JP5509550B2 - Method for manufacturing laminate for Rondel molded body, method for manufacturing Rondel molded body, and method for manufacturing tube container - Google Patents

Description

  The present invention relates to an upper member (Rondel molded body) that is used by being integrally molded with a shoulder portion and a mouth-neck portion of a tube container. In particular, the body of the tube container is formed of a laminate having an excellent gas barrier property, and the shoulder, the neck and the neck, and the spout provided integrally with one end of the body are also provided on the inner surface of the shoulder. A tube container with improved gas barrier properties of the entire container can be obtained by arranging and molding a high gas barrier Rondel molded body that has been molded in advance according to the shape of the inner surface of the head, mouth and neck, and spout Is.

Conventionally, tube containers should be used by toothpaste, kneaded wasabi, kneaded, packed with foods such as condensed milk, cosmetics, pharmaceuticals, etc. As an easy-to-use container, its use and use amount have been expanded.
Such tube containers are diversified with the expansion of applications, and in order to improve the storage stability of the contents, it is required to improve the gas barrier property of the tube container. In the tube container, the body part is formed of a laminated sheet obtained by laminating a metal foil gas barrier material such as aluminum foil, and the shoulder part of the shoulder part and the mouth-neck part formed by integral molding at one end of the body part A donut-shaped member called a Rondel molded body, in which a composite sheet obtained by laminating a heat-adhesive resin such as polyethylene on both sides of a metal foil is punched in a circle, and a hole corresponding to the mouth and neck is provided in the center A tube container made by molding and inserting a cocoon into a cap shape and integrally forming it was used (Patent Document 1).

However, even in the tube container as described above, although the thickness of the molded resin is thick at the mouth and neck, no measures for improving the gas barrier property are taken, and it is not completely airtight. In addition, the contents filled in the tube container are often low in fluidity such as pastes, so in the case of contents that are easily affected by oxygen, the contents filled in the mouth and neck during storage Discolored or changed in quality, and this is pushed out at the start of use. Therefore, it has been desired to further improve the gas barrier property for the mouth and neck.
In order to meet such a demand, the gas barrier property improving member such as the Rondel molded body is not limited to the shoulder portion of the tube container, but also from the frustoconical shoulder portion to the cylindrical mouth and neck portion that is continuous therewith. There has been proposed a tube container in which the molded member is molded into an extended shape, and the molded member is integrally molded on the shoulder portion and the mouth and neck portion of the tube container (Patent Document 2).
JP-A-5-116245 JP 2006-224467 A

  The Rondel molded body composed of the above-mentioned frustoconical shoulder and a cylindrical mouth and neck molded body continuous therewith is formed on the inner and outer peripheral surfaces of the shoulder portion of the tube container, and further inside the shoulder portion itself. Since it is applied as buried, it uses a molded body formed by cold forming such as compressed air or press forming to form a shape that fits the shoulder of the tube container, and subsequent punching forming Has been.

  A laminated sheet used in a conventional Rondel molded body has a metal foil layer at least between a surface resin layer and a sealant layer, and a laminated sheet in which polyolefin resin films are laminated on both the front and back surfaces of the metal foil layer. A Rondel molded body made of a molded body is used. In general, (1) a method in which an anchor coat layer is provided as an adhesive layer on the metal foil layer surface, and a polyolefin resin is laminated by extrusion lamination on both the front and back surfaces, or (2) two adhesive layers are provided on the metal foil layer surface. Using a dry laminating adhesive such as a liquid curable polyurethane adhesive, a method of laminating a surface resin layer and a sealant layer forming film that have been formed into a film in advance by laminating by a dry lamination method is employed. .

  First, in the extrusion laminating method of (1), the anchor coat layer is formed by a composition for forming an anchor coat agent such as an organic titanium-based, isocyanate-based, polyethyleneimine-based, or polybutadiene-based agent. When components with high permeability such as alcohol components and essential oil components are included, the anchor coat layer has insufficient resistance, and when it is stored for a long period of time, the sealant layer may delaminate from the metal foil layer. There is. For this reason, when piercing and opening the sealed spout provided on the cylindrical mouth and neck, delamination between the sealant layer and the metal foil layer occurs, and the interlayer strength decreases while in contact with the contents There was a problem in the piercing and unsealing properties, such as the unsealing performance of the sealing spout being lowered or the unsuccessful unsealing.

Similarly, when a sealant layer is bonded to the metal foil layer of (2) by the dry lamination method, the contents containing a highly permeable substance such as a fragrance, mineral oil, or an organic polar solvent are enclosed in the tube container. Then, since the highly permeable substance reaches the adhesive layer surface for dry lamination in the Rondel molded body laminated on the shoulder of the tube container, the interface between the sealant layer and the metal foil layer of the Rondel molded body is reached. The highly permeable substance stays, the resistance of the adhesive for dry laminating is insufficient, and after a long period of storage, the interlaminar strength of the portion decreases and the delamination phenomenon occurs. When producing a Rondel molded body by deep-drawing a laminated sheet having the above-described structure, the laminated sheet adhered with an adhesive has poor followability to deep-drawing processing due to insufficient strength between layers, The moldability is inferior, for example, peeling occurs, distortion is formed in the molded body, and pinholes are generated. For this reason, the original function of the Rondel molded body is impaired, and the storage performance of the contents in the tube container is lowered. Also in this case, when the sealed spout provided in the cylindrical mouth and neck was pierced and opened, there was a problem with the piercing and unsealing properties such as the unsealing performance of the sealed spout being lowered or poor opening. .
In addition, there are restrictions on the bonding method between the layers, especially the sealant layer on the content side of the metal foil layer, and thermosetting adhesives such as urethane adhesives and epoxy adhesives are bonded for dry lamination. When used as an agent, the uncondensed monomer still remaining after thermosetting may be transferred to the content through the sealant layer, which may cause alteration or discoloration.

