JP2021133959A - Tube container - Google Patents

Abstract

To provide a tube container exhibiting excellent recyclability.SOLUTION: In a tube container comprising a tube-shaped trunk part whose one end is closed, and a spout attached to the other end of the trunk part; a content of 90 mass% or more of the total of the trunk part and the spout is formed from polypropylene. The tube container after use can be easily recycled as polypropylene by forming the content of 90 mass% or more of the total of the trunk part and the spout from polypropylene.SELECTED DRAWING: Figure 1

Description

The present invention relates to a tube container.

Tube containers made of resin-based materials are widely used as packaging materials for pharmaceuticals, cosmetics, foods, and the like. For example, Patent Document 1 describes a tubing unit for extracting the contents and a tube container composed of a body portion welded to the brewing unit and accommodating the contents. In Patent Document 1, a non-adsorptive resin is used for the inner layer of the film constituting the body portion to impart non-adsorptive property to the contents, and the intermediate layer of the film constituting the same portion contains a gas barrier substance. It is described that the gas barrier property is imparted by forming the gas barrier layer.

Japanese Unexamined Patent Publication No. 2016-199280

Conventionally, tube containers have generally been discarded after use, but in recent years, there has been a demand for tube containers that can be easily recycled from the viewpoint of reducing the environmental load. As described in Patent Document 1, the performance of the tube container has been improved by combining various materials to form the tube container, but the tube container contains different materials. In addition, there is a problem in terms of ease of recycling, such as the need to separate each material and the difficulty of recycling.

Therefore, it is an object of the present invention to provide a tube container having excellent recyclability.

The tube container according to the present invention includes a tubular body portion with one end closed and a spout portion attached to the other end of the body portion, and is 90% by mass or more of the total of the body portion and the spout port portion. Includes polypropylene.

According to the present invention, it is possible to provide a tube container having excellent recyclability.

Front view showing the schematic configuration of the tube container according to the first embodiment. Cross-sectional view taken along the II-II line shown in FIG. Cross-sectional view showing a modified example of the tube container shown in FIG. Top view of the tube container shown in FIG. End view along the VV line shown in FIG. Cross-sectional view showing an example of a film constituting the body of a tube container Cross-sectional view showing another example of the film constituting the body of the tube container. Cross-sectional view showing another example of the film constituting the body of the tube container. The figure which shows an example of the usage method of the tube container shown in FIG. Front view showing the schematic configuration of the tube container according to the second embodiment. Sectional drawing which shows the schematic structure of the tube container which concerns on 3rd Embodiment Sectional view of the tube container shown in FIG. Cross-sectional view showing an example of a gas barrier laminate that can be used for the body of a tube container. It is sectional drawing which shows an example of the layer structure of the material which can be used for the body part of the tube container which concerns on the modification. It is sectional drawing which shows another example of the layer structure of the material which can be used for the body part of the tube container which concerns on the modification.

(First Embodiment)
FIG. 1 is a front view showing a schematic configuration of a tube container according to the first embodiment, and FIG. 2 is a cross-sectional view taken along the II-II line shown in FIG. Further, FIG. 3 is a cross-sectional view showing a modified example of the tube container shown in FIG. In FIG. 1, only the cap is shown by a partial breakage view.

The tube container 100 includes a tubular body portion 1 and a spout portion 2 attached to the body portion 1.

The body portion 1 is a member for accommodating the contents, and can be formed by forming a film having a pair of substantially parallel edge edges into a tubular shape. As shown in FIG. 2, for example, the body portion 1 is formed into a tubular shape by abutting and welding the inner surfaces of the band-shaped portions including each of the pair of edge edges of the film in a palm-like shape. One end 5a (lower end in FIG. 1) of the body 1 is closed by a heat seal, and the vicinity of the other end 5b (upper end in FIG. 1) is welded to the spout 2. As shown in FIG. 3, the bonding portion 7 formed on the body portion 1 by bonding the edge portions of the film may be bent and bonded to the body portion 1 along the outer surface of the body portion 1. .. The method of bonding the bonding portion 7 to the body portion 1 is not particularly limited, and both may be welded via a heat-sealing resin provided on the entire surface or a part of the film constituting the body portion 1. However, the two may be bonded via an adhesive such as hot melt. The method of bonding the body 1 shown in FIGS. 2 and 3 is an example, and the outer surface of the band-shaped region including one edge of the film constituting the body 1 and the band including the other edge of the film are included. It may be bonded to the inner surface of the area.

The spouting port 2 is a member for extracting the contents housed in the body 1 to the outside, and includes a tubular pouring cylinder 3 and a flange 4. The flange portion 4 is a flat plate-shaped portion that is connected to one end portion 6a (lower end in FIG. 1) of the dispensing cylinder portion 3 and extends outward of the dispensing cylinder portion 3. In the present embodiment, the flange portion 4 is formed so as to extend in a direction orthogonal to the axial direction of the dispensing cylinder portion 3 (left-right direction in FIG. 1). In the present embodiment, the flange portion 4 is formed in an annular shape, but the shape of the flange portion 4 is not limited as long as the body portion 1 can be joined, and the flange portion 4 may be oval, oval, polygonal, or the like. There may be.

As shown in FIG. 1, the tube container 100 may further include a screw cap 10 that can be attached and detached by screwing to the injection cylinder portion 3 of the injection outlet portion 2. When the tube container 100 includes the screw cap 10, it becomes easy to reseal after opening the tube container 100. The material of the screw cap 10 is not particularly limited, but polypropylene is preferable because it can be recycled (recycled) as a single material together with the tube container 100. However, the screw cap 10 is optional, and the tube container 100 does not have to include the screw cap 10.

