JP2001139041A - Tubular container and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tubular container of high barrier property which has a body part discontinuous from a head part, improves the gas barrier property of the head part, increases the gas barrier property as the whole tubular con tainer, and is excellent in extruding property and squeezing property, and its manufacturing method. SOLUTION: In the tubular container having the body part discontinuous from the head part, the body part comprises a cylindrical body part formed of a packaging material including at least a material layer of gas barrier property, the head part comprises a cylindrical body part formed of a molten- extruded cylindrical multi-layered hot parison, a tip portion of the cylindrical body part and a lower end portion of the cylindrical head part are compressed and nailed to each other, and fixed to each other while keeping the layer configuration, and the head part of the tubular container is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tube container and a method for producing the same, and more particularly to oral care products such as toothpaste, cosmetics, pharmaceuticals, foods and drinks, chemicals, sundries, and the like. The present invention relates to a high-barrier tube container excellent in squeezability suitable for filling and packaging of articles and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a packaging container suitable for filling and packaging of articles such as oral care products such as toothpaste, cosmetics, pharmaceuticals, food and drink, chemicals, miscellaneous goods, etc. Various types of packaging containers have been developed and proposed in consideration of the viewpoints of storability, storability, distribution, and portability. As one of them, a squeezable tube container mainly made of a plastic material or the like having excellent flexibility has been developed, and various types of tubes have been proposed. By the way, the contents packed and packed in a tube container include, for example, a material containing a component in which oxygen in the air permeates to the inside of the tube container and is oxidatively reacted therewith to change the quality. And those containing a surfactant, a solvent, an oily fragrance, etc., which have a high affinity for the material constituting the tube container and which significantly reduce the physical properties of the tube container. is there.
When the contents as described above are filled and packaged in a tube container, for example, an active ingredient or a fragrance which influences the quality of the contents is adsorbed on the inner surface of the tube container, and finally, the tube ends. −
There is a problem in that it evaporates outside the tube container and impairs the original product quality, and there is a problem that oxygen permeates to the inside of the tube container and reacts oxidatively therewith to deteriorate the quality of the contents. There is also. In order to solve these problems, as a body constituting the tube container, metal foil such as aluminum foil, polyvinylidene chloride resin, ethylene
Using a gas barrier resin such as vinyl alcohol copolymer, polyvinyl alcohol-based resin, polyacrylonitrile-based resin, polyester-based resin, polyamide-based resin, etc., and extruding the inner and outer layers by a lamination method or a dry lamination method. For example, a cylindrical body formed by laminating a polyolefin-based resin layer to produce a laminated body, and laminating the laminated body is used. Alternatively, a gas-barrier resin as described above and a plurality of other resins are used and are simultaneously extruded by a T-die extrusion sheet molding method to form a multilayer sheet including a gas-barrier resin layer. Then, a cylindrical body formed by processing this into a cylindrical shape in a body sticking step is also used. Furthermore, using a gas barrier resin as described above, a plurality of resins including the same are co-extruded simultaneously by a co-extrusion method, and a so-called seamless cylinder without a body sticking portion is formed in a die. It has also been proposed to use this as a tube container body. By the way, in a tube container, a polyolefin resin such as a high-density polyethylene resin having a high thermal stability is melt-extruded as a head material at the tip of the tube container body as described above, and is produced. Compression molding method,
Alternatively, the head is formed at the tip of the tube container body by integral molding using an injection molding method or the like. However, even when the head is formed by the above method, the polyolefin resin such as the high-density polyethylene resin constituting the head lacks gas barrier properties, so that the tube constituting the tube container is not provided. -Even though the tube container body portion has gas barrier properties, there is a problem that the head portion constituting the tube container is inferior in gas barrier properties. Therefore,
Conventionally, various methods have been developed and proposed for imparting gas barrier properties to a head portion constituting a tube container. For example, a metal foil layer such as an aluminum foil or a barrier resin layer has been proposed. A separate member (so-called Rondelle) is used as an insert material, which is placed on the tip of a tube container body constituting a tube container, and compression-molded or injection-molded. Integrally molding to form a head with a high gas barrier property, or after forming the head, a metal foil layer such as an aluminum foil as described above, or a barrier resin layer is included in the head portion A method of fitting another member (so-called Rondel) has been proposed (JP-A-4-76869). Furthermore, Chu
In order to impart gas barrier properties to the head part constituting the tube container, a gas barrier resin is used, and a tube container body and a head are formed by multi-layer extrusion direct blow molding including the resin. A method for producing a tube container rich in gas barrier properties, or a method for producing a single layer or a multilayer cold parison including the same using a gas barrier resin, and stretching the same by a uniaxial or biaxial stretching method. -A method of producing a tube container having a high gas barrier property by molding has also been proposed (JP-A-63-26687, JP-A-4-3740, etc.).

