JP6897433B2 - Laminates and liquid paper containers - Google Patents

Description

The present invention relates to a laminate having at least a paper layer and a thin-film vapor-deposited thin film layer made of an inorganic oxide and a liquid paper container, and in particular, various strong penetrations containing volatile substances such as medicinal properties and fragrance components and other volatile substances. It can be suitably used for highly permeable contents in that the lamination strength does not decrease even if the sex contents act on it.

Conventionally, as a packaging material for packaging foods and pharmaceuticals, for example, a laminated body in which each layer such as a paper layer / adhesive layer / aluminum foil layer / adhesive layer / polyester layer / adhesive layer / sealant layer is laminated. Paper containers made of are widely used. In such a method of laminating the laminated body, a two-component curable polyurethane-based adhesive is usually used, and the adhesive layer is formed by dry laminating. Such a laminate has appropriate lamination strength and gas barrier properties, and is widely used as a packaging material for packaging foods, pharmaceuticals, and the like.

However, many of the contents packaged by the packaging material contain alkaline substances, fragrances, surfactants, high boiling point organic solvents, etc., and when these highly permeable contents are packaged, the adhesive layer becomes The adhesive may be adversely affected, resulting in a decrease in the lamination strength of the laminate or peeling.

In order to deal with such situations, various improvements have been made to the adhesive used in the laminating process, which has improved resistance to highly alkaline contents and further improved adhesive strength to various plastic films and the like. Various adhesives and the like have been proposed (see, for example, Patent Document 1).

However, when the contents to be packaged are a sealant, a bathing agent, etc., these contain volatile substances, so that a laminate having the above-mentioned structure or a laminate obtained by using the above-mentioned adhesive can be used. When used as a packaging material and packaged with these contents, the strong penetrating power of the volatile substance causes, for example, the laminating strength between the polyester layer and the sealant layer of the above-mentioned laminate to decrease over time, resulting in delamination (peeling). ) Was a problem.

In order to cope with such a situation, the polyester film base material is subjected to corona treatment in-line, and the corona-treated surface is subjected to a bifunctional isocyanate monomer or a derivative of an adduct, burette, or isocyanurate type trifunctionalized monomer. A laminate in which an adhesive layer made of an isocyanate compound is provided and a sealant layer is provided on the adhesive layer has been proposed (see, for example, Patent Document 2).

As a similar countermeasure, a first adhesive layer made of an amine-containing polymer and a diisocyanate monomer or an adduct-type, burette-type, or trimmer (isocyanurate)-type derivative of the diisocyanate monomer are provided on a polyester film substrate. A laminate has been proposed in which an adhesive layer having a two-layer structure with a second adhesive layer composed of any of them is provided, and a sealant layer is provided on the second adhesive layer constituting the adhesive layer (see, for example, Patent Document 3). ..

However, when the contents such as a wet cloth and a bathing agent were packaged using the above-mentioned laminate, the polyester of the above-mentioned laminate and the sealant layer did not show a significant decrease in the laminate strength with time. Depending on the type of film used for the layer and the orientation state of the polymer, the nano-order thin surface layer of the polyester film may peel off from the polyester film, causing surface layer peeling, and as a result, a significant decrease in lamination strength may be observed.

Japanese Unexamined Patent Publication No. 10-130615 Japanese Patent No. 4852874 Japanese Patent No. 4306278

The present invention has been made to solve the above-mentioned problems, and the subject thereof is that when used as a packaging material, volatile substances such as medicinal properties and fragrance components and other volatile substances are used. It is an object of the present invention to provide a laminate capable of maintaining excellent lamination strength even when various strongly permeable contents including the same are acted on, and a liquid paper container using the laminate.

The invention according to claim 1 includes at least a thermoplastic resin layer, a paper layer, an extruded resin layer, an adhesive layer, a vapor-deposited thin film layer made of an inorganic oxide, a base material layer, an adhesive layer A, an extruded resin layer, and a sealant layer. They are stacked in this order,
The base material layer is a coextruded biaxially stretched film including a first base material layer made of a polyester resin, a thermoplastic adhesive resin layer, and a second base material layer made of a polyamide resin.
The adhesive layer A is a laminate comprising any one or more of a diisocyanate monomer or an adduct-type, burette-type, or trimmer (isocyanurate)-type derivative of the diisocyanate monomer.

The invention according to claim 2 is at least a thermoplastic resin layer, a paper layer, an extruded resin layer, an adhesive layer, a vapor-deposited thin film layer made of an inorganic oxide, a base material layer, a first adhesive layer, a second adhesive layer, and an extrusion. The resin layer and the sealant layer are laminated in this order,
The base material layer is a coextruded biaxially stretched film including a first base material layer made of a polyester resin, a thermoplastic adhesive resin layer, and a second base material layer made of a polyamide resin.
The first adhesive layer is an amine-containing polymer, and the first adhesive layer is an amine-containing polymer.
The second adhesive layer is a laminate comprising any one or more of a diisocyanate monomer or an adduct-type, burette-type, or trimmer (isocyanurate)-type derivative of the diisocyanate monomer.

The invention according to claim 3 is the laminate according to claim 1 or 2, wherein the second base material layer is on the side closer to the sealant layer in the base material layer.

The invention according to claim 4 is the laminate according to any one of claims 1 to 3, wherein the polyamide resin is nylon.

The invention according to claim 5 is the laminate according to any one of claims 1 to 4, characterized in that the thickness of the polyamide resin is 1 μm or more.

The invention according to claim 6 is a liquid paper container, which comprises using the laminate according to any one of claims 1 to 5.

