (en) * 2015-03-27 2016-10-27 東罐興業株式会社 Structure having hydrophobic uneven surface, and method for forming hydrophobic uneven surface
JP2016203527A (en) * 2015-04-24 2016-12-08 東洋製罐株式会社 Structure having surface with solid particles distributed thereon
JP2018203344A (en) * 2017-06-05 2018-12-27 東洋製罐グループホールディングス株式会社 Double construction container

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