JP2019038575A - Laminate for tube container and tube container having the same - Google Patents

Abstract

To provide a laminate for tube container capable of remarkably reducing a carbon dioxide discharge amount during incineration.SOLUTION: A laminate for tube container includes at least a first extrusion resin layer 11, a polyester resin layer 12 and a second extrusion resin layer 13 in this order, where the first extrusion resin layer 11 and/or second extrusion resin layer 13 contain a carbon dioxide absorbent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate used for manufacturing a tube container, and more particularly to a laminate for a tube container that can further reduce carbon dioxide emission during incineration and a tube container including the same.

  A tube container widely used as a container for filling food or non-food is composed of a laminate including a resin material. Laminates containing these resin materials are only partially recycled, and most of them are incinerated after disposal. Recently, carbon dioxide generated during incineration has been It is regarded as a problem as causing a problem.

  This invention is made | formed in view of the said problem, The subject which it is going to solve is providing the laminated body for tube containers which can reduce significantly the carbon dioxide discharge amount at the time of incineration.

  The laminate for a tube container of the present invention comprises at least a first extruded resin layer, a polyester-based resin layer, and a second extruded resin layer in this order, and the first extruded resin layer and / or the second extruded resin layer. The resin layer includes a carbon dioxide absorbent.

  In one embodiment, the laminate for a tube container of the present invention comprises a third extruded resin layer, a gas barrier layer, a first extruded resin layer, a polyester resin layer, and a second extruded resin layer. In order, the 1st extrusion resin layer, the 2nd extrusion resin layer, and / or the 3rd extrusion resin layer contain a carbon dioxide absorber.

  In one embodiment, the 1st extrusion resin layer with which the layered product for tube containers of the present invention is provided, the 2nd extrusion resin layer, and / or the 3rd extrusion resin layer further contain a dispersing agent.

  In one embodiment, the total content of the carbon dioxide absorbent and the dispersant in the first extruded resin layer, the second extruded resin layer, and / or the third extruded resin layer provided in the laminate for a tube container of the present invention. Are 0.1 mass% or more and 5 mass% or less, respectively.

  In one Embodiment, the gas barrier layer with which the laminated body for tube containers of this invention is provided consists of metal foil.

  In one embodiment, the laminate for a tube container of the present invention further includes a printing layer between the first extruded resin layer and the polyester resin layer.

  The tube container of this invention is equipped with the said laminated body for tube containers, It is characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body for tube containers which can reduce significantly the carbon dioxide emission amount at the time of incineration can be provided.

It is a schematic cross section which shows an example of the laminated body of this invention. It is a schematic cross section which shows an example of the laminated body of this invention. It is a fragmentary sectional view showing an example of the tube container of the present invention.

<Laminated body for tube container>
The laminated body for tube containers of this invention is demonstrated referring drawings. The example of a schematic cross section of the laminated body for tube containers of this invention is shown in FIG. 1 and FIG.
As shown in FIG. 1, the laminated body 10 for tube containers of this invention is equipped with the 1st extrusion resin layer 11, the polyester-type resin layer 12, and the 2nd extrusion resin layer 13 in this order at least. .
Moreover, in one Embodiment, as shown in FIG. 2, the laminated body 10 for tube containers of this invention is the 3rd extrusion resin layer 14, the gas barrier layer 15, the 1st extrusion resin layer 11, and a polyester type | system | group. The resin layer 12 and the second extruded resin layer 13 are provided in this order.
Moreover, in one Embodiment, the laminated body 10 for tube containers of this invention is further equipped with the printing layer 16 between the 1st extrusion resin layer 11 and the polyester-type resin layer 12, as shown in FIG. .
Moreover, in one Embodiment, the laminated body 10 for tube containers of this invention is further equipped with the anchor-coat layer 17 between arbitrary layers, as shown in FIG.
Moreover, although not shown in figure, the laminated body 10 for tube containers of this invention may be provided with other layers, such as a sealant layer and a light shielding layer.

  Hereinafter, each layer which comprises the laminated body for tube containers of this invention is demonstrated.

