JP7249531B1 - Laminate, tube body and tube - Google Patents

Abstract

A laminate having high recyclability and high interlayer adhesive strength is provided. A laminate comprising a first resin layer, a first extruded resin layer, a stretched substrate, a second extruded resin layer, a second resin layer, The laminate further comprises a design layer on the first extruded resin layer side surface and/or the second extruded resin layer side surface of the stretched base material, the first resin layer, the second A laminate in which one extruded resin layer, a stretched substrate, a second extruded resin layer and a second resin layer each contain polyethylene as a main component. [Selection drawing] Fig. 1

Description

TECHNICAL FIELD The present disclosure relates to a laminate, a tube container body and a tube container.

2. Description of the Related Art A tube container is known as a packaging container for filling paste-like semi-fluid materials such as toothpaste and facial cleansing cream and squeezing them out for use. A tube container usually comprises a tube container body and a cap. A tube container body generally includes a trunk portion closed at one end and open at the other end, and a head portion having a spout connected to the other open end of the trunk portion. By filling the contents into the body before closing one end of the body and then closing one end of the body, a tube container containing the contents is manufactured.

The body constituting the conventional tube container body includes, for example, a polyethylene film as a heat seal layer, a polyethylene terephthalate film with a printed layer as a printing base, and a polyethylene terephthalate with a vapor deposition film as a barrier base. It is manufactured using a packaging material including a film, aluminum foil, or the like (see Patent Document 1). However, it is generally difficult to separate each film from a packaging container comprising, for example, a polyethylene film and an aluminum foil. Therefore, the current situation is that such packaging containers are not suitable for recycling after use and are not actively recycled. Therefore, a packaging material having a stretched polyethylene film (stretched polyethylene film) as a base material and a polyethylene film as a heat-seal layer has been studied (see Patent Document 2).

Japanese Unexamined Patent Application Publication No. 2010-214768 JP-A-2005-053223

In order to improve the function as a tube container, in a laminate (packaging material) comprising a stretched polyethylene film as a base material and a polyethylene film as a heat seal layer, the interlayer adhesion strength between the base material and the heat seal layer is high. is desirable.

A problem to be solved by the present disclosure is to provide a laminate having high recyclability and high interlayer adhesive strength.

The laminate of the present disclosure includes at least a first resin layer, a first extruded resin layer, a stretched substrate, a second extruded resin layer, and a second resin layer, and the stretched substrate A design layer is further provided on the first extruded resin layer side surface and/or the second extruded resin layer side surface, and the first resin layer, the first extruded resin layer, the stretched substrate, the second The extruded resin layer and the second resin layer each contain polyethylene as a main component.

According to the present disclosure, it is possible to provide a laminate having high recyclability and high interlayer adhesive strength. By using the laminate of the present disclosure, for example, a packaging container such as a tube container body having high recyclability and high interlayer adhesive strength can be produced.

FIG. 1 is a schematic cross-sectional view showing one embodiment of the laminate of the present disclosure. FIG. 2 is a cross-sectional schematic diagram illustrating one embodiment of the laminate of the present disclosure. FIG. 3 is a cross-sectional schematic diagram illustrating one embodiment of the laminate of the present disclosure. FIG. 4 is a cross-sectional schematic diagram illustrating one embodiment of the laminate of the present disclosure. FIG. 5 is a cross-sectional schematic diagram illustrating one embodiment of the laminate of the present disclosure. FIG. 6 is a cross-sectional schematic diagram illustrating one embodiment of the laminate of the present disclosure. FIG. 7 is a perspective view showing an embodiment of a tube container comprising a tube container body comprising a laminate of the present disclosure and a cap. FIG. 8 is a cross-sectional view taken along line AA of FIG.

Hereinafter, embodiments of the present disclosure will be described in detail. This disclosure may be embodied in many different forms and should not be construed as limited to the description of the illustrative embodiments below. In order to make the description clearer, the drawings may schematically represent the width, thickness, shape, etc. of each layer compared to the embodiment, but this is only an example and does not limit the interpretation of the present disclosure. . In this specification and each figure, elements similar to those already described with respect to previous figures may be denoted by the same reference numerals, and detailed description thereof may be omitted as appropriate.

Hereinafter, embodiments of the laminate of the present disclosure will be described with appropriate reference to the drawings. In addition, in the following description, each of the described components (eg, polyethylene, gas barrier resin, additive, white pigment) may be used singly or in combination of two or more.

In the present disclosure, "main component" refers to a component whose content in the layer exceeds 50% by mass.

[Laminate]
The laminate of the present disclosure includes a first resin layer, a first extruded resin layer, a stretched base material, a second extruded resin layer, and a second resin layer, for example, in the thickness direction of the laminate. at least in this order. The laminate further comprises a design layer on the first extruded resin layer side surface and/or the second extruded resin layer side surface of the stretched substrate. The first resin layer, the first extruded resin layer, the stretched substrate, the second extruded resin layer and the second resin layer each contain polyethylene as a main component.

One embodiment of the laminate of the present disclosure is shown in FIGS. 1-6.
The laminate 1 in FIG. 1 includes a first resin layer 2, a first extruded resin layer 8A, a design layer 4a, a stretched substrate 4, a second extruded resin layer 8B, and a second resin layer. 6 in this order. The laminate 1 in FIG. 2 includes a first resin layer 2, a first extruded resin layer 8A, a stretched substrate 4, a design layer 4a, a second extruded resin layer 8B, and a second resin layer. 6 in this order. As shown in FIGS. 3 and 4, an anchor coat layer 4b may be provided between the extruded resin layer and the design layer.

The laminate 1 in FIG. 5 includes a first resin layer 2, a first extruded resin layer 8A, an anchor coat layer 4b, a design layer 4a, a stretched substrate 4, an anchor coat layer 4b, and a second , another substrate 7, a third extruded resin layer 8C, and a second resin layer 6 in this order. The laminate 1 of FIG. 6 includes a first resin layer 2, a first extruded resin layer 8A, an anchor coat layer 4b, a stretched substrate 4, a design layer 4a, an anchor coat layer 4b, and a second , another substrate 7, a third extruded resin layer 8C, and a second resin layer 6 in this order. An anchor coat layer (not shown) may be provided between the extruded resin layer and the design layer.

The first resin layer may have a multilayer structure (for example, three resin layers). The second resin layer may have a multilayer structure (for example, three resin layers). The stretched base material may have a multilayer structure (for example, three resin layers). Other substrates may have a multilayer structure (for example, three resin layers).

The first resin layer, the first extruded resin layer, the stretched substrate, the second extruded resin layer, and the second resin layer included in the laminate of the present disclosure are each made of the same material polyethylene as a main component. contains. Therefore, the laminate of the present disclosure has high recyclability. A tube container body including this laminate also has high recyclability.

The content of polyethylene in the entire laminate of the present disclosure is preferably 90% by mass or more, more preferably 92% by mass or more. As a result, it is possible to improve the recyclability of the laminate of the present disclosure and the main body of the tube container (particularly the laminate tube container) including the laminate.

In one embodiment, the laminate of the present disclosure does not comprise any polyethylene terephthalate film, aluminum foil or metallized film. Printability, lamination suitability, and sealing suitability can be reproduced only with polyethylene without using different materials. As a result, it is possible to improve the recyclability of the laminate of the present disclosure and the main body of the tube container (particularly the laminate tube container) including the laminate.

As used herein, the term "laminate" may refer to the original fabric itself produced on the production line, which has the above-described layer structure, and may also refer to individual laminate pieces obtained by cutting the original fabric. It is not particularly limited as long as it has the layer structure described above. A laminate piece is used, for example, to form the body of a tube container body.

<First resin layer and second resin layer>
The first resin layer contains polyethylene as a main component. The second resin layer contains polyethylene as a main component. The polyethylene contained in the first resin layer and the polyethylene contained in the second resin layer may be the same or different.

The first resin layer has heat sealability. The second resin layer has heat sealability. Therefore, the first resin layer and the second resin layer can be melted by heating and fused to each other.

When the laminate of the present disclosure is used to form the body of the tube container body, the first resin layer is a sealant layer (heat seal layer) on the outer surface of the body, and the second resin layer is the body. This is the sealant layer (heat seal layer) on the inner surface side. That is, the trunk portion includes, from the inside to the outside of the trunk portion, a second resin layer having a heat-sealing property, a second extruded resin layer, a stretched substrate, a first extruded resin layer, A first resin layer having heat sealability is provided in this order, for example. In one embodiment, the first resin layer is one surface layer of the laminate, and the second resin layer is the other surface layer of the laminate.

Polyethylene includes, for example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene and ultra low density polyethylene. Among these, medium density polyethylene, low density polyethylene and linear low density polyethylene are preferred from the viewpoint of heat sealability.

In the present disclosure, the melt flow rate (MFR) of polyethylene may be 0.1 g/10 min or more and 50 g/10 min or less, or 0.3 g/10 min or more and 30 g/10 min, from the viewpoint of film formability and processability. It may be less than or equal to 0.5 g/10 minutes or more and 10 g/10 minutes or less. The MFR of polyethylene is measured by A method in accordance with JIS K7210 under conditions of a temperature of 190° C. and a load of 2.16 kg.

In the present disclosure, high-density polyethylene can be polyethylene with a density greater than 0.945 g/cm ³ , and medium-density polyethylene can be used with a density greater than 0.926 g/cm ³ and less than or equal to 0.945 g/cm ³ . can be used as low-density polyethylene, and as low-density polyethylene, polyethylene with a density of more than 0.900 g/cm ³ and not more than 0.926 g/cm ³ can be used, and as linear low-density polyethylene, density of more than 0.900 g/cm ³ to 0.926 g/cm ³ or less, and as ultra-low density polyethylene, polyethylene with a density of 0.900 g/cm ³ or less can be used. The density of polyethylene is measured according to JIS K7112 (for example, D method (density gradient tube method, 23° C.)).