The above problems can be solved by the following present invention.
That is, the invention described in claim 1 is the production of a laminate for Rondel molded body comprising at least an unstretched thermoplastic resin layer, a metal foil protective layer, a metal foil layer, an anchor coat layer, and a thermoplastic resin layer from the outside. In this method , a metal foil protective layer is bonded to one surface of the metal foil layer via an adhesive, and an unsaturated carboxylic acid or an anhydride thereof is added to the other surface of the metal foil layer to 0.01. contained in a range of 5 mass%, and a number average particle diameter of dispersed following polyolefin copolymer resin particles 1 [mu] m, coating an aqueous dispersion substantially free of non-aqueous aid, dried Forming an anchor coat layer, laminating a thermoplastic resin layer on the anchor coat layer to produce a first laminate, heat-treating the first laminate, and then performing a cooling treatment, On the metal foil protective layer of the first laminate, By laminating an unstretched thermoplastic resin layer through the Chakuzai, characterized in that the production of Rondel molded body laminate.

According to a second aspect of the present invention, in the method for manufacturing a laminate for a Rondel molded body according to the first aspect, the first laminated body is heat-treated at 180 ° C. to 220 ° C. for 1 second to 3 seconds. It is characterized by that.

According to a third aspect of the present invention, in the method for manufacturing a laminate for a Rondel molded body according to the first or second aspect, the heat treatment is performed by bringing a heat roll into contact with the metal foil protective layer surface of the first laminated body. It is characterized by performing .

According to a fourth aspect of the present invention, in the method for manufacturing a laminate for a Rondel molded body according to any one of the first to third aspects, the cooling treatment is performed on a surface of the metal foil protective layer of the first laminated body. It is characterized by performing in contact.

The invention described in claim 5 is the method for manufacturing a laminate for a Rondel molded body according to any one of claims 1 to 4, wherein the metal foil protective layer is formed of at least two layers. .

A sixth aspect of the present invention is the method for producing a laminate for a Rondel molded body according to any one of the first to fifth aspects, wherein the thermoplastic resin layer is formed of low density polyethylene. .

The invention described in claim 7 is a process for manufacturing a laminate for a Rondel molded body by the method for manufacturing a laminate of a Rondel molded body according to any one of claims 1 to 6, and the laminate for a Rondel molded body. And manufacturing a Rondel molded body comprising a frustoconical shoulder, a cylindrical head connected to the shoulder, and a sealed spout, the sealed spout being breakable by a projection , The manufacturing method of the Rondel molded object characterized by including these .

The invention described in claim 8, the tubular body portion, and forming a multilayer laminate having a gas barrier property, the opening of the top of the barrel, the production of Rondel molded article according to claim 7 And a step of integrally forming a shoulder portion of the Rondel molded body manufactured by the method and a head portion connected to the shoulder portion .

  According to the present invention, it is possible to manufacture a laminate for a Rondel molded body that has excellent adhesion strength between layers and has good followability to deep drawing, and the Rondel molded body does not cause delamination or pinholes. Can be manufactured. When an extruded tube container is produced using this Rondel molded body, it is possible to prevent the unsealing property at the time of piercing and unsealing of the sealed spout and the occurrence of unsuccessful unsealing. In addition, the presence of the metal foil layer can completely block the outside air and contents until it is pierced by the protrusion, and the toothpaste, food, medicine, etc. containing aromatic components such as alcohol and essential oil as an extruded tube container Even if the container is stored, it is possible to prevent deterioration of the storage performance of the contents in the tube container, such as alteration or discoloration of the contents, and a tube container having excellent contents storage stability can be obtained.

Hereinafter, a method for producing a Rondel molded body laminate of the present invention, and its using Rondel molded body laminate manufactured by the manufacturing method of the method of forming Rondel molded body in detail with reference to the accompanying drawings and the like described To do.
FIG. 1 shows a configuration of a laminate 1 for a Rondel molded body manufactured by the method for manufacturing a laminate for a Rondel molded body according to the present invention. It is composed of unstretched thermoplastic resin layer 2 / metal foil protective layer 3 / metal foil layer 4 / anchor coat layer 5 / thermoplastic resin layer 6 in order from the outer side when the tube container is finally produced. The
FIG. 2 is a diagram for explaining a process of a method for producing the Rondel molded body 17 using the laminate 1 for Rondel molded body, and shows the shape of the Rondel molded body for each process in a front view. However, the step of trimming the outer periphery of the fifth molded body in the step (7) is omitted.
FIG. 3 is a cross-sectional view of the main part showing the configuration of an embodiment in which the Rondel molded body 17 produced using the Rondel molded body laminate 1 is used for the tube container 18. In addition, this invention is not limited to these drawings, unless the summary is exceeded.