The laminate of the invention according to claim 1 is at least a thermoplastic resin layer, a paper layer, an extruded resin layer, an adhesive layer, a vapor-deposited thin film layer composed of an inorganic oxide, a base material layer, an adhesive layer A, an extruded resin layer, and a sealant. The layers are laminated in this order, and the base material layer is a coextruded biaxially stretched base material having a first base material layer made of a polyester resin, a thermoplastic adhesive resin layer, and a second base material layer made of a polyamide resin. Since the adhesive layer A is a film and is composed of one or more of a diisocyanate monomer or an adduct-type, burette-type, or trimmer (isocyanurate)-type derivative of the diisocyanate monomer, this laminate is used as a liquid paper container. By using it as a resin, it is possible to maintain excellent lamination strength even when various strongly permeable contents including volatile substances such as medicinal properties and fragrance components and other volatile substances act, and further, inorganic oxides. Having a base material on which a vapor-deposited thin film layer made of the above material is formed has an effect of excellent barrier properties.

The laminate of the invention according to claim 2 is at least a thermoplastic resin layer, a paper layer, an extruded resin layer, an adhesive layer, a vapor-deposited thin film layer made of an inorganic oxide, a base material layer, a first adhesive layer, and a second adhesive layer. , Extruded resin layer and sealant layer are laminated in this order, and the base material layer includes a first base material layer made of polyester resin, a thermoplastic adhesive resin layer, and a second base material layer made of polyamide resin. It is a co-extruded biaxially stretched film, the first adhesive layer is an amine-containing polymer, and the second adhesive layer is a diisocyanate monomer or a derivative of the diisocyanate monomer adduct type, burette type, or trimmer (isocyanurate) type. Since it is composed of any one or more of the above, by using this laminate as a liquid paper container, various strongly permeable contents including volatile substances such as medicinal properties and fragrance components and other volatile substances act. However, it is possible to maintain excellent lamination strength, and further, it has an effect of excellent barrier property by having a base material on which a vapor-deposited thin film layer made of an inorganic oxide is formed.

In the laminate of the invention according to claims 3, 4, and 5, the second base material layer is on the side closer to the sealant layer, or the polyamide resin of the second base material layer is nylon, or the thickness thereof is When the thickness is 1 μm or more, the polyester resin and the polyamide resin are bonded to each other in the heat-melted state via the acid-modified polyolefin resin (thermoplastic adhesive resin) in the base material layer in the polyester resin. It has the effect that the surface layer of the resin is less likely to peel off.

The cross-sectional view which shows the layer structure in 1st Embodiment of the laminated body which concerns on this invention. The cross-sectional view which shows the layer structure in 2nd Embodiment of the laminated body which concerns on this invention. The perspective view which showed the example of the embodiment of the liquid paper container which concerns on this invention. The perspective view which showed the example of the embodiment of the liquid paper container which concerns on this invention.

Hereinafter, embodiments of the present invention will be described in detail.

The laminate and the liquid paper container according to the present invention will be described in detail with reference to the following drawings.
FIG. 1 is a cross-sectional view showing a layer structure of the laminated body according to the present invention in the first embodiment.
The laminate 1 according to the present invention has at least a thermoplastic resin layer 2, a paper layer 3, an extruded resin layer 4, an adhesive layer 5, a vapor-deposited thin film layer 6 made of an inorganic oxide, a base material layer 7, an adhesive layer A8, and an extrusion. The resin layer 9 and the sealant layer 10 are sequentially laminated.
Further, the base material layer 7 is a coextruded biaxially stretched film including a first base material layer 11 made of a polyester resin, a thermoplastic adhesive resin layer 12, and a second base material layer 13 made of a polyamide resin.

In addition to this, for example, a gas barrier coating layer may be provided between the vapor-deposited thin film layer 6 and the adhesive layer 5. Further, as will be described later, after providing the thin film deposition primer layer on the substrate, the thin film deposition thin film layer 6 may be formed on the primer layer for vapor deposition.

Further, FIG. 2 is a cross-sectional view showing a layer structure of the laminated body according to the present invention in the second embodiment. In FIG. 2, the laminate 21 has at least a thermoplastic resin layer 2, a paper layer 3, an extruded resin layer 4, an adhesive layer 5, a vapor-deposited thin film layer 6 made of an inorganic oxide, a base material layer 7, and a first adhesive layer 14. , The second adhesive layer 15, the extruded resin layer 9, and the sealant layer 10 are laminated in this order.
Further, the base material layer 7 is a coextruded biaxially stretched film including a first base material layer 11 made of a polyester resin, a thermoplastic adhesive resin layer 12, and a second base material layer 13 made of a polyamide resin.

Next, a liquid paper container made of the laminate according to the present invention will be described.
3 and 4 are perspective views showing an example of an embodiment of the liquid paper container 31 and the liquid paper container 41 according to the present invention. The liquid paper container of the present invention is not limited to these cases, and may be various forms of paper containers.

FIG. 3 is a paper container generally referred to as a Goebel top type, and FIG. 4 is a paper container generally referred to as a brick type. In each case, the spout 33 or the spout 43 is attached to the upper part of the paper container main body 32 or the paper container main body 42, which is formed by molding a laminate mainly composed of paper. These spouts are not essential and may be omitted.
These liquid paper containers using the laminate of the present invention maintain excellent lamination strength even when a highly permeable content such as a volatile substance is put therein, so that deterioration of the content can be prevented.

Hereinafter, each layer constituting the laminate according to the present invention will be described in detail.

