JP2008162599A - Laminated body for extruded tube containers - Google Patents

Abstract

Provided is a laminated body for an extruded tube container in which peeling between a barrier layer and a sealant layer does not occur due to a volatile component and a liquid component.
A laminated body for an extruded tube container according to the present invention comprises a thermoplastic resin in which an outermost layer and an innermost layer can be heat-sealed, and at least a barrier layer is provided between the outermost layer and the innermost layer. In the laminated body for an extruded tube container having a plurality of intermediate layers, an unsaturated carboxylic acid or an anhydride thereof as an anchor coat layer 5 on the interior side surface of the barrier layer 4 is in a range of 0.01 to 5% by mass, and It consists of polyolefin copolymer resin particles having a number average particle size of 1 μm or less, and is characterized in that it is a coated and dried layer of an aqueous dispersion substantially free of non-volatile aqueous additive.
[Selection] Figure 1

Description

    The present invention relates to a laminated body for an extruded tube container, which has excellent barrier properties against oxygen, water vapor, etc., content resistance, etc., and is used for filling and packaging contents such as toothpaste, food, cosmetics, pharmaceuticals, etc. The present invention relates to a laminated body for an extruded tube container used for producing a tube container having a printed display portion.

  An extruded tube container using a flexible laminate with laminated synthetic resin films is a laminate of a surface resin layer made of polyolefin resin, a plurality of intermediate layers, and a sealant layer made of polyolefin resin. Body is rolled, the surface resin layer and the surface of the sealant layer are rolled up and heat-sealed to produce a cylindrical body, and then a mouth is formed in one opening of the cylindrical body. A head composed of a head portion, a shoulder portion, and the like, and a cap is screwed into the head portion. On the other hand, the contents are filled from the other opening portion of the cylindrical body portion, and then the opening portion is sealed. The bottom seal part is formed by sealing to form an extruded tube container.

  The sealant layer of the tube container is generally made of a material having good heat sealing properties such as polyethylene and polypropylene and having resistance to the contents. In addition, the surface resin layer is made of polyethylene, polypropylene, etc., which has good heat sealability with the sealant layer, in order to perform heat sealing by superimposing the surface resin layer and sealant layer of the laminate in the process of manufacturing the tube container. Has been.

  The laminate used for the tube container has at least a barrier layer between the surface resin layer and the sealant layer, but the bonding surface between the barrier layer and the sealant layer is extremely important for maintaining the function of the laminate. In general, (1) a method in which an anchor coat layer is provided as an adhesive layer on the barrier layer surface and a polyolefin resin is laminated thereon by extrusion lamination, or (2) a two-component curable polyurethane as an adhesive layer on the barrier layer surface. A method of laminating a film for forming a sealant layer previously formed into a film shape by using a dry lamination method, using a dry laminating adhesive such as a system adhesive, is employed.

  First, in the extrusion laminating method of (1), the anchor coat layer is formed by an anchor coat agent-forming composition 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 time, there is a problem that the sealant layer peels off from the barrier layer. .

Similarly, when the sealant layer is bonded to the barrier layer in (2) by the dry lamination method, the resistance of the dry laminating adhesive is insufficient, and the barrier layer and the sealant layer are separated after a long period of storage. There is a problem of peeling.
Further, the anchor coating agent and the adhesive for dry laminating generally contain an organic solvent, and during the work, the organic solvent is released and the work environment is deteriorated.

  The laminated body for an extruded tube container of the present invention is a laminated body for an extruded tube container in which delamination between the barrier layer and the sealant layer does not occur even when a dentifrice containing an aromatic component such as alcohol or essential oil is filled. The issue is to provide