  As the unstretched thermoplastic resin layer 2, when the tube container shoulder portion and the mouth-and-neck portion 21 continuous therewith are integrally molded, the outer molded resin 22 and the Rondel molded body 17 may be strongly heat-welded. Resin that can be used, for example, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polyolefin resins such as polypropylene (homopolypropylene, block polypropylene, random polypropylene, etc.), or olefin and vinyl A polyolefin resin such as a monomer, an acrylic monomer, a copolymer with a copolymerizable monomer such as an unsaturated carboxylic acid, or a blend composition thereof is mainly used. The unstretched thermoplastic resin layer has a thickness of about 30 μm to 200 μm, preferably about 40 μm to 150 μm.

  When the above-mentioned unstretched thermoplastic resin layer 2 is used as the outermost layer of the laminate 1 for the Rondel molded body, the Rondel molded body 17 is produced by deep drawing and integrally formed with the tube container 18. The adhesion between the outer molded resin 22 and the Rondel molded body 17 that forms the shoulder portion and the continuous neck and neck portion 21 is improved, and does not peel off after filling and storing the contents.

  As the metal foil protective layer 3, it is preferable to use a film having a high film elongation rate so that the followability to the deep drawing process is good. For example, nylon, amorphous polyethylene terephthalate sheet or the like is used. The metal foil protective layer 3 may be composed of one layer using the film, or may be composed of at least two or more layers using one or more kinds of films. The thickness of the metal foil protective layer 3 is preferably 10 μm to 50 μm, and if it is 10 μm or less, the metal foil layer is easily broken at the time of deep-drawing molding, forming is difficult, and if it is 50 μm or more, the laminate for the Rondel molded body The elongation becomes worse and the molding becomes difficult, and the piercing and unsealing property of the sealed spout becomes worse.

  By protecting the surface of the metal foil layer using a film having a high film elongation rate for the metal foil protective layer 3, the followability to the deep drawing process is improved, and the occurrence of delamination and pinholes can be prevented. When the metal foil protective layer is at least two layers, the metal foil layer has higher protection than the single layer, which further improves the formability during deep drawing, It can be prevented that pinholes are generated and the barrier property is lowered.

  As the metal foil layer 4, a metal foil such as an aluminum foil can be used. The thickness of the metal foil layer 4 is preferably 30 μm to 100 μm. When the thickness is 30 μm or less, pinholes are generated during deep drawing, and when the thickness is 100 μm or more, the metal foil layer becomes too strong. The elongation of the resin is poor, tearing and pinholes occur, and the molding processability deteriorates.

  By providing the metal foil layer 4 having gas barrier properties to the laminate 1 for the Rondel molded body, a barrier action against gas and moisture can be provided.

The anchor coat layer 5 contains an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass, and consists of polyolefin resin particles having a number average particle diameter of 1 μm or less, for example, 50 nm to 200 nm. An aqueous dispersion substantially free from non-volatile aqueous additive such as emulsifier is applied and dried. This aqueous dispersion is described in JP-A-2004-9504, and is a polyolefin resin (A) composed of an unsaturated carboxylic acid or its anhydride, an olefin compound, and a (meth) acrylic ester. An aqueous dispersion and an aqueous dispersion of a polyester resin (B) having an anionic group of 20 to 700 (equivalent / 10 ⁶ g), and the mass ratio of the resin content in each aqueous dispersion is (A) / ( B) = 90/10 to 20/80, which is produced by mixing, and is commercially available from Unitika as Arrow Base SA-1200, SB-1200, SE-1200, TB-2010, etc. Are illustrated.

  The anchor coat layer 5 is thinly applied so that the thickness when dried is 0.1 to 2 μm, so that the metal foil layer 4 such as an aluminum foil is used as an application surface and adheres to the thermoplastic resin layer 6 and the like. It can be excellent in properties.

  Non-volatile aqueous additives such as emulsifiers remain in the coating film even after drying, and even if a small amount, it has a great effect on the adhesive interface, and decreases the adhesion and water resistance. No. 5, no non-volatile aqueous additive such as an emulsifier is added for the purpose of promoting aqueous formation or stabilizing the aqueous dispersion in the production process of the aqueous dispersion. For this reason, delamination does not occur, and the adhesiveness with the metal foil layer 4 is excellent and the adhesiveness with the thermoplastic resin layer 6 is also excellent. Further, even if toothpaste, food, medicine, etc. containing aromatic components such as alcohol and essential oil are stored as an extruded tube container, the anchor coat layer 5 is excellent in resistance to these components. There is no delamination with the plastic resin layer 6, and the tube container can be made excellent in the storage stability of the contents.

The thermoplastic resin layer 6 includes, for example, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene homopolymer, polypropylene copolymer, acrylonitrile polymer, polyester, ethylene / vinyl alcohol copolymer, ethylene・ Ethyl acrylate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, acid copolymer consisting of copolymer of unsaturated carboxylic acid and olefin, ethylene / vinyl acetate copolymer alone Resin or a mixed resin of two or more of these is used.
Among them, it is preferable to use low density polyethylene having high adhesiveness between the anchor coat layer 5 and the thermoplastic resin layer 6, and Rondel molding having excellent piercing openability when opening the sealing spout 19 of the tube container 18. The body laminate 1 can be produced. The thickness is about 30 μm to 100 μm, preferably about 40 μm to 60 μm.

