JP6398560B2 - Packaging materials for alkaline solutions - Google Patents

Description

  The present invention relates to a packaging material for an alkaline solution, and more particularly to a packaging material for an alkaline solution that exhibits high interlayer adhesion strength even after being brought into contact with the alkaline solution and stored for a long time.

  As containers for filling and packaging contents such as chemical products, packaging containers suitable for storage and transportation of the contents have been widely developed. As such packaging containers, flexible packaging bags made of various laminated films are used.

  However, when the content is a strong alkaline solution such as a chlorine bleach containing sodium hypochlorite as a main component, the strong alkaline solution erodes the adhesive layer in the laminated film during storage, It is known to cause delamination.

  Therefore, as a packaging container for these strong alkaline solutions, resinous bottles such as polypropylene bottles (PP bottles) having wall thicknesses of 1 to 2 mm or more are often used (Patent Document 1). Such a resinous bottle can enclose and store a strong alkaline solution, but its production requires a large amount of resin, and the production cost is high. Moreover, since it is hard and bulky, it requires a great deal of cost during transportation, storage and disposal, which is not preferable.

  Accordingly, an alkaline solution packaging material comprising a flexible laminated film that exhibits excellent alkali resistance, that is, does not erode the adhesive layer even when contacted with a strong alkaline solution over a long period of time, and thus does not cause delamination, and There is a need for an alkaline solution packaging container.

  On the other hand, Patent Document 2 is composed of a laminated film in which a base material layer and a heat-sealable resin layer are laminated via a polyurethane-based adhesive containing a urea bond, and an acidic substance, an alkaline substance, a fragrance, an oil, A packaging container for containing a liquid containing a surfactant or the like is described. Patent Document 3 describes a packaging material that is composed of a laminated film obtained by laminating a base material layer and an aluminum foil layer via an anchor coat layer and an adhesive resin layer, and exhibits resistance to contents against a strong permeable substance. Has been.

  However, none of these exhibits sufficient content resistance against strong alkaline solutions such as chlorine bleach containing sodium hypochlorite as a main component. Further, since a reactive polyurethane adhesive or an anchor coating agent is used, there is a problem that unreacted substances and residual solvent in the adhesive or the anchor coating agent can be eluted.

JP2011-148987A JP 2013-095454 A JP 2009-172834 A

  The present invention has been made to solve such a problem, and exhibits high interlayer adhesion strength even after being kept in contact with an alkaline solution for a long period of time, that is, excellent in alkali resistance, and a residual solvent from the packaging material. It aims at providing the packaging material for alkaline solutions which does not elute, ie, is excellent in low elution property, and the packaging container for alkaline solutions which consists of it.

  As a result of various studies, the present inventors have at least a base material layer, a barrier layer, an alkali-resistant adhesive layer, and a heat-sealable resin layer in this order, and the alkali-resistant adhesive layer is an alkene- (meth) acrylic acid. It has been found that an alkaline solution packaging material comprising an adhesive resin composition containing an ester-unsaturated carboxylic acid ternary copolymer and an alkaline solution packaging container comprising the same achieve the above object.

The present invention is characterized by the following points.
(1) At least a base material layer, a barrier layer, an alkali-resistant adhesive layer, and a heat-sealable resin layer are provided in this order. A packaging material for an alkaline solution, comprising an adhesive resin composition containing an original copolymer.
(2) The packaging material for an alkaline solution according to (1), further including an intermediate layer between the base material layer and the barrier layer.
(3) A plurality of adhesive layers further having a reinforcing layer at an arbitrary position between the barrier layer and the heat-sealable resin layer and positioned between the barrier layer and the heat-sealable resin layer The alkaline solution according to (1) or (2) above, which is an alkali-resistant adhesive layer composed of an adhesive resin composition containing an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer. Packaging materials.
(4) The alkaline solution according to any one of (1) to (3), wherein the amount of the unsaturated carboxylic acid component in the adhesive resin composition is 0.05% by mass or more and less than 1.0% by mass. Packaging materials.
(5) The packaging material for alkaline solutions according to any one of (1) to (4) above, wherein the amount of the (meth) acrylic acid ester component in the adhesive resin composition is 5 to 40% by mass.
(6) Alkaline solution formed by stacking the alkaline solution packaging material according to any one of the above (1) to (5) so that the heat-sealable resin layers face each other and heat-sealing the end portions. Packaging container.
(7) In the above (6), the interlayer adhesion strength between the barrier layer and the heat-sealable resin layer after being filled with an alkaline solution of pH 11 and stored at 60 ° C. for 30 days is 5 N / 15 mm width or more. The packaging container for alkaline solutions as described.
(8) The alkaline solution packaging container according to (6) or (7) above, which is a refillable pouch.
(9) A package formed by filling the packaging container according to any of (6) to (8) with an alkaline solution.
(10) The package according to (9), wherein the alkaline solution is a chlorine bleach.
(11) A method for producing an alkaline solution packaging material according to any one of (1) to (5) above, wherein the barrier layer and the heat-sealable resin layer, or the barrier layer, the reinforcing layer, and the reinforcing layer The said manufacturing method of laminating | stacking and a heat-sealable resin layer by the sandwich lamination method through the adhesive resin composition containing the terpolymer of alkene- (meth) acrylic acid ester-unsaturated carboxylic acid.

  The packaging material for an alkaline solution of the present invention can achieve extremely high interlayer adhesion strength between the barrier layer and the heat-sealable resin layer without using a dry laminate adhesive. Therefore, there are no concerns about the elution of residual solvent and low molecular weight substances, and the problem of a decrease in interlayer adhesive strength due to deterioration with time of the adhesive layer.

  In particular, the packaging material for an alkaline solution of the present invention is excellent in alkali resistance and is in contact with a strong alkaline solution (pH 10-14, particularly pH 11-14) such as a chlorine bleach containing sodium hypochlorite as a main component over a long period of time. After that, the adhesive layer is not eroded by alkali, and high interlayer adhesive strength can be maintained.

  Therefore, the packaging container which consists of the packaging material for alkaline solutions of this invention can preserve | save the alkaline solution conventionally preserve | saved in the resin bottle like PP bottle in a good state for a long term.

