Laminate for tube and tube container

Abstract

To provide a laminate for a tube and a tube container that can improve gas barrier properties and light shielding properties without using aluminum foil.SOLUTION: A laminate 10 for a tube includes: a first resin layer 11 arranged sequentially from an outer surface 101 to an inner surface 102; a barrier layer 20; and a second resin layer 12. The barrier layer 20 has a barrier substrate layer 21, a first vapor deposition layer 22, a barrier coating layer 23, and a second vapor deposition layer 24, in this order. An oxygen plasma treatment surface is formed on the barrier substrate layer 21, and the first vapor deposition layer 22 is formed on the oxygen plasma treatment surface. A plasma treatment surface is formed on the barrier coating layer 23, and the second vapor deposition layer 24 is formed on the plasma treatment surface. The first vapor deposition layer 22 is a silicon dioxide deposition film or an aluminum oxide deposition film. The second vapor deposition layer 24 is an aluminum deposition film.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] The present disclosure relates to a laminate for a tube and a tube container. [Background technology]

[0002] Tube containers including aluminum foil have been known for some time (for example, Patent Document 1). Patent Document 1 discloses a tube container that can suppress the occurrence of wrinkles in the aluminum foil layer at the side seam when the side seam is made into a cylindrical body.

[0003] As described above, a tube container provided with a metal foil such as aluminum foil has high gas barrier properties and high light blocking properties, and therefore can be used when the contents to be filled are sunscreen, food seasonings, or the like, which require high gas barrier properties and high light blocking properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2022-187819 Summary of the Invention [Problem to be solved by the invention]

[0005] However, aluminum foil can result in a large amount of CO2 emissions during production. Therefore, tubular containers containing aluminum foil have the problem of placing a heavy burden on the environment. Furthermore, tubular containers containing aluminum foil are generally incinerated when disposed of. On the other hand, when tubular containers containing aluminum foil are incinerated, metal residues are generated. Thus, the generation of metal residues is also a problem for the environment. For this reason, there is a demand for tubular containers that do not contain aluminum foil, and there is a demand for tubular containers that can improve gas barrier properties and light blocking properties without using aluminum foil.

[0006] The present disclosure has been made in consideration of these points, and aims to provide a laminate for a tube and a tube container that can improve gas barrier properties and light-shielding properties without using aluminum foil. [Means for solving the problem]

[0007] The embodiments of the present disclosure relate to the following [1] to

[13] .

[0008] [1] The insulating film includes a first resin layer, a barrier layer, and a second resin layer, which are arranged in this order from the outer surface to the inner surface, the barrier layer comprises a barrier substrate layer, a first vapor-deposited layer, a barrier coat layer, and a second vapor-deposited layer in this order; an oxygen plasma treated surface is formed on the barrier substrate layer; the first vapor deposition layer is formed on the oxygen plasma treated surface, a plasma-treated surface is formed on the barrier coat layer; the second vapor deposition layer is formed on the plasma-treated surface; the first vapor-deposited layer is a silicon oxide vapor-deposited film or an aluminum oxide vapor-deposited film; The laminate for a tube, wherein the second vapor-deposited layer is an aluminum vapor-deposited film.

[0009] [2] The laminate for a tube according to [1], further comprising a printing substrate layer provided between the first resin layer and the barrier layer.

[0010] [3] The laminate for a tube according to [1] or [2], wherein the barrier substrate layer comprises a biaxially stretched polyethylene terephthalate film.

[0011] [4] The laminate for a tube according to any one of [1] to [3], wherein the material constituting the barrier substrate layer is made of a biomass-derived resin or a recycled resin.

[0012] [5] The laminate for a tube according to any one of [1] to [4], wherein the barrier coat layer is a resin cured film of a metal alkoxide and a water-soluble polymer.

[0013] [6] The laminate for a tube according to any one of [1] to [4], wherein the barrier coat layer is a cured resin film containing a reaction product formed by the reaction of a metal oxide with a phosphorus compound.

[0014] [7] The laminate for a tube according to any one of [1] to [4], wherein the barrier coat layer is a cured resin film containing a carboxyl group-containing polymer crosslinked with a polyvalent metal compound.

[0015] [8] Oxygen permeability measured in accordance with JIS K7126-2:2006 under an environment of 23°C and 90% RH is 0.25cc / m 2 The laminate for a tube according to any one of [1] to [7], wherein the laminate is less than ·atm·day.

[0016] [9] The water vapor permeability measured in accordance with JIS K7129-2:2019 under an environment of 40°C temperature and 90% RH is 0.4 g / m 2 The laminate for a tube according to any one of [1] to [8], wherein the laminate is for less than 10 days.

[0017]

[10] The laminate for a tube according to any one of [1] to [9], wherein the light transmittance measured in accordance with JIS K7361-1:1997 is 0.2% or less over the entire wavelength range.

[0018]

[11] In a tube container, [1] to

[10] , and a body tube having the laminate for a tube according to any one of [1] to

[10] . a head member joined to one end of the body tube.

[0019]

[12] Oxygen permeability measured under an environment of 23°C and 90% RH is 0.1cc / m 2 The tube container according to

[11] , wherein the temperature is less than 100°C / day.

[0020]

[13] The water vapor permeability measured under an environment of 40°C and 90% RH is 0.01 g / m 2 The tube container according to

[11] or

[12] , wherein the duration is less than 1 day. [Effects of the Invention]

[0021] According to the present disclosure, the environmental burden can be reduced. [Brief explanation of the drawings]

[0022] [Figure 1A] FIG. 1A is a cross-sectional view showing a laminate for a tube according to one embodiment. [Figure 1B] FIG. 1B is a cross-sectional view showing a laminate for a tube according to one embodiment. [Figure 1C] FIG. 1C is a cross-sectional view showing a laminate for a tube according to one embodiment. [Figure 1D] FIG. 1D is a cross-sectional view showing a laminate for a tube according to one embodiment. [Figure 2] FIG. 2 is a partial vertical cross-sectional view showing a tube container according to one embodiment. [Figure 3] FIG. 3 is a cross-sectional view showing a method for manufacturing a tube container according to one embodiment. [Figure 4] FIG. 4 is a graph showing the measurement results of light transmittance according to the example. DETAILED DESCRIPTION OF THE INVENTION

[0023] An embodiment will now be described with reference to the drawings. FIGS. 1 to 3 are diagrams illustrating one embodiment. The following figures are schematic diagrams. Therefore, the size and shape of each part are appropriately exaggerated for ease of understanding. Furthermore, appropriate modifications can be made without departing from the technical concept. In the following figures, identical parts are denoted by the same reference numerals, and some detailed descriptions may be omitted. Furthermore, the numerical values, such as dimensions, and material names of each component described in this specification are examples of an embodiment, and are not limited to these and may be selected and used as appropriate. In this specification, terms specifying shapes or geometric conditions, such as parallel, orthogonal, and perpendicular, are interpreted not only strictly but also to include substantially the same state.

[0024] First, a laminate for a tube 10 according to this embodiment will be described with reference to FIGS. 1A to 1D.

[0025] <Laminate for tubes> 1A to 1D, the tube laminate 10 includes a first resin layer 11, a barrier layer 20, and a second resin layer 12, which are arranged in this order from an outer surface 101 to an inner surface 102. The barrier layer 20 includes a barrier substrate layer 21, a first vapor-phase deposition layer 22, a barrier coat layer 23, and a second vapor-phase deposition layer 24, in this order. As shown in FIGS. 1C and 1D, the tube laminate 10 may further include a printed substrate layer 15 disposed between the first resin layer 11 and the barrier layer 20. In the tube laminate 10 shown in FIGS. 1A to 1D, the first resin layer 11 forms the outer surface 101 of the tube laminate 10, and the second resin layer 12 forms the inner surface 102 of the tube laminate 10.

[0026] Specifically, as shown in FIG. 1A, the laminate 10 for a tube comprises, in this order from the outer surface 101 to the inner surface 102, a first resin layer 11, a first adhesive layer 16a, a second vapor-phase deposited layer 24 as a barrier layer 20, a barrier coat layer 23 as the barrier layer 20, a first vapor-phase deposited layer 22 as the barrier layer 20, a barrier substrate layer 21 as the barrier layer 20, a second adhesive layer 16b, and a second resin layer 12.