  As a process for producing the laminate 1 for a Rondel molded body as shown in FIG. 1, first, the metal foil layer 4 is bonded to one surface of the metal foil protective layer 3 via an adhesive. As a bonding method, a dry laminating method, a heat laminating method, a sandwich laminating method, or the like may be laminated, or the metal foil layer 4 may be extruded and laminated. Examples of adhesives include modified polyolefin resins, two-component curable urethane adhesives, polyester urethane adhesives, polyether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, poly Vinyl acetate adhesives, epoxy adhesives, rubber adhesives, and the like can be used.

  When the metal foil protective layer 3 is composed of at least two layers, only the first layer is bonded to the metal foil layer 4, and the second layer or more are laminated to the unstretched thermoplastic resin layer 2 via an adhesive, In the final step, they are bonded and integrated to produce a laminate 1 for Rondel molded body. Alternatively, a plurality of metal foil protective layers 3 may be formed on the metal foil layer 4 in advance via an adhesive.

  Next, the anchor coat liquid is coated on the metal foil layer 4 and dried to form the anchor coat layer 5. As a coating method, a normal coating method such as a gravure coating method can be used.

  Further, a thermoplastic resin layer 6 is formed by laminating a thermoplastic resin on the anchor coat layer 5 by an extrusion lamination method, a T-die coextrusion coating method, or the like, and a first laminate 7 is produced.

  Next, said 1st laminated body 7 is heat-processed, and also it cools. Specifically, the heat treatment and the cooling treatment are performed by sending the first laminated body 7 to a heat roller, heat-treating the metal foil protective layer 3 on a heat roll, and then applying the heat treatment to each layer of the first laminated body 7. After the molten state is melted and kept in a molten state for a certain period, it is sent to a cooling roll and rapidly cooled to solidify the entire molten layer.

The heat treatment is usually performed at 160 ° C. or higher, preferably 180 ° C. to 220 ° C., but the molten state of the first laminate 7 is at least for a certain period, preferably 1 second to 3 seconds, until the cooling roll. It is preferable to hold for a while. If the molten state holding time is too short or does not reach the molten state, adhesion between the metal foil protective layer 3 and the metal foil layer 4, the anchor coat layer 5, and the thermoplastic resin layer 6 is not achieved. It becomes sufficient, and pinholes may be generated or float (delamination) may occur due to delamination in the finally formed Londel molded body laminate 1 or the Londel molded body 17 formed by deep drawing. In some cases, a heat oven, an infrared heater, or the like can be used as a heat treatment method.
By performing the heat treatment, the compatibility between the metal foil protective layer 3, the metal foil layer 4, the anchor coat layer 5, and the thermoplastic resin layer 6 is improved, and the adhesive strength between the layers is improved.

Next, the first laminate 7 is rapidly cooled to form a strong welded layer between each layer, particularly between the metal foil layer 4 and the anchor coat layer 5. In this case, the cooling rate is 80 ° C./second or more and 1000 ° C./second or less, preferably 80 ° C./second or more and 500 ° C./second or less, and the temperature of the first laminate 7 is 70 ° C. to 0 ° C., preferably 40 ° C. to It is preferable to rapidly cool to 10 ° C.
By improving the interlaminar strength, when the Rondel molded body laminate 1 is deep-drawn to produce the Rondel molded body 17, it is excellent in formability without causing delamination and the opening of the tube container extraction port. Decline and poor opening can be prevented.

  After the heat treatment and cooling treatment, the unstretched thermoplastic resin layer 2 is bonded to the metal foil protective layer 3 of the first laminate 7 via an adhesive to produce a laminate 1 for Rondel molded body. When the metal foil protective layer is composed of at least two layers, the second or higher metal foil laminated on the unstretched thermoplastic resin layer 2 side on the first metal foil protective layer on the first laminate 7 side. The laminate 1 for Rondel molded body is produced by bonding the protective layer surfaces. Alternatively, a plurality of metal foil protective layers 3 are previously laminated on the metal foil layer 4 of the first laminate 7 via an adhesive, and the unstretched thermoplastic resin layer 2 is bonded via the adhesive. The laminate 1 for the Rondel molded body may be produced. As a bonding method, a dry laminating method, a heat laminating method, a sandwich laminating method, or the like may be laminated, or extrusion lamination may be performed on the metal foil protective layer. Examples of adhesives include modified polyolefin resins, two-component curable urethane adhesives, polyester urethane adhesives, polyether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, poly Vinyl acetate adhesives, epoxy adhesives, rubber adhesives, and the like can be used.

  In the laminate 1 for the Rondel molded body, no adhesive is used on the contents side of the metal foil layer 4, so that when the Rondel molded body 17 is produced by deep drawing the Rondel molded body laminate 1, adhesion is performed. Due to insufficient adhesive strength of the agent, delamination and pinholes do not occur, and it is possible to prevent the storage performance of the contents in the tube container from deteriorating. In addition, after filling the contents into the tube container 18 using the Rondel molded body 17, the adhesive at the interface between the thermoplastic resin layer 6 and the metal foil layer 4 of the Rondel molded body 17 is formed by the highly permeable substance of the contents. The durability is insufficient, and the deterioration of the interlayer strength after the storage for a long time, or the deterioration of the opening of the sealed extraction port 19 of the tube container 18 due to the occurrence of the delamination phenomenon can be prevented. Further, it is possible to prevent the uncondensed monomer in the adhesive from being transferred to the contents and being altered or discolored.