  The packaging material for alkaline solution of the present invention can also be applied to a self-supporting bag that requires extremely high film strength (film waist) and interlayer adhesion strength, such as a stand pouch, and is particularly refilled with alkaline solution. It can be suitably used as a pouch for use.

It is the schematic cross section which showed an example of the layer structure of the packaging material for alkaline solutions of this invention. It is the schematic cross section which showed the other example of the layer structure of the packaging material for alkaline solutions of this invention. It is the schematic cross section which showed the other example of the layer structure of the packaging material for alkaline solutions of this invention.

  The packaging material for an alkaline solution of the present invention will be described in detail with reference to the drawings.

1 to 3 are schematic cross-sectional views showing an example of a layer structure of the alkaline solution packaging material of the present invention.
As shown in FIG. 1, the packaging material for an alkaline solution of the present invention has a basic structure in which a base layer 1, a barrier layer 2, an alkali-resistant adhesive layer 3 and a heat-sealable resin layer 4 are laminated in this order. To do. Here, the alkali-resistant adhesive layer 3 is also referred to as an adhesive resin composition containing an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer (hereinafter also referred to as “adhesive resin composition of the present invention”). The adhesive resin composition is melt-extruded and the barrier layer 2 and the heat-sealable resin layer 4 are bonded by sandwich lamination.

As another aspect of the packaging material for an alkaline solution of the present invention, as shown in FIG. 2, a configuration in which an arbitrary intermediate layer 5 is laminated between a base material layer 1 and a barrier layer 2 may be used.
As still another aspect of the packaging material for an alkaline solution of the present invention, as shown in FIG. 3, an alkali resistance comprising the adhesive resin composition of the present invention between a barrier layer 2 and a heat-sealable resin layer 4. A configuration in which the reinforcing layer 6 is laminated via the adhesive layer 3 may be employed.

  Next, the material constituting the alkaline solution packaging material of the present invention, the production method thereof, and the like will be described. The resin names used in the present invention are those commonly used in the industry.

A. Base Material Layer In the alkaline solution packaging material of the present invention, as the base material layer, a single layer film or a multilayer laminated film is used, but is not particularly limited, and any film used for various packaging bags may be used. it can. Among these, a suitable one is freely selected and used according to the use conditions such as the type of contents to be packaged and the presence or absence of heat treatment after filling. Specific examples of the film preferably used as the base material layer include paper, cellophane, polyamide resin film, polyester resin film, olefin resin film, acid-modified polyolefin resin film, polystyrene resin film, uniaxial or Biaxially stretched film, K coat film such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ionomer, ethylene- (meta ) Acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-propylene copolymer, methylpentene, polyacrylonitrile, polycarbonate, polyvinyl chloride (PVC), polyvinyl chloride (PVDC), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, etc. , A K-coated stretched polypropylene film, a K-coated stretched nylon film, and a composite film obtained by laminating two or more of these films. When applied as a self-supporting bag, a polyester resin film such as a PET film, a biaxially stretched nylon film, or the like can be suitably used.

  The thickness of the base material layer is preferably 5 to 300 μm, more preferably 10 to 100 μm. The base material layer may be subjected to surface treatment for improving wettability such as corona treatment, ozone treatment, flame treatment, etc. on the barrier layer side.

B. Barrier layer In the packaging material for an alkaline solution of the present invention, the barrier layer has a gas barrier property that prevents permeation of oxygen gas, water vapor, and the like, and more preferably any barrier film or barrier film that has a barrier property against an alkaline solution. Can be used.

  As such a barrier film or barrier film, a metal foil made of aluminum foil or the like, a vapor deposition film of an inorganic substance or an inorganic oxide, a vapor deposition film having the vapor deposition film on a resin film, or an ethylene-vinyl alcohol copolymer, Examples thereof include a layer made of a barrier resin such as polyvinylidene chloride, polyvinyl alcohol, MXD6, etc., and these may be used alone or in combination.

  Usually, the thickness of a barrier layer becomes like this. Preferably it is 0.01-500 micrometers, More preferably, it is the range of 1-300 micrometers. The barrier layer may be subjected to surface treatment for improving wettability, such as corona treatment, ozone treatment, and flame treatment, on at least one surface thereof.

  In particular, since it exhibits excellent barrier properties and good interlayer adhesion strength with an alkali-resistant adhesive layer, in the present invention, the vapor-deposited film of an inorganic substance or an inorganic oxide, or the vapor-deposited film on a plastic film is used. The deposited film provided is particularly preferably used.

The barrier film used in the present invention can be appropriately selected by those skilled in the art to exhibit a necessary degree of barrier property depending on the application. For use as a pouch for refilling an alkaline solution, particularly a chlorine bleach, for example, the oxygen permeability is 1 cc / m ² / day · atm or less, more preferably 0.5 cc / m ² / day · atm or less. Yes, the water vapor transmission rate is 1 g / m ² / day or less, more preferably 0.5 g / m ² / day or less. In this application, the oxygen transmission rate is a condition of a temperature of 23 ° C. and a humidity of 90% RH using an oxygen gas transmission rate measuring device (OX-TRAN 2/20 manufactured by MOCON) in accordance with JIS K7126 isobaric method. It is a value measured by. Further, the water vapor transmission rate is measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH using a water vapor transmission rate measuring device (PERMATRAN-W 3/31 manufactured by MOCON) in accordance with JIS K7129 B method. Value.

  A vapor deposition film and a vapor deposition film are demonstrated in detail. As the plastic film for forming the vapor deposition film, a plastic film that has excellent chemical or physical strength, can withstand the conditions for forming the vapor deposition film, etc., and can be well maintained without impairing the characteristics of the vapor deposition film is used. be able to.

  As such a plastic film, for example, a polyolefin film such as polypropylene or polyethylene, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate, a film or sheet made of various resins such as a polyamide film or a polyimide film is used. can do.

  Plastic film is treated with corona treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. as necessary before providing a vapor deposition film. The pre-treatment can be arbitrarily performed. In addition, the surface pretreatment is performed as a method for improving the adhesion between the plastic film and the vapor deposition film. As a method for improving the adhesion, for example, the surface of the plastic film is preliminarily formed. In addition, a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer, or the like can be arbitrarily formed.