[0003]

By the way, polyolefin resins such as high-density polyethylene resins used for the head portion constituting the tube container are excellent in water vapor barrier properties, but are not suitable for oxygen gas. Has a very high transmittance. In general, since the oxygen gas permeability is inversely proportional to the density, soft oxygen, for example, low-density polyethylene (LDPE) or linear low-density polyethylene (LL-L) is used.
When DPE) or the like is used, the rigidity, which is a drawback in terms of usability of high-density polyethylene, is improved, but the oxygen barrier property of the tube container itself is significantly deteriorated. However, there is a problem that volatile components volatilize from the container severely and cannot withstand long-term storage. As an index indicating the permeability of oxygen gas, the permeability coefficient of oxygen gas (unit: c
m ³ · cm / cm ² · s · cm Hg at 25 ° C), high density polyethylene is 0.41 x 10 ¹⁰ , low density polyethylene is 2.89 x 10 ¹⁰ ,
Therefore, these permeability coefficients are 1st as compared with resins having excellent oxygen gas barrier properties, for example, polyvinylidene chloride, polyacrylonitrile, polyvinyl alcohol and the like.
It is about 00 to 1000 times higher. Also, high-density polyethylene is the hardest among polyethylene resins,
When this is used to form the head of a tube container, the head cannot be crushed by hand or the like, and there is a problem that the contents remain on the head. When this is used to construct the head, the head can be crushed by hand or the like, and it has an advantage over high-density polyethylene in that no contents remain on the head, but it has a gas barrier property. Is a material that is disadvantageous to oxygen gas, water vapor, and the like. As described above, when the head of the tube container is formed using a polyethylene-based resin such as high-density polyethylene which is inferior in oxygen gas barrier properties, the tube container body constituting the tube container has Even if it has a gas barrier property, the gas barrier property of the tube container as a whole does not improve so much, volatile components disappear, and the quality deteriorates. For this reason, various methods as described above have been developed and proposed in order to impart gas barrier properties to the head portion constituting the tube container, but the above-described multilayer extrusion direct blow molding method has been developed. Has the advantage that gas barrier properties can be imparted to the entire tube container. However, as a barrier resin material, an ethylene-vinyl alcohol copolymer is actually used. Most of these are configured as a sandwich structure with a polyolefin resin such as polyethylene or polypropylene, and as a result, the gas barrier properties of the trunk occupying most of the effective area of the tube container, particularly the oxygen gas barrier properties, A general tube made of aluminum foil or a resin film having an inorganic oxide vapor-deposited film, and laminated as a barrier substrate Inferior to the gas barrier properties of the body such as vessels, and has a problem that withstand long-term storage properties in terms of quality protection. For this reason, when the multilayer extrusion direct blow molding method is used, the problem of improving the gas barrier property of the tube container body still remains, and thus the gas barrier property is improved. For this purpose, in reality, there is no other way but to increase the thickness of each layer. In such a case, there is a problem that the squeezability of the tube container is lost. Further, in the above-mentioned single layer or a stretch blow tube container in which a barrier resin is compounded in the intermediate layer, it is true that
The resin is oriented by the stretching effect and has an effect of suppressing gas permeability such as oxygen gas. For example, as seen in a polyethylene terephthalate container (PET bottle) or the like,
As a container having high quality protection, it is frequently used as a container for filling and packaging beverages, seasonings and the like. However, in the above-mentioned stretch blow tube container, the squeezability required for the tube container cannot be expected, and only a highly rigid container can be manufactured as a whole, and polyethylene terephthalate can be produced. There are problems such as a high water vapor permeability as seen in containers (PET bottles) and a high oxygen gas permeability as seen in polypropylene blow containers. The fact is that it is. Accordingly, the present invention provides a tube container having a discontinuous trunk and head, improving the gas barrier properties of the head portion, increasing the gas barrier properties of the entire tube container, and further extruding and squeezing. An object of the present invention is to provide a high barrier tube container having excellent properties and a method for producing the container.

[0004]

As a result of various studies to solve the above problems, the present inventor has found that a method of manufacturing a head constituting a tube container, and a method of forming a tube container, have been proposed. Focusing on making improvements to the compression molding method of fixing the head constituting the tube container to the tip of the body portion to be made, etc., first, in a tube container in which the body portion and the head are discontinuous, Using a barrier resin, a melt-extruded cylindrical multilayer hot parison containing the same is manufactured, and cut into a size corresponding to the head constituting the tube container to form a cylindrical head, Thus, the cylindrical container head is preliminarily mounted on a tube container head forming mandrel with a cylindrical body formed of a packaging material including a gas barrier material layer. On the mandrel top of the part forming mandrel, and then The cylindrical body and the cylindrical head are compressed and rolled between an upper mold and a lower mold for forming a tube container head, and a cylinder is formed at the tip of the cylindrical body. The lower end portion of the tube-shaped head was fixed while maintaining the layer structure of both, and the tube container head was molded to produce a tube container. The present invention was completed by finding a high-barrier tube having excellent gas-barrier properties by improving the gas-barrier properties of the portion to enhance the gas-barrier properties of the entire tube, and further extruding, squeezing, etc., and a method for producing the same. Things.