A method for manufacturing the Rondel molded body 17 by deep drawing using the laminate 1 for Rondel molded body will be described.
In the manufacturing method of the Rondel molded body 17 shown in FIG. 2, in the step (1), a round and flat composite sheet 8 having a predetermined size is produced by punching from the laminate 1 for Rondel molded body manufactured above. Then, in the step (2), the circular composite sheet 8 is formed into a frustoconical shape having an inclined outer edge portion by press molding at room temperature using a first male and female molding die, and at the same time, The first portion 12 is formed into a cylindrical shape having a head portion 10 and a top portion 11, and a first molded body 12 having the head portion 10 and the top portion 11 at the center of the shoulder portion 9 is produced. Compared with the 5th molded object 16 shown to the process (6), the 1st molded object 12 produced at this process is the thing in which the diameter of the head 10 is especially large and a height is also low.
In the step (3), the area of the shoulder 9 is increased while reducing the diameter of the head 10 by pressing the first molded body 12 at room temperature using a second male and female mold. In step (4), the second molded body 13 is formed by press molding at room temperature using a third male and female mold, and the diameter of the head 10 is further reduced. The third molded body 14 is produced by molding so as to increase the area of the shoulder 9 while reducing the size of the shoulder 9, and then in the step (5), the third molded body is brought close to the final shape Rondel molded body. The body 14 is press-molded at room temperature using a fourth male and female mold, and the head 10 is further reduced in diameter to a predetermined diameter, and at the same time, the length of the head 10 is increased to a predetermined value. The fourth molded body is molded into a length and molded so as to further increase the area of the shoulder 9. 5 to produce.
Then, in the step (6), the fourth molded body 15 is subjected to press molding at room temperature using a fifth male and female mold, as shown in FIG. A sealed spout 19 is formed, and the shape of the peripheral edge of the shoulder 9 is increased to one end, and then formed into a final set shape having a substantially horizontal portion at the lower end thereof to produce a fifth molded body 16. Is.
Furthermore, the step (7) includes a step of trimming the outer periphery of the fifth molded body 16 so as to have a predetermined outer peripheral dimension to obtain the final form of the Rondel molded body 17, but the shape is Illustration is omitted to approximate the fifth molded body 16. By using a Rondel molded body 17 having a frustoconical shoulder portion 9, a cylindrical head portion 10 connected to the shoulder portion, and a sealed spout 19 in the tube container, It can block out the outside air and contents completely to achieve high airtightness, improve the gas barrier property at the tube container shoulder and the continuous neck and neck, and prevent discoloration and alteration of the contents due to the influence of oxygen etc. it can. At the time of opening, the contents can be poured out by destroying the sealed spout with a protrusion.

  In the above steps (1) to (7), due to the good followability of the metal foil protective layer 3 against the deformation of the metal foil layer 4, the unstretched thermoplastic resin layer 2 / metal foil protective layer 3 / Generation of delamination and pinholes between the metal foil layers 4 can be prevented, and a cylindrical head and a sealed spout can be formed.

Next, FIG. 3 is a cross-sectional view of the main part showing the configuration of an embodiment in which the Rondel molded body 17 produced using the above-mentioned Rondel molded body laminate 1 is used for the tube container 18. It is the figure which abbreviate | omitted the lower part of FIG.
The tube container 18 shown in FIG. 3 has a cylindrical body portion 20 formed of a multilayer laminate having gas barrier properties, and a shoulder portion of the tube container and a mouth-and-neck portion 21 continuous therewith in an opening at an upper portion of the body portion 20. When the Rondel molded body 17 manufactured by the manufacturing method described in the above steps (1) to (7) is inserted into the inner surface, the center of the top as shown in FIG. The outer molding resin 22 is formed by the compression molding method or the injection molding method so as to cover the outer surface and the peripheral end portions except for and is integrally molded. A sealed spout 19 is formed at the center of the top portion that is not covered with the outer molding resin 22.

The multilayer laminate having a gas barrier property used for the body portion 20 has a simple structure as the multilayer laminate when the barrel portion 20 is produced by thermally bonding a multilayer laminate having a gas barrier property into a cylindrical shape. A laminate in which a printing layer such as a pattern and a gas barrier layer are laminated on the intermediate layer and a polyolefin resin layer is laminated on both sides thereof can be used.
There are no particular restrictions on the position at which the printed layer such as a candy or a pattern is provided as long as it is visible from the outside. When the multilayer laminate is thermally bonded in a cylindrical shape, the surface of the outer polyolefin resin layer, that is, the outermost layer It can also be provided at a position. Even when the gas barrier layer is opaque, the intermediate layer is limited to the outer surface of the gas barrier layer, but when the gas barrier layer is transparent, it may be either the outer surface or the inner surface of the gas barrier layer.

