JP2002019015A - Laminate and packaging material using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is not affected by the oxidation and pollution of the surface when a thermoplastic resin is laminated on the aluminum or alumina surface of an aluminum foil layer, a layer on which aluminum is vapor-deposited, or a layer on which alumina is vapor-deposited and has high laminate strength which is not lowered even when various highly permeable substances are packaged by using the laminate and a packaging material with the use of the laminate. SOLUTION: The laminate using a base material in which hydrothermal conversion treatment is applied to the aluminum or alumina surface and the packaging material using the laminate are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thermoplastic resin having good adhesion to an aluminum surface or an alumina surface such as an aluminum foil layer, an aluminum vapor-deposited layer, or an alumina vapor-deposited layer provided on a substrate as a barrier layer. Regarding the laminated body having the same and the packaging material using the same, more specifically, even when the laminated body is used as various packaging materials and the highly permeable material is packaged, it is not affected by the highly permeable content. The present invention also relates to a laminate in which lamination strength between a barrier layer and a thermoplastic resin layer does not decrease.

[0002]

2. Description of the Related Art In the field of packaging, aluminum foil, aluminum-deposited film, and alumina-deposited film are used as one of barrier substrates for protecting contents from oxygen and water vapor. In addition, aluminum foil and aluminum vapor-deposited film can be provided with a light-shielding property, and aluminum foil maintains its shape when folded (dead-hold property). , To provide other functionality to the packaging material,
It is used for various packaging materials by laminating various thermoplastic resins on aluminum foil, aluminum evaporated film or alumina evaporated film.

[0003] In manufacturing various packaging materials by providing a thermoplastic resin on an aluminum surface such as an aluminum foil or an aluminum vapor-deposited film, a method for producing a laminate of a base material and a thermoplastic resin includes an aluminum foil or an aluminum vapor-deposited film. An ethylene-α, β-unsaturated carboxylic acid such as an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, or an ionic cross-linked product of an ethylene-methacrylic acid copolymer or an ionic cross-linked product thereof is coated on the aluminum surface of the film. Lamination is performed using a technique such as extrusion lamination. In addition, with respect to an aluminum foil, an aluminum vapor-deposited film, or an alumina vapor-deposited film, it is possible to laminate them using a polyurethane-based or polyethyleneimine-based adhesive. However, the laminate thus obtained has the following problems.

[0004] First, it is well known that aluminum of aluminum foil or aluminum vapor-deposited film has its surface oxidized and exists in the form of aluminum oxide. Generally, the above-mentioned ethylene-
When laminating an α, β unsaturated carboxylic acid or its ion-crosslinked product, the above-mentioned ethylene-α is used immediately after opening the aluminum foil supplied from the aluminum foil manufacturer for aluminum foil, or immediately after aluminum deposition for aluminum evaporated film. It is preferable to produce a laminate in which .beta.-unsaturated carboxylic acid or its ion-crosslinked product is laminated. However, in the manufacturing process of the laminate, ethylene-α, β is used by using an aluminum foil or an aluminum vapor-deposited film in a state where the time has passed after opening and the oxidation of the aluminum surface has progressed or the contamination has progressed.
Even when an unsaturated carboxylic acid or its ionic crosslinked product is laminated, it is difficult to obtain a good lamination strength.

The second problem is as follows. Generally, in order to laminate a thermoplastic resin on an aluminum surface of an aluminum foil or an aluminum vapor-deposited film using an extrusion lamination method, a certain amount of lamination is performed by using the above-described polyurethane-based, polyethyleneimine-based, or chlorinated polyolefin-based adhesive. It is possible to give strength. However, it is necessary for the above-mentioned adhesive to process the thermoplastic resin at a high temperature, if necessary, to oxidize the thermoplastic resin. In this case, in the case of a resin which cannot be processed at high temperature, such as a polypropylene resin, it is difficult to obtain a sufficient lamination strength even by using an adhesive. Furthermore, in the case of a thermoplastic resin in which a polar group other than the above-mentioned ethylene-α, β-unsaturated carboxylic acid or its ionic cross-linked product is introduced, similarly, sufficient strength cannot be obtained even if an adhesive layer is provided. It is the current situation.

As a third problem, when a laminate using a barrier layer such as the above-mentioned aluminum foil, aluminum-deposited film, or alumina-deposited film is used as a packaging material, a highly permeable material is packaged as the content. Then, the highly permeable content passes through the sealant layer (thermoplastic resin layer) of the packaging material and is trapped between the barrier layer and the thermoplastic resin layer. As a result, the barrier layer and the thermoplastic resin layer There is a problem that the laminate strength is reduced. In particular, when the barrier layer and the thermoplastic resin layer are laminated using an adhesive layer, such an adhesive is mainly bonded using hydrogen bonding, adhesive bonding, or the cohesive force of the adhesive layer itself. Therefore, when such contents are added, dissociation of hydrogen bonds and reduction in adhesive strength due to swelling of the resin occur. Examples of such a strong osmotic substance include a fragrance and poultice component of a bath agent, a surfactant, and a liquid content mainly containing a solvent.

[0007] In recent years, the packaging of electronic components has been increasingly using a laminate using aluminum foil. In particular, a Li-ion battery is a battery body in an aluminum package, in which an electrolyte solution obtained by dissolving a Li salt in an aprotic solvent is used alone, or a polymer gel impregnated with the electrolyte solution is used together with a positive electrode material and a negative electrode material. Is filling. Such Li salts, particularly LiPF ₆ and LiBF ₄ , hydrolyze when containing water and generate hydrofluoric acid, and the laminating strength between the aluminum foil and the thermoplastic resin decreases due to the influence of the hydrofluoric acid.
This has been a problem from the viewpoint of safety as well as deterioration of battery characteristics.