The laminated body for an extruded tube container according to the present invention comprises a plurality of intermediate layers including at least a barrier layer between the outermost layer and the innermost layer, and the outermost layer and the innermost layer are made of a heat-sealable thermoplastic resin. In the laminated body for an extruded tube container, the interior side surface of the barrier layer has an unsaturated carboxylic acid or an anhydride thereof as an anchor coat layer in a range of 0.01 to 5% by mass and a number average particle diameter of 1 μm or less. It is characterized in that it is a coated and dried layer of an aqueous dispersion which is made of the above-mentioned polyolefin copolymer resin particles and does not substantially contain a non-volatile aqueous additive.
The anchor coat layer is a coating layer having a dry film thickness of 0.1 to 2 μm, and the innermost layer is laminated as an extrusion coat layer made of polyolefin resin via the anchor coat layer, or the anchor coat layer A polyolefin-based resin sheet is laminated on a polyolefin-based resin extrusion coating layer to form an innermost layer.
The barrier layer is characterized in that an aluminum foil is adhered to the surface of the substrate, or a deposited film of metal or metal oxide.

  In the laminated body for an extruded tube container of the present invention, it contains an unsaturated carboxylic acid or its anhydride in the range of 0.01 to 5% by mass, and consists of polyolefin copolymer resin particles having a number average particle diameter of 1 μm or less, By using an aqueous dispersion coating layer that is substantially free of non-volatile aqueous additive as an anchor coat layer, it has excellent adhesion to metal foils such as aluminum foil and barrier layers such as vapor deposition films, and extrusion of sealant layers. It can also be excellent in adhesion to the coat layer. In addition, 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 is excellent in resistance to these components, or a barrier layer and a sealant layer No delamination occurs and the tube container is excellent in the storage stability of the contents. In addition, the amount of organic solvent discharged when producing the laminate is small, and the exhaust gas treatment facility can be simplified.

Below, the laminated body for extruded tube containers of this invention is demonstrated with reference to drawings.
FIG. 1 is a cross-sectional view illustrating an example of a laminated body for an extruded tube container according to the present invention. Laminate 1 has surface resin layer 2, sand layer 2a, base material layer 3, barrier layer 4, barrier layer surface anchor coat layer 5, sealant layer 6, sand layer 6a, printing surface 7, anchor coat layer 8, milk white low density. A polyethylene film 9, a sand layer 9a, and a sand layer 10 are formed.

The laminate 1 will be described in the order of the manufacturing process. After forming a desired printing surface 7 on one surface of the base material layer 3, a two-component curable urethane anchor coat agent or the like is applied to the surface of the printing surface 7, The anchor coat layer 8 is formed by drying.
Next, milk white low density polyethylene film 9 is laminated on anchor coat layer 8 by a dry lamination method using sand layer 9a. Next, an aluminum foil as a barrier layer 4 and an ethylene-methacrylic acid copolymer resin or the like as a sand layer 10 are extruded onto the surface of the milk white low density polyethylene film 9 and bonded together by a sand lamination method.
Next, the barrier layer surface anchor coat layer 5 in the present invention is formed on the barrier layer 4. On the barrier layer surface anchor coat layer 5, a sealant layer 6 is laminated by a sand lamination method by extrusion of a polyethylene sand layer 6a.
On the other hand, an anchor coat layer 8 is formed on the opposite side of the printing surface 7 of the base material layer 3 as on the printing surface 7 side, and the surface resin layer 2 made of a low density polyethylene film is formed on the anchor coating layer 8 surface. Are laminated by a sand lamination method by extrusion of a polyethylene sand layer 2a.

  In such a laminate, in addition to the biaxially stretched polyethylene terephthalate film, the base material layer 3 is transparent, such as a biaxially stretched polyester film, a biaxially stretched nylon film, or a biaxially stretched polypropylene film. A synthetic resin film having excellent characteristics can be used.

Next, the barrier layer surface anchor coat layer 5 contains an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass and has a number average particle diameter of 1 μm or less, for example, 50 nm to 200 nm. And an aqueous dispersion substantially free of non-volatile aqueous additive such as an 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.
Non-volatile aqueous additives such as emulsifiers remain in the coating 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. In other words, in the production process of the aqueous dispersion, a non-volatile aqueous additive such as an emulsifier is not added for the purpose of promoting aqueous formation or stabilizing the aqueous dispersion.