[0027] As shown in FIG. 1B , the laminate 10 for a tube includes, in this order from the outer surface 101 to the inner surface 102, a first resin layer 11, a first adhesive layer 16a, a barrier substrate layer 21 as a barrier layer 20, a first vapor-phase deposited layer 22 as the barrier layer 20, a barrier coat layer 23 as the barrier layer 20, a second vapor-phase deposited layer 24 as the barrier layer 20, a second adhesive layer 16b, and a second resin layer 12.

[0028] As shown in FIG. 1C , the laminate 10 for a tube comprises, in this order from the outer surface 101 to the inner surface 102, a first resin layer 11, a first adhesive layer 16a, a substrate layer 13 as a printed substrate layer 15, a printed layer 14 as a printed substrate layer 15, a second adhesive layer 16b, a second vapor-phase deposited layer 24 as a barrier layer 20, a barrier coat layer 23 as the barrier layer 20, a first vapor-phase deposited layer 22 as the barrier layer 20, a barrier substrate layer 21 as the barrier layer 20, a third adhesive layer 16c, and a second resin layer 12.

[0029] Furthermore, as shown in FIG. 1D , the laminate 10 for a tube comprises, in this order from the outer surface 101 to the inner surface 102, a first resin layer 11, a first adhesive layer 16a, a substrate layer 13 as a printed substrate layer 15, a printed layer 14 as a printed substrate layer 15, a second adhesive layer 16b, a barrier substrate layer 21 as a barrier layer 20, a first vapor-phase deposited layer 22 as a barrier layer 20, a barrier coat layer 23 as a barrier layer 20, a second vapor-phase deposited layer 24 as a barrier layer 20, a third adhesive layer 16c, and a second resin layer 12.

[0030] Each layer of the laminate for a tube 10 will be described below.

[0031] <<First resin layer>> The first resin layer 11 is a layer for bonding the tube laminates 10 together. This first resin layer 11 is a layer that becomes the outermost layer when a tube container 40 (described later) is produced from the tube laminate 10.

[0032] The material constituting the first resin layer 11 may be a material that melts and fuses with heat. In this case, the material constituting the first resin layer 11 is made of the same resin type as the material constituting the second resin layer 12. The first resin layer 11 may be made of, for example, polyolefin. More specifically, the first resin layer 11 may be made of one or more resins, such as low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), polypropylene, acid-modified polyolefin resins obtained by modifying polyolefin resins such as polyethylene or polypropylene with acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, or other unsaturated carboxylic acids, polyvinyl acetate resins, polyester resins, polystyrene resins, polyacrylonitrile, saturated polyesters, or polyvinyl alcohol.

[0033] The first resin layer 11 may contain a biomass-derived resin. For example, when the first resin layer 11 contains polyethylene or polypropylene, the polyethylene may be biomass polyethylene, and the polypropylene may be biomass polypropylene. When the first resin layer 11 contains a biomass-derived resin, the amount of fossil fuel used can be reduced, and the environmental impact of the tube laminate 10 can be reduced. Note that biomass polyethylene is a monomer polymer containing biomass-derived ethylene. Since biomass-derived ethylene is used as the raw material monomer, the polymerized polyolefin is biomass-derived. The content of biomass-derived ethylene in the raw material monomer does not need to be 100% by mass, and is, for example, preferably 50% or more, more preferably 80% or more. The raw material monomer may contain fossil fuel-derived ethylene or an α-olefin monomer such as butylene, hexene, or octene.

[0034] For example, biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use biomass-derived fermented ethanol obtained from plant raw materials. The plant raw material is not particularly limited, and conventionally known plants can be used. Conventionally known plants include, for example, corn, sugarcane, beet, and manioc.

[0035] The material of the first resin layer 11 may be a material to which, for example, an antiblocking agent, a lubricant (fatty acid amide, etc.), a flame retardant, an inorganic or organic filler, etc. are optionally added.

[0036] In this embodiment, the thickness of the first resin layer 11 is preferably 50 μm or more and 250 μm or less.

[0037] <<Second resin layer>> The second resin layer 12 is a layer for bonding the tube laminates 10 together. This second resin layer 12 is a layer that becomes the innermost layer when, for example, a tube container 40 described below is produced from the tube laminate 10.

[0038] The material constituting the second resin layer 12 is a material that melts and fuses when heated. That is, the material constituting the second resin layer 12 is a material of the same resin type as the material constituting the first resin layer 11. The second resin layer 12 may be made of, for example, a polyolefin. More specifically, the second resin layer 12 may be made of one or more resins, such as low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), polypropylene, acid-modified polyolefin resins obtained by modifying polyolefin resins such as polyethylene or polypropylene with acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, or other unsaturated carboxylic acids, polyvinyl acetate resins, polyester resins, polystyrene resins, polyacrylonitrile, saturated polyesters, or polyvinyl alcohol.

[0039] The second resin layer 12 may contain a biomass-derived resin. For example, when the second resin layer 12 contains polyethylene, the polyethylene may contain a biomass-derived component. When the second resin layer 12 contains a biomass-derived resin, the amount of fossil fuel used can be reduced, and the environmental impact of the tube laminate 10 can be reduced.

[0040] The material for the second resin layer 12 may be a material to which, for example, an antiblocking agent, a lubricant (fatty acid amide, etc.), a flame retardant, an inorganic or organic filler, etc. are optionally added.

[0041] In this embodiment, the thickness of the second resin layer 12 is preferably 50 μm or more and 250 μm or less.

[0042] <<Barrier layer>> As described above, the barrier layer 20 includes, in this order, the barrier substrate layer 21, the first vapor-deposited layer 22, the barrier coat layer 23, and the second vapor-deposited layer 24. First, the barrier substrate layer 21 will be described.

[0043] <<<Barrier substrate layer>>> The barrier substrate layer 21 is a layer that supports, for example, the first vapor-phase deposited layer 22 and the like and increases the strength of the entire barrier layer 20. The barrier substrate layer 21 is not particularly limited, but may be a resin film that has excellent chemical and physical strength, can withstand conditions for forming a chemical vapor deposition layer, and can maintain its film properties without impairing them. Specific examples of the barrier substrate layer 21 include films of various resins, such as polyethylene resins, polyolefin resins such as polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), poly(meth)acrylic resins, polycarbonate resins, polyvinyl alcohol resins, saponified ethylene-vinyl ester copolymers, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyurethane resins, acetal resins, and cellulose resins. Among the above resin films, it is particularly preferable to use a film of a polyester resin, a polyolefin resin, or a polyamide resin, and the barrier substrate layer 21 may contain a biaxially stretched polyethylene terephthalate film. The barrier substrate layer 21 may be any of unstretched films of the above resins and films of resins stretched uniaxially or biaxially.

[0044] The material constituting the barrier substrate layer 21 may be made of a biomass-derived resin or a recycled resin. For example, in addition to polyethylene terephthalate, which is commonly made from petroleum fuel, the following polyester films can also be used as polyester resin films.

[0045] (Polybutylene terephthalate film (PBT)) Polybutylene terephthalate films have a high heat distortion temperature, excellent mechanical strength and electrical properties, and good moldability, so when used in packaging bags for containing contents such as food, they can prevent the packaging bag from deforming or losing its strength during retort treatment. Polybutylene terephthalate films are films containing polybutylene terephthalate (hereinafter also referred to as PBT) as a main component, and are preferably resin films containing 60% by mass or more of PBT.

[0046] (Biomass-derived polyester film) The biomass-derived polyester film is made of a resin composition containing, as a main component, a polyester consisting of diol units and dicarboxylic acid units, and the resin composition contains 50 to 95% by mass, preferably 50 to 90% by mass, of polyester in which the diol units are biomass-derived ethylene glycol and the dicarboxylic acid units are fossil fuel-derived dicarboxylic acid, based on the total resin composition.

[0047] Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass such as sugarcane or corn. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide by a conventionally known method to produce ethylene glycol. Alternatively, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0048] The dicarboxylic acid units of the polyester are derived from fossil fuels. Examples of dicarboxylic acids that can be used include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and examples of aromatic dicarboxylic acid derivatives include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters. Among these, terephthalic acid is preferred, and examples of aromatic dicarboxylic acid derivatives include dimethyl terephthalate.