<Thermoplastic resin layer>
As the material of the thermoplastic resin layer 2 which is the outermost layer, a polyolefin resin such as a polyethylene resin or a polypropylene resin can be preferably used in consideration of the moisture proofing property and the waterproof property of the paper layer 3.

<Paper>
As the paper layer 3, those having a basis weight in ^{the range of 200 to 500 g / m 2} and a density of 0.6 to 1.1 g / cm ³ can be preferably used depending on the size of the paper container.

<Adhesive layer>
Any adhesive layer 5 between the extruded resin layer 4 and the thin-film vapor-deposited thin film layer 6 can be used regardless of the type, and for example, a two-component curable urethane-based adhesive can be preferably used.

<Base layer>
The base material layer 7 constituting the laminate of the present invention includes a first base material layer 11, a thermoplastic adhesive resin layer 12, and a second base material layer 13 from the outermost layer side.

(First base material layer)
As the first base material layer 11, a polyester-based resin having excellent fragrance-retaining properties for various strongly permeable contents including volatile substances such as medicinal ingredients and fragrance components and other volatile substances can be preferably used.

(Thermoplastic adhesive resin layer)
The thermoplastic adhesive resin layer 12 is for firmly retaining the adhesion between the first base material layer 11 and the second base material layer 13, and an acid-modified polyolefin-based resin can be preferably used.

(Second base material layer)
When the base material layer 7 is a single layer of polyester resin (polyester film), various strong penetrations containing volatile substances such as medicinal properties and fragrance components and other volatile substances may occur depending on the type of the film and the orientation state of the polymer. During the action of the sex content, the nano-order thin surface layer of the polyester film is peeled off from the polyester film, and surface layer peeling is likely to occur. As a result, a significant decrease in laminate strength may be observed.
Therefore, in the present invention, the second base material layer 13 is provided for the purpose of preventing such surface layer peeling. A polyamide resin that does not cause surface peeling can be preferably used for the second base material layer 13.

Further, among the polyamide-based resins, nylon, which is a polyamide containing an aliphatic skeleton, is particularly preferable. Further, when the thickness of the polyamide resin is 1 μm or more, a base material layer that does not reduce the laminate strength can be obtained by the coextrusion method, which is more preferable.

When the base material layer 7 is a single layer of polyester resin (polyester film), when the adjacent adhesive layer A8 (first embodiment) or first adhesive layer 14 (second embodiment) is provided, the surface thereof is covered. It is preferable to perform the corona treatment offline or in-line, but in the case of a polyester resin (polyester film), if the corona treatment amount is too large than necessary, the molecular weight of the film surface is significantly reduced, and as a result, the polyester film is subjected to the corona treatment. The nano-order thin surface layer is peeled off from this polyester film, and the surface layer peeling is likely to occur.

On the other hand, in the base material layer 7 constituting the laminate of the present invention, the polyester resin and the polyamide resin are adhered to each other in a heat-melted state via the acid-modified polyolefin resin, and the polyamide resin side is the sealant layer. Since it is on the near side, there is no concern about surface layer peeling in the polyester resin layer.

The thickness of the entire base material layer 7 is not particularly limited, but a thickness of 12 to 30 μm is preferable in consideration of suitability as a packaging material and cost. Of these, the thickness of the polyamide resin, which is the second base material layer 13, is preferably 1 to 5 μm in consideration of the same cost.

As a method for producing the base film layer 7, an extrusion molding method is used to heat and melt pellets made of polyester resin, pellets made of acid-modified polyolefin resin, and pellets made of polyamide resin, and all three layers are formed from the T die. A composite film can be extruded to form a composite film, and then a biaxially stretched film can be produced by a sequential biaxial stretching method using a tenter method, and this three-layer coextruded biaxially stretched film can be preferably used.

<Thin-film deposition thin film layer>
The vapor-deposited thin film layer 6 made of an inorganic oxide on the base material layer 7 is made of a simple substance such as aluminum oxide, silicon oxide, magnesium oxide, or tin oxide, or a mixture thereof, and has a gas barrier property against oxygen, water vapor, and the like. If it is good. Among them, aluminum oxide, silicon oxide, and magnesium oxide can be preferably used because they have excellent barrier properties such as oxygen permeability and water vapor permeability.

When the thin-film vapor-deposited thin film layer 6 made of an inorganic oxide is provided on the base layer 7, a corona treatment is performed on the base layer 7 side as a pretreatment in order to improve the adhesion between the base layer 7 and the thin-film vapor-deposited thin film layer 6. , Low pressure plasma treatment, atmospheric pressure plasma treatment, frame treatment, surface treatment such as ion bombard treatment, and surface treatment such as chemical treatment and solvent treatment may be performed.

In particular, in the application of a packaging material for storing various strongly permeable contents containing extremely harsh volatile substances, in order to improve the adhesion between the base material layer 7 and the thin-film vapor-deposited thin film layer 6, in order to improve the adhesion between the base material layer 7 and the vapor-deposited thin film layer 6. It is preferable to use a laminate in which a thin-film deposition primer layer (not shown) having both an organic compound and an inorganic compound is provided on the base material layer 7. As the primer layer for vapor deposition, a reaction composite of a compound having a hydroxyl group such as an acrylic polyol, an isocyanate compound having an isocyanate group, and a silane coupling agent can be used.

<Adhesive layer A>
The adhesive layer A8 constituting the laminate of the present invention is made of an isocyanate compound, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4, It is possible to use various diisocyanate-based monomers such as 4'-diphenylmethane diisocyanate and its hydrogenated compound.