Further, the end portion 6b of the dispensing cylinder portion 3 may be sealed with a film that closes the dispensing cylinder portion 3 in the unopened state of the tube container 100.

FIG. 4 is a top view of the tube container shown in FIG. 1, and FIG. 5 is a cross-sectional view taken along the VV line shown in FIG.

As shown in FIGS. 4 and 5, in a state where the inner surface of the portion within a predetermined range from the end portion 6b of the body portion 1 is folded, the outer surface of the flange portion 4, that is, the end portion of both surfaces of the flange portion 4. It is welded to the surface on the 6b side. A plurality of pleated portions 8 formed by folding the film constituting the body portion 1 are formed on the outer surface of the flange portion 4. For welding of the body portion 1 to the flange portion 4, for example, a processing device having a plurality of claw portions intermittently arranged in the circumferential direction of the flange portion 4 is used, and a film in a predetermined range from the end portion 6b of the body portion 1 is used. Is pressed against the flange portion 4 with a plurality of claw portions, and then the film protruding from between the adjacent claw portions is crushed by a ring-shaped welding device to obtain a film in a predetermined range from the end portion 6b of the body portion 1. This can be done by folding and heating and pressurizing with a welding device in a state where the claw portion to which the film is pressed is retracted.

The tube container 100 according to the present embodiment contains 90% by mass or more of polypropylene in total of the body portion 1 and the spout portion 2. In other words, more than 90% by mass of the tube container 100 is made of polypropylene.

More specifically, the spout portion 2 is formed of a resin material containing polypropylene as a main component. The molding method of the spout portion 2 is not particularly limited, but injection molding, thermoforming such as vacuum molding and hot plate pressure air molding, compression molding and the like can be used. The resin material for forming the spout portion 2 may be polypropylene only, and is generally used for molding a small amount of barrier resin, a pigment, a mold release agent, an antioxidant, a clearing agent, or the like. It may contain the additives used. However, when an additive or the like is added to the resin material of the spout portion 2, the amount of the material other than polypropylene is adjusted so that the proportion of polypropylene in the total mass of the container is 90% or more. Examples of the barrier resin blended in propylene vinyl include polyvinyl alcohol (PVOH) and ethylene-vinyl alcohol copolymer (EVOH).

The body portion 1 is formed of a film mainly composed of a polypropylene film. The film constituting the body preferably has at least a layer of stretched polypropylene and a layer of unstretched polypropylene. Hereinafter, a specific example of the film constituting the body portion 1 will be described.

6 to 8 are cross-sectional views showing an example of a film constituting the body of the tube container.

The film 11 shown in FIG. 6 is obtained by laminating a layer 16 of stretched polypropylene on a layer 15 of unstretched polypropylene. The film 12 shown in FIG. 7 is obtained by laminating a layer 17 of stretched polypropylene having a barrier property on a layer 15 of unstretched polypropylene. Further, in the film 13 shown in FIG. 8, a layer 17 of stretched polypropylene having a barrier property and a layer 16 of stretched polypropylene are laminated in this order on a layer 15 of unstretched polypropylene. The films 11 to 13 shown in FIGS. 6 to 8 can be formed by laminating the films constituting the respective layers, for example, by dry laminating.

The unstretched polypropylene layer 15 functions as a sealant and imparts heat sealability to the film constituting the body 1. By using the unstretched polypropylene layer 15 as a sealant, the weldability of the body portion to the spout portion 2 formed of the resin material containing polypropylene as a main component is also good. The film thickness of the unstretched polypropylene layer 15 is preferably 15 to 150 μm. When the film thickness of the unstretched polypropylene layer 15 is less than 15 μm, the step (see FIG. 5) caused by the superposition of the films when the body portion 1 is welded to the spout portion 2 can be filled with the melted unstretched polypropylene. It becomes difficult, welding is insufficient, and the appearance is spoiled, which is not preferable. Further, when the total film thickness of the unstretched polypropylene layer 15 exceeds 150 μm, the production cost and the amount of resin used increase, which is not preferable.

The stretched polypropylene layers 16 and 17 impart strength and stiffness to the body 1. The total film thickness of the stretched polypropylene layers 16 and 17 is preferably 15 to 200 μm. By providing the stretched polypropylene layers 16 and / or 17 within this film thickness range, the loop stiffness of the film can be 120 mN or more, and when a tube container having a tubular body 1 is constructed, the tube is formed. The shape can be stably maintained. The loop stiffness is a load required to crush a film cut out in a strip shape in a loop shape by a predetermined amount in the diameter direction of the loop, and corresponds to the crushing resistance of the loop. Further, when the tube container 100 is made of a film having the layers 16 and / or 17 of the stretched polypropylene, the tube container is not too soft in the state of being filled with the contents, and the handleability of the tube container filled with the contents is excellent. If the total film thickness of the stretched polypropylene layers 16 and 17 is less than 15 μm, the strength and stiffness required for the tube container 100 are insufficient, which is not preferable. Further, when the total film thickness of the stretched polypropylene layers 16 and 17 exceeds 200 μm, the film forming the body portion 1 becomes too hard, which makes it difficult to weld to the spout portion 2 and the manufacturing cost. And it is not preferable because the amount of resin used increases.