[0049] The polyesters that may be contained in the resin composition forming the biomass-derived polyester film at a ratio of 5% by mass to 45% by mass are polyesters derived from fossil fuels, recycled polyesters from polyester products derived from fossil fuels, and recycled polyesters from polyester products derived from biomass.

[0050] (recycled polyethylene terephthalate) A polyethylene terephthalate film containing polyethylene terephthalate recycled by mechanical recycling, specifically PET obtained by mechanically recycling PET bottles, in which the diol component is ethylene glycol and the dicarboxylic acid components are terephthalic acid and isophthalic acid. The content of the isophthalic acid component is preferably 0.5 mol % to 5 mol %, more preferably 1.0 mol % to 2.5 mol %, of the total dicarboxylic acid components constituting the PET.

[0051] Mechanical recycling is a method in which collected polyethylene terephthalate resin products such as PET bottles are generally crushed and washed with alkali to remove dirt and foreign matter from the surface of the PET resin products, and then dried at high temperature and reduced pressure for a certain period of time to diffuse and decontaminate contaminants remaining inside the PET resin, thereby removing dirt from the resin products made of PET resin and returning them to PET resin.

[0052] Recycled polyethylene terephthalate preferably contains recycled PET in a proportion of 50% by weight to 95% by weight, and may also contain virgin PET. Virgin PET may contain ethylene glycol as a typical diol component and terephthalic acid or isophthalic acid as a dicarboxylic acid component.

[0053] The thickness of the various resin films is preferably about 6 μm to 2000 μm, and more preferably about 9 to 100 μm.

[0054] (Surface treatment) In this embodiment, an oxygen plasma-treated surface is formed on the barrier substrate layer 21. Then, a first vapor-phase deposition layer 22 is formed on the oxygen plasma-treated surface. In this case, before forming the first vapor-phase deposition layer 22 on the barrier substrate layer 21, the barrier substrate layer 21 is subjected to a surface treatment with oxygen plasma in advance. This improves adhesion to the first vapor-phase deposition layer 22. For example, in-line oxygen plasma treatment can be performed to remove moisture, dust, and the like from the surface of the barrier substrate layer 21 and to smooth and activate the surface. In this embodiment, plasma discharge treatment is preferably performed as the plasma treatment, taking into consideration the plasma output, type of plasma gas, amount of plasma gas supplied, treatment time, and other conditions. Furthermore, devices such as DC glow discharge, high-frequency discharge, and microwave discharge can be used to generate plasma. Plasma treatment can also be performed by atmospheric pressure plasma treatment.

[0055] Ethylene gas or argon gas may also be used as the plasma gas in the surface treatment of the barrier substrate layer 21. By using ethylene gas in combination, a film like diamond-like carbon is formed on the surface treatment surface, which can further improve the gas barrier properties and water-resistant adhesion.

[0056] <<<First vapor-deposited layer 22>>> The first vapor-phase deposition layer 22 may be a vapor-deposited film formed by physical vapor deposition (PVD). In this embodiment, by forming an aluminum oxide vapor-deposited film as the first vapor-phase deposition layer 22, it is possible to improve the gas barrier property and the light-shielding property.

[0057] Examples of physical vapor deposition (PVD) methods include vacuum deposition, sputtering, ion plating, and ion cluster beam deposition. Specifically, an aluminum oxide vapor deposition film can be formed using a vacuum deposition method in which aluminum oxide is used as a raw material, heated to vaporize it, and then vaporized onto the oxygen plasma-treated surface of the barrier substrate layer 21 (resin film). The vapor deposition material can be heated by, for example, resistance heating, high-frequency induction heating, or electron beam heating (EB).

[0058] The thickness of the aluminum oxide vapor-deposited film is preferably 20 nm to 500 nm, more preferably 30 nm to 500 nm, and even more preferably 40 nm to 500 nm. If the thickness of the aluminum vapor-deposited film is within the above range, it is possible to further improve the light-shielding property while exhibiting sufficient gas barrier property.

[0059] The first vapor-deposited layer 22 may also be a vapor-deposited film formed by chemical vapor deposition (CVD). In this embodiment, by forming a silicon oxide vapor-deposited film as the first vapor-deposited layer 22, it is possible to improve the water-resistant adhesion to the barrier substrate layer 21 while improving the gas barrier properties.

[0060] Examples of chemical vapor deposition (CVD) methods include plasma-enhanced chemical vapor deposition, low-temperature plasma-enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. Specifically, a silicon oxide vapor deposition film can be formed on one surface of the barrier substrate layer 21 (resin film) using a low-temperature plasma-enhanced chemical vapor deposition method that uses a vapor deposition monomer gas such as an organosilicon compound as a raw material, an inert gas such as argon gas or helium gas as a carrier gas, and oxygen gas as an oxygen supply gas, and employs a low-temperature plasma generator or the like. Examples of low-temperature plasma generators that can be used include high-frequency plasma, pulsed wave plasma, and microwave plasma. It is preferable to use a high-frequency plasma generator, as this produces highly active and stable plasma.

[0061] Examples of vapor deposition monomer gases for organosilicon compounds that form silicon oxide vapor deposition films include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these, the use of 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is particularly preferred in terms of ease of handling and the properties of the continuous film formed. In addition, examples of inert gases that can be used include argon gas and helium gas.

[0062] Silicon oxide vapor-deposited films are primarily composed of silicon oxide, but may also contain, via chemical bonding, at least one compound composed of one or more of the elements carbon, hydrogen, nitrogen, silicon, and oxygen. For example, compounds containing C—H bonds, compounds containing Si-H bonds, or compounds in which the carbon units are graphite-like, diamond-like, fullerene-like, etc. may also contain, via chemical bonding, organosilicon compounds or their derivatives. Examples include hydrocarbons with CH moieties, hydrosilica such as SiH silyl and SiH silylene, and hydroxyl derivatives such as SiH OH silanol. In addition to the above, the type and amount of compounds contained in the silicon oxide vapor-deposited film can be varied by changing the conditions of the vapor deposition process.

[0063] The thickness of the silicon oxide vapor-deposited film is preferably 3 nm to 100 nm, more preferably 4 nm to 50 nm, and even more preferably 5 nm to 30 nm. If the thickness of the silicon oxide vapor-deposited film is within the above range, it is possible to further improve the water-resistant adhesion to the barrier substrate layer 21 while exhibiting sufficient gas barrier properties.

[0064] <<<Barrier Coat Layer>>> The barrier coat layer 23 is a layer having gas barrier properties, and is a resin cured film formed by applying a coating film and then drying and curing the film.

[0065] In a first embodiment of the barrier coat layer 23, the barrier coat layer 23 may be a resin cured film of a metal alkoxide and a water-soluble polymer. That is, a cured film of a hydrolysis product of a metal alkoxide and a water-soluble polymer can be used as the barrier coat layer 23. This barrier coat layer 23 can be formed, for example, from the following gas barrier coating film. The gas barrier coating film is a coating film that maintains gas barrier properties in a high-temperature, high-humidity environment, and is a coating film represented by the general formula R 1 n M(OR 2 ) m(wherein, R 1 , R 2 represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M. The coating film is made of a barrier coat composition containing at least one metal alkoxide represented by the formula (I) and a water-soluble polymer, and further obtained by polycondensation by a sol-gel method in the presence of a sol-gel catalyst, an acid, water, and an organic solvent.

[0066] The above general formula R 1 n M(OR 2 ) m Medium, R 1 The alkyl group is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 4 carbon atoms, which may be branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-hexyl group, and an n-octyl group.

[0067] The above general formula R 1 n M(OR 2 ) m Medium, R 2 The (OR) is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and particularly preferably 1 to 4 carbon atoms, which may be branched. Examples of the (OR) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. 2 ) exists, then (OR 2 ) may be the same or different.

[0068] The above general formula R 1 n M(OR 2 ) m Among these, examples of the metal atom represented by M include silicon, zirconium, titanium, and aluminum.

[0069] The above general formula R 1 n M(OR 2) m As the alkoxide represented by the formula (I), at least one of a partial hydrolyzate of an alkoxide and a hydrolysis condensate of an alkoxide can be used. The partial hydrolyzate of the alkoxide is not limited to one in which all of the alkoxy groups are hydrolyzed, but may be one in which one or more alkoxy groups are hydrolyzed, or a mixture thereof. Furthermore, as the hydrolysis condensate, a dimer or higher of a partially hydrolyzed alkoxide, specifically a dimer to hexamer, may be used.