[0008] Aluminum foil, aluminum-deposited film and alumina-deposited film are indispensable in various packaging materials because of their excellent barrier properties and functionality. There is a problem that the laminate strength is reduced due to contamination or contamination, or due to penetration of a highly permeable substance. There is a demand for a laminate improved in the above problems and a packaging material using the same.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has an aluminum foil layer, an aluminum vapor-deposited layer, and an aluminum vapor-deposited layer provided on a substrate as a barrier layer. Alternatively, when laminating a thermoplastic resin on the alumina surface, it is not affected by the state of oxidation or contamination on the surface, has good laminating strength, and wraps various strongly permeable materials using the laminated body It is an object of the present invention to provide a laminate in which the lamination strength does not decrease even if it is performed, and a packaging material using the same.

[0010]

Means for Solving the Problems In order to solve the above problems, the present invention provides an aluminum foil layer,
In laminating a thermoplastic resin on the aluminum surface or alumina surface of a substrate having an aluminum surface or an alumina surface formed of either an aluminum evaporation layer or an alumina evaporation layer, the aluminum surface or the alumina surface is subjected to a hydrothermal conversion treatment. It is a laminated body characterized by using a substrate that has been made.

According to a second aspect of the present invention, in the laminate according to the first aspect, when the surface of the aluminum surface or the alumina surface of the substrate subjected to the hydrothermal conversion treatment is measured by X-ray photoelectron spectroscopy, the aluminum ( Al) A spectral peak position derived from an oxide and a hydroxide in a 2p orbital has a binding energy of 75.4 eV or less.

According to a third aspect of the present invention, in the laminate according to the first aspect, when the surface of the aluminum surface or the alumina surface subjected to the hydrothermal modification treatment of the base material is measured by X-ray photoelectron spectroscopy, oxygen ( O) and aluminum (Al) element ratio (O
/ Al) is 1.7 or more.

According to a fourth aspect of the present invention, there is provided the laminate according to the first aspect, wherein the surface of the aluminum surface or the alumina surface on which the substrate is subjected to the hydrothermal alteration treatment is subjected to time-of-flight secondary ion mass spectrometry. In addition, a ratio (OH / O) of a hydroxyl group (OH) to oxygen (O) is 0.9 or more.

According to a fifth aspect of the present invention, in the laminate according to the first aspect, the surface of the aluminum surface or the alumina surface subjected to the hydrothermal modification treatment of the substrate is subjected to an atomic force microscope to determine a surface area ratio and a surface roughness. Is measured, the surface area ratio (hydrothermally denatured treated substrate surface area / untreated substrate surface area) is 1.5 or more, center plane average roughness (Ra) is 15 nm or more, root mean square surface roughness (RMS) Is 20 nm or more.

According to a sixth aspect of the present invention, in the laminate according to the first aspect, a fracture surface of the base material having the aluminum surface or the alumina surface subjected to the hydrothermal transformation treatment of the base material is observed by a transmission electron microscope. When observed, the thickness of the treatment layer formed by performing the hydrothermal alteration treatment is 0.1 μm or more.

The invention according to claim 7 is the invention according to claims 1 to 6
The laminate according to any one of the above, wherein the hydrothermal alteration treatment is a boehmite treatment.

The invention according to claim 8 is the invention according to claims 1 to 7
In the laminate according to any one of the above, the thermoplastic resin is polyethylene, ethylene-α-olefin copolymer, polypropylene, propylene-α-olefin copolymer, ethylene-α, β-unsaturated carboxylic acid copolymer Or its esterified or ionic crosslinked product, acid anhydride-modified polyethylene, acid anhydride-modified polypropylene, epoxy compound-modified polyolefin or its olefin polymer, silane-modified polyolefin or its olefin polymer, ethylene-vinyl acetate copolymer It is characterized by being a resin composed of a single substance or a blend of two or more kinds.

The invention according to claim 9 is the invention according to claims 1 to 8
In the laminate according to any one of the above, the thermoplastic resin layer is provided directly on the aluminum surface or the alumina surface that has been subjected to the above-mentioned hydrothermal alteration treatment.

According to a tenth aspect of the present invention, in the laminate according to any one of the first to eighth aspects, an isocyanate compound having a thickness of 5 μm is coated on the aluminum surface or the alumina surface which has been subjected to the hydrothermal modification treatment. After being provided in the following range, the thermoplastic resin is laminated.

An eleventh aspect of the present invention is a packaging material comprising at least the laminate according to the ninth or tenth aspect.

According to a twelfth aspect of the present invention, there is provided the packaging material according to the eleventh aspect, wherein the packaging material is in a soft packaging form.

According to a thirteenth aspect of the present invention, there is provided a packaging material characterized in that the packaging material according to the eleventh aspect is a composite paper container which is composited with paper.

According to a fourteenth aspect of the present invention, there is provided a packaging material characterized in that the packaging material according to the eleventh aspect is used as an exterior material of an electronic member such as a Li-ion battery.

[0024]

Embodiments of the present invention will be described below. The laminate of the present invention is obtained by laminating a thermoplastic resin on the aluminum surface or the alumina surface of a substrate having an aluminum surface or an alumina surface formed of any one of an aluminum foil layer, an aluminum evaporation layer and an alumina evaporation layer by an extrusion lamination method. In this case, a substrate obtained by subjecting the aluminum surface or the alumina surface to a hydrothermal conversion treatment is used.