That is, the present invention provides a tube container in which a body and a head are discontinuous, wherein the body comprises a cylindrical body composed of a packaging material including at least a gas barrier material layer. , The head is composed of a cylindrical head composed of a melt-extruded cylindrical multilayer hot parison, and further, the tip of the cylindrical body and the lower end of the cylindrical head are compressed and rolled. Further, the present invention relates to a tube container characterized by forming a tube container head by adhering while maintaining the layer structure, and a method for producing the tube container.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. FIG. 1 is a schematic half sectional view illustrating an example of a tube container according to the present invention, and FIGS. 2, 3 and 4 are examples of a method of manufacturing a tube container according to the present invention. It is a schematic block diagram of each process which illustrates.

First, a tube container A according to the present invention comprises:
As shown in FIG. 1, a tube in which a trunk 1 and a head 2 are discontinuous.
In the container 3, the body 1 comprises a cylindrical body 6 made of a packaging material 5 including a gas barrier material layer 4,
The head 2 is composed of a cylindrical head 9 formed by cutting a melt-extruded cylindrical multilayer hot parison 8 including a barrier resin layer 7, and further has a tip end of the cylindrical body 6. The lower end of the cylindrical head 9 is compressed and rolled,
A tube container head 10 is formed by fixing the two layers while maintaining them. In addition,
In the figure, reference numeral 11 denotes a screw portion for screwing a cap or the like.

Next, the tube according to the present invention as described above.
Explaining the method of manufacturing the tube container, as shown in FIG.
Multi-layer extruder 25 in which 3,.
And at least two extruders 21 and 22 are used. Further, at least a barrier resin is used as a material, and is extruded continuously from a die 24 in a vertical direction. Is extruded to form a cylindrical multilayer hot parison 8 containing at least one layer in the thickness direction. Next, in the present invention, as shown in FIG.
Extruded cylindrical multilayer hot parison 8
Immediately after molding, using a hot wire or a metal blade or the like (not shown), it is cut in the horizontal direction, and is melt-extruded cylindrical shape including at least the barrier resin layer 7 constituting the tube container head. A cylindrical head 9 composed of a multilayer hot parison 8 is manufactured. Thus, in the present invention, when manufacturing the cylindrical head 9, as shown in FIG. 3 described above, an extruded cylindrical multilayer hot parison 8 is used.
Immediately after molding, using a hot wire or a metal blade or the like (not shown), it is cut in the horizontal direction, and is melt-extruded cylindrical shape including at least the barrier resin layer 7 constituting the tube container head. A cylindrical head 9 composed of a multilayer hot parison 8 is manufactured, and then, while the cylindrical head 9 is in a molten state, a gas barrier material layer 4 is previously included as shown in FIG. The cylindrical body 6 made of the packaging material 5 is dropped vertically onto the mandrel top 27 of the tube container head forming mandrel 26 mounted on the tube container head forming mandrel 26. And then
Before the cylindrical head 9 is not completely cooled, the cylindrical body 6 and the cylindrical head 9 are connected to the upper mold of a tube container head forming mold (details are omitted). 28 and lower mold (fixed)
29, and the lower end portion Q of the cylindrical head 9 is fixed to the front end portion P of the cylindrical body portion 6 while maintaining the layer structure of both. Container head 10
After that, the mold is further cooled, and both of them are completely fixed, whereby a tube container A (see FIG. 1) can be manufactured. The above examples are merely examples of the tube container according to the present invention and the method for producing the same, and the present invention is not limited thereto.

In the above manufacturing method, the inner diameter of the cylindrical head 9 is set to 5 mm or more, and the thickness thereof is set to 0.2 mm to 20 mm.
It is preferably about mm, preferably about 1 mm to 10 mm, and more preferably about 2 mm to 5 mm. In the present invention, the inner diameter of the cylindrical head 9 should be at least 2 mm larger than the diameter of the mandrel 30 (see FIG. 4) constituting the mandrel top portion 27 of the tube container head forming mandrel 26. When the diameter is 2 mm or less, the clearance is small, and the cylindrical head 9 is
Is unfavorable because it adheres to the surface and makes it difficult to mold the tube container head. In the above-mentioned manufacturing method, as a method of cutting the cylindrical multilayer hot parison 8, a hot wire cutter method of heating and cutting a nichrome wire, an iron wire, a copper wire, or the like, or a heating and cutting of a metallic cutting blade. And the like. Further, in the above-mentioned manufacturing method, the cylindrical head formed of the cylindrical multilayer hot parison 8 is not completely cooled before the upper die of the die for forming the tube container head (details are omitted). 28 and the lower mold (fixed) 29 are closed, and the cylindrical head in the molten state is compressed and rolled, and simultaneously fused with the end face of the inner peripheral surface of the cylindrical body, and then the mold is cooled. By doing so, the lower end portion Q of the cylindrical head 9 is fixedly attached to the front end portion P of the cylindrical body 6 while maintaining the layer structure of the both, and the tube container head 10 is fixed. Is formed. More specifically, the resin layer forming the outermost layer and the innermost layer of the cylindrical head portion 9 and the resin layer forming the outermost layer and the innermost layer of the cylindrical body 6 are thermally fused to each other. This forms the tube container head 10. Therefore, in the present invention, the resin forming the cylindrical body portion 6 and the resin layers and the like constituting the outermost layer and the innermost layer of the cylindrical head portion 9 include:
It is desirable to use the same resin having heat fusion property, or at least a different resin material having heat fusion property.