[Extruded resin layer]
The extruded resin layer is a layer formed by a melt extrusion laminating method using a thermoplastic resin and a carbon dioxide absorbent described later.
The laminate of the present invention comprises at least two or more extruded resin layers (first extruded resin layer and second extruded resin layer).
The extruded resin layers provided in the laminate of the present invention may have the same configuration and thickness, or may have different configurations.
For example, when the laminate of the present invention includes three extruded resin layers, all of the first extruded resin layer, the second extruded resin layer, and the third extruded resin layer contain a carbon dioxide absorbent. Only one layer may contain a carbon dioxide absorbent. In addition, it goes without saying that the carbon dioxide reducing effect at the time of incineration is improved by adding a carbon dioxide absorbent to all the extruded resin layers.
The extruded resin layer may contain two or more different carbon dioxide absorbents.

Examples of the thermoplastic resin constituting the extruded resin layer include a polyethylene resin, a polypropylene resin, or a cyclic polyolefin resin, or a copolymer resin, a modified resin, or a mixture (including alloy) containing these resins as a main component. ) Can be used.
Examples of polyolefin resins include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), and metallocene catalysts. Ethylene-α / olefin copolymer, ethylene / polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene / maleic acid copolymer, ionomer resin, and interlayer adhesion In order to improve the , It can be used acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, an acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as itaconic acid.
Moreover, the resin etc. which graft-polymerized or copolymerized unsaturated carboxylic acid, unsaturated carboxylic anhydride, and ester monomer can be used for polyolefin resin.
These materials can be used alone or in combination of two or more.
As the cyclic polyolefin resin, for example, cyclic polyolefin such as ethylene-propylene copolymer, polymethylpentene, polybutene, polynorbornene, and the like can be used. These resins can be used alone or in combination.

The carbon dioxide absorbent used by mixing with the above-described thermoplastic resin can be used without particular limitation as long as it absorbs carbon dioxide chemically or physically.
Examples of the carbon dioxide absorbent include metal hydroxides such as lithium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide, metal oxides such as zinc oxide, titanium oxide, and aluminum oxide, and non-oxides. Mention may be made of crystalline aluminosilicates, natural zeolites, aluminosilicates such as synthetic zeolites, titanic acid compounds such as barium titanate, lithium silicates, silica gel, alumina and activated carbon. Among these, aluminosilicate is particularly preferable from the viewpoint of transparency of the laminate.

The shape of the carbon dioxide absorbent is not particularly limited, but is preferably a particle shape from the viewpoint of dispersibility.
The particle size is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.01 μm or more and 1 μm or less. By setting the particle size within the above numerical range, the dispersibility in the extruded resin layer can be improved while maintaining the carbon dioxide absorption performance.
In the present invention, the particle size means “average particle diameter” and can be measured by a dynamic light scattering method.

  As a method of mixing the above-described thermoplastic resin with a carbon dioxide absorbent and forming an extruded resin layer by a melt extrusion laminating method, the thermoplastic resin pellets and the carbon dioxide absorbent are supplied to the inlet of the melt extruder. Alternatively, a master batch containing a carbon dioxide absorbent may be supplied together with the thermoplastic resin pellets to the inlet of the melt extruder. In any case, it is preferable to use a dispersant in combination so that the carbon dioxide absorbent is uniformly dispersed in the thermoplastic resin during melt kneading in the melt extruder. By using the dispersant in combination, it is possible to prevent the carbon dioxide absorbent from aggregating, reducing the surface area, and reducing the carbon dioxide absorption performance.

The dispersant preferably has a hydroxyl group in the molecule.
Specifically, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, Examples thereof include polyoxypropylene-polyoxyethylene condensate. Among these, a polyoxypropylene-polyoxyethylene condensate is preferable because the dispersibility of the carbon dioxide absorbent is particularly excellent.

  The weight average molecular weight of the dispersant is preferably 1000 or more and 5000 or less, more preferably 3000 or more and 4000 or less, from the viewpoint of fluidity and prevention of bleeding out.

  When the carbon dioxide absorbent and the thermoplastic resin are melt-kneaded, it is preferable to mix the carbon dioxide absorbent with the thermoplastic resin in a state in which the carbon dioxide absorbent is taken into the lipid bilayer of the amphiphilic lipid. Examples of amphiphilic lipids include phospholipids, and more specific examples include phosphatidylcholine, dimyristoylphosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylglycerol, diphosphatidylglycerol, and sphingomyelin. The amphiphilic lipid forms a lipid bilayer in the thermoplastic resin during melt-kneading due to self-organization. By incorporating the carbon dioxide absorbent into this, the carbon dioxide absorbent is uniformly distributed in the resin. Can be dispersed.