In particular, in the case of an aluminum-deposited film or an alumina-deposited film, various substrates such as a stretched polyester film, a stretched polypropylene film and a stretched nylon film can be used as a base material for the deposition, and a primer for the deposition can be used. It is possible to select one according to various base materials. Also, the thickness is not particularly limited.

In the present invention, the hot water denaturation treatment of the aluminum surface or the alumina surface of the aluminum foil layer, the aluminum deposition layer, and the alumina deposition layer provided on the base material includes tap water and deionized water. Although any of distilled water and distilled water distilled after deionization can be used, in particular, deionized distilled water is preferable, and water having an electric conductivity of 1.0 μS / cm is preferably used as an index. Further, it is preferable for the hot water conversion treatment to add 0.1 to 1% of a small amount of a basic substance such as ammonia or triethanolamine to the treated water.

In the hydrothermal conversion treatment of an oxide such as aluminum or alumina, various hydrated oxide layers are formed depending on the treatment temperature. The treatment temperature particularly preferred in the present invention is preferably a condition under which boehmite is formed as a hydrated oxide, and is preferably from 80 to 100 ° C. under normal pressure, more preferably from 90 to 100 ° C. Is preferred. Hereinafter, the boehmite treatment will be described as an example of the hot water treatment of the present invention.

The following are examples of indices for the boehmite treatment of the substrate. First, when the surface of the aluminum surface or the alumina surface subjected to the boehmite treatment is measured by X-ray photoelectron spectroscopy, the spectral peak position derived from the oxide and hydroxide of the aluminum (Al) 2p orbit has a binding energy of 75.4 eV or less. It is characterized by being. In the spectrum of Al at 2p orbitals obtained from X-ray photoelectron spectroscopy, 72.7 eV on the low energy side
Is a peak derived from Al in a metallic state, and a peak near 74.0 to 76.0 eV on the high energy side is a peak derived from aluminum oxide and aluminum hydroxide. The peaks derived from aluminum oxide and aluminum hydroxide cannot be distinguished due to small chemical shift, but their binding energy is 75.4 eV.
If it is below, it is more excellent in adhesiveness with various functional groups.

When the surface of the aluminum surface or the alumina surface subjected to the above-described boehmite treatment is measured by X-ray photoelectron spectroscopy, the element ratio (O / Al) of oxygen (O) to aluminum (Al) is 1.7. It is characterized by the above. X
O / Al obtained from X-ray photoelectron spectroscopy is an indicator of the degree of surface oxidation of aluminum (including oxygen of hydroxide). If the O / Al ratio is 1.7 or more, adhesion to various functional groups is achieved. More excellent in properties.

Furthermore, when the surface of the aluminum surface or the alumina surface subjected to the above-described boehmite treatment is measured by time-of-flight secondary ion mass spectrometry, the ratio (OH / O) of hydroxyl group (OH) to oxygen (O) is reduced. 0.9 or more. In the time-of-flight secondary ion mass spectrometry, the degree of oxidation and the degree of hydroxylation on the aluminum surface can be distinguished. If the ratio of OH / O is 0.9 or more, bonding using a hydroxyl group, for example, If a hydrogen bond or a reaction occurs, formation of a primary bond or the like can be expected, and the adhesiveness with various functional groups is excellent.

When the surface area ratio and the surface roughness of the aluminum or alumina surface subjected to the boehmite treatment described above are measured by an atomic force microscope, the surface area ratio (the surface area of the hydrothermally denatured base material / (Surface area of the treated substrate) is 1.5 or more, the center plane average roughness (Ra) is 15 nm or more, and the root mean square roughness (RMS) is 20 nm or more. This is because the original oxide film is reduced by boehmite treatment on the untreated aluminum surface or alumina surface, crystals of hydrated oxide such as boehmite precipitate, and the hydrated oxide layer is formed. This means that the surface is significantly roughened as compared with an untreated surface, resulting in a surface with severe undulation. Therefore, the surface area increases and the surface roughness also increases. As a result, when various thermoplastic resins are laminated, it is possible to improve the adhesion area, increase the number of functional groups on the boehmite-treated surface, and improve the physical adhesion by the anchoring effect.

Finally, as an index of the boehmite treatment, a fracture surface of a substrate having an aluminum surface or an alumina surface subjected to the above-mentioned hydrothermal alteration treatment is observed by a transmission electron microscope observation. The thickness of the treatment layer formed by performing the hot water alteration treatment is 0.1 μm or more. A hydrothermal alteration treatment such as a boehmite treatment forms a hydrated oxide film through various reactions on an aluminum oxide layer that originally existed. By performing the hydrothermal alteration treatment, the originally suitable aluminum oxide layer is reduced by the treatment, while the thickness of the hydrated oxide layer is increased as the hydrated oxide layer is formed. The binding energy, the O / Al ratio, and the OH / O ratio, which have been described above, are set to values more favorable for adhesion in that the treatment proceeds when the hydrated oxide layer is formed to some extent. In addition, a thicker coating layer is advantageous for adhesion in terms of an anchoring effect.

As an index of the boehmite treatment, in addition to these, it is possible to identify even the state of the color of the treated surface when platinum is deposited. Although it is possible to use the above-mentioned content as an index of the boehmite treatment, it is possible to improve the adhesion of the thermoplastic resin to the aluminum surface or the alumina surface by extrusion lamination.