  The material for forming the deposited film may be any inorganic substance or inorganic oxide having a gas barrier property against oxygen, water vapor, etc., for example, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide. In addition, oxides such as hafnium oxide and barium oxide are used, and aluminum oxide and silicon oxide are particularly preferably used from the viewpoint of gas barrier properties and production efficiency.

  As a method for forming a deposited film, physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum deposition method, sputtering method and ion plating method, plasma chemical vapor deposition method, thermal chemical vapor deposition method, etc. And film forming methods such as chemical vapor deposition (chemical vapor deposition, CVD) such as photochemical vapor deposition.

  Moreover, the vapor deposition film may consist of a single layer formed by a single vapor deposition process, or may have a multilayer structure formed by repeating the vapor deposition process a plurality of times. In the case of a multilayer structure, each layer may be made of the same material or different materials, and may be formed by the same forming method or by different forming methods. Good. For example, a vapor deposition film made of silicon oxide may be formed on a plastic film by chemical vapor deposition, and then a vapor deposition film made of aluminum oxide may be formed by physical vapor deposition.

  The layer thickness of the deposited film can be appropriately set within the range of 1 to 200 nm, preferably 1 to 100 nm, more preferably 1 to 50 nm, and still more preferably 1 to 30 nm as the thickness of the entire layer. For example, if it exceeds 200 nm, flexibility is lowered, and there is a possibility that the deposited film may be cracked by an external force such as bending or pulling after film formation, and the stress of the material itself increases, which is not preferable. On the other hand, when the thickness of the deposited film is less than 1 nm, it is difficult to obtain a uniform layer and it is difficult to sufficiently perform the gas barrier function.

Hereinafter, as a preferred embodiment of the present invention, a deposited film of silicon oxide will be described in more detail. The vapor-deposited film (thin film) of silicon oxide is represented by the general formula: SiO _x (wherein x represents a number from 0 to 2), and the value of x is preferably 1.3 to 1.9. The silicon oxide thin film may be mainly composed of silicon oxide, and may further contain at least one kind of compound composed of one kind of carbon, hydrogen, silicon or oxygen, or two or more kinds of elements by chemical bonding or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. Moreover, when a silicon oxide thin film contains the said compound, it is preferable that content of a compound is reducing toward the depth direction from the surface of the vapor deposition film | membrane of a silicon oxide.

  As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, at the interface with the plastic film, the plastic film and the silicon oxide vapor deposition film The tight adhesion is strong.

  As the organic silicon compound used as a raw material in the case of forming a silicon oxide vapor-deposited film containing carbon as described above, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane (HMDSO) , Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltri Methoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like can be used.

In the present invention, by further providing a gas barrier coating film as described below on the above-mentioned deposited film, not only a further excellent gas barrier property can be obtained, but also a close adhesion property to an alkali-resistant adhesive layer described later. Will increase.
In the present invention, the gas barrier coating film is a film obtained by applying and drying a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method.

The alkoxide used in the gas barrier composition has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M is a metal And n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atomic valence of M).

As the water-soluble polymer, either a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer or both can be preferably used.
In the present invention, as the metal atom M, silicon, zirconium, titanium, aluminum or the like can be used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . Moreover, in this invention, the alkoxide of a single or 2 or more types of different metal atoms can be mixed and used in the same solution.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like.

In the present invention, these alkyl groups may be the same or different in the same molecule.
In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, an alkoxysilane in which M is Si can be used. As the alkoxysilane, for example, tetramethoxy Examples thereof include silane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) _{4 and the} like.

  Moreover, in this invention, it is preferable that content of a polyvinyl alcohol-type resin and / or an ethylene vinyl alcohol copolymer is the range of 5-500 weight part with respect to 100 weight part of total amounts of said alkoxide. In the above, if it exceeds 500 parts by weight, the formed gas barrier coating film becomes more brittle and its weather resistance and the like are also unfavorable.

  In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples of the polyvinyl alcohol resin include PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 (made by Kuraray Co., Ltd.) Degree of saponification = 98-99%, degree of polymerization = 2400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3500), RS-110 (degree of saponification = 99%) manufactured by the same company , Degree of polymerization = 1000), Kuraray Poval LM-20SO manufactured by the same company (degree of saponification = 40%, degree of polymerization = 2000), GOHSENOL NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization) Degree = 1400) and Gohsenol NH-18 (degree of saponification = 98-99%, degree of polymerization = 1700) and the like can be used.

  In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do. Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used.

  Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

  In the present invention, a silane coupling agent or the like can also be added to prepare a gas barrier composition for forming a gas barrier coating film according to the present invention. Suitable silane coupling agents include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Amino group-containing silane coupling agents such as aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2 -Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Coupling agent, 3-mercaptopro Examples include mercapto group-containing silane coupling agents such as rumethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane. .

The gas barrier composition used in the present invention can be prepared by hydrolyzing and polycondensing an alkoxide and a water-soluble polymer by a sol-gel method in the presence of an acid, water and an organic solvent.

  The gas barrier coating film is formed by applying the gas barrier composition on the vapor deposition film, and is 10 to 10 seconds at a temperature of 20 to 200 ° C., preferably 140 ° C. or more and below the melting point of the plastic film constituting the base material layer. It can be formed by heat treatment for minutes.

  Moreover, as an acid used in preparation of said gas-barrier composition, organic acids, such as mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, and an acetic acid, tartaric acid, etc. can be used, for example. Furthermore, as the organic solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, or the like can be used.

  Further, regarding the gas barrier composition, the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. Therefore, the type of the organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used.

  When the gas barrier composition is applied onto the vapor deposition film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and a transparent gas barrier coating film is formed.

  Furthermore, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the deposited film, the tight adhesion between the deposited film and the gas barrier coating film is improved. .

  By being formed as described above, the gas barrier coating film of the present invention includes a linear polymer having crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous portion. . Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the cohesive energy of the molecule is high. Good gas barrier properties.

  In the present invention, the vapor deposition film and the gas barrier coating film form, for example, a chemical bond, hydrogen bond, or coordination bond by hydrolysis / co-condensation, and the adhesion between these two layers is improved, synergistically. Due to the effect, a better gas barrier property can be exhibited.