Further, an adduct type in which these diisocyanate monomers are reacted with a trifunctional active hydrogen-containing compound such as trimethylolpropane or glycerol, a burette type in which these diisocyanate monomers are reacted with water, and a trimmer utilizing self-polymerization of an isocyanate group ( Trifunctional derivatives such as isocyanurate) type and higher polyfunctional derivatives can be used.

The adhesive layer A8 uses either the above-mentioned diisocyanate monomer or the adduct type of the diisocyanate monomer, the burette type, the trimmer (isocyanurate) type derivative, or a combination thereof. It is coated with a coating liquid containing a solid content ratio of 0.05 to 5.00 wt%, preferably 0.10 to 2.00 wt%, and the thickness at the time of drying is as thin as about 0.1 to 2.0 μm. It may be provided as a layer.

<First adhesive layer and second adhesive layer>
In the other laminated body 21 of the present invention, the adhesive layer between the base material layer 7 and the sealant layer 10 is composed of a first adhesive layer 14 and a second adhesive layer 15 instead of the adhesive layer A.
The first adhesive layer 14 and the second adhesive layer 15 have a two-layer structure of the first adhesive layer 14 and the second adhesive layer 15 from the base material layer 7 side, and the first adhesive layer 14 is made of an amine-containing polymer. The second adhesive layer 15 is made of an isocyanate compound.

As the amine-containing polymer, either an aqueous polymer or a solvent-based polymer such as polyethyleneimine or a primary amine graft acrylic polymer can be used. Among these, those having a number average molecular weight of about 10,000 to 100,000 are preferably used.

On the other hand, examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate and hydrogenated products thereof. It is possible to use various diisocyanate-based monomers.

Further, an adduct type in which these diisocyanate monomers are reacted with a trifunctional active hydrogen-containing compound such as trimethylolpropane or glycerol, a burette type in which these diisocyanate monomers are reacted with water, and a trimmer utilizing self-polymerization of an isocyanate group ( Trifunctional derivatives such as isocyanurate) type and higher polyfunctional derivatives can be used.

The first adhesive layer 14 and the second adhesive layer 15 are any of the above-mentioned amine-containing polymer and diisocyanate monomer, or adduct-type, burette-type, and trimmer (isocyanurate)-type derivatives of the diisocyanate monomer, or them. Using a combination of the derivatives of the above, coat with a coating solution containing a solid content ratio of 0.05 to 5.00 wt%, preferably 0.10 to 2.00 wt%, and the thickness at the time of drying. It may be provided so as to form a thin layer of about 0.1 to 2.0 μm.

<Extruded resin layer>
As a material of the extruded resin layer 9 constituting the laminate of the present invention, a layer made of a polyolefin resin such as a polyethylene resin or a polypropylene resin can be mentioned as a specific example. The polyethylene-based resin and polypropylene-based resin are preferable in terms of excellent workability and low cost.
Examples of the polyethylene-based resin include high-density polyethylene, low-density polyethylene, medium-density polyethylene, and an ethylene-α-olefin copolymer.
Further, examples of the polypropylene-based resin include homo-block-random polypropylene resins and propylene-α-olefin copolymers.
In addition, ethylene-α and β unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymer and ethylene-methacrylate copolymer, methyl ethylene-acrylate, ethyl ethylene-acrylate, ethylene-methyl methacrylate and the like Ethylene-α, β unsaturated carboxylic acid copolymer esterified such as ethylene-ethyl methacrylate, ions of ethylene-α, β unsaturated carboxylic acid copolymer with carboxylic acid moiety cross-linked with sodium ion and zinc ion Crosslinked products, acid anhydride-modified polyolefins typified by ternary copolymers such as ethylene-maleic anhydride graft copolymers and ethyl ethylene-ethyl acrylate-maleic anhydride, and epoxys such as ethylene-glycidyl methacrylate copolymers. Specific examples thereof include a single resin selected from a compound-modified polyolefin and an ethylene-vinyl acetate copolymer, or a blend of two or more kinds.

<Sealant layer>
As the innermost sealant layer 10, it is preferable to use a film of the same type as the extruded resin layer 9 in consideration of the adhesiveness with the extruded resin layer 9, but the liquid paper container can be made by using the laminate of the present invention. Since they are overlapped with each other and heat-sealed by heat during production, those having a high heat-sealing strength are desirable. Therefore, as the sealant film applied to the sealant layer, a linear low-density polyethylene film (LLDPE film) and a cast film of random polypropylene (CPP film) can be preferably used.

<Other configurations of laminated body>
Although the laminated structure used for the laminated body and the liquid paper container according to the present invention has been described above, the laminated body and the liquid paper container of the present invention are not limited to those having the above-mentioned structure, and can be used as a packaging material. In consideration of the intended use, the configuration may include other layers for the purpose of improving the rigidity and durability required for the packaging material.