In the laminate of the present invention, the thermoplastic resin used for lamination on the boehmite-treated aluminum surface or alumina surface formed on the base material includes high-density polyethylene, low-density polyethylene, medium-density polyethylene,
Ethylene-based copolymers such as ethylene-α-olefin copolymers, homo-block / random polypropylene resins, and propylene-based copolymers such as propylene-α-olefin copolymers, ethylene-acrylic acid copolymers and the like. Ethylene-α, β such as ethylene-methacrylic acid copolymer
Unsaturated carboxylic acid copolymers, esterified products of ethylene-α, β unsaturated carboxylic acid copolymers such as ethylene-methyl acrylate, ethylene-ethyl acrylate, ethylene-methyl methacrylate and ethylene-ethyl methacrylate; An ionic cross-linked product of an ethylene-α, β-unsaturated carboxylic acid copolymer, an ethylene-maleic anhydride graft copolymer, a propylene-maleic anhydride graft copolymer, Acid anhydride-modified polyolefins represented by terpolymers such as ethylene-ethyl acrylate-maleic anhydride, epoxy compound-modified polyolefins such as ethylene-glycidyl methacrylate copolymer, vinyltrimethoxysilane, vinyltriethoxysilane And methacryloxypropyl trimeth Vinyl silane such as silane or acrylic silane modified polyolefin or olefin copolymer, selected from a single or a blend of two or more resins selected from ethylene-vinyl acetate copolymer, if necessary, Various additives (antioxidants, tackifiers, fillers, various fillers, etc.) may be added to the resin. The selection of the thermoplastic resin to be laminated is variously selected depending on the function required as a packaging material, but is not limited to these types, and various resins can be used as needed. is there.

As described above, when the thermoplastic resin layer is laminated on the aluminum surface or the alumina surface of the aluminum foil layer, the aluminum vapor-deposited layer, or the alumina vapor-deposited layer provided on the base material, the aluminum surface or the alumina surface is subjected to boehmite treatment. By preparing the surface state by the method, the thermoplastic resin is strongly bonded to the aluminum surface or the alumina surface, and a good adhesive strength is given to the resin which could not be obtained by the conventional extrusion lamination method. Not only is it possible, but depending on the selection of the thermoplastic resin, even if it is used as various packaging materials and a highly permeable material is packaged, the interlayer is not affected by the highly permeable content. It is possible to obtain a laminate in which the laminate strength does not decrease.

As described above, even if a thermoplastic resin layer is directly provided on the boehmite-treated surface, it is possible to obtain a laminate having sufficiently good adhesiveness. In order to be able to be used in the contents, various isocyanate compounds are coated on the boehmite-treated surface with various coatings such as gravure to a thickness of 5 μm or less.
It is preferable that the thermoplastic resin layer is provided by 3 μm or less, more preferably 1 μm or less, and then laminated by extrusion lamination.

As described above, the provision of the urethane-based adhesive layer causes remarkable reduction in lamination strength due to dissociation of hydrogen bonds and swelling of the adhesive layer due to the highly permeable content. By forming the isocyanate-based compound alone to be very thin, the laminating strength does not decrease even if the content having a very strong permeability is filled.

Examples of the isocyanate-based compound include various diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate. These diisocyanates are trifunctional or more functional in the form of adduct, buret, or isocyanurate. Compounds in the form of a composite can also be used, and are not limited to various types or composite types other than the diisocyanate compounds described above.

The laminate of the present invention is suitably used as various packaging materials. As an example, an example in which the cover material is used will be described below. The following (1) to (4) show examples of the configuration of the lid material. Hereinafter, the substrate provided with any one of the aluminum foil layer, the aluminum vapor-deposited layer, and the alumina vapor-deposited layer in the present invention is referred to as an A layer, and the thermoplastic resin layer is referred to as a B layer. (1) Lid material: paper layer / thermoplastic resin layer (a) / A layer / B layer (sealant layer) (2) Lid material: paper layer / thermoplastic resin layer (b) / A layer / B layer / sealant Layer (3) Lid material: thermoplastic resin layer (c) / A layer / B layer (sealant layer) (4) Lid material: thermoplastic resin layer (d) / A layer / B layer / sealant layer (1) and In the example of (3), the B layer serves as a sealant layer,
The examples (2) and (4) function as an intermediate layer of the sealant layer newly provided on the layer B side.

In the case of the cover material having the structure shown in (1) and (2), various types of paper can be used as the base material of the raw material used as the cover material. The B layer itself can be used as a sealant layer because it has heat sealing properties, but another sealant layer is provided as necessary as shown in the examples of (2) and (4). You can also. Furthermore, various functions such as heat resistance, low-temperature sealability, and easy-openability can be imparted to the sealant layer.

The thermoplastic resin layers (a) and (b) are used for laminating the paper layer and the A layer, and a polyolefin resin such as a polyethylene resin or an ethylene-α-olefin copolymer is used. By performing extrusion lamination at a high temperature of 300 ° C. or more, preferably 320 ° C. or more, the paper layer and the A layer can be laminated. Also,
Depending on the type of the A layer, the A layer and the thermoplastic resin (a) and (b) may be coated with various types of adhesives such as urethane or imine by a known method such as gravure coating, reverse coating, or roll coating. It can also be laminated by dry lamination, wet lamination or non-solvent lamination.

In the cases of (3) and (4), the thermoplastic resin layer (c) and (d) may be selected from a stretched polyester film, a stretched polyamide film, a stretched polyethylene film, a stretched polypropylene film and the like. Is possible. These lamination methods can also utilize the above-described method. Further, if necessary, various ink layers can be provided by a known method such as the above-mentioned gravure coating in order to impart design properties.
The configuration of the lid material is not particularly limited as long as it includes a configuration in which the A layer and the B layer are stacked, and can be appropriately selected according to required quality.