[0070] In this embodiment, the general formula R 1 n M(OR 2 ) m As the alkoxide represented by the formula (I), an alkoxysilane in which M is Si can be suitably used. Suitable alkoxysilanes include, for example, tetramethoxysilane Si(OCH3)4, tetraethoxysilane Si(OC2H5)4, tetrapropoxysilane Si(OC3H7)4, tetrabutoxysilane Si(OC4H9)4, methyltrimethoxysilane CH3Si(OCH3)3, methyltriethoxysilane CH3Si(OC2H5)3, dimethyldimethoxysilane (CH3)2Si(OCH3)2, and dimethyldiethoxysilane (CH3)2Si(OC2H5)2. In the present embodiment, condensation polymers of these alkoxysilanes can also be used; specifically, for example, polytetramethoxysilane, polytetraethoxysilane, etc. can be used.

[0071] In this embodiment, the general formula R 1 n M(OR 2 ) m Zirconium alkoxides in which M is Zr can also be suitably used as the alkoxide represented by the formula (1). Suitable zirconium alkoxides include, for example, tetramethoxyzirconium Zr(OCH3)4, tetraethoxyzirconium Zr(OC2H5)4, tetra-i-propoxyzirconium Zr(iso-OC3H7)4, and tetra-n-butoxyzirconium Zr(OC4H9)4.

[0072] In addition, the above general formula R 1 n M(OR 2 ) m Titanium alkoxides in which M is Ti can also be suitably used as the alkoxide represented by the formula (1). Suitable titanium alkoxides include, for example, tetramethoxytitanium Ti(OCH3)4, tetraethoxytitanium Ti(OC2H5)4, tetraisopropoxytitanium Ti(iso-OC3H7)4, and tetra-n-butoxytitanium Ti(OC4H9)4.

[0073] In addition, the above general formula R 1 n M(OR 2 ) m Aluminum alkoxides in which M is Al can also be suitably used as the alkoxide represented by the formula (I). Suitable aluminum alkoxides include, for example, tetramethoxyaluminum Al(OCH3)4, tetraethoxyaluminum Al(OC2H5)4, tetraisopropoxyaluminum Al(iso-OC3H7)4, and tetra-n-butoxyaluminum Al(OC4H9)4.

[0074] In this embodiment, two or more of the above alkoxides may be used in combination. For example, when an alkoxysilane and a zirconium alkoxide are mixed and used, the toughness, heat resistance, etc. of the resulting barrier film can be improved. Furthermore, when an alkoxysilane and a titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is reduced, and the heat resistance is significantly improved.

[0075] The water-soluble polymer used in this embodiment can be a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer, either alone or in combination. In this embodiment, the use of a polyvinyl alcohol resin and / or an ethylene-vinyl alcohol copolymer can significantly improve physical properties such as gas barrier properties, water resistance, weather resistance, and the like.

[0076] The polyvinyl alcohol resin can generally be one obtained by saponifying polyvinyl acetate. The polyvinyl alcohol resin is not particularly limited and may be a partially saponified polyvinyl alcohol resin in which several tens of percent of acetate groups remain, a fully saponified polyvinyl alcohol in which no acetate groups remain, or a modified polyvinyl alcohol resin in which OH groups are modified.

[0077] The ethylene-vinyl alcohol copolymer can be a saponified copolymer of ethylene and vinyl acetate, i.e., a product obtained by saponifying an ethylene-vinyl acetate random copolymer. Examples include partially saponified products in which several tens of mol% of acetate groups remain, to completely saponified products in which only a few mol% of acetate groups remain, or even no acetate groups remain, and are not particularly limited. However, from the viewpoint of gas barrier properties, a saponification degree of 80 mol% or more is preferred, more preferably 90 mol% or more, and even more preferably 95 mol% or more is preferred. The content of repeating units derived from ethylene in the ethylene-vinyl alcohol copolymer (hereinafter also referred to as "ethylene content") is typically 0 to 50 mol%, preferably 20 to 45 mol%.

[0078] A silane coupling agent may also be added to the barrier coating layer 23. For example, a silane coupling agent having a reactive group such as an alkoxy group (e.g., a methoxy group or an ethoxy group), an acetoxy group, an amino group, or an epoxy group can be used. Specifically, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or the like can be used.

[0079] Furthermore, examples of organic solvents that can be used in the barrier coat composition include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butanol. The polyvinyl alcohol resin and / or ethylene-vinyl alcohol copolymer are preferably handled in a dissolved state in a coating solution containing the alkoxide and silane coupling agent, and the organic solvent can be appropriately selected from the above-mentioned organic solvents. For example, when a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer are used in combination, n-butanol is preferably used.

[0080] The barrier coat layer 23 can be produced by the following method: First, the above-mentioned metal alkoxide, and optionally a silane coupling agent, a water-soluble polymer, a sol-gel catalyst, an acid, water, an organic solvent, etc. are mixed to prepare a barrier coat composition (barrier coat liquid).

[0081] Next, the barrier coat composition is applied onto the first vapor-deposited layer 22. The barrier coat composition can be applied by one or more coating steps using a coating means such as roll coating (e.g., gravure roll coater), spray coating, spin coating, dipping, brushing, bar coating, or applicator, to form a coating film with a dry thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm.

[0082] Next, the film coated with the barrier coat composition is heated and dried for 3 seconds to 10 minutes at a temperature of 120°C to 200°C and below the melting point of the barrier substrate layer 21, preferably 130°C to 180°C, and more preferably 140°C to 160°C. This causes polycondensation to occur, forming the barrier coat layer 23. Alternatively, the barrier coat composition may be applied over the vapor-deposited layer to form two or more superimposed coating films, which may then be subjected to a heat-drying treatment for 3 seconds to 10 minutes at a temperature of 120°C to 200°C and below the melting point of the resin substrate, to form a composite polymer layer comprising two or more superimposed barrier coat layers 23. This process allows one or more barrier coat layers 23 to be formed from the barrier coat composition.

[0083] The thickness of the barrier coating layer 23 is not particularly limited, but is preferably 10 nm to 5000 nm, more preferably 50 nm to 1000 nm, even more preferably 100 nm to 500 nm, and even more preferably 150 nm to 400 nm. If the thickness of the barrier coating layer 23 is within the above range, it can exhibit gas barrier properties and can cover the surface of the vapor-deposited layer as a flexible layer.

[0084] A second embodiment of the barrier coat layer 23 may be a cured resin film containing a reaction product formed by the reaction of a metal oxide with a phosphorus compound. This cured resin film has gas barrier properties and has a gas barrier property of 800 to 1400 cm -1 The infrared absorption maximum wavenumber in the infrared absorption spectrum range is 1080-1130 cm -1 It is in the range of.

[0085] In the reaction product, when a bond represented by MOP is generated in which a metal atom (M) constituting the metal oxide and a phosphorus atom (P) are bonded via an oxygen atom (O), an absorption peak based on the MOP bond appears in the range of 1080 to 1130 cm -1 In the range of 800~1400cm -1 It is believed that this appears as an absorption peak with the maximum absorption wavenumber in the region.

[0086] This infrared absorption spectrum can be obtained by measuring the surface of the barrier coat layer 23 by total reflection measurement, or by measuring the infrared absorption spectrum of components scraped off from the barrier coat layer 23 by the KBr method.

[0087] The metal oxide is an oxide of magnesium, calcium, aluminum, silicon, titanium, zirconium, or the like.

[0088] The metal oxide can be obtained by hydrolyzing a compound containing the metal atom. Examples of compounds that can produce a metal oxide by hydrolysis include aluminum chloride, aluminum triethoxide, aluminum tri-normal propoxide, aluminum triisopropoxide, aluminum tri-normal butoxide, aluminum tri-s-butoxide, aluminum tri-t-butoxide, aluminum triacetate, aluminum acetylacetonate, aluminum nitrate, titanium tetraisopropoxide, titanium tetra-normal butoxide, titanium tetra(2-ethylhexoxide), titanium tetramethoxide, titanium tetraethoxide, titanium acetylacetonate, zirconium tetra-normal propoxide, zirconium tetrabutoxide, and zirconium tetraacetylacetonate. These compounds may be used alone or in combination of two or more.