Low-density polyethylene is usually polyethylene obtained by polymerizing ethylene by a high-pressure polymerization method (high-pressure low-density polyethylene). Linear low-density polyethylene is usually polyethylene obtained by polymerizing ethylene and a small amount of α-olefin by a low-pressure polymerization method (eg, a polymerization method using a Ziegler-Natta catalyst or a metallocene catalyst).

Polyethylenes with different densities or branches can be obtained by appropriately selecting the polymerization method. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, one-stage polymerization is performed by any of gas phase polymerization, slurry polymerization, solution polymerization and high-pressure ion polymerization. Alternatively, it is preferable to carry out the polymerization in multiple stages of two or more stages.

In the present disclosure, polyethylene includes copolymers of ethylene and other monomers (hereinafter also referred to as "ethylene copolymers"). In the present disclosure, the content of ethylene-derived structural units in polyethylene is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more or 95 mol%. That's it. The content ratio can be measured, for example, by nuclear magnetic resonance (NMR).

Examples of ethylene copolymers include copolymers of ethylene and α-olefins having 3 to 20 carbon atoms. Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene and 6-methyl-1-heptene. Polyethylene may be a copolymer of ethylene and vinyl acetate or (meth)acrylic acid ester.

As the polyethylene, biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene (hereinafter also referred to as “biomass polyethylene”) may be used. Since such biomass polyethylene is a carbon-neutral material, it is possible to reduce the environmental load in producing the laminate of the present disclosure.

As polyethylene, polyethylene recycled by mechanical recycling or chemical recycling may be used. As a result, the environmental impact of the laminate or packaging material can be reduced. Mechanical recycling generally involves pulverizing collected polyethylene film, washing with alkali to remove dirt and foreign matter from the surface of the film, and then drying it for a certain period of time under high temperature and reduced pressure until it remains inside the film. This is a method of decontaminating by diffusing contaminants, removing dirt from the film, and returning it to polyethylene again. Chemical recycling is generally a method of decomposing a recovered polyethylene film or the like down to the level of monomers and polymerizing the monomers again to obtain polyethylene.

The content of polyethylene in the first resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. The content of polyethylene in the second resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. With such a configuration, for example, the recyclability of packaging containers including the laminate of the present disclosure can be improved.

The first resin layer may contain additives. The second resin layer may contain additives. Additives include, for example, cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments and modifying resins. be done.

The second resin layer may contain pigment such as white pigment. With such a configuration, for example, it is possible to impart a hiding power (for example, white hiding feeling) to the laminate without using ink such as white ink. When ink is used, it is necessary to volatilize and remove the solvent, which tends to impose a load on the environment during the production of the laminate.

White pigments include, for example, titanium oxide, barium titanate, strontium titanate, aluminum oxide, magnesium oxide, zinc oxide, barium sulfate, magnesium carbonate, barium carbonate, zirconium oxide, calcium carbonate, white carbon, clay, talc and sulfuric acid. Barium is mentioned.

The second resin layer may be, for example, a polyethylene film having a total light transmittance of 10% or more and 40% or less as measured according to JIS K7375. Thereby, for example, a layered product can be provided with hiding power.

The first resin layer may have a multilayer structure. The second resin layer may have a multilayer structure. Multilayer structures include, for example, structures comprising a layer containing medium density polyethylene, a layer containing medium density polyethylene, and a layer containing medium density polyethylene.

The first resin layer may be a film containing polyethylene as a main component. The second resin layer may be a film containing polyethylene as a main component. The film may be a stretched film or an unstretched film. As the film, an unstretched film is preferable from the viewpoint of heat sealability. The second resin layer may be a film containing polyethylene and white pigment.

A surface treatment may be applied to the surface of the first resin layer. A surface treatment may be applied to the surface of the second resin layer. Thereby, the adhesion between these resin layers and the layers adjacent to the resin layers can be improved. Surface treatment methods include, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and/or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation treatment using chemicals. Chemical treatment can be mentioned.

An anchor coat layer may be formed on the surface of the first resin layer using a conventionally known anchor coat agent. An anchor coat layer may be formed on the surface of the second resin layer using a conventionally known anchor coat agent.

The thickness of the first resin layer is preferably 30 μm or more and 250 μm or less, more preferably 50 μm or more and 200 μm or less. The thickness of the second resin layer is preferably 30 μm or more and 250 μm or less, more preferably 50 μm or more and 200 μm or less. When the thickness is 30 µm or more, the heat sealability can be further improved. When the thickness is 250 µm or less, the workability of the laminate can be improved.

The first resin layer and the second resin layer can be produced, for example, by forming a film from a resin composition containing polyethylene using a T-die method, an inflation method, or the like. The first resin layer and the second resin layer can be laminated via, for example, an extruded resin layer, which will be described later.

The second resin layer may include a polyethylene layer and a gas barrier resin layer. The second resin layer comprises, for example, a first polyethylene layer, a first adhesive resin layer, a gas barrier resin layer, a second adhesive resin layer, and a second polyethylene layer in this order. You may prepare. By providing the second resin layer with a gas-barrier resin layer, barrier properties such as oxygen barrier properties and water vapor barrier properties in the laminate can be improved without using different materials such as vapor-deposited films and aluminum foils. In the following description, when the first polyethylene layer and the second polyethylene layer are not particularly distinguished, they are simply referred to as a polyethylene layer.

When the second resin layer is provided with a gas barrier resin layer, the content of polyethylene is preferably more than 50% by mass and 95% by mass or less, more preferably 55% by mass or more and 90% by mass, based on the second resin layer. Below, more preferably 60% by mass or more and 85% by mass or less. When the second resin layer has a gas barrier resin layer, the content of the gas barrier resin is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass, based on the second resin layer. % by mass or less, more preferably 5% by mass or more and 15% by mass or less. With such a configuration, for example, the balance of recyclability and gas barrier properties of the laminate can be improved.

The gas barrier resin layer contains a gas barrier resin.
Gas barrier resins include, for example, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile; polyamides such as nylon 6, nylon 6,6 and poly-meta-xylylene adipamide; ) acrylic resins. Among these, EVOH is preferable from the viewpoint of heat resistance and gas barrier properties.

EVOH is obtained, for example, by copolymerizing ethylene and a vinyl ester monomer and then saponifying the copolymer. Copolymerization of ethylene and a vinyl ester monomer can be carried out by any known polymerization method, such as solution polymerization, suspension polymerization, emulsion polymerization, and the like.

Vinyl acetate is generally used as the vinyl ester monomer, but other vinyl ester monomers may be used. Other vinyl ester monomers include, for example, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate and vinyl versatate. aliphatic vinyl esters; and aromatic vinyl esters such as vinyl benzoate.

In the ethylene-vinyl alcohol copolymer (EVOH), the content ratio of structural units derived from ethylene (ethylene content ratio) is preferably 20 mol% or more and 60 mol% or less, more preferably 25 mol% or more and 50 mol% or less. be. When the ethylene content is at least the lower limit, for example, the workability of the laminate can be improved. When the ethylene content is equal to or lower than the upper limit, for example, the oxygen barrier properties and/or water vapor barrier properties of the laminate can be improved. The ethylene content is measured by the NMR method.

From the viewpoint of heat resistance, the melting point (Tm) of EVOH is preferably 140° C. or higher and 200° C. or lower, more preferably 145° C. or higher and 195° C. or lower, still more preferably 150° C. or higher and 190° C. or lower. The Tm of EVOH is obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121.

From the viewpoint of gas barrier properties, the average saponification degree of the vinyl ester component in EVOH may be 90 mol % or more, 95 mol % or more, or 99 mol % or more. The average degree of saponification is measured according to JIS K6726 (however, EVOH uses a solution that is uniformly dissolved in water/methanol solvent).

The melt flow rate (MFR) of EVOH may be 0.1 g/10 min or more and 50 g/10 min or less, or 0.3 g/10 min or more and 30 g/10 min or less, from the viewpoint of film formability and workability. It may be 0.5 g/10 minutes or more and 10 g/10 minutes or less. The MFR of EVOH is measured according to ASTM D1238 under conditions of a temperature of 190° C. and a load of 2.16 kg, but the measurement temperature may be 210° C. depending on the melting point of EVOH.

EVOH may be modified by known methods such as urethanization, acetalization, cyanoethylation and oxyalkylenation.

The content of the gas barrier resin in the gas barrier resin layer is preferably 50% by mass or more, more preferably 75% by mass or more, and still more preferably 80% by mass or more, 85% by mass or more, or 90% by mass or more. As a result, for example, barrier properties such as oxygen barrier properties and water vapor barrier properties of the laminate can be improved.

The thickness of the gas barrier resin layer may be 3 μm or more and 30 μm or less, or 5 μm or more and 20 μm or less. When the thickness is at least the lower limit, for example, the effect of the gas barrier resin layer can be enhanced. When the thickness is equal to or less than the upper limit, for example, the recyclability of the laminate can be improved. The ratio of the thickness of the gas barrier resin layer to the total thickness of the second resin layer may be 3% or more and 20% or less, or may be 5% or more and 15% or less.

A polyethylene layer contains polyethylene as a main component.
Details of the polyethylene are as described above. Examples of polyethylene contained in the polyethylene layer include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Density polyethylene and linear low density polyethylene are preferred. As polyethylene, biomass polyethylene, or mechanically or chemically recycled polyethylene may be used.

The content of polyethylene in the polyethylene layer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. With such a configuration, for example, the recyclability of packaging containers including the laminate of the present disclosure can be improved.

The polyethylene layer may contain the above additives.

The ratio of the thickness of the first polyethylene layer to the total thickness of the second resin layer may be 10% or more and 45% or less, 15% or more and 43% or less, or 20% or more and 40% or less. The ratio of the thickness of the second polyethylene layer to the total thickness of the second resin layer may be 10% or more and 45% or less, 15% or more and 43% or less, or 20% or more and 40% or less.