(Gas barrier coating layer)
For example, a gas barrier coating layer may be provided between the thin-film vapor-deposited thin film layer 6 made of an inorganic oxide and the adhesive layer 5. As the gas barrier coating layer, for example, a composite structure formed by reacting the following compounds (1) and (2) can be used.
(1) A silicon compound represented by the general formula Si (OR ³ ) ₄ (R ³ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH _{3) or a hydrolyzate thereof.}
(2) Water-soluble polymer In addition to these (1) and (2), a composite structure formed by reacting the compound of (3) may be used.
(3) General formula (R ⁴ Si (OR ⁵ ) ₃ ) n (R ⁴ is an organic functional group, R ⁵ is CH ₃ , C ₂ H ₅ ,
Alternatively, a silicon compound represented by (representing C ₂ H ₄ OCH _{3) or a hydrolyzate thereof.}

The silicon compound represented by these general formula Si (OR ³ ) _{4 is tetraalkoxysilane.} For example, tetramethoxysilane and tetraethoxysilane. Examples of the water-soluble polymer include organic polymers having a vinyl alcohol moiety such as polyvinyl alcohol, polyvinyl acetate, and ethylene-vinyl acetate copolymer. Further, the silicon compound represented by the general formula (R ⁴ Si (OR ⁵ ) ₃ ) n is a silane coupling agent. For example, an aminosilane coupling agent, a vinylsilane coupling agent, an acrylicsilane coupling agent, or the like can be used. Further, it may be a silane coupling agent having an isocyanate group or an epoxy group. By adding these silane coupling agents, it is possible to prevent the gas barrier coating layer from swelling due to the permeation of the strongly permeable substance and improve the adhesion.

The gas barrier coating layer can be formed by dissolving or dispersing each of these components to prepare a coating liquid, applying the coating liquid, heating and drying, and reacting each of these components. As a method of mixing the silicon component and the like, it is sufficient that the silicon component and the like are visually and uniformly mixed in the solvent. Since tetraalkoxysilane is difficult to uniformly disperse in an aqueous solvent, it may be hydrolyzed before use. In addition, in consideration of the ink of the gas barrier coating layer, adhesion to the adhesive, wettability, and prevention of cracks due to shrinkage, clay minerals such as colloidal silica and smectite, stabilizers, colorants, and clay adjustments are added to the coating liquid. Known additives such as agents can be added within a range that does not impair gas barrier properties and water resistance.

As a method of applying this coating liquid, a usual coating method can be used. For example, a dipping method, a roll coat, a gravure coat, a reverse coat, an air knife coat, a comma coat, a die coat, a screen printing method, a spray coat, a gravure offset method and the like can be used. If the thickness of the gas barrier coating layer exceeds 50 μm, cracks may easily occur, so it is desirable to set the thickness to 0.01 to 50 μm. Further, as the heating method, hot air heating, heat roll drying, high frequency irradiation, infrared irradiation, UV irradiation and the like can be adopted.

A laminate having a laminated structure of the laminate of the present invention, for example, a thermoplastic resin layer / paper / extruded resin layer / adhesive layer / thin-film vapor deposition layer / base material layer / adhesive layer A / extruded resin layer / sealant layer. An example of the manufacturing method of the above will be described.

First, the LDPE (thermoplastic resin layer 2) / paper layer 3 in which low-density polyethylene (LDPE) is formed as the thermoplastic resin layer 2 on one side of the paper layer 3, and the thin-film vapor deposition thin film layer 6 on one side of the base material layer 7. The formed vapor-deposited thin film layer 6 / base material layer 7 is prepared. Then, while applying corona treatment on the paper layer 3 of the LDPE / paper layer 3 by a tandem extrusion laminator, the vapor-deposited thin film layer 6 / base material layer 7 is fed out from the sand shaft, and two-component curing is performed on the vapor-deposited thin film layer 6. A coating liquid made of a mold urethane adhesive using ethyl acetate as a diluting solvent and having a solid content ratio of 0.05 to 5.00% by weight, preferably 0.10 to 2.00% by weight. Is coated at the anchor coating agent coating portion to provide an adhesive layer 5, dried in an oven, and then laminated with an extruded resin layer 4 made of low-density polyethylene extruded from the T die of the first extruder. An LDPE / paper layer / extruded resin layer / adhesive layer / vapor-deposited thin film layer / base material layer is prepared, and immediately after that, acetic acid composed of an isocyanate compound having a bifunctional or higher functional isocyanate group on the inner base material layer 7. A coating liquid prepared by using ethyl as a diluting solvent at a solid content ratio of 0.05 to 5.00% by weight, preferably 0.10 to 2.00% by weight was applied to the anchor coating agent coating part. The adhesive layer A8 is provided by coating, and after drying in an oven, the T of the second extruder is fed out from the sand shaft while feeding out a linear low-density polyethylene film (LLDPE film) to be the innermost sealant layer 10. The extruded resin layer 9 made of low-density polyethylene extruded from the die is laminated to form LDPE / paper layer / extruded resin layer / adhesive layer / vapor-deposited thin film layer / base material layer / adhesive layer A / extruded resin layer / LLDPE film. 1 can be obtained.
Next, the liquid paper container of the present invention can be obtained by processing the laminated body 1 into a Goebel top type or brick type container by using a conventional processing method.

The liquid paper container of the present invention is suitable for packaging contents containing a highly permeable substance. Examples of the strongly permeable substance include volatile substances (fragrances, medicinal ingredients, organic solvents (including alcohol and the like), etc.), surfactants, acidic substances, alkaline substances and the like.