  In the present invention, the gas barrier composition may be applied by one or more times by a coating means such as a roll coat such as a gravure roll coater, a spray coat, dipping, a brush, a bar coat, or an applicator. With this coating, it is possible to form a gas barrier coating film having a dry film thickness of 0.01 to 100 μm, preferably 0.1 to 50 μm. If the dry film thickness exceeds 100 μm, cracks may occur, which is not preferable.

  In the present invention, in order to obtain a higher gas barrier property, after providing a gas barrier coating film, a vapor deposition film and a gas barrier coating film are alternately laminated in this order one or more times. Preferably, the gas barrier coating film may be formed as an outermost layer to form a transparent gas barrier film.

C. Alkali-resistant adhesive layer In the present invention, the adhesive layer located between the barrier layer and the heat-sealable resin layer has alkali resistance and is an alkene- (meth) acrylate-unsaturated carboxylic acid ternary copolymer. It consists of the adhesive resin composition of this invention containing coalescence.

  Moreover, when it has further layers, such as a reinforcement layer, between a barrier layer and a heat-sealable resin layer, it is preferable to use the adhesive resin composition of the said invention also at the time of adhesion | attachment with this further layer. That is, it is preferable that all the adhesive layers located between the barrier layer and the heat-sealable resin layer are made of the adhesive resin composition of the present invention.

  Since the adhesive resin composition of the present invention has a functional group such as a carboxyl group, it chemically bonds with the surface of the barrier layer and the heat-sealable resin layer and the reactive group, thereby exhibiting alkali resistance and strong strength. Even after long-term exposure to an alkaline solution, high interlayer adhesion strength can be maintained.

Further, when the alkali-resistant adhesive layer of the present invention is provided, it is not necessary to use an anchor coat agent that is used in ordinary melt extrusion. Furthermore, the adhesive resin composition of the present invention does not contain an organic solvent. Therefore, this invention does not have a concern about the elution of the residual solvent and the low molecular weight substance derived from the organic solvent contained in the anchor coating agent or the resin composition.
The adhesive resin composition of the present invention may be composed of only an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer.

  In another embodiment, the adhesive resin composition of the present invention may further comprise a polyolefin resin, a polyamide resin, a polyester resin, an ethylene-vinyl alcohol copolymer, as desired, in addition to the ternary copolymer. And a modifying resin such as polyvinyl chloride and polyvinylidene chloride.

  In addition, the adhesive resin composition of the present invention has, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, Various plastic compounding agents and additives can be added for the purpose of improving and improving the mechanical properties, strength, etc., and the addition amount is from a very small amount to several tens of percent depending on the purpose. , Can be optionally added. As a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment and the like can be used.

  In the production of the terpolymer, examples of the alkene serving as a comonomer include ethylene, propylene, butene, isobutene, pentene, hexene, and the like. In particular, α-olefins such as ethylene and propylene are preferably used.

  Moreover, (meth) acrylic acid ester used as a comonomer includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, ( Examples include tert-butyl (meth) acrylate, ethyl-2-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and methyl acrylate, ethyl acrylate, and butyl acrylate are preferred, and methyl acrylate is more preferred. It is.

  Examples of the unsaturated carboxylic acid serving as a comonomer include acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, and derivatives thereof such as acid anhydrides, esters, amides, imides, and the like. Examples thereof include monomethyl maleate, maleic anhydride, citraconic anhydride, itaconic anhydride and the like. In particular, unsaturated dicarboxylic acid, maleic anhydride and the like can be preferably used. These may be used alone or in a mixture of two or more.

The ternary copolymer of the present invention is obtained by graft polymerization or ternary copolymerization of the alkene, (meth) acrylic acid ester, and unsaturated carboxylic acid. The ternary copolymer may contain a comonomer other than the above as long as the object of the present invention is not impaired. For example, an ethylene- (meth) acrylic acid ester-maleic anhydride terpolymer resin can be preferably used.
In the present invention, the polymerization reaction can be produced by various conventional methods using a comonomer as a raw material.

  For example, a polymer consisting of an alkene is dry blended with an unsaturated carboxylic acid and, if necessary, an organic peroxide and a radical initiator at a predetermined mixing ratio using a Henschel mixer, etc., and the system is purged with nitrogen gas. The mixture is put into a kneading machine such as a Banbury mixer or a double screw mixer, and melt-kneaded at a temperature of 120 to 300 ° C. for 0.1 to 30 minutes. At the time of the grafting reaction, the reaction can be carried out efficiently by adding a conventional radical generator.

  Although it does not specifically limit as a radical generator, For example, hydroperoxides, such as diisopropyl benzene hydroperoxide and 2, 5- dimethyl- 2, 5- di (hydroperoxy) hexane; Di-t-butyl peroxide Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; organic peroxides such as diacyl peroxides such as benzoyl peroxide, or azobisisobutyronitrile An azo compound such as These radical generators may be used alone or as a mixture of two or more. The addition amount of the radical generator is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the comonomer components.

  In the present invention, in particular, in order to obtain good handling while suppressing hygroscopicity, the preferred blending ratio of each component of the terpolymer is (meth) with respect to the total mass of the adhesive resin composition. The acrylate ester-derived component (residue) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.

  Further, the unsaturated carboxylic acid-derived component (residue) is contained in an amount of 0.05 to 3.0% by mass, more preferably less than 0.05 to 1.0% by mass, and the rest is an alkene-derived component ( Residue), a modifying resin, an additive, and the like.

  When the amount of the unsaturated carboxylic acid component in the adhesive resin composition containing the terpolymer of the present invention is more than the above range, the acid content of the laminate is increased, so that the hygroscopicity is increased and foaming is performed during coextrusion. there's a possibility that. Moreover, there exists a concern that the residual monomer of unsaturated carboxylic acid may elute from an adhesive layer.

  Further, when the amount of the unsaturated carboxylic acid component is too small, chemical interaction with the resin film constituting the barrier layer or the reinforcing layer is less likely to occur, which may cause a decrease in interlayer adhesive strength.

  When the content of the (meth) acrylic acid ester-derived component is more than the above range, the resin itself is liable to be liquefied, resulting in poor handling. Moreover, when content of the component derived from (meth) acrylic acid ester is less than the said range, the adhesion | attachment by reaction of an acrylate becomes difficult to generate | occur | produce.

  It is preferable that MFR of the adhesive resin composition of this invention is 3-100 g / 10min in 190 degreeC, More preferably, it is 5-20 g / 10min. When the MFR is outside the above range, there is a problem that extrusion becomes difficult.