The second resin layer may have an adhesive resin layer between the polyethylene layer and the gas barrier resin layer. Thereby, for example, the adhesion between the polyethylene layer and the gas barrier resin layer can be improved.

The adhesive resin layer contains an adhesive resin.
Examples of adhesive resins include polyolefins such as polyethylene, modified polyolefins, vinyl resins, polyethers, polyesters, polyamides, polyurethanes, silicone resins, epoxy resins and phenolic resins. Among these, polyolefins and modified polyolefins are preferable, and modified polyolefins such as acid-modified polyolefins are more preferable, from the viewpoint of recyclability and adhesion. Modified polyolefins include, for example, modified polyolefins (especially graft-modified polyolefins) with unsaturated carboxylic acids such as maleic acid and fumaric acid, or their acid anhydrides, esters or metal salts. Among adhesive resins, modified polyolefins such as modified polyethylene are preferable, acid-modified polyolefins such as acid-modified polyethylene are more preferable, and maleic anhydride-modified polyethylene is even more preferable, from the viewpoint of obtaining a structure suitable for monomaterial packaging materials. .

The adhesive resin layer may contain the above additives.

The ratio of the thickness of the first adhesive resin layer to the total thickness of the second resin layer may be 1% or more and 20% or less, 3% or more and 18% or less, or 5% or more and 15% or less. . The ratio of the thickness of the second adhesive resin layer to the total thickness of the second resin layer may be 1% or more and 20% or less, 3% or more and 18% or less, or 5% or more and 15% or less. .

In one embodiment, the second resin layer including the gas barrier resin layer is a coextruded resin film. A co-extruded resin film can be produced by forming a film using, for example, an inflation method or a T-die method. The second resin layer comprising a gas barrier resin layer includes, for example, a linear low-density polyethylene layer, an adhesive resin layer, an ethylene-vinyl alcohol copolymer layer, an adhesive resin layer and a linear low-density polyethylene layer. For example, coextruded resin films provided in this order may be used.

<Stretched substrate>
The stretched base material contains polyethylene as a main component, that is, polyethylene in an amount exceeding 50% by mass. The resin material constituting the stretched base material is polyethylene, which is the same type of resin material as the resin material constituting the first resin layer and the second resin layer. It can be suitably used as a packaging material for producing a material packaging container.

For example, polyethylene includes high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene, which are classified into the same type of resin material. On the other hand, for example, polyethylene and polyester are not classified as the same type of resin material.

From the viewpoint of strength and heat resistance, the stretched substrate preferably contains at least one selected from medium-density polyethylene and high-density polyethylene. As polyethylene, biomass polyethylene, or mechanically or chemically recycled polyethylene may be used.

The MFR of the polyethylene constituting the stretched substrate is preferably 0.1 g/10 min or more and 50 g/10 min or less, more preferably 0.2 g/10 min or more and 30 g/10 min, from the viewpoint of film formability and workability. Below, it is more preferably 0.2 g/10 min or more and 10 g/10 min or less, and particularly preferably 0.2 g/10 min or more and 5.0 g/10 min or less.

For example, when a stretched base material is produced by the T-die method, the MFR of polyethylene constituting the stretched base material is preferably 3.0 g/10 min or more and 20 g/10 min or less from the viewpoint of film-forming properties and workability. . For example, when a stretched base material is produced by an inflation method, the MFR of polyethylene constituting the stretched base material is preferably 0.2 g/10 min or more and 5.0 g/10 min or less from the viewpoint of film-forming properties and workability. be.

From the viewpoint of heat resistance, the melting point of polyethylene constituting the stretched substrate is preferably 100° C. or higher and 140° C. or lower, more preferably 110° C. or higher and 140° C. or lower, further preferably 120° C. or higher and 140° C. or lower.

The content of polyethylene in the stretched substrate is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. With such a configuration, for example, the recyclability of the laminate can be improved. When the stretched substrate has a multilayer structure, the content of polyethylene in each layer constituting the stretched substrate is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass. That's it. With such a configuration, for example, the recyclability of the laminate can be improved.

The stretched base material may contain the above additives.

The haze of the stretched substrate, in one embodiment, may be 25% or less, 15% or less, or 10% or less. The lower limit of haze may be 0.1% or 1%. The haze of the stretched substrate is measured according to JIS K7136.

The stretched substrate may contain pigments such as white pigments. With such a configuration, for example, it is possible to impart a hiding power (for example, white hiding feeling) to the laminate without using ink such as white ink. When ink is used, it is necessary to volatilize and remove the solvent, which tends to impose a load on the environment during the production of the laminate. When the stretched base material of such an aspect is used, the laminate preferably has a design layer on the first resin layer side surface of the stretched base material.

White pigments include, for example, titanium oxide, barium titanate, strontium titanate, aluminum oxide, magnesium oxide, zinc oxide, barium sulfate, magnesium carbonate, barium carbonate, zirconium oxide, calcium carbonate, white carbon, clay, talc and sulfuric acid. Barium is mentioned.

The stretched base material may be, for example, a polyethylene film having a total light transmittance of 10% or more and 40% or less as measured according to JIS K7375. Thereby, for example, a layered product can be provided with hiding power.

The stretched base material is a polyethylene base material that has been stretched. The stretching treatment can improve, for example, the printability, heat resistance and strength of the polyethylene substrate. Such a stretched base material can satisfy physical properties required for a base material constituting, for example, the body of a tube container.

The stretching may be uniaxial stretching or biaxial stretching. In one embodiment, the draw ratio in the longitudinal direction (MD) of the stretched base material is preferably 2 times or more and 10 times or less, more preferably 3 times or more and 7 times or less. In one embodiment, the draw ratio in the transverse direction (TD) of the stretched base material is preferably 2 times or more and 10 times or less, more preferably 3 times or more and 7 times or less. When the draw ratio is 2 times or more, for example, the rigidity, strength and heat resistance of the polyethylene base material can be improved, the printability on the polyethylene base material can be improved, and the transparency of the polyethylene base material can be improved. If the draw ratio is 10 times or less, for example, the film can be stretched satisfactorily without causing breakage or the like. The stretched substrate, in one embodiment, is a uniaxially stretched film, more specifically a uniaxially stretched film that has been stretched in the machine direction (MD).

The stretched base material may be subjected to the surface treatment described above. Thereby, for example, the adhesiveness between the stretched base material and the layer laminated on the stretched base material can be improved. An anchor coat layer may be formed on the surface of the stretched substrate using a conventionally known anchor coat agent.

The thickness of the stretched substrate is preferably 10 μm or more and 60 μm or less, more preferably 15 μm or more and 50 μm or less. Rigidity and strength can be improved as the thickness of the stretched base material is 10 μm or more. Workability can be improved as the thickness of the stretched base material is 60 μm or less.

The stretched substrate may have a single-layer structure or a multi-layer structure. Hereinafter, a stretched base material having a multilayer structure is also referred to as a "stretched multilayer base material". A stretched multilayer base material is preferable from the viewpoint that its strength, heat resistance and stretchability can be improved.

A stretched multilayer substrate has a multilayer structure of two or more layers. In one embodiment, the number of layers of the stretched multilayer substrate is 2 or more and 7 or less, for example, 3 or more and 7 or less, or 3 or more and 5 or less. The number of layers of the stretched multilayer substrate is preferably an odd number, for example 3, 5 or 7 layers. When the stretched multilayer base material has a multilayer structure, the balance between rigidity, strength, heat resistance, printability and stretchability can be improved. Each layer of the stretched multilayer substrate also preferably contains polyethylene as a main component.

Several examples of embodiments of the stretched multilayer substrate are described below. Hereinafter, a layer having a high density polyethylene content of 80% by mass or more is referred to as a "high density polyethylene layer", and a layer having a medium density polyethylene content of 80% by mass or more is referred to as a "medium density polyethylene layer". A layer having a low-density polyethylene content of 80% by mass or more is referred to as a “low-density polyethylene layer”, and a layer having a linear low-density polyethylene content of 80% by mass or more is referred to as a “linear low-density polyethylene layer”. A layer containing 80% by mass or more of ultra-low-density polyethylene is referred to as an "ultra-low-density polyethylene layer".

The stretched multilayer base material of the first embodiment comprises a high-density polyethylene layer and a medium-density polyethylene layer in this order in the thickness direction. By using a high-density polyethylene layer as the surface resin layer of the stretched substrate, for example, the strength and heat resistance of the stretched substrate can be improved. By including a medium-density polyethylene layer in the stretched base material, for example, the stretchability of the unstretched laminate can be improved.

The stretched multilayer base material of the second embodiment includes a high-density polyethylene layer, a medium-density polyethylene layer, and a high-density polyethylene layer in this order in the thickness direction. With such a configuration, for example, the strength and heat resistance of the stretched base material can be improved, the occurrence of curling in the stretched base material can be suppressed, and the stretchability of the unstretched laminate can be improved.

The stretched multilayer substrate of the third embodiment includes a high density polyethylene layer, a medium density polyethylene layer, a low density polyethylene layer, a linear low density polyethylene layer or an ultra low density polyethylene layer (for simplicity of description, these The three layers are collectively described as "a low-density polyethylene layer, etc."), a medium-density polyethylene layer, and a high-density polyethylene layer are provided in this order in the thickness direction. With such a configuration, for example, the stretchability of the unstretched laminate can be improved, the strength and heat resistance of the stretched substrate can be improved, and the occurrence of curling in the stretched substrate can be suppressed.