The anchor coat layer is applied so as to have a thickness of 0.1 to 2 μm when dried, thereby forming a barrier layer such as a metal foil such as an aluminum foil or a metal oxide vapor-deposited film such as SiO ₂ or Al ₂ O _3. As a coating surface, a good adhesive layer is formed on a plastic film, a polyolefin resin layer that is extrusion-coated as a sealant layer, and the like.

FIG. 2 is a partially cutaway view showing an example of the tube container of the present invention.
The tube container 20 rolls up the laminate described above, superimposes the surface resin layer surface 2 that is the outermost layer at both ends of the laminate and the sealant layer 6 that is the innermost layer, and superposes the polymerization end portions thereof. A welded portion 21 is formed by welding to produce a cylindrical portion 22 constituting the tube container. Next, a head portion 25 including a shoulder portion 23 and a mouth portion 24 constituting a tube container is formed on the upper portion of one opening portion of the tubular portion 22. Moreover, the surface of the cylindrical part 22 has a printing layer 26 for characters, figures, symbols, patterns, and the like by various printing methods. Next, a cap 27 for sealing is attached to the mouth portion 14 of the head portion 25, and after the mouth portion 24 is sealed, contents 29 such as toothpaste, kneaded mustard, and kneaded wasabi are placed in the opening portion 28 of the cylindrical portion 22. After the fixed amount is filled, the opening 28 is welded to form the bottom welded portion 30, and the tube container 20 filled with the contents 29 can be obtained.
The tube container of the present invention is not limited to the one having the structure shown in the figure, and can be applied to a self-solid body such as a three-way seal body and a standing pouch.
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Example 1
A desired printing pattern is applied to the back surface of a 12 μm thick biaxially stretched polyethylene terephthalate film, and then a two-component curable urethane anchor coating agent (“EL-540” manufactured by Toyo Morton Co., Ltd.) is dried on the printed surface. A milk white low-density polyethylene film having a thickness of 0.5 μm and a thickness of 50 μm was laminated by a sand lamination method with a thickness of a polyethylene layer of 20 μm.
Next, an aluminum foil having a thickness of 10 μm is extruded on the side of the milky white low density polyethylene film of the above laminate by an ethylene-methacrylic acid copolymer resin (EMAA, Mitsui-Du Pont Chemical Co., Ltd. “Nucrel N1108C”) by a sand lamination method. Bonding was performed with a sand layer having a thickness of 25 μm. Further, an aqueous dispersion of a polyolefin copolymer resin containing 2% by mass of maleic anhydride on the aluminum foil surface, in which particles having a number average particle diameter of 0.6 μm are dispersed, an aqueous dispersion containing no emulsifier (Unitika “SE-1200” manufactured by Co., Ltd. was applied to a dry thickness of 0.5 μm and dried by heating to form an anchor coat layer.
Subsequently, a low-density polyethylene film having a thickness of 50 μm was laminated by a sand lamination method in which polyethylene was extruded and a sand layer having a thickness of 20 μm was formed.
A two-component curable urethane anchor coating agent (“EL-540” manufactured by Toyo Morton Co., Ltd.) with a dry film thickness of 0.5 μm is applied to the biaxially stretched polyethylene terephthalate film side of the obtained laminate. A 40 μm low density polyethylene film (“FC-S” manufactured by Tosero Co., Ltd.) was extruded and laminated with a 25 μm polyethylene layer by a sand lamination method to produce a laminate for an extruded tube container.

The laminated structure and film thickness (μm) of the obtained extruded tube container laminate are as follows.
PE (40) / PE (25) / AC (urethane) / PET (12) / Printing / AC (urethane) / PE (20) / milk white PE (50) / EMAA (25) / AL (10) / AC (anchor coat layer of the present invention) / PE (20) / PE (50)

  The obtained laminate is cut into a size of 150 mm × 120 mm, the laminate is rounded, the polymerization end portion is heat-sealed to form a tubular portion of the tube container, and further, at one end of the tubular portion A high-density polyethylene was injection-molded to form a shoulder portion and a mouth portion with an inner diameter of 38 mm, and a cap made of high-density polyethylene was attached to the mouth portion.

  Next, an evaluation test was performed by the following test method in which the contents were put in a tube container, and the results are shown in Table 1.