Next, an example in which the laminate of the present invention is used as a soft packaging material will be described below. The following (5) and (6) show examples of the configuration. (5) Soft packaging material: thermoplastic resin layer (e) / A layer / B layer (sealant layer) (6) Soft packaging material: thermoplastic resin layer (f) / A layer / B layer /
Sealant Layer The above configuration is a relatively simple configuration used as a soft packaging material, but of course, other layers can be interposed depending on the functionality. The stretched polyester film described above as the thermoplastic resin layer (e) and (f),
Various films such as a stretched polypropylene film and a stretched nylon film can be used as the base material, and the above-described method can be used as a laminating method. Another sealant layer provided on the layer B side can also be provided for the reasons described above. This soft packaging material can be used in various forms such as primary packaging such as a package stored in a paper secondary packaging container and a pouch filled with a liquid material. Also, packaging materials for electronic components such as Li polymer batteries can be developed with this configuration.

Next, an example in which the laminate of the present invention is used as a packaging material for a composite paper container will be described below. The following (7) and (8) show an example of the configuration. (7) Composite paper container: thermoplastic resin layer (g) / paper layer / thermoplastic resin layer (h) / A layer / B layer (sealant layer) (8) Composite paper container: thermoplastic resin layer (g) / Paper layer / thermoplastic resin layer (nu) / A layer / B layer / sealant layer

In these examples, the configuration is made in consideration of a composite paper container represented by a liquid paper container or the like, but it can also be used for other purposes, for example, as a composite paper container filled with a bath agent powder. Since the thermoplastic resin layers (g) and (g) are used as the outermost layers, it is possible to provide a polyolefin-based resin such as a polyethylene resin or a polypropylene resin in consideration of moisture resistance and waterproofing of the paper layer. ,
In addition, various film bases described above can be used. The sealant layer provided on the layer B side shown in the example of (8) can use the above-mentioned polyolefin-based resin, but in order not to adsorb various components such as flavor components and medicinal components of the contents, It is also possible to use a low-adsorption polyester-based sealant.

The method for laminating the laminate of the present invention is not particularly limited, but a thermoplastic resin is coated on the aluminum surface or alumina surface of an aluminum foil layer, an aluminum vapor deposition layer, or an alumina vapor deposition layer provided on a substrate. A method of laminating by extrusion lamination is preferred. The laminate of the present invention can be applied to various kinds of soft packaging materials such as the above-mentioned lid material, soft packaging material, and composite paper container. Without being affected, it is possible to obtain a laminate in which the laminate strength between the barrier layer and the thermoplastic resin layer does not decrease.

[0047]

EXAMPLES Examples will be specifically described below. The present invention is not limited to these examples.

As the materials used in the following examples, the respective materials of the thermoplastic resin forming the A layer and the B layer provided with the aluminum foil layer, the aluminum deposition layer, and the alumina deposition layer on the base material are shown below. The temperature in parentheses of the layer B indicates the extrusion temperature of each thermoplastic resin when forming the layer B. [Material] <A layer> A-1 Aluminum foil (7 μm) A-2 Aluminum evaporated PET film (12 μm) A-3 Alumina evaporated PET film (12 μm) <B layer> B-1 Low density polyethylene (340 ° C.) B -2 ethylene-methacrylic acid copolymer (310 ° C) B-3 ethylene-glycidyl methacrylate copolymer (280 ° C) B-4 ethylene-epoxidized vegetable oil blend (340 ° C) B-5 ethylene-ethyl acrylate / Ethylene-vinyl acetate-glycidyl methacrylate-methacryloxypropyltrimethoxysilane (230 ° C) B-6 High density polyethylene (325 ° C) B-7 Maleic anhydride-modified polypropylene (290 ° C)

The evaluation samples prepared in the following Examples 1 to 7 were prepared based on the following evaluation sample preparation method. [Preparation of Sample for Evaluation] As the aluminum foil, a polyester film substrate (12 μm) and an aluminum foil (A-1) were previously laminated by dry lamination using a urethane-based adhesive. Further, the aluminum vapor-deposited film (A-2) and the alumina vapor-deposited film (A-3) were produced by a known method, and these three types of samples were cut into A4 sizes to obtain cut samples. These cut samples were immersed in treated water distilled after boiling deionized water adjusted to pH 7 to 9 for 3 minutes, so that the surface of the layer A was subjected to boehmite treatment. Thereafter, a layer B is formed at a predetermined temperature using an extrusion laminator. At this time, a cut sample is previously attached to a through substrate of the extrusion laminator so that the layer B is formed on the layer A of the cut sample. Laminated. The processing speed at this time is 50 m / min. so,
The thickness of the layer B is 30 μm. As a sample for measuring the initial peel strength, a PET film (25 μm) / adhesive / low-density polyethylene (40 μm) or a PET film (25 μm) / adhesive / cast polypropylene prepared at the same time as the production of the laminate. By using a film (20 μm) as a sand substrate,
The evaluation was performed by producing a laminate having the following configuration. The sample for measuring the initial peel strength was evaluated by preparing a laminate having the structure of A layer / B layer as the sample for evaluating the layer A / B layer / sand substrate, and the sample for evaluating the strong permeation resistant contents. .

[Surface Condition Analysis Method 1] Before the lamination with the thermoplastic resin layer, the surface of layer A subjected to boehmite treatment was treated with X
By X-ray photoelectron spectroscopy (XPS), spectral peak positions derived from oxides and hydroxides in Al2p orbitals were determined.
When calculating the spectral peak positions derived from the oxides and hydroxides in the Al2p orbit, the charge correction was performed. First, the C1s peak position was corrected to 285.0 eV, and the metal A
The peak position of 1 was corrected to 72.7 eV. Metal A
The sample in which the 1 peak was not observed was corrected by the same amount as the amount shifted to 72.7 eV (about +1.6 eV) in the sample in which other metal Al peaks were observed. The measuring device is JPS-90MXVmic manufactured by JEOL Ltd.
ro, and non-monochromatic MgKα (125
3.6 eV), the output is 100 W (10 kV-10)
mA).