  Moreover, it is preferable that the thickness of the contact bonding layer which consists of adhesive resin compositions is 0.1-200 micrometers, More preferably, it is 1-100 micrometers. When the film thickness is not more than the above range, it is difficult to extrude easily and the adhesive strength is not exhibited. When the film thickness exceeds the range, problems such as adhesive strength are solved, but the packaging material cost increases due to excessive use of the resin.

The adhesion mechanism of the adhesive layer comprising the adhesive resin composition of the present invention includes a mechanism for adhering by the flexibility of the adhesive resin composition, a mechanism for adhering by compatibilization with the resin, the surface of the counterpart substrate and the unsaturated carboxylic acid There are a mechanism for adhering by chemical interaction with the substrate, a mechanism for adhering by chemical interaction of unsaturated carboxylic acid and acrylate to the surface of the counterpart substrate, and a mechanism for adhering by radical generation by extrusion at high temperature.
The adhesive layer made of the adhesive resin composition of the present invention is not necessarily bonded by one bonding mechanism, and is bonded by utilizing at least two or more of the above reactions.

D. Heat-sealable resin layer The heat-sealable resin layer of the present invention is a layer made of a heat-sealable resin that can be melted by heat and fused to each other.

  Examples of the heat-sealable resin suitably used in the present invention include low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, and ionomer. Resin, ethylene- (meth) acrylic acid ethyl copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid , Polyolefin resins modified with unsaturated carboxylic acids such as maleic anhydride, fumaric acid, etc., ethylene- (meth) acrylate-unsaturated carboxylic acid terpolymer resins, cyclic polyolefin resins, cyclic olefin copolymers, Polyethylene terf Can be mentioned rate (PET), polyacrylonitrile (PAN) 1 kind or resin comprising more like. A film or sheet made of these resins may be used, and the surface thereof may be subjected to corona treatment, flame treatment, ozone treatment or the like as desired.

  The thickness of the heat-sealable resin layer is not particularly limited, but is preferably 5 to 500 μm, more preferably 10 to 250 μm. If it is thinner than 5 μm, sufficient interlayer adhesion strength cannot be obtained even if heat-sealing, and it does not function as a packaging container. When it is thicker than 500 μm, the cost increases and the film becomes hard and workability deteriorates.

E. Intermediate Layer and Reinforcing Layer In the alkaline solution packaging material of the present invention, an intermediate layer can be provided between the base material layer and the barrier layer as desired. Similarly, a reinforcing layer can be provided as desired between the barrier layer and the heat-sealable resin layer.

The intermediate layer and the reinforcing layer may be any functional layer that imparts the desired physical and chemical properties. For example, a polyamide resin film is provided as an intermediate layer in order to improve functions such as flex resistance and impact resistance of the laminate. By increasing the bending resistance, it is possible to suppress a decrease in gas barrier properties due to bending.
The polyamide resin film contains an aliphatic polyamide and / or an aromatic polyamide.

  Examples of the aliphatic polyamide include aliphatic nylon and copolymers thereof. Specifically, polycapramide (nylon-6), poly-ω-aminoheptanoic acid (nylon-7), poly-ω-aminononanoic acid (nylon-9), polyundecanamide (nylon-11), polylauryllactam ( Nylon-12), polyethylenediamine adipamide (nylon-2,6), polytetramethylene adipamide (nylon-4,6), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene Bacamide (nylon-6,10), polyhexamethylene dodecamide (nylon-6,12), polyoctamethylene adipamide (nylon-8,6), polydecamethylene adipamide (nylon-10,8) , Caprolactam / lauryl lactam copolymer (nylon-6 / 12), caprolactam / ω-aminononanoic acid copolymer Body (nylon-6 / 9), caprolactam / hexamethylenediammonium adipate copolymer (nylon-6 / 6,6), lauryllactam / hexamethylenediammonium adipate copolymer (nylon-12 / 6,6), Ethylenediamine adipamide / hexamethylene diammonium adipate copolymer (nylon-2,6 / 6,6), caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon-6 / 6,6) / 6,10), ethyleneammonium adipate / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon-6 / 6,6 / 6,10), etc. Even if you mix the aliphatic polyamide There.

  Preferred aliphatic polyamides include nylon-6, nylon-6,6, nylon-6 / 6,6 (copolymer of nylon 6 and nylon 6,6), more preferably nylon-6, nylon. -6/6, 6 and more preferably nylon-6. As the two or more kinds of aliphatic polyamides, a combination of nylon-6 and nylon-6 / 6,6 (mass ratio of about 50:50 to 95: 5) is preferable.

  As the aromatic polyamide, for example, an aromatic diamine such as metaxylenediamine and paraxylenediamine and a dicarboxylic acid such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid, or a derivative thereof can be used. Examples thereof include crystalline aromatic polyamides obtained by a condensation reaction. A crystalline aromatic polyamide such as polymetaxylene adipamide (MXD-nylon) is preferable. Specific examples include S-6007 and S-6011 (both manufactured by Mitsubishi Gas Chemical Co., Inc.).

  Alternatively, an amorphous aromatic polyamide (amorphous nylon) obtained by a polycondensation reaction between an aliphatic diamine such as hexamethylenediamine and a dicarboxylic acid such as terephthalic acid or isophthalic acid or a derivative thereof can be used. Preferred is a copolymer of hexamethylenediamine-terephthalic acid-hexamethylenediamine-isophthalic acid. Specific examples include sealer PA (manufactured by Mitsui DuPont Polychemical Co., Ltd.) and the like.

Preferred combinations of the aliphatic polyamide and the aromatic polyamide include a combination of nylon-6 and MXD-nylon, and a combination of nylon-6 and amorphous aromatic polyamide (amorphous nylon).
Particularly preferable polyamide-based resins include meta-xylenediadipamide (MXD-6) -based nylon, 6-nylon, and 6,6 nylon.