The total content of carbon dioxide absorbent and dispersant contained in each extruded resin layer is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more, It is below mass%. By setting the contents of the carbon dioxide absorbent and the dispersant within the above numerical range, the carbon dioxide emission during incineration can be further reduced.
Moreover, generation | occurrence | production of the delamination with the layer adjacent to an extrusion resin layer can be suppressed.
Furthermore, since the transparency of the extruded resin layer can also be maintained, when the printed layer is present as a layer adjacent to the extruded resin layer, a decrease in visibility can be suppressed.

  As long as the properties of the present invention are not impaired, the extruded resin layer contains additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a flame retardant, a crosslinking agent, and a colorant. Can be included.

  The thickness of the extruded resin layer is not particularly limited, but is preferably 5 μm or more and 60 μm or less. By setting the thickness of the extruded resin layer in the above numerical range, it is possible to obtain a laminate for a tube container that can further reduce carbon dioxide emission during incineration and can solve the problems of transparency and delamination.

[Polyester resin layer]
In one embodiment, the laminate of the present invention includes a polyester resin layer.
When the laminate of the present invention is provided with a polyester resin layer, the mechanical strength of the laminate can be improved.
Examples of the polyester resin contained in the polyester resin layer include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polytetramethylene terephthalate, and polycyclohexane. Examples include dimethylene terephthalate (PCT).

  The polyester resin layer may be provided with a vapor deposition film for the purpose of improving barrier properties. The deposited film is formed by a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method or a photochemical vapor deposition method. It can be formed by a conventionally known method such as a vapor deposition method (CVD method).

  As long as the properties of the present invention are not impaired, the polyester resin layer is made of additives such as antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, antiblocking agents, flame retardants, crosslinking agents, and coloring agents. Can be included.

The polyester resin layer may be provided with a printing layer (not shown) using a conventionally known printing ink. The printing layer is used for decoration, content display, best-of-life display, manufacturer, seller, etc., and other display and aesthetics, including letters, numbers, pictures, figures, symbols, patterns, etc. It is a layer for forming a desired arbitrary printed pattern. The print layer may be provided on the entire surface of the paper substrate, or may be provided on a part thereof. The printing layer can be formed using a conventionally known pigment or dye, and the printing method is not particularly limited, and a conventionally known method such as gravure printing, flexographic printing, or screen printing can be used. .
When a printing layer is provided on the polyester resin layer, an extruded resin layer adjacent to the printing layer functions as a protective layer, and deterioration of printing over time can be prevented.

  Examples of the material for forming the deposited film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), and boron (B). , Titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), and other inorganic substances or inorganic oxides.

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1,5 for boron (B), titanium (Ti) Can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5. In the above, when X = 0, it is a complete inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are suitably used for the packaging material, silicon (Si) is in the range of 1.0 to 2.0, and aluminum (Al) is in the range of 0.5 to 1.5. Can be used.

  In the present invention, the film thickness of the inorganic material or inorganic oxide vapor-deposited film as described above varies depending on the kind of inorganic material or inorganic oxide used, but is, for example, about 50 to 2000 mm, preferably about 100 to 1000 mm. It is desirable to select and form arbitrarily within the range.

  More specifically, in the case of an aluminum vapor-deposited film, the film thickness is preferably about 50 to 600 mm and in the range of 100 to 450 mm, and in the case of an aluminum oxide or silicon oxide vapor-deposited film, the film thickness is 50 to 500 mm. About 100 to 300 mm is desirable.

  Although the thickness of a polyester-type resin layer is not specifically limited, It is preferable that they are 5 micrometers or more and 500 micrometers or less, and it is more preferable that they are 10 micrometers or more and 200 micrometers or less.

[Barrier layer]
In one embodiment, the laminate of the present invention includes a barrier layer between arbitrary layers.
The barrier layer is provided to extend the storage period of the contents, and is made of metal foil such as aluminum, zinc, fungus, silver and alloys thereof, ethylene-vinyl alcohol copolymer (EVOH), polychlorinated. A resin layer having gas barrier properties such as vinylidene resin (PVDC) and aromatic polyamide such as nylon MXD6 can be used.
Moreover, you may provide the vapor deposition film | membrane of an inorganic substance or an inorganic oxide as above-mentioned. Further, on the vapor deposition layer, a general formula R1nM (OR2) m (wherein R1 and R2 represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n is 0 or more) M represents an integer of 1 or more, and n + m represents a valence of M.) and at least one alkoxide represented by the above-mentioned polyvinyl alcohol-based resin and / or A gas barrier coating film comprising an ethylene / vinyl alcohol copolymer and further obtained by a transparent gas barrier composition that is polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent May be provided.