Contents containing volatile substances include powder bathing agents or liquid bathing agents (including limonene, menthol, citronellyl acetate, ethanol, etc.), perma solutions (including ethanol, etc.), and agricultural disinfectants (chloropicrin, PCNB, etc.). Hydroxyisoxazole, dithiocarbamate, organic phosphorus, benzoimidazole, dicarboxyimide, phenylmamide, etc.), repellent (including DCIP (dichlorodiisopropyl ether), etc.), pesticide (cartap, fenitrothione, etc.) , Pyretrin, rotenoid, chrysanthemum ester, etc.), disinfectant (including cresol, ethanol, formaldehyde, phenols, etc.), automobile, household, building cleaning agent (including ethanol, etc.), mouthwash (including ethanol, etc.) Ethanol, menthol, methyl salicylate, etc.), mouthwash (including povidone iodine, etc.), wipes (including menthol, camphor, methyl salicylate, etc.), toothpaste (including menthol, etc.), face lotion (including menthol, etc.) , Hair tonic (including menthol, etc.), hair restorer (including menthol, etc.), shampoo (including menthol, etc.), alcoholic beverage (including ethanol, etc.), various adhesives, inks, paints (toluene, ethyl acetate, methanol, (Including solvents such as isopropyl alcohol, methyl ethyl ketone, xylene, acetone, n-hexane, isobutyl acetate), floor waxes, engine oils, motor oils, household oils, cosmetic oils and the like.

Applications of surfactants include detergents, emulsifiers, dispersants, foaming agents, defoaming agents, antistatic agents and the like. Contents containing surfactants include detergents for automobiles, households, and buildings (including aliphatic soaps, alkylbenzene sulfonates, polyoxyethylene nonylphenyl ethers, etc.), cosmetics (aliphatic soaps, alkylbenzene sulfonic acids, etc.). (Including salts, polyoxyethylene nonylphenyl ether, etc.).

Examples of the content containing an acidic substance include vinegar (including acetic acid and the like). Contents containing alkaline substances include perm solution (including monoethanolamine, etc.), disinfectant (including sodium hypochlorite, etc.), bleach (including sodium hypochlorite, etc.), floor release agent. (Including morpholine, monoethanolamine, etc.), cement (including sodium hydroxide, etc.) and the like.

According to the laminate produced by the above procedure and the liquid paper container using the laminate, the initial lamination strength is good, and various volatile substances such as medicinal properties and fragrance components and other volatile substances are contained. It has become possible to obtain a liquid paper container whose laminating strength does not decrease even when a highly permeable content acts on it.

Hereinafter, examples of the present invention will be described.

<Preparation of 3-layer coextruded biaxially stretched film>
Using an extrusion molding method, pellets made of polyethylene terephthalate (PET) resin, pellets made of maleic anhydride-modified polyolefin, and pellets made of nylon (Ny) resin were heated and melted, and three layers were coextruded from the T-die. A composite film having a three-layer structure of PET / adhesive resin / Ny] (= corresponding to the base material layer) was molded, and the composite film was subjected to a sequential biaxial stretching method by a tenter method to prepare a biaxially stretched film. The total thickness of this biaxially stretched film was 15 μm, and the thicknesses of the PET layer, the adhesive resin layer, and the Ny layer were 11 μm, 1 μm, and 3 μm, respectively.

<Example 1>
A base paper having a basis weight of 400 g / m ² was used as the paper, and low-density polyethylene (LDPE) was formed as a thermoplastic resin layer while corona treatment was performed on one side thereof with an extrusion laminator to obtain an LDPE / paper layer.
Further, both sides of the 15 μm three-layer coextruded biaxially stretched film [PET / adhesive resin / Ny] produced above are subjected to corona treatment, and an aluminum oxide vapor deposition layer is formed on the PET side thereof to form an aluminum oxide vapor deposition layer. / [PET / adhesive resin / Ny] was obtained.
Then, while applying corona treatment to the LDPE / paper using a tandem extrusion laminator, aluminum oxide / [PET / adhesive resin / Ny] is fed out from the sand shaft, and a two-component curable urethane system is applied onto the aluminum oxide. A low-density ethyl acetate coating solution using an adhesive with a solid content ratio of 2.0% by weight is applied to form an adhesive layer, dried in an oven, and then extruded from the T-die of the first extruder. An extruded resin layer made of low-density polyethylene (LDPE) having a thickness of 20 μm is laminated to prepare LDPE / paper / LDPE / two-component curable urethane adhesive / aluminum oxide / [PET / adhesive resin / Ny]. Immediately after that, an ethyl acetate diluted coating liquid having a solid content ratio of 2.0% by weight using an adduct type of linear low density isocyanate (TDI) was applied onto this inner Ny to form an adhesive layer A. After being formed and dried in an oven, a linear low-density polyethylene film (LLDPE film) having a thickness of 40 μm, which is the innermost layer of the sealant layer, is fed out from the sand shaft and extruded from the T-die of the second extruder to have a thickness of 20 μm. An extruded resin layer made of low-density polyethylene (LDPE) was laminated to obtain a laminate. The processing conditions for the extrusion laminate at this time were a temperature under the die of 320 ° C. and a processing speed of 80 m / min.
Next, after aging at 50 ° C. for 3 days using this laminate, it was processed into a Goebel top type paper container to obtain a liquid paper container according to Example 1.
This liquid paper container was filled with a liquid bathing agent (including menthol, ethanol, etc.) as a content, sealed, and a storage test was conducted at 40 ° C. for 6 months. After that, as a result of opening this liquid paper container, no delamination due to the contents was observed.

<Example 2>
The laminate and liquid paper container according to Example 2 were prepared in the same manner as in Example 1 except that silicon oxide was formed as the vapor-deposited thin film layer and a hexamethylene diisocyanate (HDI) burette type was used as the adhesive layer A. Obtained.
This liquid paper container was filled with a mouthwash (including povidone iodine) as a content, sealed, and stored at 40 ° C. for 6 months. After that, as a result of opening this liquid paper container, no delamination due to the contents was observed.