When the example of the structure of the said multilayer laminated body is shown in an order from the outer side when heat-bonding to a cylinder shape, the following structures are mentioned.
(A) Polyolefin-based resin layer / adhesive layer / biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) / printing layer such as a pattern / adhesive layer / transparent or opaque gas barrier layer / adhesive layer / polyolefin-based resin layer (B) Polyolefin-based resin layer / adhesive layer / transparent gas barrier layer / printed layer such as pattern / adhesive layer / polyolefin-based resin layer (c) Printed layer such as pattern / polyolefin-based resin layer / adhesive layer / transparent or opaque in addition the gas barrier layer / adhesive layer / polyolefin resin layer, it is also possible to produce the body of the tubular container by using the Rondel molded body laminate 1.

The tube container 18 rolls up the laminated body described above, superimposes the surface resin layer surface, which is the outermost layer at both ends of the laminated material, and the sealant layer, which is the innermost layer, and welds the polymerization end portions thereof. The body part 20 which forms a welding container and forms a tube container is produced. Moreover, the surface of the trunk | drum 20 has printing layers, such as a character, a figure, a symbol, a design, by various printing methods.
The laminated body is not limited to the tube container structure shown in the figure, but can be applied to a self-solid body such as a three-way seal body or a standing pouch.

In addition, compression molding is used as the outer molding resin 22 that is integrally molded with the Rondel molded body 17 to form the tube container shoulder and the mouth-neck part 21 continuous therewith in the opening at the top of the body 20 of the tube container 18. In addition to moldability of injection molding, it has heat-weldability with the polyolefin resin layers on both sides of the barrel 20 and the unstretched thermoplastic resin layer 2 of the Rondel molded body 17, and is continuous with the tube container shoulder. It is also necessary to be able to impart an appropriate hardness to the mouth-and-neck portion 21, and for that purpose, it is the same as the polyolefin resin used on both surfaces of the body portion 20 and the unstretched thermoplastic resin layer 2 used for the Rondel molded body 17. Resin can be used.
Since the heat of the resin heated and melted for compression molding or injection molding is used for heat welding to the edge of the barrel 20 and the Rondel molded body 17, the outer molding resin 22 has a melting temperature. It is preferable to use a high polyolefin-based resin, and it is more preferable to use medium density polyethylene or high density polyethylene in order to combine the required performance.

Next, a cap to be sealed is attached to the mouth / neck portion 24, and after the mouth / neck portion 24 is sealed, a predetermined amount of contents such as toothpaste, kneaded mustard, kneaded wasabi are filled from the opening of the trunk portion 20, and the opening Is welded to form a bottom welded portion, and a tube container filled with the contents can be obtained.
The tube container 18 equipped with the Rondel molded body 17 obtained by molding the Rondel molded body laminate 1 manufactured by the Rondel molded body laminate manufacturing method according to the present invention is particularly excellent in gas barrier properties such as water vapor and oxygen. In addition, the outside air and the contents can be completely shut off, the contents in the tube container can be stably stored, and the contents can be suitably used particularly for contents that are altered by the presence of air (oxygen). The discharge port of the contents is closed by the Rondel molded body 17 before opening, and the sealing performance during storage is perfect. The discharge port is, for example, a protrusion provided on the cap or a separate protrusion. Thus, it can be easily formed by tearing the Rondel molded body portion of the sealing spout 19.
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Example 1
A laminate for a Rondel molded body was produced by the following procedure.
(Production of the first laminate )
A urethane adhesive (Rock Paint Co., Ltd. RU004) is coated on the easy-adhesion treated surface of a 15 μm-thick easy-adhesive nylon substrate (ON) (Unitika Co., Ltd. ONM-BRT), and a thickness of 50 μm is coated thereon. Aluminum foil (AL) (Toyo Aluminum Co., Ltd. 8079) was laminated by a dry laminating method.
An aqueous dispersion of a polyolefin copolymer resin containing 2% by mass of maleic anhydride as an anchor coating agent on the aluminum foil surface, in which particles having a number average particle size of 0.6 μm are dispersed and not containing an emulsifier A dispersion (Unitika Ltd. “Arrow Base SE-1200”) was applied so as to have a dry film thickness of 0.5 μm, and dried by heating to form an anchor coat layer (AC). Then, on the anchor coat layer, to a thickness of 50μm low density polyethylene (PE), and laminated by extrusion laminating method to prepare the first laminate of the following construction.
ON (15 μm) / AL (50 μm) / AC (0.5 μm) / PE (50 μm)
(Preparation of a laminate for Rondel molded body (a))
Next, using the first laminate, a laminate (a) for Rondel molded body was produced by the following procedure.
The 1st laminated body was sent to the feed roller of the dry laminator which installed the heat roll and the cooling roll, and it set so that the easily-adhesive nylon base material surface of said 1st laminated body might contact | connect a heat roll and a cooling roll. The surface temperature of the heat roll at the heat treatment set temperature was 190 ° C., and the surface temperature of the cooling roll was 20 ° C. The first laminate was transported at a transport speed of 50 m / min and subjected to heat treatment and cooling treatment.
Thereafter, a urethane adhesive (Rock Paint Co., Ltd. RU004) is coated on the surface of the above easily laminated nylon base material of the first laminate , and after drying, a 50 μm thick polyethylene film (PEF) (Tamapoly Co., Ltd.) UB-3) was laminated by a dry laminating method to produce a laminate (a) for Rondel molded body having the following configuration.
PEF (50 μm) / ON (15 μm) / AL (50 μm) / AC (0.5 μm) / PE (50 μm)
(Production of Rondel molded body (a))
A Rondel molded body comprising a truncated cone-shaped shoulder, a cylindrical head connected to the shoulder, and a sealed spout by deep drawing using the laminate (a) for the Rondel molded body (A) (Head height 12 mm, outer diameter Φ10 mm) was prepared. This was inserted into the shoulder portion of the laminate tube to prepare a tube container, filled with toothpaste (Sato Pharmaceutical “Ace”) as the contents, and stored at 60 ° C. The Rondel molded body (a) was cut out from the tube container before and after storage, and the cross section was visually checked for delamination. The results are shown in Table 1.