In the present invention, the polyamide-based resin film may be composed of the above-mentioned polyamide-based resin. However, a known flex resistance improver, inorganic or organic additive may be added as necessary without departing from the effects of the present invention. An agent or the like can be blended. Examples of the bending resistance improver include polyolefins, polyester elastomers, polyamide elastomers, and the like, and they can be appropriately blended in the range of about 0.5 to 10% by mass. Examples of inorganic or organic additives include antiblocking agents, nucleating agents, water repellents, antioxidants, thermal stabilizers, lubricants, antistatic agents, and the like. For example, if it is an antiblocking agent, a silica, a talc, a kaolin etc. can be mix | blended suitably in the range of about 100-5000 ppm. Note that it is possible to provide not only one polyamide-based resin layer but also two or more layers.
For example, the polyamide-based resin film is longitudinally stretched 2 to 4 times by a roll stretching machine at 50 to 100 ° C., and further stretched 3 to 5 times by a tenter stretching machine in an atmosphere at 90 to 150 ° C. It can be obtained by heat treatment in an atmosphere of 100 to 240 ° C. with the same tenter. The stretched film may be subjected to simultaneous biaxial stretching and sequential biaxial stretching, and the obtained multilayer stretched film may be provided with any surface treatment layer on both surfaces or one surface thereof, if necessary.

  In the present invention, the above-described resin film or sheet is used. For example, the above-described adhesive resin composition of the present invention is used, and the sandwich layer method or the like is used, and the barrier layer and the heat sealability are used. It can be held between the resin layers. Alternatively, any adhesive layer can be used and sandwiched between the substrate layer and the barrier layer.

  As the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, and the like, and if it is too thick, the cost increases. On the other hand, if it is too thin, improvement in strength, puncture resistance and the like cannot be obtained. In the present invention, from the above reasons, 1 to 100 μm, preferably 5 to 50 μm is preferable.

  In particular, in order to use as a self-supporting bag for an alkaline solution, particularly a refill pouch for an alkaline solution, a polyamide resin film is provided between the base material layer and the barrier layer in order to obtain the waist and strength necessary for self-supporting. It is preferable to provide as an intermediate layer. In general, polyamide-based resin films are susceptible to erosion by an alkaline solution, so that it has been known that delamination occurs when used as a packaging material for an alkaline solution. However, in the present invention, even if the adhesive layer made of the adhesive resin composition of the present invention includes a polyamide-based resin film in the layer structure in order to block the penetration of the alkaline solution into the laminate, No delamination occurs and the alkaline solution can be stored stably over a long period of time.

F. Lamination By laminating the base material layer, (intermediate layer), barrier layer, (reinforcing layer), and heat-sealable resin layer, the packaging material for an alkaline solution of the present invention is obtained.
The base layer, the intermediate layer, and the barrier layer can be laminated by any method using a conventional adhesive resin or the like. If desired, they may be laminated by sandwich lamination via the adhesive resin composition of the present invention. Moreover, you may laminate | stack a further layer on the surface on the opposite side to the barrier layer of a base material layer.

  On the other hand, the barrier layer and the heat-sealable resin layer are laminated by sandwich lamination via an alkali-resistant adhesive layer made of the adhesive resin composition of the present invention. Similarly, when providing a reinforcing layer, between the barrier layer and the reinforcing layer and between the reinforcing layer and the heat-sealable resin layer, via an alkali-resistant adhesive layer made of the adhesive resin composition of the present invention, Laminated by sandwich lamination.

The sandwich laminate via the adhesive resin composition of the present invention is such that each of the films to be laminated is fed out at a constant speed, and the heated and melted adhesive resin composition of the present invention is extruded into a thin film between the fed films. It is performed by laminating a film using a cooling roll, a pressure roll, or the like.
Alternatively, the heat-sealable resin layer can be laminated together with the adhesive resin composition of the present invention on the barrier layer or the reinforcing layer by a coextrusion coating method.

  Since the adhesive resin composition of the present invention exhibits a high bonding force to the laminated surface of the film, it is not necessary to apply an anchor coating agent to the laminated surface in advance. If necessary, the laminated surface of the film may be subjected to surface treatment such as corona treatment in advance.

  The extrusion temperature of the adhesive resin composition of the present invention is in the range of 280 to 330 ° C, more preferably 290 to 320 ° C. When the resin temperature is 280 ° C. or lower, it is difficult for radicals to occur in the adhesive layer, and sufficient interlayer adhesion strength with the barrier layer, the reinforcing layer, and the heat-sealable resin layer cannot be exhibited. On the other hand, if the temperature is 330 ° C. or higher, thermal decomposition of the ternary copolymer occurs, so that sufficient interlayer adhesion strength cannot be obtained, which is not preferable.

G. Alkaline solution packaging container and packaging body The alkaline solution packaging material of the present invention is folded or overlapped so that the heat-sealable resin layer is the innermost layer, and the peripheral edge thereof is, for example, a side-sealed mold, two Heat by heat seal type such as side seal type, three side seal type, four side seal type, envelope sticker seal type, palm seal sticker type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type Various forms of packaging containers can be manufactured by sealing. In particular, the packaging material for an alkaline solution of the present invention has a high interlayer adhesion strength, further exhibits excellent content resistance, particularly alkali resistance, and prevents the occurrence of delamination over a long period of time. Therefore, it can be suitably used as a self-supporting bag such as a heavy weight bag or a refill stand pouch.

  As a method of manufacturing a stand pouch, the packaging material for alkaline solution of the present invention is used as the body of the bag, that is, the laminate for the body forming the side surface, and the laminate for the bottom material that forms the bottom, and these heats are used. It is obtained by arranging the surfaces of the sealing resin layer facing each other and heat-sealing them into a stand-pouch type.

  As a more specific manufacturing method of the stand pouch, for example, two laminates for the body material are prepared, and the surfaces of the heat-sealable resin layers are arranged to face each other. Next, a bottom material laminate having a mountain fold in the center with the sealant surface facing outward is inserted into these lower ends, and a gusset portion is provided to heat seal the peripheral portion. A self-supporting bottom can be formed by heat-sealing the gusset portion into a boat bottom seal type. Moreover, you may provide a spout part in the corner part of a pouch upper part using the bag making machine provided with the heat seal part which forms a spout part, and the punching part for notching the both sides.

  In order to manufacture a package by filling an alkaline solution, for example, a chlorine bleach, after filling the contents from the filling port left without sealing, the filling port is heat sealed by, for example, a degassing seal or the like. And seal.