Next, in the present invention, the materials used in the above-described tube container according to the present invention and the method for producing the same, and the method for producing the same will be described. First, the cylindrical body constituting the tube container according to the present invention will be described.
(1) A multilayer extruded cylinder formed by extrusion molding with a multilayer extrusion molding machine using at least a gas barrier resin, and (2) a back laminated portion of a multilayer laminate having at least a gas barrier resin layer laminated by heat fusion. The formed cylindrical body for a laminating tube container, or (3) at least a gas-barrier resin is used, and the back bonded portion of a multilayer sheet extruded with a T-die multilayer extruder is heat-sealed. For example, a cylindrical body for a tube container formed by the above method can be used.

[0011] (1) Multilayer extruded cylinder obtained by extrusion molding with a multilayer extrusion molding machine using at least a gas-barrier resin, The gas-barrier resin constituting the multilayer extrusion cylinder is, for example, polychlorinated resin. Vinyl (PVC), polyvinylidene chloride (PVD)
C), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (PVOH), polyacrylonitrile (PAN), polyethylene terephthalate (PE)
T), a heat-adhesive resin material composed of various resins such as an acid component partially modified heat-sealable polyester, an alcohol component partially modified heat-sealable polyester, polycarbonate and polyamide. Can be used. Further, as the resin constituting the innermost layer, the outermost layer, and the like of the gas barrier resin layer made of the above gas barrier resin, it is possible to use a resin that is melted by heat and has mutual heat-fusion properties. Are, for example, low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), ethylene-α-
Metallocene catalyst polymerization linear low density polyethylene (L-LDPE), medium density polyethylene (MDPE), high density polyethylene (HDP) composed of olefin copolymer, etc.
E), ethylene-vinyl acetate copolymer (EVA), polypropylene (homo), polypropylene (copolymer),
Use a blend of one or more polyolefin resins such as polybutadiene, polystyrene, ethylene-propylene copolymer, ionomer, ethylene-methacrylic acid copolymer, acid-modified heat-adhesive polyolefin resin, and others. be able to. As the above blend, specifically, for example, low density polyethylene (LDP)
E) and a metallocene-based catalyst-polymerized linear low-density polyethylene (L-LD) comprising ethylene-α-olefin copolymer and the like.
Blended with PE, linear low density polyethylene (L-
A blend of LDPE) and an ethylene-methacrylic acid copolymer can be used. In the present invention, in addition to the gas barrier resin as described above, the innermost layer of the gas barrier resin layer, the resin constituting the outermost layer and the like,
If necessary, other resins can be optionally used. Further, in the present invention, the above-mentioned resin includes, as necessary, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent, and a flame retardant. A plastic compounding agent such as a flameproofing agent, a foaming agent, a fungicide, a coloring agent such as a pigment or a dye, and the like can be arbitrarily added. Thus, in the present invention, at least the gas barrier resin is used, and the innermost layer,
Using a resin or the like that constitutes the outermost layer, etc., co-extrude a multi-layer pipe in the horizontal direction from one die connecting two or more extruders, and then cut it to an appropriate length to obtain a multi-layer extruded cylinder. Can be manufactured.

(2) The above-mentioned cylindrical body for a laminating tube formed by heat-sealing the back-attached portion of the multilayer laminate having at least the gas barrier resin layer laminated thereon is used for the laminating tube container described above. As the gas barrier resin forming the gas barrier resin layer constituting the cylindrical body, the above-described gas barrier resin can be used in the same manner. Further, in the present invention, in addition to the gas barrier resin described above, further, as a gas barrier material, for example, aluminum foil, aluminum evaporated polyethylene terephthalate film, aluminum evaporated polypropylene film, aluminum evaporated nylon film, etc. Film, an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., on a resin film, physical vapor growth method, or an inorganic oxide obtained by vapor deposition using a chemical vapor growth method or the like. A resin film having a deposited film,
Gas barrier materials such as polyvinylidene-coated polyethylene terephthalate film and others can also be used. Further, in the present invention, as a material to be laminated on and / or below the gas barrier resin layer, one or two or more of polyolefin-based resins which are melted by the above-mentioned heat and have mutual heat-fusion properties are used. Blends can be used as well. In the present invention, in addition to the gas barrier resin layer as described above, the resin laminated on the gas barrier resin layer above and below, and the like, if necessary, another resin may optionally be laminated. can do. Thus, in the present invention, the above-mentioned gas barrier resin layer or gas barrier material layer is used for the intermediate layer.
Polyolefin-based resin layer below, further, if necessary, other resin layers and the like are arbitrarily laminated to produce a multilayer laminate having at least a gas-barrier resin layer laminated, and then, the laminated body, both ends Parts are overlapped with each other, and the end of the polymerized portion is heat-sealed to produce a sleeve body. Thereafter, the sleeve body is cut into a predetermined length, and the sleeve body is cut into a predetermined length. A cylindrical body can be manufactured.