(Example 2)
(Preparation of laminate for Rondel molded body (b))
Using the first laminate produced in Example 1, a laminate (b) for Rondel molded product was produced by the following procedure.
A corona-treated surface of 16 μm thick A-PET (Toray Film Processing Co., Ltd .: F865) is coated with urethane adhesive (Rock Paint Co., Ltd. RU004), and after drying, a 50 μm thick polyethylene film (PEF) ( The corona-treated surfaces of Tamapoly Co., Ltd. UB-3) were bonded together by a dry laminating method to produce a laminate B.
On the other hand, the 1st laminated body produced in Example 1 is sent to the feeding roller of the dry laminator which installed the hot roll and the cooling roll, and the easily bonding nylon base material surface of said 1st laminated body is a hot roll and cooling. Set to touch the roll. The surface temperature of the heat roll at the heat treatment set temperature was 190 ° C., and the surface temperature of the cooling roll was 20 ° C. The first laminate was transported at a transport speed of 50 m / min and subjected to heat treatment and cooling treatment.
Thereafter, a urethane adhesive (Rock Paint Co., Ltd. RU004) is coated on the easily adhesive nylon base surface of the first laminate , and after drying, the A-PET surface of the laminate B is pasted by a dry lamination method. A laminate (b) for a Rondel molded body having the following configuration was produced.
PEF (50 μm) / A-PET (16 μm) / ON (15 μm) / AL (50 μm) / AC (0.5 μm) / PE (50 μm)
(Production of Rondel molded body (b))
A Rondel molded body comprising a frustoconical shoulder, a cylindrical head connected to the shoulder, and a sealed spout by deep drawing using the laminate (b) for Rondel molded body ( b) (Head height 12 mm, outer diameter Φ10 mm) was prepared. This was inserted into the shoulder portion of the laminate tube to prepare a tube container, filled with toothpaste (Sato Pharmaceutical “Ace”) as the contents, and stored at 60 ° C. The Rondel molded body (b) was cut out from the tube container before and after storage, and the cross section was visually checked for delamination. The results are shown in Table 1.

(Comparative Example 1)
(Preparation of laminate for Rondel molded body (c))
Using the first laminate produced in Example 1, a Rondel molded product laminate (c) was produced by the following procedure.
A urethane adhesive (Rock Paint Co., Ltd. RU004) is coated on the easy-adhesive nylon substrate surface of the first laminate produced in Example 1, and after drying, a polyethylene film (PEF) having a thickness of 50 μm (PEF) ( Tamapoly Co., Ltd. UB-3) was laminated by a dry laminating method to produce a laminate (c) for Rondel molded article having the following constitution.
PEF (50 μm) / ON (15 μm) / AL (50 μm) / AC (0.5 μm) / PE (50 μm)
(Production of Rondel molded body (c))
Rondel molding comprising a truncated cone-shaped shoulder, a cylindrical head connected to the shoulder, and a sealing spout by deep drawing using the laminate (c) for Rondel molded body. A body (c) (head height 12 mm, outer diameter Φ10 mm) was prepared. This was inserted into the shoulder portion of the laminate tube to prepare a tube container, filled with toothpaste (Sato Pharmaceutical “Ace”) as the contents, and stored at 60 ° C. The Rondel molded body (c) was cut out from the tube container before and after storage, and the cross section was visually checked for delamination. The results are shown in Table 1.

(Comparative Example 2)
(Preparation of laminate for Rondel molded body (d))
A laminate (d) for Rondel molded body was prepared by the following procedure.
A urethane adhesive (Rock Paint Co., Ltd. RU004) is coated on the easy-adhesion treated surface of a 15 μm-thick easy-adhesive nylon substrate (ON) (Unitika Co., Ltd. ONM-BRT), and a thickness of 50 μm is coated thereon. Aluminum foil (AL) (Toyo Aluminum Co., Ltd. 8079) was laminated by a dry laminating method.
The surface of the aluminum foil was coated with a urethane adhesive, and after drying, A-PET (Toray Film Processing Co., Ltd .: F865) having a thickness of 16 μm was laminated by a dry laminating method. Thereafter, a urethane adhesive is coated on the surface of the laminate of the above-mentioned easy-bonding nylon, and after drying, a 100 μm thick polyethylene film (PEF) (Tamapoly Co., Ltd. UB-3) is laminated by a dry laminating method. A laminate (d) for Rondel molded body having the following configuration was produced.
(Production of Rondel molded body (d))
Using a laminate (d) for Rondel molded body, a Rondel molded body comprising a frustoconical shoulder, a cylindrical head connected to the shoulder, and a sealed spout (by deep drawing) ( d) (Head height 12 mm, outer diameter Φ10 mm) was prepared. This was inserted into the shoulder portion of the laminate tube to prepare a tube container, filled with toothpaste (Sato Pharmaceutical “Ace”) as the contents, and stored at 60 ° C. Before and after storage, the shoulder portion of the tube container was cut in the longitudinal direction, and the cross section was visually observed to confirm the presence or absence of delamination of the Rondel molded body (d). The results are shown in Table 1.
PEF (100 μm) / ON (15 μm) / AL (50 μm) / A-PET (16 μm)