  In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

The alkaline solution packaging material of the present invention has no problem that the adhesive layer is eroded by contents such as alcohol during long-term storage, resulting in delamination. Moreover, there is no problem that low molecular weight substances such as decomposition products and unreacted monomers are eluted. Therefore, the packaging material for an alkaline solution of the present invention can be suitably used particularly as a strong alkaline solution having a pH of 10 to 14, more preferably 11 to 14, such as a packaging container for a chlorine bleach.
Next, the present invention will be specifically described with reference to examples.

[Example 1]
A 12 μm thick biaxially stretched PET film (T-4102 manufactured by Toyobo Co., Ltd.) and a 7 μm thick aluminum foil (1N30, Toyo Aluminum Co., Ltd.) were set in an extrusion laminating machine as a base material layer. From a die, an adhesive resin composition comprising an ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd., maleic anhydride component amount: 0.3% by mass, methyl acrylate (Component amount: 19% by mass) was melt extruded at 310 ° C. to a thickness of 7 μm, and the corona-treated surface of the PET film and an aluminum foil were sandwich-laminated.

Next, the laminated film obtained above and a linear low density polyethylene (LLDPE) film (L-6PE, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm were set in an extrusion laminating machine. -Melt extrusion of an adhesive resin composition composed of a methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) at 310 ° C. to a thickness of 20 μm, and aluminum of the laminated film The foil side surface and the LLDPE film were sandwich-laminated to obtain an alkaline solution packaging material of the present invention.

[Example 2]
A biaxially stretched PET film with a thickness of 12 μm with corona treatment on one side is used, and this film is attached to a feed roll of a plasma chemical vapor deposition apparatus. Hexamethyldisiloxane, an organosilicon compound, is used as a raw material on the corona treatment surface. As a result, a silicon oxide vapor deposition film having a thickness of 200 nm was formed. Next, plasma treatment was performed on the surface of the deposited film.

  On the other hand, according to the composition shown in Table 1 below, the composition a. EVOH (ethylene copolymerization ratio of 29%) in an EVOH solution prepared by dissolving it in a mixed solvent of isopropyl alcohol and ion-exchanged water. A hydrolyzed liquid composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixture of polyvinyl alcohol, silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

Next, the plasma-treated surface on the deposited film surface is coated with the gas barrier composition produced above, and heat-treated at 100 ° C. for 30 seconds to form a gas barrier having a thickness of 0.4 g / m ² (dry operation state). An adhesive coating film was formed.

Next, the transparent gas barrier film formed above is set in an extrusion laminating machine, and the adhesive resin composition comprising an ethylene-methyl acrylate-maleic acid terpolymer is formed on the surface of the gas barrier coating film from a die. The product (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) was melt extruded at 310 ° C. to a thickness of 20 μm, and at the same time, a 50 μm thick LLDPE film (Toyobo Co., Ltd., L-6100) was fed out. By laminating by sandwich lamination, the packaging material for alkaline solution of the present invention was obtained.

[Example 3]
A 12 μm thick biaxially stretched PET film (T-4102 manufactured by Toyobo Co., Ltd.) and a 15 μm thick nylon film (manufactured by Kojin Film & Chemicals Co., Ltd., Bonil QC) are extruded as a base material layer. Set in a laminating machine, an adhesive resin composition (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) made of ethylene-methyl acrylate-maleic acid terpolymer from T-die at 310 ° C. with a thickness of 10 μm It was melt-extruded so that the corona-treated surface of the PET film and a nylon film were sandwich-laminated.

Next, the laminated film obtained above and an aluminum foil (1N30, Toyo Aluminum Co., Ltd.) having a thickness of 7 μm were set in an extrusion laminating machine, and similarly, ethylene-methyl acrylate-maleic acid ternary copolymer weight. Adhesive resin composition (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) made of coalesced is melt extruded at 310 ° C. to a thickness of 10 μm, and the laminated film is sandwich laminated with the nylon film side surface of the laminated film and aluminum foil did.

Further, similarly, the surface of the laminated film on the side of the aluminum foil and the LLDPE film having a thickness of 50 μm (L-6100, manufactured by Toyobo Co., Ltd.) were combined with an ethylene-methyl acrylate-maleic acid terpolymer. Was laminated via an adhesive resin composition (Lotader ^(R) 4503, thickness: 20 μm, manufactured by Arkema Co., Ltd.) to obtain a packaging material for an alkaline solution of the present invention.

[Example 4]
In the same manner as in Example 1, except that an unstretched polypropylene (CPP) film having a thickness of 70 μm (ZK99S, manufactured by Toray Film Processing Co., Ltd.) was used as the heat-sealable resin layer instead of the LLDPE film. The alkaline solution packaging material of the invention was produced.

[Comparative Example 1]
A 12 μm thick biaxially stretched PET film (T-4102 manufactured by Toyobo Co., Ltd.) and a 7 μm thick aluminum foil (1N30, Toyo Aluminum Co., Ltd.) were set in an extrusion laminating machine. Density polyethylene (LC600A manufactured by Nippon Polyethylene Co., Ltd.) was melt extruded to a thickness of 15 μm, and the corona-treated surface of the PET film and an aluminum foil were sandwich-laminated.

Next, the surface of the laminated film obtained above was coated with an anchor coating agent (Archibase ^(R) , SE-1200, manufactured by Unitika Ltd.) at a thickness of 0.3 μm on the surface of the aluminum foil side, A packaging material was manufactured by extrusion coating low density polyethylene (LC600A manufactured by Nippon Polyethylene Co., Ltd.) to a thickness of 25 μm.

[Comparative Example 2]
On the corona-treated surface of a 12 μm thick biaxially stretched PET film (T-4102 manufactured by Toyobo Co., Ltd.), a two-component curable urethane adhesive (manufactured by Rock Paint Co., Ltd., main agent RU-004 / curing agent H1) 3-5 μm was applied, and a 7 μm thick aluminum foil (1N30, Toyo Aluminum Co., Ltd.) was bonded. Next, 3-5 μm of a two-component curable urethane adhesive (manufactured by Rock Paint Co., Ltd., main agent RU-004 / hardening agent H1) is applied to the aluminum foil side surface, and a linear low density polyethylene having a thickness of 50 μm. A packaging material was manufactured by laminating a film (Toyobo Co., Ltd., L-6100).