(3) A cylinder for a tube container formed by heat-sealing a back-attached portion of a multilayer sheet extruded by a T-die multilayer extruder using at least a gas barrier resin. As the gas barrier resin constituting the above-mentioned tube container cylinder, the above-mentioned gas barrier resin can be used in the same manner. Further, in the present invention, together with the above-mentioned gas barrier resin, one or more blends of one or more polyolefin-based resins which are melted by the above-mentioned heat and have mutual heat-fusion properties may be similarly used. it can. In the present invention, if necessary, other resins can be optionally used. Thus, in the present invention, the above-mentioned gas barrier resin is used, and further, a polyolefin-based resin laminated on top and bottom, and further, if necessary, using other resins and the like,
In addition, a multilayer sheet is manufactured by co-extrusion using a T-die method in which two or more extruders are connected, and then the multilayer sheet is overlapped at both ends, and the polymerized portion is formed. The end of the sleeve is heat-sealed to produce a sleeve, and then the sleeve is cut into a predetermined length to produce a tube container cylinder.

In the present invention, (1) a multilayer extruded cylinder, (2) a cylinder for a laminating tube container, or (3) a cylinder for a tube container constituting the cylindrical body. The body thickness is 0.1mm ~ 2mm
The position is preferably about 0.2 mm to 1 mm, more preferably about 0.3 mm to 0.6 mm.

First, the cylindrical head constituting the tube container according to the present invention will be described. The cylindrical head is formed of a melt-extruded cylindrical multilayer hot parison including at least a gas barrier resin layer. Things can be used. Furthermore, in the present invention, the cylindrical head specifically includes at least a gas-barrier resin layer, and further includes a heat-extruded cylindrical multilayer hot layer including a heat-sealing resin layer as an inner layer and an outer layer. Those composed of parisons can be used. Thus, in the present invention, as the gas barrier resin forming the gas barrier resin layer constituting the cylindrical head,
The aforementioned gas barrier resins can be used in the same manner. In the present invention, as the heat-sealing resin forming the heat-sealing resin layer constituting the cylindrical head, a blend of one or more of the above-mentioned olefin-based resins is used. Can be used as well. In the present invention, if necessary, other resins can be similarly used. By the way, in the present invention, the above materials are used, and the resin is melt-kneaded in a number of extruders corresponding to the type of the resin layer constituting the cylindrical multilayer hot parison, and then in a multilayer multiple die. After the molten resin is joined so as to have a predetermined multilayer structure, it is simultaneously extruded through a die orifice of a circular die to form a multi-layer parison, and extruded vertically into a cylindrical shape in a molten state to produce a cylindrical multi-layer hot parison. Then, while the cylindrical multilayer hot parison is still in a molten state without being completely cooled, it can be cut horizontally by a hot wire or a metal blade to produce a cylindrical head. is there. In the above, the number of extruders is, for example, two in the case of a two-layer configuration, and 2-3 in the case of a three-layer configuration.
In the case of a four-layer configuration, two to four units, in the case of a five-layer configuration,
Three to five extruders are used and can be freely selected depending on the desired multilayer structure, and the layer configuration is arbitrary. In the present invention, the number of layers of the cylindrical multilayer hot parison is 2
10 to 10 layers, desirably 3 to 7 layers are good, and at least one layer is constituted by at least a gas barrier resin layer. In the present invention, the lamination position of the gas barrier resin layer can be laminated at an arbitrary position, but may be any position between each layer such as an outer layer, a middle layer, and an inner layer. It may be composed of

In the present invention, as described above, the cylindrical body and the cylindrical head are used to fix the both, and a cap for sealing the mouth is screwed to the head. The tube container according to the present invention is manufactured by screwing with a thread screw or the like. Thus, although not shown, the tube container manufactured as described above is provided with an opening at the lower end thereof, for example, a hair dye, a dye, a pharmaceutical, a cosmetic, a toothpaste, a food, a chemical, and the like. A tube according to the present invention in which various contents such as viscous materials are filled and packaged in appropriate amounts, and then the openings are welded to form a lower end seal portion and the like, and the contents are filled and packaged. A tube package comprising a tube container can be manufactured.

[0017]

Next, the present invention will be described more specifically with reference to examples. Example 1 (1). Diameter 25mm, effective screw length 1000m
m single screw extruder is directly connected to a circular die, the following resins are simultaneously melt-extruded from each extruder, and from the outermost layer to the innermost layer, from the outermost layer / adhesive resin layer / gas barrier resin layer Thus, three types of three-layer cylindrical multilayer hot parisons were formed. Extruder 1: high density polyethylene (HDPE, density 0.
(951 g / cm ³ , melting point: 132 ° C.) Extruder 2: Maleic anhydride-modified polyolefin Extruder 3: Ethylene-vinyl alcohol copolymer In the above, the molding conditions of each of the extruders 1 to 3 are shown in Table 1 below. It was as follows. The inner diameter of the cylindrical multilayer hot parison is 5 mm, and the outer diameter is 7.3 m.
m.