As a stretched multilayer substrate of another embodiment, a high density polyethylene layer, a high density polyethylene layer, a blend layer of medium density polyethylene and high density polyethylene, a high density polyethylene layer, and a high density polyethylene layer are formed to a thickness of Stretched base material provided in this order in the direction; A medium density polyethylene layer, a high density polyethylene layer, a linear low density polyethylene layer, a high density polyethylene layer, and a medium density polyethylene layer provided in this order in the thickness direction Also included are oriented substrates.

In addition, a high-density polyethylene layer, a blend layer of high-density polyethylene and medium-density polyethylene, a low-density polyethylene layer, etc., a blend layer of high-density polyethylene and medium-density polyethylene, and a high-density polyethylene layer are arranged in the thickness direction. Stretched substrates provided in this order are also included.

The stretched multilayer substrate of the fourth embodiment includes a medium density polyethylene layer, a high density polyethylene layer, a blend layer of medium density polyethylene and high density polyethylene, a high density polyethylene layer, and a medium density polyethylene layer. Prepare in this order in the vertical direction. With such a configuration, for example, the printability of the stretched base material can be improved, the strength and heat resistance can be improved, and the stretchability of the unstretched laminate can be improved.

The stretched multilayer substrate of the fifth embodiment includes a medium density polyethylene layer, a medium density polyethylene layer, a blend layer of medium density polyethylene and linear low density polyethylene, a medium density polyethylene layer, and a medium density polyethylene layer. are provided in this order in the thickness direction. With such a configuration, for example, the printability of the stretched base material can be improved, the strength and heat resistance can be improved, and the stretchability of the unstretched laminate can be improved.

The oriented multi-layer substrate of the sixth embodiment includes a blend layer of medium density polyethylene and high density polyethylene, a blend layer of medium density polyethylene and linear low density polyethylene, a linear low density polyethylene layer, and a medium density polyethylene layer. A blend layer of polyethylene and linear low density polyethylene and a blend layer of medium density polyethylene and high density polyethylene are provided in this order in the thickness direction. With such a configuration, for example, the printability of the stretched base material can be improved, the strength and heat resistance can be improved, and the stretchability of the unstretched laminate can be improved.

The stretched multilayer substrate of the seventh embodiment includes a blend layer of high density polyethylene and medium density polyethylene, a layer of medium density polyethylene, a blend layer of linear low density polyethylene and medium density polyethylene, and a layer of medium density polyethylene. , and a blend layer of high density polyethylene and medium density polyethylene in this order in the thickness direction. With such a configuration, for example, the printability of the stretched base material can be improved, the strength and heat resistance can be improved, and the stretchability of the unstretched laminate can be improved.

The oriented multilayer substrate of the eighth embodiment comprises a first layer containing medium density polyethylene and high density polyethylene, a second layer containing high density polyethylene, and a second layer containing linear low density polyethylene. 3 layers, a fourth layer containing high density polyethylene, and a fifth layer containing medium density polyethylene and high density polyethylene are provided in this order in the thickness direction. The second layer and the fourth layer may each independently further contain low density polyethylene. Thereby, the balance of heat resistance, rigidity and workability of the stretched base material can be further improved. The third layer may further contain low density polyethylene.

The thickness of each of the second layer and the fourth layer may be independently 0.5 μm or more and 15 μm or less, 1 μm or more and 10 μm or less, or 1 μm or more and 8 μm or less. Thereby, the heat resistance of the stretched base material can be further improved. The thickness of the third layer may be 1 μm or more and 50 μm or less, 2 μm or more and 40 μm or less, or 5 μm or more and 30 μm or less. This can further improve the balance between heat resistance, rigidity and stretchability.

In the stretched multilayer substrates of the fourth to eighth embodiments, the thickness of each of the two surface resin layers may be independently 0.5 μm or more and 10 μm or less, 1 μm or more and 8 μm or less, or 1 μm or more and 5 μm. It can be below. Thereby, for example, the heat resistance and printability of the stretched base material can be further improved. In the stretched multilayer substrates of the fourth to eighth embodiments, the thickness of each of the two surface resin layers is preferably smaller than the total thickness of the inner three layers (multilayer intermediate layer). The ratio of the thickness of each of the two surface resin layers to the total thickness of the multilayer intermediate layer (surface resin layer/multilayer intermediate layer) may be 0.05 or more and 0.8 or less, or 0.1 or more and 0.7 or less. , or 0.1 or more and 0.4 or less. Thereby, for example, the rigidity, strength and heat resistance of the stretched base material can be further improved.

At least one layer selected from the layers constituting the stretched multilayer substrate may contain a slip agent. Thereby, for example, the workability of the stretched base material can be improved. For example, in the stretched multilayer substrate of the eighth embodiment described above, the third layer may contain a slip agent, and all of the first to fifth layers may contain a slip agent. Slip agents include, for example, amide lubricants, fatty acid esters such as glycerin fatty acid esters, hydrocarbon waxes, higher fatty acid waxes, metallic soaps, hydrophilic silicones, silicone-modified (meth)acrylic resins, silicone-modified epoxy resins, and silicones. modified polyethers, silicone-modified polyesters, block-type silicone (meth)acrylic copolymers, polyglycerol-modified silicones and paraffins. Among slip agents, amide-based lubricants are preferred. Amide lubricants include, for example, saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides and aromatic bisamides. Among these, unsaturated fatty acid amides are preferred, and erucic acid amides are more preferred.

In the stretched multilayer substrate, the content of the slip agent in the layer containing the slip agent may be, for example, 0.01% by mass or more and 3% by mass or less, or may be 0.03% by mass or more and 1% by mass or less. Thereby, the workability of the stretched base material can be further improved.

The stretched multilayer base material may be provided with the gas barrier resin layer described above. By providing a gas-barrier resin layer in the stretched multi-layer base material, barrier properties such as oxygen barrier properties and water vapor barrier properties in the laminate can be improved without using different materials such as vapor-deposited films and aluminum foils. Such a stretched multilayer substrate may comprise a polyethylene layer and a gas barrier resin layer, for example, a first polyethylene layer, a first adhesive resin layer, a gas barrier resin layer and a second An adhesive resin layer and a second polyethylene layer may be provided in this order, for example, a medium density polyethylene layer, an adhesive resin layer, an ethylene-vinyl alcohol copolymer layer, an adhesive resin layer and a medium density polyethylene layer. in this order, a linear low-density polyethylene layer, an adhesive resin layer, an ethylene-vinyl alcohol copolymer layer, an adhesive resin layer, and a linear low-density polyethylene layer in this order. The details of the gas-barrier resin layer such as the polyethylene layer, the adhesive resin layer, and the ethylene-vinyl alcohol copolymer layer are as described above for the second resin layer having the gas-barrier resin layer.

A stretched base material can be produced, for example, by forming a film of polyethylene or a polyethylene composition by an inflation method or a T-die method and stretching the film. The stretched multilayer base material can be produced, for example, by film-forming a plurality of polyethylenes or polyethylene compositions by an inflation method or a T-die method to form a laminate, and stretching the obtained laminate. The stretching treatment can improve the transparency, rigidity, strength and heat resistance of the polyethylene layer, and the stretched substrate can be suitably used, for example, as a substrate for packaging materials. Stretching can also be performed in an inflation film forming machine.

In one embodiment, the stretched multilayer substrate is a coextruded resin film, and each layer constituting the stretched multilayer substrate is a coextruded resin layer. A co-extruded resin film can be produced by forming a film using, for example, an inflation method or a T-die method.

In one embodiment, the stretched multilayer substrate is obtained by stretching a laminate (precursor) having a multilayer structure. Specifically, the resin materials constituting each layer can be co-extruded into a tubular shape to form a film, thereby producing a laminate. Alternatively, a laminate can be produced by co-extrusion of the resin materials constituting each layer into a tubular shape, and then pressing the opposing layers together with a rubber roll or the like. By manufacturing a laminate by such a method, the number of defective products can be significantly reduced, and production efficiency can be improved.

<Other base material (intermediate base material)>
In the laminate of the present disclosure, between the first resin layer and the second resin layer, for example, between the second extruded resin layer and the second resin layer, another base material (intermediate base material) may be further provided. Other substrates contain polyethylene as the main component. Other substrates include, for example, the coextruded resin film described as the second resin layer having a gas barrier resin layer. For the coextruded resin film, the same configuration as that of the second resin layer having a gas barrier resin layer can be adopted. Since the second resin layer provided with the gas barrier resin layer is as described above, detailed description in this section is omitted.

<Design layer>
A laminate of the present disclosure includes a design layer such as a printed layer. The laminate of the present disclosure may comprise a design layer on one side or both sides of the stretched substrate. The design layer may be provided on the first resin layer side surface of the stretched substrate, or may be provided on the second resin layer side surface of the stretched substrate. The design layer is usually in contact with the stretched substrate.

A laminate of the present disclosure, in one embodiment, comprises a printed substrate having a stretched substrate and a printed layer provided on at least one side of the stretched substrate.

The design layer has an image. Images include, for example, characters, graphics, patterns, symbols, and combinations thereof. The image may include textual information such as the product name, the name of the contents in the packaging container, the manufacturer and the raw material name. The image may be a solid monochrome image (so-called solid image).

The design layer contains, for example, a coloring agent and a resin component.
The design layer is formed, for example, using a resin composition such as a thermoplastic resin composition, a thermosetting resin composition, and an energy ray-curable resin composition each containing a colorant. The design layer contains, for example, a resin component such as a cured product of a thermoplastic resin, a thermosetting resin, or a cured product of an energy ray-curable resin, and a colorant.

A thermoplastic resin composition contains a thermoplastic resin and a colorant. Examples of thermoplastic resins include polyolefins, chlorinated polyolefins, polystyrene, (meth)acrylic resins, vinyl resins, acetal resins, polyesters, polyurethanes, polycarbonates, polyamides, polyimides, cellulose resins, petroleum resins and fluorine resins. The thermoplastic resin composition may contain the above additives.