1. Test of resistance to contents Toothpaste A (Lion's "Prime STAIN OFF"), Toothpaste B (Sato Pharmaceutical's "Asses"), and test mustard filled with 150g each Ten pieces were produced.
Each test tube container was stored at 40 ° C. for 3 months, and the presence or absence of delamination of the laminate after storage was visually confirmed. About the number which carried out delamination, it shows by the number of ten produced.
2. Laminate strength test of laminate AL / PE The laminate strength of AL / PE of laminate before and after the test was measured using a tensile tester (A & D Tensilon) at a tensile speed of 50 mm / min and a sample width of 15 mm. did.

Example 2
A desired printing pattern is applied to the back surface of a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm, and then a two-component curable urethane anchor coating agent (“EL-540” manufactured by Toyo Morton Co., Ltd.) ) Was applied at a dry film thickness of 0.5 μm, and a low-density polyethylene film having a thickness of 50 μm was laminated by a sand lamination method with a thickness of a polyethylene layer of 20 μm.
Next, a urethane-based AC agent (manufactured by Toyo Morton Co., Ltd.) was applied to the non-deposited surface of the PET film in which aluminum oxide was vapor-deposited to a thickness of 400 mm on one surface of a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film. EL-540 ") was applied with a dry film thickness of 0.5 [mu] m, and the laminate prepared above was laminated with an extruded polyethylene layer of 20 [mu] m by a sand lamination method.
Next, an aqueous dispersion of a polyolefin copolymer resin containing 2% by mass of maleic anhydride is dispersed on the vapor deposition surface of the obtained laminate, and particles containing a number average particle diameter of 0.6 μm are dispersed and no emulsifier is contained. An aqueous dispersion (“SE-1200” manufactured by Unitika Co., Ltd.) was applied to a dry thickness of 0.5 μm and dried by heating to obtain an anchor coat layer.
Subsequently, a low-density polyethylene film having a thickness of 50 μm was laminated by a sand lamination method in which polyethylene was extruded and a sand layer having a thickness of 20 μm was formed.
A two-component curable urethane anchor coating agent (“EL-540” manufactured by Toyo Morton Co., Ltd.) with a dry film thickness of 0.5 μm is applied to the biaxially stretched polyethylene terephthalate film side of the obtained laminate. A 40 μm low density polyethylene film (“FC-S” manufactured by Tosero Co., Ltd.) was extruded and laminated with a 25 μm polyethylene layer by a sand lamination method to produce a laminate for an extruded tube container.
The laminated structure and film thickness (μm) of the obtained extruded tube container laminate are as follows.
PE (40) / PE (25) / AC (urethane-based) / PET (12) / printing / AC (urethane-based) / PE (20) / PE (50) / AC (urethane-based) / PET having a vapor deposition layer Lamination / AC (AC layer of the present invention) / PE (20) / PE (50) with (12) the PET side as the AC (urethane-based) side and the vapor deposition layer as the AC (AC layer of the present invention) side
Next, a tube container was produced in the same manner as in Example 1, and an evaluation test was performed in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 1
In Example 1, a two-component curable urethane anchor coating agent (“EL-540” manufactured by Toyo Morton Co., Ltd.) was used instead of the coating layer made of an aqueous dispersion of a polyolefin copolymer resin formed on the aluminum foil surface. A laminate was prepared in the same manner as in Example 1 except that was applied with a dry film thickness of 0.5 μm.
The laminated structure and film thickness (μm) of the obtained extruded tube container laminate are as follows.
PE (40) / PE (25) / AC (urethane) / PET (12) / Printing / AC (urethane) / PE (20) / milk white PE (50) / EMAA (25) / AL (10) / AC (urethane) / PE (20) / PE (50)
Next, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2
A desired printing pattern is applied to the back surface of a 12 μm thick biaxially stretched polyethylene terephthalate film, and then a two-component curable urethane anchor coating agent (“EL-540” manufactured by Toyo Morton Co., Ltd.) is dried on the printed surface. A milk white low-density polyethylene film having a thickness of 0.5 μm and a thickness of 50 μm was laminated by a sand lamination method with a thickness of a polyethylene layer of 20 μm.
Next, an aluminum foil having a thickness of 10 μm is extruded on the side of the milky white low-density polyethylene film of the above laminate by an ethylene-methacrylic acid copolymer resin (EMAA, “Nucleel N1108C” manufactured by Mitsui DuPont Chemical Co., Ltd.) by a sand lamination method. And a sand layer having a thickness of 30 μm. Further, a low-density polyethylene film having a thickness of 50 μm was laminated on the aluminum foil surface by a sand lamination method with 20 μm of an extruded ethylene-methacrylic acid copolymer resin (EMAA, “Nucleel N1108C” manufactured by Mitsui DuPont Chemical Co., Ltd.).
A two-component curable urethane anchor coating agent (“EL-540” manufactured by Toyo Morton Co., Ltd.) with a dry film thickness of 0.5 μm is applied to the biaxially stretched polyethylene terephthalate film side of the obtained laminate. A 40 μm low density polyethylene film (“FC-S” manufactured by Tosero Co., Ltd.) was extruded and laminated with a 25 μm polyethylene layer by a sand lamination method to produce a laminate for an extruded tube container.
The laminated structure and film thickness (μm) of the obtained extruded tube container laminate are as follows.
PE (40) / PE (25) / AC (urethane) / PET (12) / Printing / AC (urethane) / PE (20) / milk white PE (50) / EMAA (25) / AL (10) / EMAA (20) / PE (50)
Next, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1. Note that the number of delaminations of the sealant layer is indicated by the number of the 10 created. Further, in Table 1, ^* means that 3 out of 10 pieces cannot be measured by peeling, and 7 are measured values out of 10 pieces.