The stretched polypropylene layer 17 having a barrier property is a gas barrier laminate in which a barrier layer made of a thin film of an inorganic compound such as silica or alumina is laminated on a stretched polypropylene film, or a barrier containing a barrier resin such as PVA or EVOH or an inorganic filler. It is formed by a gas barrier laminate in which a barrier layer made of a coating agent is laminated. By providing the layer 17 of stretched polypropylene having a barrier property, it is possible to impart a gas barrier property to the body portion 1 while improving the polypropylene ratio of the film constituting the body portion 1.

However, the film constituting the body portion 1 may include at least a layer 15 of unstretched polypropylene and a layer 16 of stretched polypropylene as in the film 11 shown in FIG. If the film constituting the body 1 is provided with two layers of unstretched polypropylene and stretched polypropylene, the body 1 can be imparted with the strength, elasticity and heat sealability required for a tube container. However, depending on the contents and application of the tube container, the above-mentioned barrier layer may be provided, or a stretched polypropylene layer may be further provided. The barrier layer may be laminated on the unstretched polypropylene layer, or may be laminated on both the unstretched polypropylene layer and the stretched polypropylene layer. In addition to the barrier layer, a printing ink layer, an adhesive, or the like can be appropriately laminated on one or both of the unstretched polypropylene layer and the stretched polypropylene layer.

If 90% by mass or more of the total of the body portion 1 and the spout portion 2 is made of polypropylene, the entire tube container 100 can be regarded as a single resin, so that the used tube container 100 is recycled as polypropylene. It becomes possible. From the viewpoint of further promoting the monomaterialization of the tube container 100, the ratio of polypropylene shown in the total of the body portion 1 and the spout portion 2 is preferably 95% by mass or more, and more preferably 99% or more.

The thickness (total thickness) of the film constituting the body portion 1 is not particularly limited, but is preferably 30 to 250 μm. If the thickness of the film constituting the body 1 is within this range, the body 1 can be easily processed into a tubular shape by using a bag making machine, a pillow stick wrapping machine, or the like.

FIG. 9 is a diagram showing an example of how to use the tube container shown in FIG.

As described above, the tube container 100 according to the present embodiment is configured by welding a portion within a predetermined range from the end portion 5b of the body portion 1 to the outer surface of the flange portion 4 of the spout portion 2. With this configuration, as shown in FIG. 9, the body portion 1 can be bent along the outer peripheral edge of the flange portion 4. Therefore, when the contents of the tube container 100 are reduced, the contents can be easily squeezed out by folding the body portion 1 along the outer peripheral edge of the flange portion 4 as shown in FIG. When the body portion 1 is formed by using a film having a thickness of 30 to 250 μm, it is possible to further facilitate the squeezing of the contents by folding the body portion 1.

Further, in the tube container 100 according to the present embodiment, since the flange portion 4 has a flat plate shape orthogonal to the central axis of the pouring cylinder portion 3, the flange portion 4 provides a space for the contents to remain. Not formed. Therefore, by pushing down the spout portion 2 in the direction of the arrow in FIG. 9 to make the flange portion 4 and the body portion 1 substantially flat, it is possible to squeeze out all the contents.

On the other hand, in the case of a general laminated tube, since the portion corresponding to the flange portion of the spout portion is formed in a tapered shape, even if it is folded in the same manner as in FIG. 9, the spout portion has a tapered shape. The contents tend to remain in the space. Further, in a general laminated tube, a peripheral wall portion coaxial with the pouring cylinder portion and having a cylindrical shape is provided on the outer peripheral surface of the flange portion of the spouting port portion, and one end of the body portion is welded to the outer peripheral surface of the peripheral wall portion. Therefore, the contents tend to remain in the space formed by the peripheral wall portion for welding the body portion.

As described above, in the tube container 100 according to the present embodiment, since 90% by mass or more of the total of the body portion 1 and the spout portion 2 is made of polypropylene, the body portion 1 and the spout portion 2 are separated. It can be recycled as polypropylene as it is without doing so. Therefore, according to the present embodiment, the tube container 100 having excellent recyclability can be realized.

Further, by forming the body portion 1 with a film containing a layer of stretched polypropylene and a layer of unstretched polypropylene, it is possible to impart the strength and elasticity required for the tube container and the heat-sealing property to the body portion 1. .. Further, in the present embodiment, since the spout portion 2 is formed of a resin material containing polypropylene as a main component, the flange portion 4 of the spout portion 2 and the unstretched polypropylene layer of the film constituting the body portion 1 are formed. Excellent weldability with (sealant layer).

Further, by laminating a barrier layer on a layer of stretched polypropylene on a film constituting the body portion 1, it is possible to obtain a tube container 100 having excellent gas barrier properties.

Further, when the body portion 1 is formed of a film having a thickness of 30 to 250 μm, the body portion 1 can be easily processed by using a bag making machine, a pillow stick wrapping machine, or the like, and the contents can be easily squeezed. Can be improved. In addition to this, if the film has a thickness of 30 to 250 μm, gravure printing capable of expressing fine shading is possible, so that highly cosmetic printing can be performed on the outer surface of the body 1.

Further, the body portion 1 is formed in a tubular shape by rolling a film having a pair of substantially parallel edge edges and joining the inner surfaces of the band-shaped portions including each of the pair of edge edges. When the body portion 1 is formed in this way, the sealant layer need only be provided on one surface of the film, so that the film constituting the body portion 1 can be thinned and the amount of resin can be reduced.

Further, as described with reference to FIG. 9, the flange portion 4 of the pouring outlet portion 2 has a flat plate shape orthogonal to the central axis of the pouring cylinder portion 3, and the outer surface of the flange portion 4 (the end portion of the pouring cylinder portion 3). Since the inner surface of the body portion 1 is welded to the surface on the 6b side), it is easy to squeeze out the contents by folding the body portion 1, and the residual contents in the spout portion 2 can be reduced.