<Example 3>
Both sides of the 15 μm three-layer coextruded biaxially stretched film [PET / adhesive resin / Ny] produced above are subjected to corona treatment, and the PET side of the 15 μm three-layer coextruded biaxially stretched film [PET / adhesive resin / Ny] has a primer layer for vapor deposition and an aluminum oxide vapor deposition layer having the composition described below. A gas barrier film layer having the composition described below was formed to obtain a gas barrier film layer / aluminum oxide vapor deposition layer / vapor deposition primer layer / [PET / adhesive resin / Ny].
Then, while applying corona treatment to the LDPE / paper prepared above by a tandem extrusion laminator, the gas barrier coating layer / aluminum oxide vapor deposition layer / vapor deposition primer layer / [PET / adhesive resin / Ny ] Is fed out, and an ethyl acetate diluted coating liquid having a solid content ratio of 2.0% by weight using a two-component curable urethane-based adhesive is applied onto this gas barrier coating layer to form an adhesive layer. Then, after drying in an oven, an extruded resin layer made of an ethylene-methacrylic acid copolymer (EMAA) having a thickness of 20 μm extruded from the T-die of the first extruder is laminated, and LDPE / paper / EMAA / two-component curing is performed. A type urethane adhesive / gas barrier coating layer / aluminum oxide vapor deposition layer / vapor deposition primer layer / [PET / adhesive resin / Ny] was prepared, and immediately after that, a number average molecular weight of 50, A coating solution prepared by adjusting the solid content ratio of 000 polyethyleneimines to 1.0 wt% is applied to form a first adhesive layer, and then isophorone diisocyanate (IPDI) is formed on the first adhesive layer.
) A coating liquid prepared so that the solid content ratio of the monomer is 2.0 wt% is applied to form a second adhesive layer, and after drying in an oven, it becomes a sealant layer which is the innermost layer from the sand shaft. While feeding out a linear low-density polyethylene film (LLDPE film) with a thickness of 40 μm, an extruded resin layer made of an ethylene-methacrylic acid copolymer (EMAA) with a thickness of 20 μm extruded from the T die of the second extruder is laminated. A laminate was obtained. The processing conditions for the extrusion laminate at this time were a temperature under the die of 300 ° C. and a processing speed of 80 m / min.
Next, after aging at 50 ° C. for 3 days using this laminate, it was processed into a Goebel top type paper container to obtain a liquid paper container according to Example 3.
This liquid paper container was filled with vinegar (including acetic acid, etc.) as the content, sealed, and stored at 40 ° C. for 6 months. After that, as a result of opening this liquid paper container, no delamination due to the contents was observed.

<Method of forming primer layer for vapor deposition>
A coating liquid containing an acrylic polyol, an isocyanate compound, and a silane coupling agent was applied and dried to form a primer layer for vapor deposition.

<Composition of gas barrier coating agent and method of forming gas barrier coating layer>
A gas barrier coating agent obtained by mixing the following liquids C and D at a ratio of 60/40 (weight ratio) was applied and dried to form a gas barrier coating layer.
Solution C: Hydrolyzed solution of 3.0% by weight (SiO2 equivalent) of solid content obtained by adding 89.6 g of 0.1N hydrochloric acid to 10.4 g of tetraethoxysilane and stirring for 30 minutes. Solution D: 3 of polyvinyl alcohol 0.0% by weight, water / isopropyl alcohol solution (water: isopropyl alcohol weight ratio 90:10)

<Example 4>
Silicon oxide was formed as the vapor deposition layer, a primary amine graft acrylic polymer was used for the first adhesive layer, an adduct type of tolylene diisocyanate (TDI) was used for the second adhesive layer, and a zinc ionomer (Zn ionomer) having a thickness of 20 μm was used as the extruded resin layer. A laminate and a liquid paper container according to Example 4 were obtained in the same manner as in Example 3 except for the above. The processing conditions for the extrusion laminate at this time were a temperature under the die of 300 ° C. and a processing speed of 80 m / min.
This liquid paper container was filled with a perm solution (including ethanol, monoethanolamine, etc.) as a content, sealed, and a storage test was conducted at 40 ° C. for 6 months. After that, as a result of opening this liquid paper container, no delamination due to the contents was observed.

<Example 5>
Silicon oxide is formed as a vapor deposition layer, a primary amine graft acrylic polymer is used as the first adhesive layer, an adduct type of xylylene diisocyanate (XDI) is used as the second adhesive layer, random polypropylene (random PP) having a thickness of 20 μm is used as the extruded resin layer, and a sealant layer. A laminate and a liquid paper container according to Example 5 were obtained in the same manner as in Example 3 except that a random polypropylene cast film (CPP film) having a thickness of 40 μm was used. The processing conditions for the extrusion laminate at this time were a temperature under the die of 275 ° C. and a processing speed of 80 m / min.
This liquid paper container was filled with a floor release agent (including morpholine, monoethanolamine, etc.) as a content, sealed, and stored at 40 ° C. for 6 months. After that, as a result of opening this liquid paper container, no delamination due to the contents was observed.

<Comparative example 1>
The laminate and liquid paper container according to Comparative Example 1 were obtained in the same manner as in Example 1 except that a single layer of 12 μm polyester film (PET) was used as the base material layer.
This liquid paper container was filled with a liquid bathing agent (including menthol, ethanol, etc.) as a content, sealed, and a storage test was conducted at 40 ° C. for 6 months.
After that, as a result of opening this liquid paper container, remarkable delamination due to the contents was observed, and as a result of analysis by X-ray photoelectron spectroscopy in order to confirm this peeled surface, tolylene diisocyanate which is the adhesive layer A ( It was found that a slight polyester having a thickness of nano-order was adhered on the adduct type layer of TDI), and it was found that the surface layer of the single-layer PET was peeled off, and it was found that it was not suitable as a liquid paper container.