[Surface Condition Analysis Method 2] Before lamination with the thermoplastic resin layer, the O / Al ratio of the layer A, on which the boehmite treatment was performed, was determined by the method described above. The O / Al ratio is
It was determined as the ratio of the value obtained by multiplying the area of each peak intensity of O1s and Al2p by the relative sensitivity of each peak.

[Surface Condition Analysis Method 3] Before laminating the layer A with the thermoplastic resin layer, the surface of the layer A subjected to the boehmite treatment was subjected to time-of-flight secondary ion mass spectrometry (TOF-SIM).
The ratio of OH / O was determined by S). The OH / O ratio is
The intensity ratio was determined as the intensity ratio between the OH (17) peak and the O (16) peak obtained from the mass spectrum of the negative ion. The measurement was performed using TRIFT II manufactured by Physical Electronics, Ga ions were used as an ion source, and the acceleration voltage was measured at 15 keV.

[Surface Condition Analysis Method 4] Before laminating a thermoplastic resin layer, the surface of layer A, which had been subjected to boehmite treatment, was
The center surface roughness (Ra) and the root mean square surface roughness (RMS) were measured with an atomic force microscope. The measuring device is NanoScope III manufactured by Digital Instruments.
a, AR5-NCH having a radius of curvature of a tip of 10 nm, a half cone angle of 5 °, and an aspect ratio of 7: 1 was used as an AFM probe using system D3100. The measurement area was 1 × 1 μm, and the measurement was performed in a tapping mode at a scan rate of 0.5 Hz.

[Surface Condition Analysis Method 5] Before laminating a thermoplastic resin layer, the surface of layer A, which had been subjected to boehmite treatment, was
The thickness of the treated layer was measured by a transmission electron microscope. The measuring device used was H-8000 manufactured by Hitachi, Ltd. The acceleration voltage is 200 kV.

[Evaluation Method] A peeling trigger was prepared in advance between layer A and layer B of the sample obtained by the above method, and the peeling strength of the sample was measured. In that case,
Sample width 15mm, T-type peeling, peeling speed 300mm / mi
n. I went in. The content of the strong permeation resistance was evaluated as bath agent, poultice, bactericide for turf (solvent system), electrolyte for Li ion battery (1.5M solution of LiPF _{6 in} a mixed solution of ethylene carbonate and propylene carbonate). And packed in a pouch made using the above sample.
The peel strength between the A layer and the B layer when stored at 0 ° C. for 4 weeks was measured. However, in the evaluation of the electrolyte for Li-ion battery, the evaluation was performed on the one using the base material A-1 in the following examples. Further, the configuration for evaluating the Li-ion electrolyte was a boehmite-treated surface. On the applied aluminum foil, trimethylolpropane adduct type of tolylene diisocyanate diluted to 5 wt% with ethyl acetate was applied by a coater added to an extrusion laminating machine (with a dry thickness). After that, a resin extruded in-line was used.

<Example 1> A laminate was prepared from the substrates A-1 and B-1 based on the above-described method for preparing a sample for evaluation. The surface analysis of the A layer and the initial peel strength before and after the preservation test of the strong permeation content and the peel strength after the test were measured. Table 1 shows the evaluation results.

Example 2 An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that A-1 and B-2 were used as the base material. Table 1 shows the results.

<Example 3> An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that A-1 and B-3 were used as the base material. Table 1 shows the results.

Example 4 An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that A-2 and B-4 were used as the base material. Table 1 shows the results.

Example 5 An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that A-3 and B-5 were used as the base material. Table 1 shows the results.

Example 6 A sample for evaluation was prepared and evaluated in the same manner as in Example 1 except that A-1 and B-6 were used as the base materials. Table 1 shows the results.

Example 7 An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that A-1 and B-7 were used as the base material. Table 1 shows the results.

Comparative Examples 1 to 7 correspond to Examples 1 to 7 except that the layer A not subjected to the above-mentioned surface treatment was used.
A sample for evaluation was prepared and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0064]

[Table 1]

[0065]

[Table 2]

<Example 8> A laminated body having the structure of the lid (2) described above was prepared as follows. Using the aluminum foil layer that has been subjected to the above surface treatment in advance,
Low density polyethylene layer (16μm) / aluminum foil (7μ
m) was prepared first, and then a layer B and a sealant layer having easy peelability were formed by coextrusion. Finally, a paper layer / thermoplastic resin layer (b) / A layer / B layer / sealant layer was formed (the thermoplastic resin layer (b) was a low-density polyethylene, and the sealant layer was an easy-peeling layer for polyethylene). Was used). At that time, the layer B is an ethylene-methacrylic acid copolymer (B-
2), B layer (20 μm), sealant layer (15 μm)
m) and extruded at 295 ° C. The lid material thus produced was used as a lid material for a composite container obtained by compounding paper and plastic, and a bath agent (powder) was used as the content. The storage evaluation was performed at 40 ° C. for 4 weeks. As a result, the bonding state between the layer A and the layer B is very good, and even if the container is actually sealed with the lid as a cover material and opened, there is no decrease in the laminate strength due to the influence of the contents.
No obstacle (double lid) as a lid material occurred.

<Comparative Example 8> A laminate was prepared and evaluated in the same manner as in Example 6 except that the aluminum foil layer was not subjected to the layer A, which was not subjected to the boehmite treatment. As a result, the laminating strength between the layer A and the layer B was remarkably reduced, and the problem of a double lid occurred, and it was not practical as a lid material.