[0089] The phosphorus compound may have a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom. Specific examples include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Examples of polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, and polyphosphoric acid in which four or more phosphoric acids are condensed. Examples of derivatives include salts, (partial) ester compounds, halides (chlorides, etc.), and dehydrates (diphosphorus pentoxide, etc.) of phosphoric acid, polyphosphoric acid, phosphorous acid, and phosphonic acid.

[0090] The reaction product can be formed by mixing and reacting a metal oxide with a phosphorus compound. At this time, the phosphorus compound to be mixed may be in the form of itself or in the form of a composition containing the phosphorus compound and an additive resin.

[0091] Such additive resins include polyvinyl alcohol, partially saponified polyvinyl acetate, polyethylene glycol, polyhydroxyethyl (meth)acrylate, polyacrylic acid, polymethacrylic acid, poly(acrylic acid / methacrylic acid) and salts thereof, ethylene-vinyl alcohol copolymer, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride alternating copolymer, ethylene-acrylic acid copolymer, and saponified ethylene-ethyl acrylate copolymer.

[0092] In this embodiment, this barrier coat layer 23 can be laminated by coating a coating liquid containing a mixture of a metal oxide and a phosphorus compound onto the first vapor-phase deposition layer 22 and drying it, and its thickness is 0.05 to 1 μm.

[0093] The coating solution can be prepared by first dispersing and dissolving a compound capable of producing a metal oxide by hydrolysis to produce a metal oxide, and then adding the resulting aqueous solution to a solvent in which a phosphorus compound is dispersed and dissolved, or to a solvent in which a composition containing a phosphorus compound and an additive resin is dispersed and dissolved.

[0094] A third embodiment of the barrier coat layer 23 may be a cured resin film containing a carboxyl group-containing polymer crosslinked with a polyvalent metal compound. This cured resin film has gas barrier properties.

[0095] The carboxyl group-containing polymer is a polymer containing two or more carboxyl groups, and specifically includes polyacrylic acid, polymethacrylic acid, a copolymer of acrylic acid and methacrylic acid, or a mixture of two or more of these.

[0096] The polyvalent metal compounds include metal compounds of beryllium, magnesium, calcium, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and aluminum, as well as their oxides, carbonates, and organic acid salts. Examples of these oxides and carbonates include oxides such as zinc oxide, magnesium oxide, copper oxide, nickel oxide, and cobalt oxide; carbonates such as calcium carbonate; and organic acid salts such as calcium lactate, zinc lactate, and calcium acrylate. A resin film containing a carboxyl group-containing polymer crosslinked by a polyvalent metal compound can be produced as a cured resin film by mixing a carboxyl group-containing polymer with a polyvalent metal compound.

[0097] Another form of this resin film can be produced by laminating a layer containing a polyvalent metal compound adjacent to a resin layer containing a carboxyl group-containing polymer to form a two-layer structure. The resin layer containing the carboxyl group-containing polymer is ionically crosslinked by polyvalent metal ions migrated from the adjacent layer containing the polyvalent metal compound, forming a cured resin film.

[0098] The resin layer containing a carboxyl group-containing polymer may contain polyalcohols such as polyvinyl alcohol and glycerin in addition to the polymer containing two or more carboxyl groups. The polymer containing two or more carboxyl groups and the polyvinyl alcohol are mixed in a weight ratio of 99:1 to 20:80.

[0099] The layer containing a polyvalent metal compound is a layer in which the above-mentioned metal compound is mixed with at least one resin selected from the group consisting of alkyd resin, melamine resin, acrylic resin, urethane resin, nitrocellulose, epoxy resin, polyester resin, phenol resin, amino resin, fluororesin, and isocyanate as a mixing resin. The weight ratio of the polyvalent metal compound to the resin (metal compound / resin) is 0.01 to 1000. The polyvalent metal compound is mixed in the resin layer in the form of particles with an average particle size of 15 nm to 500 nm.

[0100] In this embodiment, this barrier coating layer 23 can be laminated by coating the first vapor-deposited layer 22 with a coating liquid prepared by dispersing or dissolving a resin mixed with a carboxyl group-containing polymer and a polyvalent metal compound in a single or mixed solution of water, alcohols such as methyl alcohol, ethyl alcohol, or isopropyl alcohol, or N,N-dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, or butyl acetate, and then drying the coating, and the thickness of the barrier coating layer 23 is 0.1 to 10 μm.

[0101] As another method, a layer containing a carboxyl group-containing polymer is first laminated on the first vapor-deposited layer 22. This lamination is achieved by coating and drying a coating liquid in which the carboxyl group-containing polymer and other necessary additives are dissolved or dispersed in a solvent such as water, alcohols such as methyl alcohol, ethyl alcohol, or isopropyl alcohol, or N,N-dimethyl sulfoxide, N,N-dimethylformamide, or dimethylacetamide, to a thickness of 0.1 to 10 μm.

[0102] Next, a coating solution prepared by dissolving or dispersing a polyvalent metal compound and a resin in a solvent such as acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, or butyl acetate, in addition to the above-mentioned solvent, is used to coat a resin layer containing a carboxyl group-containing polymer and then dried, thereby laminating a layer containing a polyvalent metal compound to a thickness of 0.1 to 10 μm.

[0103] By laminating a layer containing a polyvalent metal compound on a resin layer containing a carboxyl group-containing polymer in this way, the carboxyl group-containing polymer is ion-crosslinked by polyvalent metal ions migrated from the layer containing the polyvalent metal compound, resulting in a cured resin film. To promote the migration of polyvalent metal ions, after forming the two layers, aging may be performed in a heated environment of 30 to 130 degrees.

[0104] (Surface treatment) In this embodiment, a surface treatment may be further performed on the barrier coating layer 23 to improve adhesion to the second vapor-deposited layer 24. Examples of such surface treatments include corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, and pretreatments such as oxidation treatment using chemicals.

[0105] Among these surface treatments, corona treatment and plasma treatment are particularly preferred. For example, a plasma-treated surface may be formed on the barrier coat layer 23, and the second vapor-phase deposition layer 24 may be formed on the plasma-treated surface. For example, plasma treatment involves surface modification using plasma gas generated by ionizing gas through arc discharge. In addition to the above, inorganic gases such as oxygen gas, nitrogen gas, argon gas, and helium gas can be used as the plasma gas. For example, in-line plasma treatment can remove moisture and dust from the surface and also smooth and activate the surface. Plasma treatment can also be performed after deposition to improve adhesion. In this embodiment, plasma discharge treatment is preferably performed, taking into consideration the plasma output, type of plasma gas, amount of plasma gas supplied, treatment time, and other conditions. Furthermore, devices such as DC glow discharge, high-frequency discharge, and microwave discharge can be used to generate plasma. Plasma treatment can also be performed using atmospheric pressure plasma treatment.

[0106] <<<Second vapor deposition layer>>> The second vapor-deposited layer 24 is a vapor-deposited film formed by physical vapor deposition (PVD). In this embodiment, it is preferable to form an aluminum vapor-deposited film as the second vapor-deposited layer 24. By forming an aluminum vapor-deposited film as the second vapor-deposited layer 24, it is possible to improve the gas barrier property and the light-shielding property.

[0107] Examples of physical vapor deposition (PVD) methods include vacuum deposition, sputtering, ion plating, and ion cluster beam deposition. Specifically, a vapor deposition film can be formed using a vacuum deposition method in which aluminum is used as a raw material, heated to vaporize it, and then vapor-deposited onto one side of a base layer (resin film). The deposition material can be heated by, for example, resistance heating, high-frequency induction heating, or electron beam heating (EB).

[0108] The thickness of the aluminum vapor-deposited film is preferably 20 nm to 500 nm, more preferably 30 nm to 500 nm, and even more preferably 40 nm to 500 nm. If the thickness of the aluminum vapor-deposited film is within the above range, it is possible to further improve the light-shielding property while exhibiting sufficient gas barrier property.

[0109] <<Printing base layer>> The printed substrate layer 15 has a substrate layer 13 and a printed layer 14. First, the substrate layer 13 will be described.