Hereinafter, the second and third embodiments will be described. In the second and third embodiments, the same parts as those in the first embodiment are designated by the same reference numerals as those in the first embodiment and the description thereof is omitted, and the differences from the first embodiment are omitted. Will be mainly explained.

(Second Embodiment)
FIG. 11 is a front view showing a schematic configuration of the tube container according to the second embodiment.

The tube container 200 according to the present embodiment is different from the tube container 100 according to the first embodiment in that the flange portion 25 of the spout portion 2 has a tapered shape. Even when the flange portion 25 of the spout portion 2 has a tapered shape, by using polypropylene for 90% by mass or more of the total of the body portion 1 and the spout portion 2, recyclability is achieved as in the first embodiment. An excellent tube container 200 can be realized.

(Third Embodiment)
FIG. 12 is a cross-sectional view showing a schematic configuration of the tube container according to the third embodiment, and FIG. 13 is a cross-sectional view of the tube container shown in FIG.

The tube container 300 according to the present embodiment is provided with a partition wall 26 inside the spouting cylinder portion 3 of the spouting port portion 2 and a hinge cap 29 that can be opened and closed via a hinge at the spouting port portion 2. This is different from the tube container 100 according to the first embodiment. The tube container 300 does not necessarily have to include the hinge cap 29.

The partition wall 26 inside the dispensing cylinder 3 is a member provided to keep the inside of the tube container 300 in a sealed state in an unopened state. The partition wall 26 is provided with a circular half-cut 27. A pull ring 28 is connected to a portion of the partition wall 26 surrounded by the half cut 27. The pull ring 28 is composed of an annular ring portion 30 and a connecting portion 31 connecting the ring portion 30 and the partition wall 26. When opening the tube container 300, the user pulls the pull ring 28 to break the half-cut 27 portion of the partition wall 26 to remove a part of the partition wall 26 surrounded by the half-cut 27 from the body 1. An opening for pouring the contents into the pouring tube portion 3 can be formed.

The hinge cap 29 is a member for resealing the tube container 300, like the screw cap 10 in the first embodiment. In the present embodiment, the hinge cap 29 is attached to the spout portion 2 by fitting the inner ring provided on the hinge cap 29 and the spout portion 2, but the hinge cap 29 is spouted by screwing. It may be attached to the part 2.

Also in this embodiment, by using polypropylene for 90% by mass or more of the total of the body portion 1 and the spout portion 2, a tube container 300 having excellent recyclability can be realized as in the first embodiment.

(Other variants)
FIG. 13 is a cross-sectional view showing an example of a gas barrier laminate that can be used for the body of the tube container. The gas barrier laminate shown in FIG. 13 can be used, for example, to form the layer 17 having the gas barrier property shown in FIGS. 7 and 8.

The gas barrier laminate 19 is obtained by laminating a resin layer 21 having a vinyl alcohol unit, an inorganic thin film layer 22, and a resin layer 23 having a vinyl alcohol unit on the base material layer 20 in this order. The resin layer 21 having a vinyl alcohol unit, the inorganic thin film layer 22, and the resin layer 23 having a vinyl alcohol unit correspond to the barrier layer.

The base material layer 20 is a layer containing polyolefin as a main component. Examples of the polyolefin include polyethylene (PE), polypropylene (PP), polybutene (PB), cycloolefin polymer and the like. Examples of the polyolefin include acid-modified polyolefins obtained by graft-modifying a polyolefin with an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like. A small amount of ethylene, butene or the like may be blended as a raw material monomer for polypropylene synthesis. In the present invention, the base material layer 20 is preferably made of polypropylene so that the proportion of polypropylene constituting the tube container 100 is 90% by mass or more of the total of the body portion 1 and the spout portion 2. However, as long as the proportion of polypropylene is 90% by mass or more of the total of the body portion 1 and the spout portion 2, a film made of polyolefin other than polypropylene can be used for the base material layer 20.

The film constituting the base material layer 20 may be either a stretched film or an unstretched film. However, from the viewpoint of impact resistance, heat resistance, water resistance, dimensional stability, etc., the film constituting the base material layer 20 is preferably a stretched film. The stretching method is not particularly limited, and any method may be used as long as a film having stable dimensions can be supplied, such as stretching by inflation, uniaxial stretching, or biaxial stretching.

The thickness of the base material layer 20 is not particularly limited, but is preferably 9 to 100 μm, more preferably 15 to 30 μm, from the viewpoint of obtaining excellent impact resistance and excellent gas barrier properties.

The film constituting the base material layer 20 is subjected to various pretreatments such as corona treatment, plasma treatment, and frame treatment within a range that does not impair the barrier performance, and a coat layer such as an easy-adhesion layer is provided on the laminated surface. You may.

The film constituting the base material layer 20 may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, and a lubricant, if necessary.

The resin layer 21 having a vinyl alcohol unit (hereinafter, simply referred to as “resin layer”) 21 is a layer containing PVA or EVOH as a main component. EVOH can be preferably used from the viewpoint of heat resistance and gas barrier properties.

As the PVA, for example, vinyl esters such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate, and vinyl versatic acid are independently polymerized. Next, a saponified resin can be mentioned.