  The laminated body for an extruded tube container of the present invention is suitable for a tube container for packaging of paste-like toothpaste or food containing a component having a large permeability to the sealant layer, and even if the component permeates over a long period of time. The laminated body for an extruded tube container does not peel off the barrier layer and the sealant layer in the laminated body and does not cause problems such as breakage of the tube container.

FIG. 1 is a cross-sectional view for explaining an example of a laminate used for manufacturing the tube container of the present invention. FIG. 2 is a partially cutaway view showing an example of the tube container of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Laminated body, 2 ... Surface resin layer, 2a ... Sand layer, 3 ... Base material layer, 4 ... Barrier layer, 5 ... Barrier layer surface anchor coat layer, 6 ... Sealant layer, 6a ... Sand layer, 7 ... Printing surface, DESCRIPTION OF SYMBOLS 8 ... Anchor coat layer, 9 ... Milk white low density polyethylene film, 9a ... Sand layer, 10 ... Sand layer, 20 ... Tube container, 21 ... Welded part, 22 ... Cylindrical part, 23 ... Shoulder part, 24 ... Mouth Part 25 ... head part 26 ... printing layer 27 ... cap 28 ... opening part 29 ... content 30 ... bottom weld part

Claims (3)

In the laminated body for an extruded tube container, wherein the outermost layer and the innermost layer are made of a heat-sealable thermoplastic resin and have a plurality of intermediate layers including at least a barrier layer between the outermost layer and the innermost layer. The interior side surface of the layer is composed of polyolefin copolymer resin particles having an unsaturated carboxylic acid or anhydride thereof in the range of 0.01 to 5% by mass and a number average particle size of 1 μm or less as a anchor coat layer, and is non-volatile A laminated body for an extruded tube container, characterized in that it is a coated and dried layer of an aqueous dispersion substantially free of an aqueous additive. The anchor coat layer is a coating layer having a dry film thickness of 0.1 to 2 μm, and the innermost layer is laminated as an extrusion coat layer made of a polyolefin resin via the anchor coat layer, or the anchor coat layer The laminate for an extruded tube container according to claim 1, wherein a polyolefin resin sheet is laminated through an extrusion coating layer of a polyolefin resin to form an innermost layer. The laminated body for an extruded tube container according to claim 1, wherein the barrier layer is an aluminum foil adhered to the surface of the base material or a metal or metal oxide deposited film.

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