<Comparative example 2>
A laminate according to Comparative Example 2 in the same manner as in Example 2 except that a single 12 μm polyester film (PET) was used as the base material layer and an ethylene-methacrylic acid copolymer (EMAA) was used as the extruded resin layer. And obtained a liquid paper container.
This liquid paper container was filled with a mouthwash (including povidone iodine) as a content, sealed, and stored at 40 ° C. for 6 months.
After that, as a result of opening this liquid paper container, remarkable delamination due to the contents was observed, and as a result of analysis by X-ray photoelectron spectroscopy in order to confirm this peeled surface, hexamethylene diisocyanate (adhesive layer A) (hexamethylene diisocyanate) (adhesive layer A) It was found that a slight polyester having a thickness of nano-order was adhered on the burette type layer of HDI), and it was found that the surface layer of the single layer PET was peeled off, and it was found that it was not suitable as a liquid paper container.

<Comparative example 3>
The laminate and liquid paper container according to Comparative Example 3 were used in the same manner as in Example 3 except that a single 12 μm polyester film (PET) was used as the base material layer and zinc ionomer (Zn ionomer) was used as the extruded resin layer. Got
This liquid paper container was filled with a perm solution (including ethanol, monoethanolamine, etc.) as a content, sealed, and a storage test was conducted at 40 ° C. for 6 months.
After that, as a result of opening this liquid paper container, remarkable delamination due to the contents was observed, and as a result of analysis by X-ray photoelectron spectroscopy in order to confirm this peeled surface, the polyethyleneimine layer which is the first adhesive layer was obtained. A small amount of polyester having a thickness of nano-order was adhered on the surface, and it was found that the surface layer of the single-layer PET was peeled off, and it was found that it was not suitable as a liquid paper container.

<Comparative example 4>
The laminate and liquid paper container according to Comparative Example 4 were obtained in the same manner as in Example 5 except that a single layer of 12 μm polyester film (PET) was used as the base material layer.
This liquid paper container was filled with a floor release agent (including morpholine, monoethanolamine, etc.) as a content, sealed, and stored at 40 ° C. for 6 months.
After that, as a result of opening this liquid paper container, remarkable delamination due to the contents was observed, and as a result of analysis by X-ray photoelectron spectroscopy in order to confirm this peeled surface, a primary amine graft which is the first adhesive layer was obtained. It was found that a slight polyester having a thickness of nano-order was adhered on the acrylic polymer layer, and it was found that the surface layer of the single-layer PET was peeled off, and that it was not suitable as a liquid paper container.

Table 1 summarizes the results of the presence or absence of delamination in the liquid paper container stored at 40 ° C. for 6 months, which was carried out in Examples 1 to 5 and Comparative Examples 1 to 4 above.

From the results shown in Table 1, according to the laminate according to the present invention and the liquid paper container using the same, various strongly permeable contents containing volatile substances such as medicinal properties and fragrance components and other volatile substances. It was found that excellent laminating strength can be maintained even if the above action is applied, and that the gas barrier property is also excellent.

1, 21 Laminated body 2 Thermoplastic resin layer 3 Paper layer 4 First extruded resin layer 5 Adhesive layer 6 Deposited thin film layer 7 Base material layer 8 Adhesive layer A
9 Second extruded resin layer 10 Sealant layer 11 First base material layer (polyester resin)
12 Thermoplastic adhesive resin layer 13 Second base material layer (polyamide-based resin)
14 First adhesive layer 15 Second adhesive layer 31, 41 Liquid paper container 32, 42 Paper container body 33, 43 Mouth plug

Claims (6)

At least, a thermoplastic resin layer, a paper layer, an extruded resin layer, an adhesive layer, a vapor-deposited thin film layer composed of an inorganic oxide, a base material layer, an adhesive layer A, an extruded resin layer, and a sealant layer are laminated in this order.
The base material layer is a coextruded biaxially stretched film including a first base material layer made of a polyester resin, a thermoplastic adhesive resin layer, and a second base material layer made of a polyamide resin.
A laminate characterized in that the adhesive layer A is made of any one or more of a diisocyanate monomer or an adduct-type, burette-type, or trimmer (isocyanurate)-type derivative of the diisocyanate monomer. At least, the thermoplastic resin layer, the paper layer, the extruded resin layer, the adhesive layer, the vapor-deposited thin film layer composed of an inorganic oxide, the base material layer, the first adhesive layer, the second adhesive layer, the extruded resin layer, and the sealant layer are laminated in this order. Has been
The base material layer is a coextruded biaxially stretched film including a first base material layer made of a polyester resin, a thermoplastic adhesive resin layer, and a second base material layer made of a polyamide resin.
The first adhesive layer is an amine-containing polymer, and the first adhesive layer is an amine-containing polymer.
A laminate characterized in that the second adhesive layer is made of any one or more of a diisocyanate monomer or an adduct-type, burette-type, or trimmer (isocyanurate)-type derivative of the diisocyanate monomer. The laminate according to claim 1 or 2, wherein in the base material layer, the second base material layer is on the side closer to the sealant layer. The laminate according to any one of claims 1 to 3, wherein the polyamide resin is nylon. The laminate according to any one of claims 1 to 4, wherein the thickness of the polyamide resin is 1 μm or more. A liquid paper container using the laminate according to any one of claims 1 to 5.

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