The PVA may be a copolymerized or post-modified modified PVA. The copolymerized PVA can be obtained, for example, by copolymerizing a vinyl ester with an unsaturated monomer copolymerizable with the vinyl ester and then saponifying the vinyl ester. The post-modified PVA can be obtained by copolymerizing an unsaturated monomer with PVA obtained by saponifying vinyl ester in the presence of a polymerization catalyst. The amount of modification in the modified PVA can be less than 50 mol% from the viewpoint of exhibiting sufficient gas barrier properties, and can be 10 mol% or more from the viewpoint of obtaining the effect of modification.

Examples of the unsaturated monomer include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, and α-octadecene; 3-butene-1-ol, 4-pentyne-1-ol, and 5-hexene-. Hydroxy group-containing α-olefins such as 1-ol; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, and undecylene acid; nitriles such as acrylonitrile and metaacrylonitrile; diacetone acrylamide. , Amid such as acrylamide and methacrylicamide; olefin sulfonic acid such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid; alkyl vinyl ether, dimethyl allyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2 Vinyl compounds such as −dialkyl-4-vinyl-1,3-diokinlane, glycerin monoallyl ether, 3,4-diacetoxy-1-butene; vinylidene chloride, 1,4-diacetoxy-2-butene, vinylene carbonate, polyoxy Examples thereof include propylene and polyoxypropylene vinylamine. From the viewpoint of gas barrier properties, the unsaturated monomer is preferably an olefin, more preferably ethylene.

Examples of the polymerization catalyst include radical polymerization catalysts such as azobisisobutyronitrile, benzoyl peroxide, and lauryl peroxide. The polymerization method is not particularly limited, and bulk polymerization, emulsion polymerization, solvent polymerization and the like can be adopted.

The degree of polymerization of PVA is preferably 300 to 3000. If the degree of polymerization is less than 300, the barrier property tends to decrease, and if it exceeds 3000, the viscosity is too high and the coating suitability tends to decrease. The degree of saponification of PVA is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 98 mol% or more. Further, the degree of saponification of PVA may be 100 mol% or less or 99.9 mol% or less. The degree of polymerization and the degree of saponification of PVA can be measured according to the method described in JIS K 6726 (1994).

EVOH is generally a copolymer of ethylene and an acid vinyl ester such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate, vinyl versatic acid, etc. Is obtained by kensing.

The ethylene unit content of EVOH is 10 mol% or more, more preferably 15 mol% or more, further preferably 20 mol% or more, and particularly preferably larger than 35 mol%. The ethylene unit content of EVOH is preferably 65 mol% or less, more preferably 55 mol% or less, and even more preferably less than 50 mol%. When the ethylene unit content is 10 mol% or more, the gas barrier property or dimensional stability under high humidity can be kept good. On the other hand, when the ethylene unit content is 65 mol% or less, the gas barrier property can be enhanced. The ethylene unit content of EVOH can be determined by the NMR method.

The saponification can be carried out with an alkali or an acid, but an alkali can be used from the viewpoint of the saponification rate. Examples of the alkali include alkali metal oxides such as sodium hydroxide and potassium hydroxide, and alkali metal alkoxides such as sodium ethylate, potassium ethylate and lithium methylate.

The thickness of the resin layer 21 is not particularly limited, but is preferably 0.05 to 5 μm, more preferably 0.1 to 2 μm, from the viewpoint of barrier properties and processability.

The mass per unit area of the resin layer 21 can be ^{0.1 to 10 g / m 2.} When this mass is 0.1 g / m ² or more, the surface of the resin layer 21 can be formed sufficiently smooth even if the surface of the base material layer 20 is insufficiently smooth, so that the resin layer 21 can be formed sufficiently. It is possible to reduce the defects of the inorganic thin film layer 22 laminated on the surface of the above. On the other hand, if this mass is 10 g / m ² or less, it is advantageous in terms of realizing a monomaterial for the packaging material and reducing the material cost.

The arithmetic mean height Sa of the surface of the resin layer 21 can be, for example, 0.2 μm or less, and more preferably 0.01 to 0.1 μm or 0.02 to 0.1 μm. When the arithmetic mean height Sa of the surface of the resin layer 21 is 0.2 μm or less, the inorganic thin film layer 22 having excellent gas barrier properties can be formed. On the other hand, when the arithmetic mean height Sa of the surface of the resin layer 21 is 0.01 μm or more, the adhesion between the resin layer 21 and the inorganic thin film layer 22 is improved by the anchor effect as compared with the case where it is less than 0.01 μm. can.

When a propylene monopolymer film (monopolymer layer) is used as the base material layer 20, the propylene monopolymer film has excellent heat resistance, but has a drawback that the surface thereof tends to be leaf vein-like. Therefore, even if the inorganic thin film layer 22 is directly formed on the surface of the base material layer 20, sufficient barrier properties cannot be achieved. Therefore, excellent gas barrier properties can be achieved by interposing the resin layer 21 between the propylene monopolymer film and the inorganic thin film layer 22.

From the viewpoint of achieving excellent oxygen barrier properties, the surface of the resin layer 21 has a logarithmic decrement at 100 ° C. measured by a rigid pendulum type physical property tester, for example, 0.20 or less, and a logarithmic decrement at 125 ° C. For example, it is preferably 0.30 or less. This logarithmic decrement can be measured by the rigid pendulum method (rigid pendulum type physical property tester RPT-3000W manufactured by A & D Co., Ltd.). RBP-020 is used as the pipe edge, and the measurement is performed by heating from 30 ° C. to 130 ° C. at a heating rate of 10 ° C./min. Measurements are performed at three points under these conditions, and the average value of the logarithmic decay rate at 100 ° C. and 125 ° C. is calculated, respectively. A small logarithmic decrement means that the resin molecules that make up the surface to be measured do not move easily even when exposed to heat.