[0018]

(2). The three types and three layers of the cylindrical multi-layer hot parison formed above are extruded in the vertical direction.
Cut horizontally with a nichrome wire heated to 00 ° C, length 1
A cylindrical head of 5 mm was formed, and the hollow portion of the cylindrical head was dropped so as to be positioned on the mandrel of the tube container forming mandrel. Thus, the above described mandrel for forming a tube container has a low-density polyethylene layer having a thickness of 100 μm / adhesive layer / thickness of 1 μm from the outermost layer to the innermost layer.
2 μm biaxially oriented polyethylene terephthalate film / 25 μm thick ethylene-methacrylic acid copolymer layer /
Heat sealing is performed by polymerizing the end of a laminated sheet having a layer structure of 15 μm thick aluminum foil / 25 μm thick ethylene-methacrylic acid copolymer layer / 150 μm thick low density polyethylene layer. 35mm inside diameter, height 215
mm cylindrical body is mounted, then the cylindrical body and the cylindrical head, the low-density polyethylene layer, the high-density polyethylene layer, etc. that constitute the outermost and innermost layers Integrate by the compression molding method like thermocompression,
A tube container according to the present invention having three types of three-layered shoulders was manufactured.

Example 2 In Example 1 described above, the thickness of the cylindrical body used in Example 1 was changed from the outermost layer to the innermost layer by 80%.
μm low-density polyethylene layer / 120 μm-thick medium-density polyethylene layer / adhesive layer / 12 μm-thick biaxially stretched polyethylene terephthalate film having a silicon oxide vapor deposition film (the silicon oxide vapor deposition film is the outside) / An inner diameter of 35 mm, which is obtained by heat-sealing the end of a laminated sheet having a layer structure of an ethylene-methacrylic acid copolymer layer having a thickness of 30 μm / a low-density polyethylene layer having a thickness of 120 μm, and having a height of 35 mm. A tube container according to the present invention was manufactured in the same manner as in Example 1 except that a cylindrical body of 215 mm was used.

Embodiment 3 (1). Diameter 25mm, effective screw length 1000m
m single screw extruders are directly connected to a circular die, and the following resins are simultaneously melt-extruded from each extruder, and from the outermost layer to the innermost layer, the outermost layer / adhesive resin layer / gas barrier resin layer / A cylindrical multi-layer hot parison of three types and five layers consisting of an adhesive resin layer / the innermost layer was formed. Extruder 1: Low-density polyethylene (LDPE, using both outermost and innermost layers) Extruder 2: Ethylene-vinyl alcohol copolymer Extruder 3: Maleic anhydride-modified polyolefin (using two layers of adhesive resin layer together) In the above, the molding conditions of each of the extruders 1 to 3 were as shown in Table 2 below. The inner diameter of the above cylindrical multilayer hot parison is 6.5 mm, and the outer diameter is 9.
4 mm.

[0022]

(2). The three-layer, five-layer, cylindrical multilayer hot parison molded above is extruded in the vertical direction.
Cut horizontally with a nichrome wire heated to 50 ° C, length 1
A cylindrical head of 6 mm was formed, and the hollow portion of the cylindrical head was dropped so as to be positioned on the mandrel of the tube container forming mandrel. The tube container forming mandrel has an inner diameter of 35 m as shown in the first embodiment.
m, a cylindrical body having a height of 215 mm is similarly mounted, and then the cylindrical body and the cylindrical head are connected to a low-density polyethylene layer or the like constituting the outermost and innermost layers thereof. Are integrated by a compression molding method so that
A tube container according to the present invention having three types and five layers of shoulders was manufactured.

Example 4 In Example 3 above, the cylindrical body used in Example 3 was replaced with an 80 μm-thick from the outermost layer to the innermost layer used in Example 2 above. Low-density polyethylene layer / Medium-density polyethylene layer having a thickness of 120 μm / adhesive layer / biaxially stretched polyethylene terephthalate film having a thickness of 12 μm having a silicon oxide deposition film (the silicon oxide deposition film is on the outside) / thickness An end of a laminated sheet having a layer structure of a 30 μm ethylene-methacrylic acid copolymer layer / a 120 μm thick low density polyethylene layer is polymerized and heat-sealed, and has an inner diameter of 35 mm and a height of 215 mm. A tube container according to the present invention was manufactured in the same manner as in Example 3 except that a cylindrical body was used.

Embodiment 5 (1). Diameter 25mm, effective screw length 1000m
m single screw extruder is directly connected to a circular die, the following resins are simultaneously melt-extruded from each extruder, and from the outermost layer to the innermost layer, from the gas barrier resin layer / adhesive resin layer / innermost layer Thus, three types of three-layer cylindrical multilayer hot parisons were formed. Extruder 1: Ethylene-vinyl alcohol copolymer Extruder 2: Maleic anhydride-modified polyolefin Extruder 3: Ethylene-α-olefin copolymer In the above, the molding conditions of each of the extruders 1 to 3 are shown in the following table. As shown in FIG. The inner diameter of the cylindrical multilayer hot parison is 4.5 mm, and the outer diameter is 6.
It was 0 mm.