  The thickness of the barrier layer is preferably 3 μm or more and 15 μm or less, and more preferably 4 μm or more and 12 μm or less. By setting the thickness of the barrier layer within the above numerical range, the generation of carbon dioxide during incineration can be suppressed, the amount of carbon dioxide absorbent used can be reduced, and the gas barrier properties of the tube container can be improved. Can be made.

[Anchor coat layer]
In one embodiment, the laminate of the present invention includes an anchor coat layer between arbitrary layers for the purpose of improving the adhesion between adjacent layers.
As an anchor coat agent that can be used for forming an anchor coat layer, an anchor coat made of any resin having a heat-resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, or polyethyleneimine. An anchor coating agent that is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups in the structure and an isocyanate compound as a curing agent is preferably used. can do. Moreover, a silane coupling agent may be used in combination as an additive, and nitrified cotton may be used in combination in order to improve heat resistance.
The anchor coat layer can be formed by applying and drying an anchor coat agent on an arbitrary layer.

[Other layers]
[Sealant layer]
In one embodiment, the laminate of the present invention includes a sealant layer as the outermost layer.
When manufacturing a tube container using a laminated body, a sealant layer is arrange | positioned at the contents side of a tube container, and has a function which seals laminated bodies. Even in the case of a laminate having the melt-extruded layer as an inner layer, the laminates can be sealed by heat sealing, but by providing a sealant layer, workability and sealing performance at the time of sealing can be improved. The resin contained in the sealant layer is not particularly limited as long as it can be fused to each other by heat. For example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (Linear) Low-density polyethylene (LLDPE), ethylene-α / olefin copolymer polymerized using metallocene catalyst, ethylene / polypropylene random or block copolymer, polypropylene, ethylene-vinyl acetate copolymer (EVA) ), Ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ionomer resin Heat-sealable ethylene / vinyl alcohol resin, , Copolymerized resin methylpentene resin, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene, polypropylene or cyclic olefin copolymer, polyolefin resin such as acrylic acid, methacrylic acid, maleic acid, Examples thereof include acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic anhydride, fumaric acid, and itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, and polyvinyl chloride resins.

  Among the above-mentioned resins, it is preferable to use polyethylene resins such as low density polyethylene and linear low density polyethylene, and polyolefin resins such as polypropylene, from the viewpoints of adhesion and manufacturing cost. The sealant layer is preferably made of an unstretched film.

  Linear low density polyethylene is obtained by polymerizing ethylene and a small amount of α-olefin by low pressure polymerization (gas phase polymerization using Ziegler-Natta catalyst or liquid phase polymerization using metallocene catalyst). . Linear low density polyethylene has many short molecular chains in the molecular chain and is excellent in sealing performance.

  The sealant layer may be a single layer or a multilayer. When the above-described linear low-density polyethylene derived from biomass is used for the sealant layer, a sealant layer including three layers of an inner layer, an intermediate layer, and an outer layer may be used. In this case, the intermediate layer is preferably made of biomass-derived linear low density polyethylene, and the inner layer and the outer layer are preferably made of conventionally known fossil fuel-derived linear low density polyethylene.

  The thickness of the sealant layer is preferably 25 μm or more and 150 μm or less, and more preferably 40 μm or more and 70 μm or less. By setting the thickness of the sealant layer within the above numerical range, the generation of carbon dioxide during incineration can be suppressed, and the amount of carbon dioxide absorbent used can be reduced.

  The sealant layer may contain a carbon dioxide absorbent and a dispersant.

[Shading layer]
In one embodiment, the laminate of the present invention includes a light shielding layer between arbitrary layers.
The light shielding layer is a layer provided to prevent ultraviolet rays and / or visible light from reaching the contents. The light shielding layer can be formed using white ink mainly containing titanium oxide or the like, black ink mainly containing carbon black, or gray ink mainly containing aluminum paste. As described above, when a metal foil such as an aluminum foil is used as the barrier layer, the barrier layer may also serve as a light shielding layer.