(Comparative Example 3)
A laminate for a Rondel molded body (e) was produced by the following procedure.
A 50 μm thick aluminum foil (AL) (Toyo Aluminum Co., Ltd. 8079) is coated on both sides with a urethane adhesive (Rock Paint Co., Ltd. RU004), dried, and then 150 μm thick polyethylene film (PEF) (Tamapoly) UB-3) was laminated by a dry laminating method to produce a laminate (e) for Rondel molded article having the following configuration.
PEF (150 μm) / AL (50 μm) / PEF (150 μm)
Although deep drawing was performed using the laminate (e) for the Rondel molded body, delamination occurred at the interface between the aluminum foil and the polyethylene film, and the Rondel molded body could not be molded.

  In the laminates (a), (b) and the Rondel molded products (a), (b) used in Examples 1 and 2, delamination and pinholes occurred before and after the storage test. It did not occur and had good barrier properties.

By using the Rondel molded body obtained by molding the Rondel molded body laminate manufactured by the Rondel molded body manufacturing method according to the present invention , a tube container having particularly excellent barrier properties can be provided. The contents in the container can be stored stably.

It is the laminated body for Rondel molded objects manufactured by the manufacturing method of the laminated body for Rondel molded objects which concerns on this invention . It is a figure explaining the process of shape | molding the laminated body for Rondel molded objects and manufacturing a Rondel molded object. It is sectional drawing of the principal part which shows the structure of one Example which used the Rondel molded object produced by shape | molding the laminated body for Rondel molded objects for the shoulder part and mouth neck part of a tube container.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laminated body for molded bodies 2 Unstretched thermoplastic resin layer 3 Metal foil protective layer 4 Metal foil layer 5 Anchor coat layer 6 Thermoplastic resin layer 7 First laminated body 8 Circular composite sheet 9 Shoulder 10 Head 11 Top part 12 1st molded object 13 2nd molded object 14 3rd molded object 15 4th molded object 16 5th molded object 17 Rondel molded object 18 Tube container 19 Sealing outlet 20 Body part 21 Tube container shoulder part The mouth and neck part 22 which continues to it and the outside molding resin 23 The tube container shoulder part 24 The mouth and neck part

Claims (8)

At least a method for producing a laminate for a Rondel molded body comprising an unstretched thermoplastic resin layer, a metal foil protective layer, a metal foil layer, an anchor coat layer, and a thermoplastic resin layer from the outside,
A metal foil protective layer is bonded to one surface of the metal foil layer via an adhesive, and an unsaturated carboxylic acid or anhydride thereof is added in an amount of 0.01 % by mass to 5 % by mass on the other surface of the metal foil layer. %, And a polyolefin copolymer resin particle having a number average particle size of 1 μm or less is dispersed, and an aqueous dispersion substantially free of a non-volatile aqueous agent is applied and dried to form an anchor coat layer. Forming a first laminate by laminating a thermoplastic resin layer on the anchor coat layer,
Apply heat treatment to the first laminate, then subject to cooling treatment,
A laminate for a Rondel molded body, wherein a laminate for a Rondel molded body is manufactured by laminating an unstretched thermoplastic resin layer via an adhesive on the metal foil protective layer of the first laminate. Manufacturing method. The method for producing a laminate for a Rondel molded body according to claim 1, wherein the first laminate is subjected to heat treatment at 180 ° C to 220 ° C for 1 second to 3 seconds. 3. The method for manufacturing a laminate for a Rondel molded body according to claim 1, wherein the heat treatment is performed by contacting a heat roll with the metal foil protective layer surface of the first laminate. The method for producing a laminate for a Rondel molded body according to any one of claims 1 to 3, wherein the cooling treatment is performed by bringing a cooling roll into contact with the metal foil protective layer surface of the first laminate. The said metal foil protective layer is formed in at least 2 layers, The manufacturing method of the laminated body for Rondel molded objects in any one of Claim 1 thru | or 4 characterized by the above-mentioned. The said thermoplastic resin layer is formed from low density polyethylene, The manufacturing method of the laminated body for Rondel molded objects in any one of Claim 1 thru | or 5 characterized by the above-mentioned. A step of producing a laminate for a Rondel molded article by the method for producing a Rondel molded article laminate according to any one of claims 1 to 6 ;
Using the Londel molded body laminate, it is composed of a frustoconical shoulder, a cylindrical head connected to the shoulder, and a sealed spout, and the sealed spout can be broken by protrusions. Manufacturing a simple Rondel molded body,
The manufacturing method of the Rondel molded object characterized by including this. A cylindrical body portion, and forming a multilayer laminate having a gas barrier property,
The step of integrally molding the shoulder portion of the Rondel molded body manufactured by the manufacturing method of the Rondel molded body according to claim 7 and the head connected to the shoulder portion in the opening of the upper portion of the trunk portion ;
The manufacturing method of the tube container characterized by including .