The inorganic thin film layer 22 is a layer made of an inorganic compound containing Si or Al (atom). Examples of the inorganic compound include metal oxides such as silicon oxide (SiOx) and aluminum oxide (AlOx), metallic aluminum (Al), silicon nitride (SiN), and silicon oxynitride (SiON). From the viewpoint of transparency and barrier property, the inorganic compound constituting the inorganic thin film layer 22 is preferably aluminum oxide or silicon oxide. Further, from the viewpoint of excellent tensile stretchability during processing, the inorganic compound constituting the inorganic thin film layer 22 is preferably silicon oxide. By using the inorganic thin film layer 22, high barrier properties can be obtained while suppressing the thickness of the entire gas barrier laminate 19.

The layer thickness of the inorganic thin film layer 22 can be 5 to 80 nm. When the layer thickness is 5 nm or more, sufficient gas barrier properties can be obtained. Further, when the layer thickness is 80 nm or less, it is possible to suppress the occurrence of cracks due to the deformation of the thin film due to the internal stress, and to suppress the deterioration of the gas barrier property. If the layer thickness exceeds 80 nm, the cost tends to increase due to an increase in the amount of material used and a long film formation time, which is not preferable from an economical point of view. From the above viewpoint, the layer thickness of the inorganic thin film layer 22 is more preferably 10 to 50 nm, further preferably 20 to 40 nm.

The resin layer (hereinafter, simply referred to as “resin layer”) 23 having a vinyl alcohol unit is a layer containing polyvinyl alcohol (PVA) or an ethylene-vinyl alcohol copolymer (EVOH) as a main component, similarly to the resin layer 21. be. EVOH can be preferably used from the viewpoint of heat resistance and gas barrier properties.

The resin layer 23 may contain a silane compound. Examples of the silane compound include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, reactive group-containing trialkoxysilanes such as glycidoxypropyltrimethoxysilane and acryloxypropyltrimethoxysilane, and silazanes such as hexamethyldisilazane. Can be mentioned. As the silane compound, a compound generally used as a silane coupling agent or a polysiloxane compound having a siloxane bond may be used. Further, as the silane compound, vinyl trimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyl. It is preferable to use a silane coupling agent such as dimethoxysilane and 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate.

The mass ratio of the silane compound to the mass of the resin layer 23 can be 0.005 to 0.80 from the viewpoint of adhesion to the inorganic thin film layer 22 and maintenance of gas barrier properties.

The thickness of the resin layer 23 is not particularly limited, but is preferably 0.05 to 2 μm, more preferably 0.1 to 0.6 μm, from the viewpoint of barrier properties and processability.

The gas barrier laminate 19 is, for example, a step of forming a resin layer 21 on a base material layer 20, a step of forming an inorganic thin film layer on the resin layer 21, and a step of forming a resin layer 23 on the inorganic thin film layer 22. It can be manufactured by a manufacturing method including.

The resin layer 21 can be formed by applying a coating liquid containing PVOH or EVOH and a solvent to the base material layer 20. As the solvent, water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, amines such as ethylenediamine and diethylenetriamine, etc. alone or in combination of two or more. Can be used in combination. From the viewpoint of reducing the environmental load, it is preferable to use water as the solvent.

The coating liquid can be applied to the base material layer by any suitable method. The coating liquid can be applied by, for example, a wet film forming method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, and a die coater. The coating temperature and the drying temperature of the coating liquid are not particularly limited, and may be, for example, 50 ° C. or higher.

The resin layer 21 may be formed on the base material layer 20 by an extrusion method. In the case of the extrusion method, multi-layer extrusion using a T-die may be adopted. Examples of the adhesive that can be used during extrusion include maleic anhydride-modified polypropylene resin. An adhesive layer may be formed on the base material layer 20 in advance by applying this adhesive onto the base material layer 20 and then drying the adhesive. The thickness of the adhesive layer can be 0.1 to 50 μm from the viewpoint of adhesiveness, followability, processability, etc., and is preferably 0.5 to 20 μm.

The inorganic thin film layer 22 can be formed, for example, by vacuum film formation. In the vacuum film formation, a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of the physical vapor deposition method include, but are not limited to, a vacuum deposition method, a sputtering method, and an ion plating method. Examples of the chemical vapor deposition method include, but are not limited to, a thermal CVD method, a plasma CVD method, and an optical CVD method.

In the above vacuum deposition, resistance heating type vacuum deposition method, EB (Electron Beam) heating type vacuum deposition method, induction heating type vacuum deposition method, sputtering method, reactive sputtering method, dual magnetron sputtering method, plasma chemical vapor deposition method (PECVD method) and the like are particularly preferably used. However, considering productivity, the vacuum vapor deposition method is currently the best. As the heating means of the vacuum vapor deposition method, it is preferable to use any one of an electron beam heating method, a resistance heating method, and an induction heating method.

The resin layer 23 can be formed by a coating method or an extrusion method in the same manner as in the step of forming the resin layer 21.

When the resin layer 23 is formed by the coating method, the coating liquid may contain a silane compound. When the coating liquid contains a silane compound, the coating liquid may further contain an acid catalyst, an alkali catalyst, a photoinitiator, and the like.

Further, as the film or sheet constituting the body of the tube container according to the present invention, a film or sheet having the following layer structure may be used.

14 and 15 are cross-sectional views showing an example of a layer structure of a material that can be used for the body of the tube container according to the modified example.