<Example 9> A laminated body having the structure of the lid (4) described above was prepared as follows. A polyester film (25 μm) / urethane-based adhesive layer / aluminum foil (7 μm) is prepared first by using the aluminum foil layer which has been subjected to the above surface treatment in advance, and then a layer B and a sealant layer having easy peelability are formed. Was formed by coextrusion. Finally, the thermoplastic resin layer (d) / A layer / B
Layer / sealant layer (thermoplastic resin layer (d)
Is a polyester film, and the sealant layer is a sealant having an easy peel property for polypropylene). At this time, the layer B was a maleic anhydride-modified polypropylene resin (B-7), and both the layer B (20 μm) and the sealant layer (10 μm) were extruded at 290 ° C. The lid material thus produced was used as a lid material for a cup obtained by injection molding of a polypropylene resin. At that time, a bath agent (powder) was used as the content. The storage evaluation was performed at 40 ° C. for 4 weeks. As a result, the adhesion state of the layer A and the layer B is very good, and even when the container is actually sealed with the container as a lid and opened, the laminate strength is not reduced by the influence of the contents, and the lid material is No injury (double lid) occurred.

<Comparative Example 9> A laminate was prepared and evaluated in the same manner as in Example 9 except that the aluminum foil layer was not subjected to the boehmite treatment but not to the layer A. As a result, the laminating strength between the layer A and the layer B was remarkably reduced, and the problem of a double lid occurred, and it was not practical as a lid material.

<Example 10> A laminated body having the structure exemplified by the above-mentioned soft packaging material (5) was produced as follows. The laminate has a configuration of paper layer / thermoplastic resin layer (e) / layer A / layer B (sealant layer) (the thermoplastic resin layer (e) used low-density polyethylene). However, the layer A in this case uses an aluminum vapor-deposited film subjected to the above-mentioned surface treatment. This laminate was sealed in a pouch-like manner, and a poultice was used as the contents. The storage evaluation was performed at 40 ° C. for 4 weeks. As a result, peeling between the layer A and the layer B due to the contents was not observed.

<Comparative Example 10> A laminate was prepared and evaluated in the same manner as in Example 10 except that the aluminum deposited layer was not treated with the layer A in which the boehmite treatment was not performed. As a result, separation between the layer A and the layer B was observed, and the contents could not be easily taken out.

<Example 11> A laminate having the same structure as that of the composite paper container laminate (7) was prepared as follows. The composition is as follows: thermoplastic resin layer (g) / paper layer /
It was a thermoplastic resin layer (H) / A layer / B layer (sealant layer). As the A layer, an alumina vapor-deposited film was used.
A layer obtained by previously laminating the surface-treated A layer, a thermoplastic resin layer (g) and a paper layer, was laminated by sand lamination using the thermoplastic resin layer (h).
In this case, the thermoplastic resin layer (g) is made of low-density polyethylene, and the thermoplastic resin layer (h) is extruded at a high temperature, so that it can be laminated with corona-treated PET without an adhesive. -An acrylic acid terpolymer was used. This container was used as a Goebel top type liquid container, and was manufactured by using an end face processing technique such as skiving as needed. As a content, a turf fungicide was used. The storage evaluation was performed at 40 ° C. for 4 weeks. As a result, peeling between the layer A and the layer B due to the contents was not observed.

Comparative Example 11 A laminate was prepared and evaluated in the same manner as in Example 11, except that the alumina layer was not treated with the A layer, which was not subjected to the boehmite treatment. As a result, peeling between layer A / layer B was observed, and the functionality and appearance as a container were inferior.
I didn't come to practical use.

<Example 12> A laminate having the structure exemplified by the above-mentioned soft packaging material (5) was produced as follows. This laminate has a structure of thermoplastic resin layer (e) / layer A / layer B (sealant layer) (a stretched nylon film was used for the thermoplastic resin layer (e)). However,
The layer A in this case is a 40 μm aluminum foil subjected to a boehmite treatment. The non-boehmite-treated side of this 40 μm aluminum foil is laminated to a stretched nylon film by dry lamination, and then the coating layer of a trimethylolpropane adduct of tolylene diisocyanate is formed inline using an extrusion laminator to a thickness of 1 mm.
After being provided at a thickness of not more than μm, a high-density polyethylene (B-6) was laminated at 325 ° C. for 30 μm. This laminate was sealed in a pouch shape from side to side, and filled with the above-mentioned electrolyte for a Li-ion battery as a content. The storage evaluation was performed at 40 ° C. for 4 weeks. As a result, peeling between the layer A and the layer B due to the contents was not observed.

<Comparative Example 12> A laminate was prepared and evaluated in the same manner as in Example 12 except that the aluminum foil layer was not treated with the layer A in which the boehmite treatment was not performed. As a result, peeling between the A layer and the B layer was observed, the aluminum was corroded, and the electrolyte leaked, leaving a problem in safety as a battery.