  The thickness of the light shielding layer is preferably 4 μm or more and 12 μm or less, and more preferably 5 μm or more and 9 μm or less.

<Method for producing tube container laminate>
The manufacturing method of the laminated body of this invention is not specifically limited, It can manufacture using conventionally well-known methods, such as a dry lamination method and a sand lamination method.

  The laminate of the present invention is provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / abrasion / lubricating functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. For the purpose, it is also possible to perform secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.). The laminate of the present invention can also be subjected to laminating (dry laminating or extrusion laminating), bag making, and other post-processing.

[Tube container]
Next, the case where a tube container is formed using the laminated body for tube containers by this invention is demonstrated.
FIG. 3 is a partial cross-sectional view schematically showing an example of a tube container. As shown in FIG. 3, the tube container 20 includes a head portion 21 and a cylindrical body portion 22.

  The head 21 includes a hollow conical shoulder 23 and a spout 24 and is integrally formed.

  The cylindrical body portion 22 is connected to the shoulder portion 23 of the head portion 21. The cylindrical trunk | drum 22 can be formed using the laminated body of this invention.

For example, in the case where the laminated body shown in FIG. 2 is used, the cylindrical body portion 22 includes a second extruded resin layer and a third extruded resin layer positioned at both ends of the cylindrical body portion 22. It is produced by stacking so that the extruded resin layer is on the inside, and heat-sealing and welding the overlapped portion.
Moreover, you may adhere | attach this overlap part with a conventionally well-known adhesive agent.
In addition, the both ends of the cylindrical trunk | drum 22 are not limited to the method of laminating | stacking a 2nd extruded resin layer and a 3rd extruded resin layer, A 2nd extruded resin layer or a 3rd extruded resin layer You may overlap each other.

  As a heat sealing method, a conventionally known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or a flame seal can be used.

  An example of the manufacturing method of the tube container 20 is demonstrated. The head 21 is connected to one opening of the cylindrical body 22 by a normal method such as compression molding. Thereafter, the contents are filled from the other open end connected to the head portion 21 of the cylindrical body portion 22, and the open end is thermally welded to form the bottom seal portion 25. Thereby, the tube container 20 filled and packaged with the contents can be obtained. A cap can be attached to the spout portion 24 by various methods such as screwing or fitting, for example, corresponding to the shape of the spout portion 24.

  The tube container 20 can be suitably used as a tube container for, for example, toothpaste, cosmetics, glue, paste hot pepper, paste wasabi, cream, paint, cartilage, pharmaceuticals, and other conventionally known products.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

[Example 1]
A biaxially stretched PET film having a thickness of 12 μm was prepared as a polyester resin layer, and a printed layer was formed on one surface thereof by gravure printing.

  Next, a two-component curable urethane anchor coat layer agent was applied onto the printed layer by a gravure method so that the film thickness after drying was 0.5 μm, and dried to form an anchor coat layer.

  Next, a mixture of a carbon dioxide absorbent (aluminosilicate, average particle size: 0.1 μm) and a dispersant (polyoxypropylene-polyoxyethylene condensate) is added to low-density polyethylene at 0.6 to the whole. It is added at a ratio of mass%, and extrusion lamination is performed at a temperature of 330 degrees using an extruder at a thickness of 15 μm, and the above-described anchor coat layer surface and an aluminum foil having a thickness of 7 μm as a gas barrier layer, It bonded together through the 1st extrusion resin layer.

  A two-component curable urethane anchor coat layer agent was applied to the other surface of the PET film by a gravure method so that the film thickness after drying was 0.5 μm, and dried to form an anchor coat layer.

  In the anchor coat layer, a mixture of a carbon dioxide absorbent (aluminosilicate, average particle size: 0.1 μm) and a dispersant (polyoxypropylene-polyoxyethylene condensate) is added to low density polyethylene with respect to the whole. It was added at a ratio of 0.6% by mass, and extrusion coating was performed at a temperature of 330 ° C. using an extruder at a thickness of 20 μm to form a second extruded resin layer.

  Next, a two-component curable urethane anchor coat layer agent was applied onto the aluminum foil by a gravure method so that the film thickness after drying was 0.5 μm, and dried to form an anchor coat layer.