The material 41 shown in FIG. 14 is obtained by laminating an adhesive layer 44, a polypropylene layer 45 having a barrier property, an adhesive layer 46, and an unstretched polypropylene layer 47 on a layer 43 of unstretched polypropylene in this order. The adhesive layers 44 and 46 are formed, for example, by an adhesive for dry laminating. The polypropylene layer 45 having a barrier property can be formed, for example, by the gas barrier laminate 19 shown in FIG.

The material 42 shown in FIG. 15 is obtained by laminating an adhesive resin layer 48, a polypropylene layer 45 having a barrier property, an adhesive resin layer 49, and an unstretched polypropylene layer 47 on the unstretched polypropylene layer 43 in this order. .. The adhesive resin layers 48 and 49 can be formed, for example, by a mixture of polypropylene and modified polypropylene. Modified polypropylene is a compound that exhibits adhesiveness by graft-modifying polypropylene with an organic acid such as maleic anhydride.

Both the material 41 shown in FIG. 14 and the material 42 shown in FIG. 15 are made of a resin mainly composed of polypropylene. Therefore, by welding the body portion made of the material 41 or 42 and the spout portion made of a resin mainly composed of polypropylene, a tube container in which 90% by mass or more of the total of the body portion and the spout portion is polypropylene. Can be configured. Therefore, by using the film or sheet material shown in FIGS. 14 and 15, a tube container having excellent recyclability can be realized.

The material 41 shown in FIG. 14 and the material 42 shown in FIG. 15 may be formed as a thin film having a total thickness of 250 μm or less, or may be formed as a sheet material having a thickness of about 300 to 500 μm that can be used for a laminated tube. You can also do it. By forming the body of the laminated tube using the sheet material having the layer structure shown in FIG. 14 or FIG. 15 and welding it to the spout portion made of a resin mainly composed of polypropylene, the total of the body and the spout is It is possible to construct a highly recyclable laminated tube containing 90% by mass or more of polypropylene.

Hereinafter, examples of concrete implementation of the present invention will be described.
(Example 1)
A stretched polypropylene film with a thickness of 20 μm (FOA, manufactured by Futamura Chemical Co., Ltd.) and an unstretched polypropylene film with a thickness of 80 μm (FHK2, manufactured by Futamura Chemical Co., Ltd.) are dry-laminated using a two-component curable urethane adhesive. A film for forming the body was prepared by laminating. The obtained film was processed into a tubular shape by a bag making machine to form a tube having a diameter of 35 mm. The spout portion was formed by injection molding polypropylene. After welding the obtained tube to the spout portion, water was poured into the body portion to close one end of the body portion to prepare the tube container shown in FIG.

(Example 2)
A barrier coating agent containing montmorillonite and PVA was applied to a stretched polypropylene film having a thickness of 20 μm (FOA, manufactured by Futamura Chemical Co., Ltd.) to obtain a stretched polypropylene film having a barrier property. The obtained barrier-type stretched polypropylene film and an unstretched polypropylene film having a thickness of 80 μm (Futamura Chemical Co., Ltd., FHK2) are bonded together by dry laminating using a two-component curable urethane adhesive for forming the body. Film was prepared. The obtained film was processed into a tubular shape by a bag making machine to form a tube having a diameter of 35 mm. The spout portion was formed by injection molding a barrier resin obtained by adding EVOH of 10% of the total mass to polypropylene. After welding the obtained tube to the spout portion, water was poured into the body portion to close one end of the body portion to prepare the tube container shown in FIG.

(Example 3)
A stretched polypropylene film with a thickness of 20 μm (FOA, manufactured by Futamura Chemical Co., Ltd.), an aluminum vapor-deposited stretched polypropylene film with a thickness of 20 μm (manufactured by Mitsui Chemicals Tohcello Co., Ltd., OP102), and an unstretched polypropylene film with a thickness of 60 μm (manufactured by Futamura Chemical Co., Ltd.). , FHK2) were bonded in this order by dry laminating using a two-component curable urethane adhesive to prepare a film for forming a body. The obtained film was processed into a tubular shape by a bag making machine to form a tube having a diameter of 35 mm. The spout portion was formed by injection molding a barrier resin obtained by adding EVOH of 10% of the total mass to polypropylene. After welding the obtained tube to the spout portion, water was poured into the body portion to close one end of the body portion to prepare the tube container shown in FIG.

(Comparative Example 1)
A silica-deposited polyester film with a thickness of 12 μm (GL-RD manufactured by Letterpress Printing Co., Ltd.) and an unstretched polypropylene film with a thickness of 100 μm (Futamura Chemical Co., Ltd., FHK2) are used with a two-component curable urethane adhesive. A film for forming the body was prepared by laminating in this order by dry laminating. The obtained film was processed into a tubular shape by a bag making machine to form a tube having a diameter of 35 mm. The spout portion was formed by injection molding a barrier resin obtained by adding EVOH of 10% of the total mass to polypropylene. After welding the obtained tube to the spout portion, water was poured into the body portion to close one end of the body portion to prepare the tube container shown in FIG.

(Comparative Example 2)
A silica-deposited polyester film with a thickness of 12 μm (GL-RD manufactured by Letterpress Printing Co., Ltd.), a stretched polypropylene film with a thickness of 12 μm (manufactured by Toray Co., Ltd., P60), and an unstretched polypropylene film with a thickness of 80 μm (manufactured by Futamura Chemical Co., Ltd., FHK2) was bonded in this order by dry laminating using a two-component curable urethane adhesive to prepare a film for forming a body. The obtained film was processed into a tubular shape by a bag making machine to form a tube having a diameter of 35 mm. The spout portion was formed by injection molding a barrier resin obtained by adding EVOH of 10% of the total mass to polypropylene. After welding the obtained tube to the spout portion, water was poured into the body portion to close one end of the body portion to prepare the tube container shown in FIG.