[0026]

(2). The three-layer, three-layer cylindrical multi-layered hot parison molded above is extruded in the vertical direction.
14m length cut horizontally with a metal blade heated to 00 ° C
m was formed, and the hollow portion of the cylindrical head was dropped so as to be positioned on the mandrel of the tube container forming mandrel. Thus, the tube container forming mandrel has a thickness of 45 from the outermost layer to the innermost layer.
A 38 mm inner diameter, 195 mm long seamless formed by a multi-layer coextrusion method comprising a low-density polyethylene layer having a thickness of 0 μm / an acid-modified polyethylene layer having a thickness of 150 μm / an ethylene-vinyl alcohol copolymer having a thickness of 100 μm. The cylindrical body is mounted, and then the cylindrical body and the cylindrical head constitute the outermost and innermost layers of an ethylene-vinyl alcohol copolymer and a low-density polyethylene. Layer, ethylene-α-olefin copolymer,
An adhesive resin layer and the like were integrated by a compression molding method so as to be thermocompression-bonded, and a tube container according to the present invention having three types of three shoulder portions was manufactured.

Example 6 In Example 5 described above, the thickness of the cylindrical body used in Example 5 was changed from the outermost layer to the innermost layer by 70 mm.
Biaxially oriented polyethylene terephthalate film having a thickness of 12 μm having an ethylene-vinyl alcohol copolymer layer having a thickness of μm / adhesive layer / a low-density polyethylene layer having a thickness of 120 μm / adhesive layer / a silicon oxide vapor-deposited film (oxidized The deposited silicon film has a layer structure of outer layer) / ethylene-methacrylic acid copolymer layer having a thickness of 25 μm / acid-modified polyethylene layer having a thickness of 25 μm / ethylene-vinyl alcohol copolymer layer having a thickness of 50 μm. The present invention was carried out in the same manner as in Example 5 except that a cylindrical body having an inner diameter of 35 mm and a height of 215 mm formed by heat sealing the ends of the sheet was used. The tube container was manufactured.

Comparative Example 1 The cylindrical body used in Example 1 was mounted on a mandrel for forming a tube container, and then the high-density polyethylene melt was extruded by a compression molding method. The cylindrical head was thermally fused to the cylindrical body to produce a tube container.

Comparative Example 2 The cylindrical body used in the above Example 2 was mounted on a mandrel for forming a tube container, and then molten low-density polyethylene was extruded by a compression molding method. The cylindrical head was thermally fused to the cylindrical body to produce a tube container.

Comparative Example 3 The cylindrical body used in Example 5 above was mounted on a tube container forming mandrel, and then a molten ethylene-vinyl alcohol copolymer was molded by an injection molding machine. A cylindrical head was thermally fused to the cylindrical body to produce a tube container.

Experimental Examples The tube containers manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to the following evaluation tests. (1). Tube Container Barrier Property Test For each of the tube containers manufactured in the above Examples 1 to 6 and Comparative Examples 1 to 3, an aluminum seal lid was attached to the stopper of the shoulder portion with epoxy resin. A gas permeable jig is attached to the bottom, and the void is completely embedded in epoxy resin, and the oxygen permeability and water vapor permeability of the tube container are measured by the MOCON method. It was measured. The measurement conditions were as follows. Oxygen permeability: 23 ° C / 90% RH Water vapor permeability: 40 ° C / 90% RH (2). Tube Container Squeezability Test Each of the tube containers manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 is filled with a commercially available toothpaste as a viscous content, and the bottom is heat-sealed. After squeezing, the squeezability of the contents was evaluated. The evaluation was made in the following three stages. ：: Good squeezability of the contents, with residual amount less than 5% △: Poor squeezability of the contents, but poor residual amount of less than 5% ×: squeezability of the contents Bad, with a residual amount of 5% or more The results of the above evaluation tests are shown in Table 4 below.

[0033] In Table 4 above, the oxygen permeability is cc / container · da
It is a unit of y · atm, and the water vapor permeability is g / container ·
It is a unit of day.atm.

As is clear from the results shown in Table 4 above, each of the tube containers of Examples 1 to 6 has an oxygen permeability of 0.03 cc / container-day-atm and a water vapor permeability. Is less than 0.005 g / container-day-atm, showing extremely good gas barrier properties.
The tube containers of Comparative Example 1 and Comparative Example 2 had relatively good water vapor permeability, but had an oxygen permeability of 0.05.
cc / container / day / atm or more, and the tube container of Comparative Example 3 has good oxygen permeability, but practical water vapor permeability of 0.1 g / container / day / atm or more. The water vapor permeability was poor. Regarding the squeezability, it was confirmed that the tube containers of Examples 3 to 6 which did not use high-density polyethylene exhibited extremely good squeezability.

[0035]

As is apparent from the above description, the present invention relates to a method of manufacturing a head constituting a tube container, and a method of manufacturing a tube container at a tip end of a body constituting a tube container. Focusing on making improvements to the compression molding method for fixing the head that constitutes the above, in a tube container in which the body and the head are discontinuous, first, a barrier resin is used, and the melt containing the resin is used. An extruded cylindrical multi-layered hot parison is manufactured, and cut into a size corresponding to the head constituting the tube container to form a cylindrical head. In advance,
A cylindrical body made of a packaging material including a gas barrier material layer is placed on a mandrel top of the tube container head forming mandrel mounted on the tube container head forming mandrel, Then, the cylindrical body and the cylindrical head are compressed and rolled between an upper mold and a lower mold for a tube container head forming mold, and the cylindrical body is formed. The lower end of the cylindrical head is fixedly attached to the tip of the tube while maintaining the layer structure of the two, and the tube container head is formed to produce a tube container. It is possible to significantly improve the gas barrier properties of the constituent head portion, thereby enhancing the gas barrier properties of the entirety of the tube container, and produce a high-barrier tube container having excellent pushability and squeezability. That is.