A thermosetting resin composition is a composition that contains a thermosetting resin, a coloring agent, and, if necessary, a curing agent, and is cured by heating. The thermosetting resin composition is, for example, so-called thermosetting ink. Thermosetting resins include, for example, phenolic resins, melamine resins, urea resins, epoxy resins, unsaturated polyesters, thermosetting polyurethanes and silicone resins; and polyester (meth)acrylates, urethane (meth)acrylates, epoxy (meth) (Meth)acrylic thermosetting resins such as acrylates, polyether (meth)acrylates, polyol (meth)acrylates, melamine (meth)acrylates and triazine (meth)acrylates. Curing agents include, for example, epoxy curing agents and isocyanate curing agents. The thermosetting resin composition may contain the above additives.

The energy ray-curable resin composition is a composition that contains a compound having an energy ray-curable functional group (hereinafter also referred to as “energy ray-curable compound”) and a coloring agent, and is cured by energy ray irradiation. The energy ray-curable resin composition is, for example, so-called UV-curable ink, preferably (meth)acrylic UV-curable ink.

Energy rays include, for example, electromagnetic waves such as ultraviolet rays, infrared rays, X-rays and gamma rays; and charged particle rays such as electron beams, proton beams and neutron beams. Among these, ultraviolet rays are preferred from the viewpoint of curing speed, availability of irradiation sources, and price. Ultraviolet radiation sources include, for example, mercury lamps, high pressure mercury lamps, extra high pressure mercury lamps, xenon lamps, metal halides and LEDs. The irradiation dose of ultraviolet rays is, for example, 5 mJ/cm ² or more and 5,000 mJ/cm ² or less.

Energy ray-curable functional groups include, for example, ethylenically unsaturated groups such as (meth)acryloyl groups, vinyl groups and allyl groups; and epoxy groups and oxetanyl groups.

The energy ray-curable compound includes, for example, a compound having an ethylenically unsaturated group, preferably a compound having two or more ethylenically unsaturated groups, and more preferably a polyfunctional (meth)acrylate compound. Both monomers and oligomers can be used as polyfunctional (meth)acrylate compounds.

Examples of polyfunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy di(meth)acrylate, bisphenol A tetrapropoxy di(meth)acrylate and 1,6-hexanediol di(meth)acrylate. ) bifunctional (meth)acrylate monomers such as acrylates; Tri- or higher functional (meth)acrylate monomers such as (meth)acrylates and isocyanuric acid-modified tri(meth)acrylates can be mentioned. The number of energy ray-curable functional groups in the polyfunctional (meth)acrylate monomer is preferably 2 or more and 6 or less, more preferably 2 or more and 3 or less.

The polyfunctional (meth)acrylate monomer may have a partially modified molecular skeleton, and for example, monomers modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, etc. can be used.

Polyfunctional (meth)acrylate oligomers include, for example, polyester (meth)acrylates, urethane (meth)acrylates, epoxy (meth)acrylates and polyether (meth)acrylates.

When the energy-ray-curable compound is an ultraviolet-curable compound, the energy-ray-curable composition (ultraviolet-curable resin composition) contains at least one selected from a photopolymerization initiator and a photopolymerization accelerator. is preferred.

Photoinitiators include, for example, acetophenones, benzophenones, thioxanthones, α-hydroxyalkylphenones, Michler's ketone, benzoin, benzyldimethylketal, benzoylbenzoate and α-acyloxime esters.

The photopolymerization accelerator is a component capable of reducing polymerization inhibition caused by air during curing and increasing the curing speed, and examples thereof include isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate.
The energy ray-curable resin composition may contain the above additives.

Examples of coloring agents include pigments such as inorganic pigments and organic pigments; dyes such as acid dyes, direct dyes, disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes, and sublimation dyes. Specific examples of pigments include titanium oxide, zinc white, carbon black, iron oxide, iron yellow, ultramarine blue, metallic pigments, pearl pigments, and fluorescent pigments. The design layer may be a high-brightness layer having a high metallic luster.

The content of the resin component in the design layer may be 10% by mass or more and 99% by mass or less, 30% by mass or more and 97% by mass or less, or 50% by mass or more and 95% by mass or less. The content of the colorant in the design layer may be 1% by mass or more and 90% by mass or less, 3% by mass or more and 70% by mass or less, or 5% by mass or more and 50% by mass or less.

The design layer composition can contain an organic solvent or water from the viewpoint of improving coatability and the like. Examples of organic solvents include hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, cellosolve acetate and butyl cellosolve acetate; and alcohols such as propanol.

For example, the design layer composition is applied to a stretched base material and dried, followed by heating at a temperature necessary for curing in the case of a thermosetting resin composition, and energy rays in the case of an energy ray-curable resin composition. A design layer can be formed by irradiating with. Drying is not necessary when the design layer composition does not contain an organic solvent or water.

Examples of methods for forming the design layer include letterpress printing, flexographic printing, gravure printing, offset printing, screen printing, inkjet printing and thermal transfer printing. When the design layer is formed by letterpress printing or flexographic printing, an energy ray-curable resin composition is preferably used, and an ultraviolet-curable resin composition is more preferably used. The design layer may contain, for example, a sublimation dye. The design layer of this embodiment can be formed, for example, by sublimation transfer printing using a thermal transfer sheet.

The thickness of the design layer is preferably 0.01 μm or more and 30 μm or less, more preferably 0.5 μm or more and 10 μm or less, and still more preferably 1 μm or more and 5 μm or less.
<Extruded resin layer>
The laminate of the present disclosure includes a first extruded resin layer containing polyethylene as a main component between the first resin layer and the stretched substrate. The laminate of the present disclosure includes a second extruded resin layer containing polyethylene as a main component between the stretched substrate and the second resin layer. The extruded resin layer functions as an adhesive layer between the two. If the laminate further comprises another substrate, the laminate may further comprise a third extruded resin layer.

The laminate of the present disclosure includes an extruded resin layer containing polyethylene as the main component as the adhesive layer, so that the interlayer adhesion strength in the laminate of monomaterial specifications is increased compared to the case where an adhesive is used. It can be improved, for example, the stretched substrates described above can be used as the substrates that make up the printing substrates. In addition, it is possible to suppress a decrease in the interlayer adhesive strength after the contents are stored in the packaging container. In addition, since a plurality of components (eg, a stretched base material and a sealant film) can be laminated by extrusion lamination, process control is simplified.

By providing an extruded resin layer containing polyethylene as a main component in the laminate of the present disclosure as the adhesive layer, compared with the case where a conventional non-polyethylene adhesive (for example, a two-liquid curing polyurethane adhesive) is used. As a result, the content of polyethylene in the laminate can be made higher. Thereby, the recyclability of the laminate can be further improved.

The extruded resin layer contains polyethylene as a main component. Details of the polyethylene are as described above. The polyethylene in the extruded resin layer and the polyethylene contained in the first resin layer and the second resin layer may be the same or different.

In the laminate of the present disclosure, the polyethylene constituting the extruded resin layer is preferably low-density polyethylene, linear low-density polyethylene and ultra-low density polyethylene from the viewpoint of adhesiveness. Polyethylene is more preferred. As polyethylene, biomass polyethylene, or mechanically or chemically recycled polyethylene may be used.

The melt flow rate (MFR) of polyethylene constituting the extruded resin layer is preferably 0.1 g/10 min or more and 50 g/10 min or less, more preferably 0.2 g/10 min, from the viewpoint of film-forming properties and workability. 30 g/10 min or more, more preferably 3.0 g/10 min or more and 20 g/10 min or less. The MFR of polyethylene is measured by A method in accordance with JIS K7210 under conditions of a temperature of 190° C. and a load of 2.16 kg.

The melting point (Tm) of polyethylene constituting the extruded resin layer is preferably 100° C. or higher and 140° C. or lower, more preferably 100° C. or higher and 130° C. or lower, still more preferably 100° C. or higher, from the viewpoint of the balance between heat resistance and adhesiveness. 120° C. or less. The Tm of polyethylene is obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121.

The content of polyethylene in the extruded resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. With such a configuration, for example, adhesion and recyclability can be improved.

In the laminate of the present disclosure, the thickness of each of the extruded resin layers such as the first extruded resin layer, the second extruded resin layer and the third extruded resin layer is preferably 5 μm or more and 40 μm or less, more preferably 10 μm. It is more than 30 micrometers or less. This can improve adhesion and recyclability, for example.

An extruded resin layer can be formed, for example, by melting polyethylene or a polyethylene composition and extruding it onto, for example, a oriented substrate. The melting temperature at this time is, for example, 280° C. or higher and 340° C. or lower, preferably 290° C. or higher and 335° C. or lower.

In the present disclosure, as a method of bonding a stretched substrate or other substrate and a film as a first resin layer or a second resin layer, for example, melt extrusion using a molten resin containing polyethylene as a main component A lamination method, in particular a sand lamination method, can be used. Thereby, the polyethylene content ratio of the laminate can be increased. In addition, the time required for the drying process and the aging process can be reduced compared to the case of laminating these by dry lamination, for example, so that the production efficiency of the laminate can be improved.

<Anchor coat layer>
The laminate of the present disclosure may further include an anchor coat layer between arbitrary layers such as between the design layer and the extruded resin layer, between the stretched base material and the extruded resin layer, and the like. Thereby, for example, the adhesion between layers in the laminate can be improved. The anchor coat layer is formed of, for example, an anchor coat agent. In this embodiment, the extruded resin layer is in contact with the anchor coat layer.

Examples of anchor coating agents include polyurethane, polyolefin, polyethyleneimine, and epoxy resin anchor coating agents. In one embodiment, the anchor coating agent is a two-pack curing resin, and is composed of, for example, polyol as a main agent and polyisocyanate as a curing agent.

Polyols include, for example, polyether polyols, polyester polyols and (meth)acrylic polyols. Polyisocyanates include, for example, aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate.