(Comparative Example 3)
A silica-deposited polyester film with a thickness of 12 μm (GL-RD manufactured by Letterpress Printing Co., Ltd.), a stretched nylon film with a thickness of 15 μm (manufactured by Unitika Ltd., ONBC), and an unstretched polyethylene film with a thickness of 60 μm (manufactured by Tamapoli Co., Ltd., SE620L). ) And were bonded in this order by dry laminating using a two-component curable urethane adhesive to prepare a film for forming a body. The obtained film was processed into a tubular shape by a bag making machine to form a tube having a diameter of 35 mm. The spout portion was formed by injection molding a barrier resin obtained by adding EVOH of 10% of the total mass to polypropylene. After welding the obtained tube to the spout portion, water was poured into the body portion to close one end of the body portion to prepare the tube container shown in FIG.

(Comparative Example 4)
Uniaxially stretched polyethylene with a thickness of 50 μm (PE3K-BT manufactured by Futamura Chemical Co., Ltd.), stretched polyester film with a thickness of 12 μm (manufactured by Toray Industries, Inc., P60), and unstretched polyethylene film with a thickness of 80 μm (manufactured by Tamapoli Co., Ltd., SE620L). And were bonded in this order by dry laminating using a two-component curable urethane adhesive to prepare a film for forming a body. The obtained film was processed into a tubular shape by a bag making machine to form a tube having a diameter of 35 mm. The spout portion was formed by injection molding polypropylene. After welding the obtained tube to the spout portion, water was poured into the body portion to close one end of the body portion to prepare the tube container shown in FIG.

(Comparative Example 5)
By extrusion tube molding, a barrier tube having a layer structure of polypropylene (42 μm) / adhesive resin layer (3 μm) / EVOH (10 μm) / adhesive resin layer (3 μm) / polypropylene (42 μm) having a thickness of 100 μm and a diameter of 35 mm was produced. The spout portion was formed by injection molding polypropylene. After welding the obtained tube to the spout portion, water was poured into the body portion to close one end of the body portion to prepare the tube container shown in FIG.

The loop stiffness of the films produced in each Example and each Comparative Example and the firmness of the tube container containing water were evaluated as follows.

(Loop stiffness)
A measurement sample obtained by cutting the film or tube produced in each Example and each Comparative Example into a rectangular shape of 15 mm × 60 mm was prepared, and set in a loop-stiffness tester (registered trademark, Toyo Seiki Seisakusho Co., Ltd.) in a loop shape. Loop stiffness was measured.

(Stiffness)
Sensory evaluation of the firmness when the water-filled tube container prepared in each example and each comparative example was touched was evaluated, and "◎: very firm, ○: firm, △: slight stiffness. There is, but it is insufficient, ×: The container is soft and difficult to handle. "

Table 1 also shows the layer structure, total thickness, loop stiffness (LS) value, firmness, and gravure printing availability of each example and each comparative example.

As shown in Table 1, in Examples 1 to 3, the film constituting the body has a desirable loop stiffness as a tube container, and even when a tube container is produced using this film, a sufficient elasticity is felt. was gotten. Further, the films according to Examples 1 to 3 are also suitable for gravure printing, and it is possible to perform highly cosmetic printing on the body of the tube container.

On the other hand, in Comparative Examples 1, 4 and 5, the loop stiffness of the film itself constituting the body was insufficient, and the tube container produced using this film was soft and firm. Further, in Comparative Examples 2 and 3, the loop stiffness of the film constituting the body was a desirable value for the tube container, but when the tube container was manufactured using this film, there was some stiffness, but the handling was handled. The ease was insufficient. Further, in Comparative Example 5, since the body portion is composed of an extruded tube and gravure printing cannot be performed, it is disadvantageous in that cosmetic printing cannot be performed.

The tube container according to the present invention can be used as a packaging material for pharmaceuticals, cosmetics, foods, and the like.

1 Body 2 Injection outlet 3 Injection cylinder 4 Flange 5a, 5b End 6a, 6b End 15 layers (unstretched polypropylene)
16 and 17 layers (stretched polypropylene)

Claims (6)

A tubular body with one end closed and
A spout portion attached to the other end of the body portion is provided.
A tube container containing 90% by mass or more of polypropylene in total of the body portion and the spout portion. The spout portion is made of a resin material containing polypropylene as a main component.
The tube container according to claim 1, wherein the body portion is made of a film containing a layer of stretched polypropylene and a layer of unstretched polypropylene. The tube container according to claim 2, wherein a barrier layer having a barrier property is laminated on the stretched polypropylene layer. The tube container according to claim 2 or 3, wherein the thickness of the film constituting the body portion is 30 to 250 μm. The body portion is a molded body obtained by molding the film having a pair of substantially parallel edge edges into a tubular shape.
The tube container according to claim 2, wherein the inner surfaces of the strip-shaped portions including each of the pair of edge edges are joined to each other. The spout part
Cylindrical pouring tube and
A flat plate-shaped flange portion connected to one end of the dispensing cylinder portion and extending outward of the dispensing cylinder portion and extending in a direction orthogonal to the axial direction of the dispensing cylinder portion is provided.
The tube container according to any one of claims 1 to 5, wherein the inner surface near the other end of the body portion is joined to the surface of the flange portion on the other end side of the ejection cylinder portion.

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