[Alkali resistance evaluation]
(Interlayer adhesion strength test)
The packaging materials of Examples 1 to 4 and Comparative Examples 1 to 2 were heat-sealed so that the heat-sealable resin layer sides overlapped to produce a 180 × 160 mm three-way pouch. This pouch was filled with 40 ml of a chlorine bleach of pH 11 consisting of hypochlorous acid, sodium hydroxide and a surfactant, and the upper part was sealed to form a 4-way pouch. This was stored under dry conditions at 60 ° C. for 1 week, 2 weeks and 30 days. Initially, after 1 week storage, after 2 weeks storage and after 30 days storage, a strip-shaped test piece having a width of 15 mm is cut out, and in accordance with JISK6854, using a Tensilon tensile tester, the tensile speed is adjusted in a 25 ° C. atmosphere. It peeled in 90 degree direction as 50 mm / min, and measured the interlayer adhesive strength.

  If the interlayer adhesion strength after storage for 30 days is 5N / 15mm width or more, more preferably 6N / 15mm width or more, 7N / 15mm width or more, 8N / 15mm width or more, more preferably 9N / 15mm width or more, It is determined that the material has sufficient durability for practical use, does not cause delamination, that is, has alkali resistance. The results are shown in Table 2.

(Dissolution test)
Using the packaging materials of Examples and Comparative Examples, heat-sealable resin layers were overlapped to produce a three-sided bag body. About the obtained three-way bag body, 200 ml of clean water was enclosed in a test method according to the elution test of the plastic drug container test method of the Japanese Pharmacopoeia, and this pouch was kept at 121 ° C. for 25 minutes (Example 4). Alternatively, it was subjected to steam sterilization at 105 ° C. for 30 minutes (Examples 1 to 3 and Comparative Examples 1 to 2). The pouch was opened and the collected test solution was examined for foaming, pH, potassium permanganate reducing substance, ultraviolet absorption spectrum and evaporation residue as follows.

(Bubbles)
5 mL of the test solution was placed in a stoppered test tube having an inner diameter of 15 mm and a length of 200 mm, and vigorously shaken for 3 minutes, and the time until the generated foam disappeared was measured.

(PH)
1 mL of 1 g / L aqueous potassium chloride solution was added to 20 mL each of the test solution and clean water (control), and the pH was measured to determine the difference from the control.

(Potassium permanganate reducing substance)
To 20 mL of the test solution, 20 mL of 0.002 mol / L potassium permanganate solution and 1 mL of dilute sulfuric acid were added and cooled after boiling for 3 minutes. Thereafter, 0.1 g of potassium iodide was added and left for 10 minutes. After standing, it was titrated with 0.001 mol / L sodium thiosulfate solution (indicator: starch reagent). The difference in consumption of 0.002 mol / L potassium permanganate solution relative to the test solution and control (clean water) was determined.

(UV absorption spectrum)
With respect to the test solution and the control (clean water), the maximum absorbance was measured in each of the wavelength of 220 to 240 nm and the wavelength of 241 to 350 nm by the UV-visible absorbance measurement method.

(Evaporation residue)
20 mL of each test solution was evaporated to dryness on a water bath, the residue was dried at 105 ° C. for 1 hour, and its mass was measured.

  The results are shown in Table 3 below. In addition, the standard in a table | surface points out the standard of the elution thing test | inspection of the Japanese Pharmacopoeia plastic drug container test method.

  From the above results, the packaging material of the present invention can be applied to various resin films, vapor-deposited films, and metal foils. In any case, the packaging material stably exhibits sufficiently high interlayer adhesive strength, and has excellent alkali resistance. Demonstrated. In addition, components derived from packaging materials such as organic substances did not migrate into the contents, and sufficiently satisfied the elution test standard of the Japanese Pharmacopoeia plastic drug container test method.

1. Base material layer 2. 2. barrier layer 3. Adhesive layer 4. Heat sealable resin layer Intermediate layer 6. Reinforcement layer

Claims (9)

At least a substrate layer, a barrier layer, an alkali-resistant adhesive layer and a heat-sealable resin layer in this order,
The alkali-resistant adhesive layer is an adhesive resin composition comprising an alkene- (meth) acrylic ester-unsaturated carboxylic acid terpolymer,
Or one or more selected from alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymers and polyolefin resins, polyamide resins, polyester resins, polyvinyl chloride, and polyvinylidene chloride. An adhesive resin composition comprising a modifying resin;
The unsaturated carboxylic acid component amount in the adhesive resin composition is 0.05% by mass or more and less than 1.0% by mass, the (meth) acrylic acid ester component amount is 5 to 40% by mass,
The MFR of the adhesive resin composition is 3 to 100 g / 10 min at 190 ° C.
Packaging material for pH 10-14 alkaline solution.   The packaging material for alkaline solutions according to claim 1, further comprising an intermediate layer between the base material layer and the barrier layer. A reinforcing layer is further provided at an arbitrary position between the barrier layer and the heat-sealable resin layer,
A plurality of adhesive layers located between the barrier layer and the heat-sealable resin layer are all from an adhesive resin composition containing an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer. The packaging material for alkaline solutions according to claim 1 or 2, which is an alkali-resistant adhesive layer. A packaging container for an alkaline solution, wherein the packaging material for an alkaline solution according to any one of claims 1 to 3 is overlapped so that the heat-sealable resin layers face each other and the ends thereof are heat-sealed. The alkaline solution according to claim 4 , wherein an interlayer adhesive strength between the barrier layer and the heat-sealable resin layer after being filled with an alkaline solution of pH 11 and stored at 60 ° C for 30 days is 5 N / 15 mm width or more. Packaging container. The packaging container for alkaline solutions according to claim 4 or 5 , which is a refillable pouch. A package formed by filling the packaging container according to any one of claims 4 to 6 with an alkaline solution. The package according to claim 7 , wherein the alkaline solution is a chlorine bleach. It is a manufacturing method of the packaging material for alkaline solutions of any one of Claims 1-3 , Comprising: A barrier layer and a heat-sealable resin layer, or a barrier layer, a reinforcement layer, a reinforcement layer, and heat-sealability The said manufacturing method of laminating | stacking a resin layer by the sandwich lamination method through the adhesive resin composition of Claim 1 .

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