The anchor coat layer consists in one embodiment of a polyurethane obtained by reacting a polyol with a polyisocyanate. Polyurethanes specifically include polyether polyurethanes, polyester polyurethanes and poly(meth)acrylic polyurethanes.

The anchor coat layer can be formed, for example, by applying an anchor coat agent to the design layer forming surface of the stretched base material. The anchor coating agent can be applied, for example, by a coating method such as a roll coating method, a gravure roll coating method and a kiss coating method, or a printing method.

The thickness of the anchor coat layer is preferably 0.05 μm or more and 3.0 μm or less, more preferably 0.1 μm or more and 2.0 μm or less, and still more preferably 0.2 μm or more and 1.0 μm or less.

<Structure of laminate>
In one embodiment, the laminate of the present disclosure includes one stretched substrate between the first resin layer and the second resin layer, for example, the first resin layer and the first extruded resin A layer, a printing substrate, a second extruded resin layer, and a second resin layer are provided in this order.

In one embodiment, the laminate of the present disclosure may include two or more stretched substrates between the first resin layer and the second resin layer, for example, a printing substrate and a stretched substrate. may In this case, the laminate comprises an extruded resin layer between each substrate. For example, the laminate includes a first resin layer, a first extruded resin layer, a printing substrate, a second extruded resin layer, a stretched substrate, a third extruded resin layer, and a second and a resin layer in this order.

In one embodiment, the laminate of the present disclosure is a coextruded resin layer described as a second resin layer comprising a stretched substrate and a gas barrier resin layer between the first resin layer and the second resin layer. It may also be provided with other substrates such as films. In this case, the laminate comprises an extruded resin layer between each substrate. For example, the laminate includes a first resin layer, a first extruded resin layer, a printing substrate, a second extruded resin layer, a coextruded resin film having a gas barrier resin layer, and a third An extruded resin layer and a second resin layer are provided in this order.

Specific examples of the structure of the laminate of the present disclosure are described below.
- First resin layer/first extruded resin layer/anchor coat layer/printing base material (printing layer/stretching base material)/second extruded resin layer/second resin which may have a gas barrier resin layer Layers First resin layer/first extruded resin layer/printing base material (stretching base material/printing layer)/anchor coat layer/second extruded resin layer/second resin layer with gas barrier properties Resin layer A co-polymer comprising a first resin layer/first extruded resin layer/anchor coat layer/printing base material (printing layer/stretching base material)/anchor coat layer/second extruded resin layer/gas barrier resin layer Extruded resin film/third extruded resin layer/second resin layer/first resin layer/first extruded resin layer/anchor coat layer/printing substrate (stretching substrate/printing layer)/anchor coat layer/ Second Extruded Resin Layer/Co-extruded Resin Film Having Gas Barrier Resin Layer/Third Extruded Resin Layer/Second Resin Layer “/” indicates an interlayer between each layer. A printed substrate (stretched substrate/printed layer) means that the stretched substrate faces the first resin layer side and the printed layer faces the second resin layer side. A printed substrate (printed layer/stretched substrate) means that the stretched substrate faces the second resin layer side and the printed layer faces the first resin layer side.

[Tube container body]
The tube container main body of the present disclosure includes the laminate described above.
Hereinafter, the tube container body of the present disclosure will be described with reference to the drawings. 7 is a diagram schematically showing the configuration of the tube container 20, and FIG. 8 is a cross-sectional view taken along line AA of FIG. As shown in FIG. 7, the tube container main body 21 includes a head portion 22 and a body portion 23, and the body portion 23 is composed of the laminate of the present disclosure.

<head>
The head portion 22 has a shoulder portion 24 connected to one end of the body portion 23 and an extraction port portion 25 connected to the shoulder portion 24 . In one embodiment, spout portion 25 includes threads 27 for screwing cap 26 thereon.

In one embodiment, the head is composed of a resin composition containing polyethylene. Thereby, the recyclability of the tube container main body can be improved. Polyethylene includes, for example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene and ultra low density polyethylene. Among these, high-density polyethylene is preferable from the viewpoint of shape retention and moldability. As polyethylene, biomass polyethylene, or mechanically or chemically recycled polyethylene may be used.

The resin composition may contain the additive.

The head can be manufactured by a conventionally known method. For example, the head can be manufactured by a compression molding method or an injection molding method and joined to the trunk.

When a tube container body is manufactured using a compression molding method, after mounting a barrel portion on a male mold having a convex portion on the top, the male mold and female mold are opposed to each other, and a molten resin composition is obtained. is supplied into the male and female, compression molding is performed to form the head, and the head is joined to one opening of the body, whereby a tube container body having a head and a body can be manufactured.

When manufacturing the tube container body using the injection molding method, after the body is attached to the male mold with a convex portion on the top, the male mold and the female mold are opposed to each other, and the melted resin is injected from the gate. A tube container body having a head portion and a body portion can be manufactured by supplying the composition, forming a head portion by injection molding, and joining the head portion to one opening of the body portion.

<Torso>
In the tube container main body 21 of the present disclosure, the body portion 23 is connected to the shoulder portion 24 of the head portion 22 . For example, the trunk portion 23 is formed into a cylindrical shape by overlapping the first resin layer side surface of one end of the laminate of the present disclosure and the second resin layer side surface of the other end of the laminated body of the present disclosure. It has a weld 28 formed by heat sealing the rolled and overlapped portions. The trunk portion 23 includes a bottom seal portion 29 formed by, for example, heat-sealing an opening of a laminated body rolled into a cylinder.

Examples of heat sealing methods include conventionally known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, ultrasonic sealing and flame sealing.

In one embodiment, the first resin layer side surface of one end of the laminate of the present disclosure and the second resin layer side surface of the other end are overlapped and rolled into a cylindrical shape, A cylindrical body is produced by heat sealing the overlapped portions. From the viewpoint of heat sealability, it is preferable that one end of the overlap is the first resin layer and the other end is the second resin layer. In this case, the first resin layer and the second resin layer are melted and joined to form a welded portion.

In the above description, the welded portion is formed by overlapping, but the same surfaces of both end portions of the laminate may be butted against each other and the second resin layers may be heat-sealed to join. In this case, a bonding tape may be attached to the outer surface of the body so as to cover the bonding portion. The bonding tape may be provided on both the inner surface and the outer surface of the body.

[Tube container]
Hereinafter, the tube container of the present disclosure will be described with reference to the drawings. As shown in FIG. 7 , the tube container 20 of the present disclosure includes a tube container body 21 and a cap 26 attached to the head 22 .

<Tube container body>
Since the tube container main body has been described above, description thereof is omitted here.

<Cap>
The cap is detachably attached to the extraction opening of the head and serves to close the extraction opening.

In one embodiment, the cap is made of a resin composition containing a thermoplastic resin. Thermoplastic resins include, for example, polyolefins such as polyethylene and polypropylene, polyesters, cellulose resins and vinyl resins. Polyethylene is particularly preferred from the viewpoint of recyclability. Polyethylene includes, for example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene and ultra low density polyethylene. Among these, high-density polyethylene is preferable from the viewpoint of shape retention and openability. As polyethylene, biomass polyethylene, or mechanically or chemically recycled polyethylene may be used.

The resin composition may contain the additive.

As shown in FIG. 7, the cap may be of a screw type having grooves on the inner surface of the cap so as to be screwed into the threads 27 of the extraction port 25. It may be a plugging type that is fitted by plugging.

The present disclosure relates to, for example, the following [1] to [15].
[1] A laminate comprising a first resin layer, a first extruded resin layer, a stretched substrate, a second extruded resin layer, and a second resin layer At least the laminate further comprises a design layer on the first extruded resin layer side surface and/or the second extruded resin layer side surface of the stretched substrate, and the first resin A laminate in which a layer, the first extruded resin layer, the stretched substrate, the second extruded resin layer, and the second resin layer each contain polyethylene as a main component.
[2] The laminate according to [1], wherein at least one selected from the stretched substrate and the second resin layer comprises a gas barrier resin layer.
[3] The laminate according to [1] or [2], wherein at least one selected from the stretched substrate and the second resin layer comprises a polyethylene layer and a gas barrier resin layer.
[4] At least one selected from the stretched base material and the second resin layer is a first polyethylene layer, a first adhesive resin layer, a gas barrier resin layer, and a second adhesive resin. The laminate according to any one of [1] to [3], comprising a layer and a second polyethylene layer.
[5] The gas barrier resin layer contains a gas barrier resin, and the content ratio of the gas barrier resin in the second resin layer is 1% by mass or more and 30% by mass or less, the above [2] to [ 4], the laminate according to any one of the items.
[6] The above [1], wherein the first resin layer and the second resin layer each independently contain at least one selected from medium density polyethylene, low density polyethylene and linear low density polyethylene. ] to [5].
[7] At least one selected from the stretched substrate and the second resin layer is a polyethylene film having a total light transmittance of 10% or more and 40% or less (measured according to JIS K7375). The laminate according to any one of [1] to [6].
[8] The oriented base material according to any one of [1] to [7], wherein the oriented base material is a uniaxially oriented polyethylene base material containing at least one selected from medium density polyethylene and high density polyethylene. laminate.
[9] The laminate further comprises an intermediate base material and a third extruded resin layer between the second extruded resin layer and the second resin layer, and the intermediate base material is a polyethylene layer. and a gas barrier resin layer, wherein the third extruded resin layer contains polyethylene as a main component, the laminate according to the above [1].
[10] The laminate according to any one of [1] to [9], wherein the content of polyethylene in the entire laminate is 90% by mass or more.
[11] A laminate for forming a body portion of a tube container body, wherein the first resin layer is a sealant layer on the outer surface side of the body portion, and the second resin layer is a sealant layer on the inner surface side of the body portion. The laminate according to any one of [1] to [10] above, which is a layer.
[12] A tube container body comprising a head and a body, wherein the head comprises a shoulder connected to one end of the body and an extraction port connected to the shoulder, A tube container main body, wherein the portion is composed of the laminate according to any one of [1] to [11].
[13] The tube container main body according to [12], wherein the head is made of a resin composition containing polyethylene.
[14] A tube container comprising the tube container body according to [12] or [13] and a cap.
[15] The tube container according to [14], wherein the cap is made of a resin composition containing polyethylene.