[0076]

According to the present invention, an aluminum surface or an alumina surface such as an aluminum foil layer, an aluminum vapor-deposited layer, or an alumina vapor-deposited layer provided on a substrate as a barrier layer is subjected to a hydrothermal conversion treatment (boehmite treatment). When the surface state is measured by X-ray photoelectron spectroscopy, the position of the spectral peak derived from the oxide and hydroxide in the aluminum (Al) 2p orbital is 75.4 eV or less in the binding energy, and the oxygen (O) When the element ratio (O / Al) of aluminum (Al) is 1.7 or more, and the time-of-flight secondary ion mass spectrometry is performed, the ratio of hydroxyl (OH) to oxygen (O) (OH / O) ) Is 0.9 or more, and further, when the surface area ratio and the surface roughness are measured by an atomic force microscope,
The surface area ratio (the surface area of the hydrothermally modified substrate / the surface area of the untreated substrate) is 1.5 or more and the center plane average roughness (Ra) is 15 or more.
nm or more, the root mean square roughness (RMS) is 20 nm or more, and when observed by transmission electron microscopy, the thickness of the treated layer formed by performing the hydrothermal denaturation treatment is 0.1 μm or more. By using a material, it is possible to sufficiently obtain the adhesive strength even in a configuration in which lamination strength between the aluminum foil layer and the thermoplastic resin has not been obtained until now. Also, if necessary, a laminate having excellent content resistance can be obtained by interposing an isocyanate compound between the aluminum surface or the alumina surface and the thermoplastic resin.

Even when this laminate is used as various packaging materials and a highly permeable material is packaged, the laminate strength between the barrier layer and the thermoplastic resin layer is not affected by the highly permeable content. A laminate that did not decrease was obtained. Further, the laminate of the present invention can be used as a packaging material for lid materials, various soft packaging materials, composite paper containers, electronic members, and the like.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // B32B 9/00 B32B 9/00 A (72) Inventor Hideyuki Yamakawa 1-1-5 Taito, Taito-ku, Tokyo Letterpress In Printing Co., Ltd. (72) Inventor Hiroshi Umeyama 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd. F-term (reference) 3E086 BA04 BA13 BA15 BB85 CA40 DA08 4F100 AA19A AA19C AB10A AB33A AK01B AK04B AK07B AK62B AK66B AK68B AK70B AL06B AL07B AL08B BA03 BA04 BA07 BA10A BA10B BA42A DD07C DG10 EH66A EJ64A EJ68A GB15 GB16 JB16B JK06 JL11 5H011 AA01 AA17 BB03 CC02 CC06 CC10 KK00 EJ01 AJ01 DJ01

Claims (14)

[Claims] 1. A method of laminating a thermoplastic resin on an aluminum surface or an alumina surface of a base material having an aluminum surface or an alumina surface comprising any one of an aluminum foil layer, an aluminum evaporation layer, and an alumina evaporation layer. A laminate characterized by using a substrate having an alumina surface subjected to a hydrothermal alteration treatment. 2. The X-ray photoelectron spectroscopic measurement of the surface of the aluminum or alumina surface of the base material subjected to the hydrothermal conversion treatment, the spectrum peak derived from the oxide and hydroxide of the aluminum (Al) 2p orbit. Position is its binding energy 7
2. The laminate according to claim 1, wherein the laminate is at most 5.4 eV. 3. An X-ray photoelectron spectroscopic measurement of the surface of the aluminum or alumina surface of the substrate subjected to the hydrothermal conversion treatment, the elemental ratio of oxygen (O) to aluminum (Al) (O /
2. The laminate according to claim 1, wherein Al) is 1.7 or more. 4. A time-of-flight secondary ion mass spectrometry measurement of the surface of the aluminum or alumina surface of the base material subjected to the hydrothermal conversion treatment, the ratio of hydroxyl (OH) to oxygen (O) (OH) The laminate according to claim 1, wherein (/ O) is 0.9 or more. 5. When the surface area ratio and surface roughness of the aluminum or alumina surface of the substrate subjected to the hydrothermal denaturation treatment are measured by an atomic force microscope, the surface area ratio (hydrothermal denaturation treated substrate) 2. The laminate according to claim 1, wherein the surface area / untreated substrate surface area is 1.5 or more, the center plane average roughness (Ra) is 15 nm or more, and the root mean square roughness (RMS) is 20 nm or more. body. 6. When a fracture surface of a substrate having an aluminum surface or an alumina surface subjected to the hydrothermal modification treatment of the substrate is observed by a transmission electron microscope, the substrate is formed by performing the hydrothermal modification treatment. 2. The laminate according to claim 1, wherein the thickness of the treatment layer is 0.1 μm or more. 7. The laminate according to claim 1, wherein the hydrothermal alteration treatment is a boehmite treatment. 8. The thermoplastic resin as claimed in claim 1, wherein the thermoplastic resin is polyethylene, ethylene-α-olefin copolymer, polypropylene, propylene-α-olefin copolymer, ethylene-α, β-unsaturated carboxylic acid copolymer or its esterified product or ionically crosslinked. Product, acid anhydride-modified polyethylene, acid anhydride-modified polypropylene, epoxy compound-modified polyolefin or its olefin-based polymer, silane-modified polyolefin or its olefin-based polymer, ethylene-vinyl acetate copolymer alone or in a blend of two or more The laminate according to any one of claims 1 to 7, wherein the laminate is made of a resin. 9. The laminate according to claim 1, wherein the thermoplastic resin layer is provided directly on the aluminum surface or the alumina surface which has been subjected to the hydrothermal conversion treatment. 10. The method according to claim 1, wherein the isocyanate compound is provided in a range of 5 μm or less on the aluminum surface or the alumina surface subjected to the hydrothermal conversion treatment, and then the thermoplastic resin is laminated. 9. The laminate according to any one of items 8 to 8. 11. A packaging material comprising at least the laminate according to claim 9 or 10. 12. A packaging material according to claim 11, wherein said packaging material is in a soft packaging form. 13. A packaging material according to claim 11, wherein said packaging material is a composite paper container made of a composite with paper. 14. A packaging material characterized in that the packaging material according to claim 11 is used as an exterior material of an electronic member such as a Li-ion battery.