In the anchor coat layer, a mixture of a carbon dioxide absorbent (aluminosilicate, average particle size: 0.1 μm) and a dispersant (polyoxypropylene-polyoxyethylene condensate) is added to low density polyethylene with respect to the whole. Addition at a ratio of 0.6% by mass, extrusion coating is performed at a temperature of 330 ° C. using an extruder at a thickness of 20 μm to form a third extruded resin layer, and a laminate for a tube container 1 was produced.
In addition, the structure of the laminated body 1 for tube containers was as follows.
Third extruded resin layer / anchor coat layer / gas barrier layer / first extruded resin layer / anchor coat layer / printing layer / polyester resin layer / anchor coat layer / second extruded resin layer

[Example 2]
In Example 1, the blending amount of the mixture of the carbon dioxide absorbent and the dispersant was changed from 0.6% by mass to 0.2% by mass, and the first extruded resin layer and the second extruded resin layer were changed. And the laminated body 2 for tube containers was manufactured like Example 1 except having formed the 3rd extrusion resin layer.

[Comparative Example 1]
A tube was obtained in the same manner as in Example 1 except that the carbon dioxide absorbent and the dispersant were not used and the first extruded resin layer, the second extruded resin layer, and the third extruded resin layer were formed. The laminated body 3 for containers was manufactured.

<Measurement of carbon dioxide emissions>
The amount of carbon dioxide discharged when each of the tube container laminates obtained above was incinerated was determined by measuring the residual amount by a TG / DTA test.
The amount of carbon dioxide discharged when the tube container laminate 1 of Example 1 was incinerated was 0 of the amount of carbon dioxide discharged when the tube container laminate 3 of Comparative Example 1 was incinerated. .60 times.

  The amount of carbon dioxide discharged when the tube container laminate 2 of Example 2 was incinerated was the amount of carbon dioxide discharged when the tube container laminate 3 of Comparative Example 1 was incinerated. It was 0.86 times.

<Evaluation of transparency>
When the transparency of the 2nd extrusion resin layer with which the laminated bodies 1-3 for tube containers obtained as mentioned above were equipped was evaluated by the appearance of a printing layer, the laminated body 1 for tube containers of Examples 1-2. No difference was observed between the laminates 2 and 2 and the tube container laminate 3 of Comparative Example 1.

<Evaluation of laminate strength>
About each of the laminated bodies 1 to 3 for tube containers obtained as described above, the following laminate strength was measured using a tensile tester at a test width of 15 mm and a tensile speed of 50 mm / min. The measurement results are shown in Table 1.

<Odor evaluation>
When the sensitivity evaluation was performed on the laminates for tube containers of Examples and Comparative Examples, none of the carbon dioxide absorbents and dispersants smelled and was odorless.

10: Laminate for tube container 11: First extruded resin layer 12: Polyester resin layer 13: Second extruded resin layer 14: Third extruded resin layer 15: Gas barrier layer 16: Printing layer 17: Anchor coat layer 20: Tube container 21: Head 22: Cylindrical body 23: Shoulder 24: Extraction port 25: Bottom seal

Claims (7)

At least a laminated body for a tube container comprising a first extruded resin layer, a polyester-based resin layer, and a second extruded resin layer in this order,
The laminate for a tube container, wherein the first extruded resin layer and / or the second extruded resin layer contains a carbon dioxide absorbent. A third extruded resin layer, a gas barrier layer, a first extruded resin layer, a polyester resin layer, and a second extruded resin layer are provided in this order,
The laminate for a tube container according to claim 1, wherein the first extruded resin layer, the second extruded resin layer, and / or the third extruded resin layer includes a carbon dioxide absorbent.   The laminate for a tube container according to claim 1 or 2, wherein the first extruded resin layer, the second extruded resin layer, and / or the third extruded resin layer further contains a dispersant.   The total content of the carbon dioxide absorbent and the dispersant in the first extruded resin layer, the second extruded resin layer and / or the third extruded resin layer is 0.1% by mass or more, respectively. The laminated body for tube containers of Claim 3 which is 5 mass% or less.   The laminate for a tube container according to any one of claims 2 to 4, wherein the gas barrier layer is made of a metal foil.   The laminated body for tube containers as described in any one of Claims 1-5 further equipped with a printing layer between said 1st extrusion resin layer and said polyester-type resin layer.   A tube container provided with the laminated body for tube containers as described in any one of Claims 1-6.

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