EXAMPLES Hereinafter, the laminate of the present disclosure will be described in more detail with reference to examples, but the laminate of the present disclosure is not limited to the following examples.

[Preparation of stretched substrate]
The polyethylene used in the production of the stretched base material is described below.
-Medium density polyethylene (hereinafter referred to as "MDPE"):
Product name Enable4002MC
Density: 0.940 g/cm ³ Melting point: 128°C MFR: 0.25 g/10 minutes
High-density polyethylene (1) manufactured by ExxonMobil (hereinafter referred to as "HDPE (1)"):
Product name Elite5960G
Density: 0.960 g/cm ³ Melting point: 134°C MFR: 0.8 g/10 minutes
Dowchemical high-density polyethylene (2) (hereinafter referred to as “HDPE (2)”):
Product name H619F
Density: 0.965 g/cm ³ Melting point: 135°C MFR: 0.7 g/10 minutes
Linear low-density polyethylene manufactured by SCG (hereinafter referred to as “LLDPE”):
Product name Exceed XP8656ML
Density: 0.916 g/cm ³ Melting point: 121°C MFR: 0.5 g/10 minutes
Low-density polyethylene manufactured by ExxonMobil (hereinafter referred to as "LDPE"):
Product name LD2420F
Density: 0.922 g/cm ³ Melting point: 112° C. MFR: 0.75 g/10 minutes
MB containing slip agent manufactured by PTT:
Product name SLIP61 10061-K
Density: 0.910 g/cm ³ , MFR: 10 g/10 minutes,
Polyethylene base, containing 5% by mass of erucamide-based slip agent,
Made by Ampacet

70 parts of MDPE and 30 parts of HDPE (1) were mixed to obtain blend polyethylene A1 (hereinafter referred to as "blend PE (A1)"). 70 parts of HDPE (2) and 30 parts of LDPE were mixed to obtain a blend polyethylene B1 (hereinafter referred to as "blend PE (B1)"). 98 parts of LLDPE and 2 parts of slip agent-containing MB were mixed to obtain a blended polyethylene C1 (hereinafter referred to as "blended PE (C1)").

Blend PE (A1), blend PE (B1) and blend PE (C1) were formed into blend PE (A1) layer (15 μm)/blend PE (B1) layer (22.5 μm)/blend PE (C1) by inflation molding method. ) layer (50 μm)/blend PE (B1) layer (22.5 μm)/blend PE (A1) layer (15 μm) layer thickness ratio of 5 layers co-extruded to form a tubular film with a total thickness of 125 μm A polyethylene film was obtained, and the tubular film was folded at the nip to form a double layer. Numbers in parentheses indicate layer thicknesses. The polyethylene film prepared above was stretched in the longitudinal direction (MD) at a draw ratio of 5 times, and the blended PE (A1) layer (surface layer) on one side was subjected to corona discharge treatment, and then the ends were stretched. It was slit and divided into two pieces.

As described above, a monoaxially stretched polyethylene multilayer substrate having a thickness of 25 μm was obtained. The haze of the stretched multilayer base material was measured according to JIS K7136 and found to be 5.6%.

[Preparation of EVOH-containing polyethylene film]
Linear low-density polyethylene (DOWLEX2045G manufactured by Dow Chemical, density 0.920 g/cm ³ ), adhesive resin (Admer NF557 manufactured by Mitsui Chemicals), and ethylene-vinyl alcohol copolymer (EVAL H171B manufactured by Kuraray, density 1.17 g/cm ³ , ethylene content 38 mol %), adhesive resin (Mitsui Chemicals, Admer NF557), and linear low-density polyethylene (Dow Chemicals, DOWLEX2045G, density 0.920 g/cm ³ ). were co-extruded into 5 layers by the inflation method to obtain an EVOH-containing polyethylene film having a thickness of 170 μm or 75 μm. In the film, the thickness of the ethylene-vinyl alcohol copolymer layer was about 10% and the thickness of the linear low density polyethylene layer was about 40% of the total thickness of the film.

[Polyethylene film]
The following polyethylene films were used.
・Antistatic agent-containing polyethylene film 1 having a thickness of 100 μm or 80 μm (made of a mixture of polyethylene (density: 0.931 g/cm ³ , MFR: 2.1 g/10 min) and an antistatic agent)
・Polyethylene film 2 with a thickness of 100 μm (made of a mixture of polyethylene (density: 0.931 g/cm ³ , MFR: 2.1 g/10 min) and white pigment, milky white type, total light transmittance: about 20%)
・Antistatic agent-containing polyethylene film 3 having a thickness of 130 μm (made of a mixture of polyethylene (density: 0.920 g/cm ³ , MFR: 1.9 g/10 min) and an antistatic agent)
・Polyethylene film 4 with a thickness of 130 μm (made of a mixture of polyethylene (density: 0.920 g/cm ³ , MFR: 1.9 g/10 min) and white pigment, milky white type, total light transmittance: about 20%)

[Example 1]
A uniaxially stretched high-density polyethylene film having a thickness of 25 μm (manufactured by Tokyo Ink, Hi-Bron SMKQW, milky white grade) was used as a stretched base material. A urethane-based gravure ink (NEW-LP Super manufactured by Toyo Ink Co., Ltd.) was applied to the stretched base material by gravure printing and dried to form a printed layer having a thickness of 1 μm. Thus, a printed substrate was obtained.

Each layer was laminated onto the printed substrate using a tandem extrusion laminator. Specifically, a high-pressure low-density polyethylene melted at 335° C. (Novatec LLC602A manufactured by Japan Polyethylene, density: 0.919 g/cm ³ , melting point: 107° C., MFR: 8.2 g/10 min, LDPE) was extruded to form an extruded resin layer with a thickness of 20 μm, and an EVOH-containing polyethylene film with a thickness of 170 μm was laminated on the extruded resin layer. . Next, an anchor coating agent (EL510/CAT-RT80 manufactured by Toyo-Morton, dilution solvent: ethyl acetate) was applied to the surface of the printing substrate on which the printing layer was to be formed so that the thickness after drying was 1 μm, followed by drying. On the coated surface, the above high-pressure low-density polyethylene (LC602A) melted at 335 ° C. is extruded to form an extruded resin layer with a thickness of 20 μm, and an antistatic agent with a thickness of 100 μm is added on the extruded resin layer. The containing polyethylene film 1 was laminated. A laminate was obtained as described above.

The laminate consists of (outermost layer) antistatic agent-containing polyethylene film 1 (100 μm), extruded resin layer (20 μm), anchor coat layer (1 μm), printed layer (1 μm), uniaxially oriented high-density polyethylene film (HyBron SMKQW, 25 μm ), an extruded resin layer (20 μm) and an EVOH-containing polyethylene film (170 μm) (innermost layer).

[Example 2]
Lamination was carried out in the same manner as in Example 1, except that the uniaxially oriented polyethylene multilayer substrate was used as the stretched substrate constituting the printed substrate, and the printed substrate was arranged so that the printed layer faced the EVOH-containing polyethylene film side. got a body

The laminate consists of (outermost layer) antistatic agent-containing polyethylene film 1 (100 μm), extruded resin layer (20 μm), uniaxially oriented polyethylene multilayer substrate (25 μm), printed layer (1 μm), anchor coat layer (1 μm), extruded A resin layer (20 μm) and an EVOH-containing polyethylene film (170 μm) (innermost layer) are provided in order.

[Example 3]
Each layer was laminated onto the printed substrate using a tandem extrusion laminator. Specifically, the anchor coating agent is applied to the print layer forming surface of the printing base material so that the thickness after drying is 1 μm, dried, and the high pressure melted at 335 ° C. is applied to the coated surface. A 20 μm-thick extruded resin layer was formed by extruding a low-density polyethylene (LC602A), and a 75 μm-thick EVOH-containing polyethylene film was laminated on the extruded resin layer. Furthermore, on the film surface, the high-pressure low-density polyethylene (LC602A) melted at 335 ° C. is extruded to form an extruded resin layer with a thickness of 20 μm, and a polyethylene film with a thickness of 100 μm is formed on the extruded resin layer. 2 (milky white type) was laminated.

On the surface of the printing substrate opposite to the surface on which the printed layer is formed, the anchor coating agent is applied so that the thickness after drying is 1 μm, dried, and the above-mentioned melted at 335° C. is applied to the coated surface. A 20 μm-thick extruded resin layer was formed by extruding high-pressure low-density polyethylene (LC602A), and an 80 μm-thick antistatic agent-containing polyethylene film 1 was laminated on the extruded resin layer.
A laminate was obtained as described above.

The laminate consists of (outermost layer) antistatic agent-containing polyethylene film 1 (80 μm), extruded resin layer (20 μm), anchor coat layer (1 μm), uniaxially oriented polyethylene multilayer substrate (25 μm), printed layer (1 μm), anchor A coat layer (1 μm), an extruded resin layer (20 μm), an EVOH-containing polyethylene film (75 μm), an extruded resin layer (20 μm) and polyethylene film 2 (opalescent type, 100 μm) (innermost layer) are provided in this order.

[Comparative Example 1]
As a substrate, a vapor-deposited film (IB-PET-WUB manufactured by Dai Nippon Printing Co., Ltd.) in which a vapor-deposited film was formed on a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. A urethane-based gravure ink (NEW-LP Super, manufactured by Toyo Ink Co., Ltd.) was applied to the vapor-deposited film of the substrate by gravure printing and dried to form a printed layer having a thickness of 1 μm. Thus, a printed substrate was obtained.