[0110] <<<Base material layer>>> The substrate layer 13 is a layer that supports, for example, the first resin layer 11 and the second resin layer 12, etc., and increases the overall strength of the tube laminate 10. A resin film that constitutes a typical packaging material may be used as the substrate layer 13. Materials that can be used for the substrate layer 13 include, for example, polyester-based resins, polyamide-based resins, polyaramid-based resins, polyolefin-based resins, polycarbonate-based resins, polyacetal-based resins, fluorine-based resins, and other tough resin films or sheets. For example, the substrate layer 13 may contain polyethylene terephthalate. When the substrate layer 13 contains a polyester-based resin, the polyester-based resin may contain a biomass polyester. Biomass polyester refers to a polyester obtained from a raw material containing a biomass-derived monomer.

[0111] The resin film or sheet may be an unstretched film, a uniaxially or biaxially stretched film, etc. Among these, in the present embodiment, a biaxially stretched polyester resin film is preferred because of its excellent printability.

[0112] In this embodiment, the thickness of the base layer 13 is preferably 10 μm or more and 25 μm or less.

[0113] <<<Print layer>>> Next, the printed layer 14 will be described. The printed layer 14 is a layer for enhancing the design of the tube laminate 10 and the like. This printed layer 14 is a layer on which a predetermined character, figure, pattern, color-coded or other design is formed using ink. Known inks may be used. For example, the ink may contain at least one of an organic pigment and an inorganic pigment, and a binder resin, and may further contain various additives as necessary. The printed layer 14 can be formed, for example, on the base layer 13 by a known printing method, such as gravure printing, offset printing, letterpress printing, or screen printing.

[0114] <<adhesive layer>> The adhesive layers, such as the first adhesive layer 16a, the second adhesive layer 16b, and the third adhesive layer 16c, are layers for bonding together the first resin layer 11, the barrier layer 20, the printing substrate layer 15, the second resin layer 12, etc. The material constituting the adhesive layer can be appropriately selected depending on the resin constituting the layer to be bonded.

[0115] The adhesive layer may be formed using an anchor coating agent such as an isocyanate (urethane), polyethyleneimine, polybutadiene, or organic titanium. Alternatively, the adhesive layer may be formed using any of a polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, or other laminating adhesive.

[0116] Suitable materials for forming the adhesive layer include, for example, polyethylene, polypropylene, ethylene-vinyl alcohol, ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer, ionomer, and maleic anhydride-modified polyolefin resin.

[0117] 1C, when an adhesive is used as the second adhesive layer 16b, the adhesive can be applied to the printing layer 14 serving as the printing substrate layer 15, rather than to the second vapor-phase deposited layer 24. This prevents the second vapor-phase deposited layer 24 from being scratched. This prevents the light-blocking properties of the laminate for a tube 10 from being reduced.

[0118] In this embodiment, the thickness of each adhesive layer is preferably 3 μm or more and 60 μm or less.

[0119] <<Other Layers>> The tube laminate 10 may further include other layers. Examples of such layers include an intermediate layer. The intermediate layer is a layer for increasing the overall strength of the tube laminate 10. The intermediate layer is preferably made of a material that is impact resistant and pinhole resistant. For example, a polyamide resin film such as a biaxially oriented nylon film may be used as the intermediate layer. The thickness of the intermediate layer may be determined appropriately depending on the application and function of the tube laminate 10. The thickness of the intermediate layer may be, for example, approximately 15 μm or more and 25 μm or less. Furthermore, although not shown, a layer formed of ink, such as a printed layer 14, may be formed on the outer surface side of the first resin layer 11.

[0120] In such a laminate for a tube 10, the first resin layer 11, the barrier layer 20, the printed substrate layer 15, the second resin layer 12, etc. may be laminated to one another by, for example, wet lamination, dry lamination, solventless dry lamination, extrusion lamination, co-extrusion lamination, inflation, or any other method. Furthermore, when performing the above-mentioned lamination, the films constituting each layer may be subjected to pretreatment such as corona treatment or ozone treatment.

[0121] The laminate 10 for a tube has an acid permeability of 0.25 cc / m2 measured in accordance with JIS K7126-2:2006 (Part 2: constant pressure method) under an environment of 23°C temperature and 90% RH. 2 In this case, the oxygen permeability is 0.20 cc / m 2 ·atm·day or less is acceptable, 0.10cc / m 2 ·atm·day or less. If the oxygen permeability is within the above range, the material has suitable oxygen barrier properties and can be used in a variety of applications where oxygen barrier properties are required. The oxygen permeability can be measured using an oxygen permeability measuring device (OX-TRAN manufactured by MOCON).

[0122] In addition, the water vapor permeability of the laminate 10 for a tube, measured in accordance with JIS K7129-2:2019 under an environment of a temperature of 40°C and a humidity of 90% RH, was 0.4 g / m 2 In this case, the water vapor permeability is 0.2 g / m 2 -day or less, 0.1g / m 2 ·day or less. If the water vapor permeability is within the above range, the film has suitable water vapor barrier properties and can be used in a variety of applications where water vapor barrier properties are required. The water vapor permeability can be measured using a water vapor permeability measuring device (PERMATRAN manufactured by MOCON).

[0123] Furthermore, the light transmittance measured in accordance with JIS K7361-1:1997 may be 0.2% or less across the entire wavelength range. In this case, the light transmittance may be 0.1% or less across the entire wavelength range, or 0.05% or less. If the light transmittance is within the above range, the film has suitable light-blocking properties and can be used in a variety of applications requiring light-blocking properties. The light transmittance can be measured using a haze meter (HM-150, manufactured by Murakami Lighting Laboratory Co., Ltd.).

[0124] Next, a tube container 40 including the laminate for tubes 10 according to this embodiment will be described.

[0125] 2, the tube container 40 includes a body tube 41, which is a laminated molded tube, and a head member 43 joined to one end 42 of the body tube 41. The body tube 41 has a generally cylindrical shape as a whole. The body tube 41 includes a laminated body 10 for a tube. In this case, the body tube 41 may be configured such that an outer surface 101 of the laminated body 10 for a tube faces away from the contents, and an inner surface 102 faces the contents.

[0126] The body tube 41 has a body seal portion 44 where the laminate for a tube 10 is joined together. This body seal portion 44 is formed along the longitudinal direction of the body tube 41. Such a body tube 41 may be obtained, for example, by rolling the laminate for a tube 10 into a cylindrical shape, overlapping opposing ends, and joining them together by, for example, heat sealing.

[0127] The body tube 41 also has a bottom seal portion 45 where the laminated bodies for tubes 10 are joined together. This bottom seal portion 45 is a portion where the laminated bodies for tubes 10 are joined together near an opening (not shown) formed at the other end 46 of the body tube 41 after an appropriate amount of content C is filled through the opening.

[0128] The head member 43 has a shoulder portion 47 and a mouth portion 48. A cap 49 is attached to the mouth portion 48. The head member 43 is molded by, for example, compression molding. The head member 43 is made of, for example, a resin material such as high-density polyethylene (HDPE).

[0129] In addition, the acid permeability measured in the tube container 40 under an environment of a temperature of 23°C and a humidity of 90% RH was 0.1 cc / m 2 In this case, the oxygen permeability is 0.05 cc / m 2 ·atm·day or less is acceptable, 0.03cc / m 2 ·atm·day or less. If the oxygen permeability is within the above range, the material has suitable oxygen barrier properties and can be used in a variety of applications where oxygen barrier properties are required. The oxygen permeability can be measured using an oxygen permeability measuring device (OX-TRAN manufactured by MOCON).

[0130] The water vapor permeability of the tube container 40 measured under an environment of a temperature of 40°C and a humidity of 90% RH was 0.01 g / m 2 In this case, the water vapor permeability is 0.005 g / m 2 -day or less, 0.003g / m 2 ·day or less. If the water vapor permeability is within the above range, the film has suitable water vapor barrier properties and can be used in a variety of applications where water vapor barrier properties are required. The water vapor permeability can be measured using a water vapor permeability measuring device (PERMATRAN manufactured by MOCON).

[0131] Next, a method for manufacturing the tube container 40 will be described.

[0132] First, a laminate for a tube 10 is prepared. Next, the laminate for a tube 10 is rolled up and the opposing edges are joined together by, for example, heat sealing to form a cylindrical tube, thereby producing a body tube 41.

[0133] Next, the joined laminate for a tube 10 (body tube 41) is used to manufacture the above-mentioned tube container 40 by compression molding.