[Brief description of the drawings]

FIG. 1 is a schematic half sectional view illustrating an example of a tube container according to the present invention.

FIG. 2 is a schematic configuration diagram of each step illustrating an example of a method for manufacturing a tube container according to the present invention.

FIG. 3 is a schematic configuration diagram of each step illustrating an example of a method for manufacturing a tube container according to the present invention.

FIG. 4 is a schematic configuration diagram of each step illustrating an example of a method for manufacturing a tube container according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Body 2 Head 3 Tube container 4 Gas barrier material layer 5 Packaging material 6 Cylindrical body 7 Barrier resin layer 8 Cylindrical multilayer hot parison 9 Cylindrical head 10 Tube container head 11 Screw Part 21, 22, 23 Extruder 24 Die 25 Multi-layer extruder 26 Mandrel for forming tube container head 27 Mandrel top part 28 Upper mold 29 Lower mold (fixed) 30 Mandrel A Tube container P Cylindrical The tip of the torso 6 The lower end of the cylindrical head 9

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 3E065 AA02 BA12 BB02 CA09 DA04 FA06 GA01 GA10 HA01 HA06 4F100 AA17A AB33A AK01B AK01C AK03 AK05 AK06 AK27A AK41A AK42 AK46A AK69A AK70 AL03 BA03 BA06 BA03 BA03 BA03 BA03 JD02 JD02A JL05 JL12B JL12C 4F213 AA07 AA19 AA20 AA24 AA29 AG03 AH54 WA04 WA06 WA15 WA52 WA53 WA54 WA63 WA92 WA97 WB01 WB22 WC01 WC05 WF29

Claims (9)

[Claims] 1. A tube container in which a body and a head are discontinuous, wherein the body comprises a cylindrical body composed of a packaging material containing at least a gas barrier material layer, and the head comprises a cylindrical body. , A cylindrical head composed of a melt-extruded cylindrical multilayer hot parison, and further, the tip of the cylindrical body and the lower end of the cylindrical head are compressed and rolled, A tube container formed by adhering to form a tube container head while maintaining the structure. 2. A multilayer extruded cylinder formed by extruding a cylindrical body made of a packaging material containing at least a gas barrier material layer with a multilayer extrusion molding machine using at least a gas barrier resin, and at least a gas barrier resin. A laminating tube container cylindrical body formed by heat-sealing the back affixed part of the multilayer laminated body in which the layers are laminated, or at least using a gas barrier resin, and extruding with a T-die multilayer extrusion molding machine. 2. The tube container according to claim 1, comprising a tube container cylindrical body formed by heat-sealing the back affixed portion of the multilayer sheet. 3. The gas-barrier resin is at least one selected from the group consisting of ethylene-vinyl alcohol copolymer, polyacrylonitrile resin, polyamide resin, polyester resin, metal foil, and metal or metal oxide deposited film. 3. The tube container according to claim 1, wherein the tube container comprises at least one species. 4. A cylindrical body made of a packaging material including at least a gas barrier material layer, wherein an inner layer and an outer layer thereof are formed of a heat-sealing resin layer. 4. The tube container according to 2 or 3. 5. The method according to claim 1, wherein the cylindrical head comprises a melt-extruded cylindrical multilayer hot parison including at least a gas barrier resin layer.
5. The tube container according to 3 or 4. 6. A cylindrical hot parison, wherein the cylindrical head includes at least a gas-barrier resin layer, and further includes an inner layer and an outer layer each formed of a melt-extruded cylindrical multilayer hot parison including a heat-sealing resin layer. Claims 1 and 2 above
Or the tube container according to 3. 7. The method according to claim 1, wherein the gas barrier resin comprises at least one selected from an ethylene vinyl alcohol copolymer, a polyacrylonitrile resin, a polyamide resin, and a polyester resin. Item 7. A tube container according to item 5 or 6. 8. A cylindrical body and a cylindrical head made of a packaging material including at least a gas barrier material layer melt a heat-sealing resin layer constituting an inner layer and an outer layer thereof.
The tube container according to any one of claims 1, 2, 3, 4, 5, 6, and 7, wherein the tube container is fixed and joined. 9. A tube container having a body and a head discontinuous, wherein a cylindrical body made of a packaging material including at least a gas barrier material layer is mounted on a tube container head forming mandrel. Then, the cylindrical head formed by cutting the melt-extruded cylindrical multilayer hot parison is placed on the mandrel top portion of the tube container head forming mandrel, and then the cylindrical head is formed. The cylindrical body and the cylindrical head are compressed and rolled between an upper mold and a lower mold for forming a tube container head, and the tip of the cylindrical body and a cylinder are formed. A method for producing a tube container, comprising fixing a tube container head to a lower end of a tube-shaped head while maintaining its layer structure.