Each layer was laminated onto the printed substrate using a tandem dry laminator. Specifically, a urethane-based two-liquid curing adhesive (manufactured by Rock Paint, solvent-based adhesive, main agent: RU-004, curing agent: H-1) is applied to the printing layer forming surface of the printing substrate, It was dried to form an adhesive layer with a thickness of 3.0 μm, and a polyethylene film 4 (milky white type) with a thickness of 130 μm was laminated on this adhesive layer. Next, the urethane-based two-liquid curing adhesive (main agent: RU-004, curing agent: H-1) is applied to the surface of the printing substrate opposite to the surface on which the printing layer is formed, dried, and thickened. An adhesive layer having a thickness of 3.0 μm was formed, and an antistatic agent-containing polyethylene film 3 having a thickness of 130 μm was laminated on the adhesive layer. A laminate was obtained as described above.

The laminate includes (outermost layer) antistatic agent-containing polyethylene film 3 (130 μm), adhesive layer (3.0 μm), vapor deposition film (IB-PET-WUB, 12 μm), printed layer (1 μm), adhesive layer ( 3.0 μm) and polyethylene film 4 (milky white type, 130 μm) (innermost layer).

[Preparation of tube container]
The laminates obtained in Examples and Comparative Examples were processed into laminate pieces having a width of 157.3 mm using a bobbin cutter, and both ends in the width direction were overlapped so that the overlap width was about 1.2 mm. After being combined, both ends of the stack were heat-sealed under the conditions of 0.1 MPa, 120° C., and 1.0 second to obtain a cylinder-shaped raw fabric bonded to a tube. The raw fabric thus obtained was cut so as to have a length of 184.2 mm to produce a cylindrical body portion which will be the body portion of the tube container. The cylindrical body is mounted on a mandrel for forming a tube container, and a head consisting of a truncated cone-shaped shoulder and a continuous cylindrical extraction port is attached to one end of the cylindrical body. A tube container main body as shown in FIG. 7 was fabricated by compression molding using density polyethylene (Suntec J345 manufactured by Asahi Kasei, density 0.956 g/cm ³ ). The spout portion of the head portion of the obtained tube container body had an outer diameter of 30.4 mm and a height of 9.5 mm, and a screw thread was provided on the side surface of the spout portion. Moreover, the outer diameter of the shoulder portion is 50 mm. Next, the high-density polyethylene was injected into a mold for cap molding and molded to produce a cap. A tube container was obtained as described above.

[Evaluation of the physical properties]
<Physical property evaluation of tube container (seal strength and lamination strength)>
(Side seam strength)
A test piece was obtained by cutting the body portion of the tube container into a strip having a width of 15 mm in the direction perpendicular to the side seam (place where the tube is stuck). In accordance with JIS K6854-2, this test piece is pulled at a test speed of 300 mm / min with a tensile tester (STA-1150, manufactured by Orientec), and the strength (side seam strength) when the test piece breaks. It was measured.
(shoulder adhesive strength)
A test piece was obtained by cutting a strip of 15 mm in width in the direction of the skirt portion at two locations where the body and shoulder of the tube container are bonded, namely, the location where the cylinder is attached and the location 180° opposite to it. This test piece was pulled at a test speed of 300 mm/min using a tensile tester (STA-1150, manufactured by Orientec) to measure the peel strength when the body peeled from the shoulder.

(Laminate strength)
Regarding the above test pieces prepared for measuring the side seam strength, the lamination strength between the printing base material / the sealant layer (EVOH-containing polyethylene film) on the inner surface side of the body part was measured in the example, and the printing base material / body part in the comparative example. The laminate strength between sealant layers (polyethylene films) on the inner surface side was measured. The average laminate strength was measured under the condition of a tensile speed of 50 mm/min. A case where the initial lamination strength was 2.0 N or more was judged to be acceptable.

The above tube container was filled with 180 g of Lux Super Rich Treatment (manufactured by Unilever Japan) and 100 g of Denters Spearmint (manufactured by Lion) and stored at 50° C. dry for one month. The physical properties (seal strength and lamination strength) of the tube container after storing the contents were measured.

<Loop evaluation>
A product name "LOOP STIFFNESS TESTER" manufactured by Toyo Seiki Co., Ltd. was used as a measuring device. Each of the laminates obtained in Examples and Comparative Examples was cut into a size of 15 mm in width and 100 mm in length (flow direction during film formation: MD, direction perpendicular to the flow direction during film formation: TD). , was used as a measurement sample. Next, with the innermost layer of the measurement sample on the inside, both ends of the measurement sample were clipped and fixed to form a circular loop with a loop length of 70 mm at the central portion in the length direction. The resulting circular loop was pushed in from the opposite side of the clip at a pushing speed of 3.3 mm/sec, and the load required to reach a load range of 5000 mN was taken as the loop stiffness value.

<Withstanding pressure test>
The tube container was filled with 180 g of Lux Super Rich Treatment (manufactured by Unilever Japan), and a load of 60 kgf was applied for 1 minute to check for leakage of the contents from the tube container.

<Mono-material>
The content ratio of polyethylene (monomaterial ratio) was calculated from the specific gravity of the material constituting each layer of the laminates obtained in Examples and Comparative Examples and the thickness of each layer. In addition, the laminates obtained in Examples and Comparative Examples were judged as monomaterials in accordance with CEFLEX guidelines. When the CEFLEX guideline was conformed, it was evaluated as "O", and when it was not conformed, it was evaluated as "X".

1: Laminate 2: First resin layer 4: Stretched base material 4a: Design layer 4b: Anchor coat layer 6: Second resin layer 7: Other base material 8A: First extruded resin layer 8B: Second Extruded resin layer 8C: Third extruded resin layer 20: Tube container 21: Tube container body 22: Head 23: Body 24: Shoulder 25: Extraction port 26: Cap 27: Thread 28: Welding portion 29 : Bottom sealing part

Claims (18)

A laminate,
The laminate is
a first resin layer;
a first extruded resin layer;
a stretched substrate;
a second extruded resin layer;
an intermediate substrate;
a third extruded resin layer;
a second resin layer;
with at least
The laminate further comprises a design layer on the first extruded resin layer side surface and/or the second extruded resin layer side surface of the stretched base material, provided that the laminate is a vapor-deposited without a membrane ,
The intermediate base material comprises a polyethylene layer and a gas barrier resin layer,
The first resin layer, the first extruded resin layer, the stretched substrate, the second extruded resin layer, the third extruded resin layer, and the second resin layer each contain polyethylene as a main component. contains as
laminate. The intermediate substrate is a coextruded resin film comprising a first polyethylene layer, a first adhesive resin layer, a gas barrier resin layer, a second adhesive resin layer, and a second polyethylene layer. The laminate according to claim 1, comprising: The laminate according to claim 1 or 2, wherein the gas-barrier resin layer contains a gas-barrier resin, and the content of the polyethylene in the intermediate substrate is more than 50% by mass and 95% by mass or less. The laminate according to any one of claims 1 to 3, wherein the second resin layer contains polyethylene and a white pigment. The laminate according to any one of claims 1 to 4, wherein the second resin layer is a polyethylene film having a total light transmittance of 10% or more and 40% or less (measured according to JIS K7375). . A laminate,
The laminate is
a first resin layer;
a first extruded resin layer;
a stretched substrate;
a second extruded resin layer;
a second resin layer;
with at least
The laminate further comprises a design layer on the first extruded resin layer side surface and/or the second extruded resin layer side surface of the stretched base material, provided that the laminate is a vapor-deposited without a membrane ,
At least one selected from the stretched base material and the second resin layer comprises a gas barrier resin layer,
The first resin layer, the first extruded resin layer, the stretched substrate, the second extruded resin layer and the second resin layer each contain polyethylene as a main component,
laminate. The laminate according to claim 6, wherein at least one selected from the stretched substrate and the second resin layer comprises a polyethylene layer and a gas barrier resin layer. At least one selected from the stretched base material and the second resin layer is a first polyethylene layer, a first adhesive resin layer, a gas barrier resin layer, a second adhesive resin layer, 8. Laminate according to claim 6 or 7, comprising a second polyethylene layer. 9. The gas barrier resin layer according to any one of claims 6 to 8, wherein the gas barrier resin layer contains a gas barrier resin, and the content of the polyethylene in the second resin layer is more than 50% by mass and 95% by mass or less. Laminate as described. At least one selected from the stretched substrate and the second resin layer is a polyethylene film having a total light transmittance of 10% or more and 40% or less (measured according to JIS K7375), claims 6- 10. The laminate according to any one of 9. The method of claims 1 to 10, wherein the first resin layer and the second resin layer each independently contain at least one selected from medium density polyethylene, low density polyethylene and linear low density polyethylene. The laminate according to any one of the items. Laminate according to any one of claims 1 to 11, wherein the oriented substrate is a uniaxially oriented polyethylene substrate containing at least one selected from medium density polyethylene and high density polyethylene. The laminate according to any one of claims 1 to 12, wherein the content of polyethylene in the entire laminate is 90% by mass or more. A laminate for forming a body of a tube container body, wherein the first resin layer is a sealant layer on the outer surface side of the body, and the second resin layer is a sealant layer on the inner surface of the body. , The laminate according to any one of claims 1 to 13. A tube container body comprising a head and a body,
The laminate according to any one of claims 1 to 14, wherein the head comprises a shoulder connected to one end of the body and an extraction opening connected to the shoulder, and the body is the laminate according to any one of claims 1 to 14. composed of
tube container body. 16. The tube container main body according to claim 15, wherein the head is made of a resin composition containing polyethylene. a tube container body according to claim 15 or 16;
A tube container comprising a cap. The tube container according to claim 17, wherein the cap is made of a resin composition containing polyethylene.

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