[0134] 3(a), the cylindrical laminate 10 for a tube (body tube 41) is wound around a mandrel 82, and a mold 83 for compression molding the head member 43 is attached to one end of the mandrel 82. That is, the laminate 10 for a tube (body tube 41), which has been previously molded into a cylindrical shape, is wound around the mandrel 82, the tip of which serves as a core for compression molding the head member 43, and is then advanced to a predetermined position into the cavity of the mold 83 for molding the head member 43.

[0135] Next, molten resin is supplied from a resin supply device (not shown) into the mold 83 to compression-mold the head member 43. In this case, one end 42 of the body tube 41 is inserted into the mold 83 to mold the head member 43, and at the same time, the body tube 41 is fused integrally to the head member 43. Thereafter, the integrated head member 43 and body tube 41 are removed from the mold 83 and mandrel 82 to obtain the tube container 40 (see FIG. 3(b)).

[0136] When manufacturing the tube container 40 with a cap, the cap 49 is prepared in parallel with the production of the tube container 40. In this case, the cap 49 is produced by injection molding using, for example, an injection molding machine (not shown). Then, the cap 49 is screwed onto the opening 48 of the head member 43 of the tube container 40, thereby obtaining the tube container 40 with a cap shown in FIG.

[0137] Thereafter, the contents are filled into the body tube 41 of the tube container 40 from the bottom side, and the bottom of the body tube 41 is sealed, thereby obtaining a tube container with a cap and contents filled as a product.

[0138] As described above, according to this embodiment, the tube laminate 10 includes a first resin layer 11, a barrier layer 20, and a second resin layer 12, which are arranged in this order from the outer surface 101 to the inner surface 102. The barrier layer 20 includes a barrier substrate layer 21, a first vapor-phase deposition layer 22, a barrier coat layer 23, and a second vapor-phase deposition layer 24, in this order. An oxygen plasma-treated surface is formed on the barrier substrate layer 21, and the first vapor-phase deposition layer 22 is formed on the oxygen plasma-treated surface. A plasma-treated surface is formed on the barrier coat layer 23, and the second vapor-phase deposition layer 24 is formed on the plasma-treated surface. The first vapor-phase deposition layer 22 is a silicon oxide vapor-deposited film or an aluminum oxide vapor-deposited film. The second vapor-phase deposition layer 24 is an aluminum vapor-deposited film. This improves the gas barrier properties and light-blocking properties of the tube laminate 10 without using aluminum foil. The improvement of the gas barrier properties and light-blocking properties of the tube laminate 10 will be explained in the examples described below. [Example]

[0139] Next, a specific example of the above embodiment will be described.

[0140] Example 1 A laminate shown in Fig. 1B was produced by first preparing a resin film (thickness 150 µm) containing linear low-density polyethylene as the first resin layer.

[0141] A barrier film was prepared as the barrier layer. First, a biaxially oriented polyethylene terephthalate (PET) film with a thickness of 12 μm was prepared as the barrier substrate layer. Next, the PET film was subjected to a surface treatment using oxygen plasma under the following conditions. (Plasma treatment conditions) ·Input power 0.3kW Gas composition O2 Gas flow rate 900sccm Chamber pressure 3Pa Film transport speed: 4m / min

[0142] The PET film was then attached to the delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and a 20-nm-thick aluminum oxide vapor-deposited film (first vapor-deposited layer) was formed on the oxygen plasma-treated surface of the PET film using a reactive resistance heating method as the heating means for the vacuum deposition method under the following conditions: (Aluminum oxide film formation conditions) ·Vacuum degree: 8.1×10 -2 Pa

[0143] Furthermore, a hydrolyzed liquid of composition B, which had been prepared in advance, was added to a mixed liquid of composition A prepared according to the formulation shown in Table 1 and stirred to obtain a colorless and transparent barrier coat composition.

[0144] [Table 1]

[0145] Next, the barrier coating composition prepared above was coated onto the aluminum oxide vapor-deposited film by a direct gravure method, followed by heat treatment at 140°C for 60 seconds to form a barrier coating layer with a thickness of 0.3 μm (in a dry state).

[0146] Next, a glow discharge plasma generator was used to apply plasma treatment to the barrier coat layer by applying argon at 1.0 slm and a current of 20 A. After that, the plasma-treated surface was subjected to vacuum deposition using an electron beam heating method using aluminum as a raw material, with the vacuum in the vacuum chamber reduced to 2 × 10 -4 The vacuum level in the deposition chamber was 2.0 × 10 mbar. -2 A 40 nm thick aluminum vapor deposition film (second vapor deposition layer) was formed under conditions of 100 mbar, yielding a barrier film (layer structure: polyethylene terephthalate film (oxygen plasma treated surface) / aluminum oxide vapor deposition film (first vapor deposition layer) / barrier coat layer (plasma treated surface) / aluminum vapor deposition film (second vapor deposition layer)).

[0147] Furthermore, a resin film (thickness: 180 μm) containing linear low-density polyethylene was prepared as the second resin layer.

[0148] Next, the first resin layer, the barrier layer, and the second resin layer were laminated together by dry lamination. The layer structure of the obtained laminate for a tube is as follows. LLDPE / adhesive layer / PET / aluminum oxide vapor deposition film / barrier coat layer / aluminum vapor deposition film / adhesive layer / LLDPE In the above, "LLDPE" means linear low-density polyethylene film (hereinafter the same), and "PET" means polyethylene terephthalate film (hereinafter the same).

[0149] Next, a tube container shown in Fig. 2 was produced from the obtained laminate. At this time, high density polyethylene (HDPE) was used as the material for the head member.

[0150] Example 2 A laminate for a tube and a tube container were produced in the same manner as in Example 1, except that the laminate shown in Figure 1C was produced, a polyethylene terephthalate film (thickness: 12 µm) was used as the base layer of the printed base layer, a printed layer was formed on the inner surface of the base layer of the printed base layer, and the first resin layer, the printed base layer, the barrier layer, and the second resin layer were laminated together by a dry lamination method. The layer structure of the obtained laminate for a tube is as follows. LLDPE / adhesive layer / PET / printing layer / adhesive layer / aluminum vapor deposition film / barrier coat layer / aluminum oxide vapor deposition film / PET / adhesive layer / LLDPE

[0151] Example 3 A laminate for a tube and a tube container were produced in the same manner as in Example 1, except that the laminate shown in Figure 1D was produced, a polyethylene terephthalate film (thickness 12 µm) was used as the base layer of the printed base layer, a printed layer was formed on the inner surface of the base layer of the printed base layer, and the first resin layer, the printed base layer, the barrier layer, and the second resin layer were laminated together by a dry lamination method. The layer structure of the obtained laminate for a tube is as follows. LLDPE / adhesive layer / PET / printing layer / adhesive layer / PET / aluminum oxide vapor deposition film / barrier coat layer / aluminum vapor deposition film / adhesive layer / LLDPE

[0152] Example 4 A laminate for a tube and a tube container were produced in the same manner as in Example 1, except that the laminate shown in Figure 1D was produced, an unstretched polypropylene film (thickness 120 µm) was used as the first resin layer, a biaxially oriented polypropylene film (thickness 25 µm) was used as the base layer of the printing base layer, a printed layer was formed on the inner surface of the base layer of the printing base layer, an unstretched polypropylene film (thickness 25 µm) was used as the barrier base layer, an unstretched polypropylene film (thickness 120 µm) was used as the second resin layer, and polypropylene (PP) was used as the material of the head member. The layer structure of the obtained laminate for a tube is as follows. CPP / adhesive layer / OPP / printing layer / adhesive layer / aluminum vapor deposition film / barrier coat layer / aluminum oxide vapor deposition film / CPP / adhesive layer / CPP In the above, "CPP" means unstretched polypropylene film (the same applies hereinafter), and "OPP" means biaxially stretched polypropylene film (the same applies hereinafter).

[0153] (Comparative Example 1) A laminate for a tube was produced in the same manner as in Example 3, except that the thickness of the first resin layer was 130 μm and a biaxially oriented polyethylene terephthalate film (thickness 12 μm) with an aluminum vapor deposition layer was used as the barrier layer. The layer structure of the obtained laminate for a tube is as follows. LLDPE / adhesive layer / PET / printed layer / adhesive layer / aluminum vapor deposition film / PET / adhesive layer / LLDPE

[0154] (Comparative Example 2) A laminate for a tube was produced in the same manner as in Example 3, except that the thickness of the first resin layer was 130 μm and an aluminum foil (thickness 9 μm) was used as the barrier layer. The layer structure of the obtained laminate for a tube is as follows. LLDPE / adhesive layer / PET / printing layer / adhesive layer / aluminum foil / adhesive layer / LLDPE

[0155] (1) Measurement of oxygen permeability The laminates for tubes according to Examples 1 to 4 and the laminates for tubes according to Comparative Examples 1 and 2 were measured for oxygen permeability (cc / m) in accordance with JIS K7126-2:2006 (Part 2: constant pressure method) using an oxygen permeability measuring device (OX-TRAN manufactured by MOCON) under an environment of 23°C temperature and 90% RH. 2 ·atm·day) was measured.

[0156] Furthermore, the tube containers according to Examples 1 to 4 and the tube containers according to Comparative Examples 1 and 2 were measured for oxygen permeability (cc / m) using an oxygen permeability measuring device (OX-TRAN manufactured by MOCON) under an environment of a temperature of 23°C and a humidity of 90%. 2 The viscosity (atm·day) was measured. At this time, the tube container was set in a jig, and then the tube container was sealed. At this time, the mouth of the tube container (head member) was sealed with a barrier film containing aluminum foil. In addition, the opening formed at the other end of the body tube (other end 46 shown in Figure 2) was sealed with an adhesive. Thereafter, the inside of the tube container was purged with nitrogen, and the amount of oxygen that permeated from outside the tube container under atmospheric pressure conditions was measured using an oxygen permeability measuring device.

[0157] (2) Measurement of water vapor permeability The tube laminates of Examples 1 to 4 and Comparative Examples 1 and 2 were measured for water vapor permeability (g / m) in accordance with JIS K7129-2:2019 using a water vapor permeability measuring device (PERMATRAN manufactured by MOCON) under an environment of a temperature of 40°C and a humidity of 90%RH. 2·day) was measured.

[0158] Furthermore, the tube containers according to Examples 1 to 4 and the tube containers according to Comparative Examples 1 and 2 were measured for water vapor permeability (g / m) using a water vapor permeability measuring device (PERMATRAN manufactured by MOCON) under an environment of a temperature of 40°C and a humidity of 90% RH. 2 ·day) was measured. At this time, calcium chloride was filled into the tube container, and then the tube container was sealed. At this time, the mouth of the tube container (head member) was sealed with a barrier film containing aluminum foil. In addition, the opening formed at the other end of the body tube (other end 46 shown in Figure 2) was sealed by heat welding. Thereafter, it was stored for one week in an environment of 40°C and 90% RH, and the water vapor transmission rate (g / m 2 ·day) was measured.

[0159] (3) Measurement of light transmittance The light transmittance of the tube laminates according to Examples 1 to 4 and Comparative Examples 1 and 2 was measured using a haze meter (HM-150 manufactured by Murakami Lighting Research Institute Co., Ltd.) in accordance with JIS K7361-1:1997.

[0160] The results are shown in Table 2 and FIG.

[0161] [Table 2]

[0162] As a result, as shown in Table 2, the laminate for a tube according to Comparative Example 1 had an oxygen permeability of 0.29 cc / m 2 On the other hand, the laminates for tubes according to Examples 1 to 4 had an oxygen permeability of 0.10 cc / m 2 In particular, in the laminates for tubes according to Examples 1 to 3, the oxygen permeability was 0.03 cc / m 2·atm·day. In addition, the tube container according to Comparative Example 1 had an oxygen permeability of 0.100 cc / m 2 In contrast, the oxygen permeability of the tube containers according to Examples 1 to 4 was 0.090 cc / m 2 In particular, in the laminates for tubes according to Examples 1 to 3, the oxygen permeability was 0.080 cc / m 2 It was ATM day.

[0163] Furthermore, as shown in Table 2, the laminate for a tube according to Comparative Example 1 had a water vapor permeability of 0.46 g / m 2 In contrast, the laminates for tubes according to Examples 1 to 4 had a water vapor permeability of 0.09 g / m 2 In particular, in the laminates for tubes according to Examples 1 to 3, the water vapor permeability was 0.03 g / m 2 ·day. In addition, the tube container according to Comparative Example 1 had a water vapor permeability of 0.010 g / m 2 In contrast, the water vapor permeability of the tube containers according to Examples 1 to 4 was 0.004 g / m 2 In particular, in the laminates for tubes according to Examples 1 to 3, the water vapor permeability was 0.001 g / m 2 ·day.

[0164] Therefore, it was found that the laminate for a tube and the tubular container according to this embodiment can improve the gas barrier properties of the laminate for a tube and the tubular container without using aluminum foil.

[0165] 4, the tube laminate according to Comparative Example 1 had a light transmittance of about 0.7% in the wavelength range of about 320 nm or more and 420 nm or less. In contrast, the tube laminates according to Examples 1 to 4 had a light transmittance of 0.2% or less (about 0.1% or less) over the entire wavelength range. Therefore, it was found that the tube laminate according to this embodiment can improve the light-blocking properties of the tube laminate without using aluminum foil.

[0166] It is also possible to combine the multiple components disclosed in the above embodiments as needed, or to delete some of the components disclosed in the above embodiments. [Explanation of symbols]

[0167] 10. Laminate for tube 11 First resin layer 12 Second resin layer 15 Printing base material layer 20 Barrier Layer 21 Barrier substrate layer 22 First vapor deposition layer 23 Barrier coat layer 24 Second vapor deposition layer 40 tube containers 41 Body tube 42 one end 43 Head member 101 Exterior 102 Inside

Claims

1. The insulating film includes a first resin layer, a barrier layer, and a second resin layer, which are arranged in this order from the outer surface to the inner surface, the barrier layer comprises a barrier substrate layer, a first vapor-deposited layer, a barrier coat layer, and a second vapor-deposited layer in this order; an oxygen plasma treated surface is formed on the barrier substrate layer; the first vapor deposition layer is formed on the oxygen plasma treated surface, a plasma-treated surface is formed on the barrier coat layer; the second vapor deposition layer is formed on the plasma-treated surface; the first vapor-deposited layer is a silicon oxide vapor-deposited film or an aluminum oxide vapor-deposited film; The laminate for a tube, wherein the second vapor-deposited layer is an aluminum vapor-deposited film.

2. The laminate for a tube according to claim 1 , further comprising a printing substrate layer provided between the first resin layer and the barrier layer.

3. 10. The tubing laminate of claim 1, wherein the barrier substrate layer comprises a biaxially oriented polyethylene terephthalate film.

4. The laminate for a tube according to claim 1 , wherein the material constituting the barrier substrate layer is made of a biomass-derived resin or a recycled resin.

5. The laminate for a tube according to claim 1 , wherein the barrier coat layer is a resin cured film of a metal alkoxide and a water-soluble polymer.

6. 2. The laminate for a tube according to claim 1, wherein the barrier coat layer is a cured resin film containing a reaction product formed by a reaction between a metal oxide and a phosphorus compound.

7. 2. The laminate for a tube according to claim 1, wherein the barrier coat layer is a cured resin film containing a carboxyl group-containing polymer crosslinked with a polyvalent metal compound.

8. The oxygen permeability measured in accordance with JIS K7126-2:2006 under an environment of 23°C temperature and 90% RH is 0.25 cc / m ２ 2. The laminate for a tube according to claim 1, wherein the laminate has a viscosity of less than 1 / 2 atm / day.

9. The water vapor permeability measured in accordance with JIS K7129-2:2019 under an environment of 40°C temperature and 90% RH is 0.4 g / m ２ 2. The laminate for a tube according to claim 1, wherein the laminate has a viscosity of less than 1000 sq. m.

10. 2. The laminate for a tube according to claim 1, wherein the light transmittance measured in accordance with JIS K7361-1:1997 is 0.2% or less over the entire wavelength range.

11. In a tube container, A body tube having the tube laminate according to any one of claims 1 to 10; a head member joined to one end of the body tube.

12. The oxygen permeability measured under an environment of 23°C and 90% RH is 0.1 cc / m ２ The tube container according to claim 11, wherein the temperature is less than 100°C / atm / day.

13. The water vapor permeability measured under an environment of 40°C temperature and 90% RH is 0.01 g / m ２ The tube container according to claim 11, wherein the storage time is less than 1 day.

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