JP5549064B2 - Laminated body - Google Patents

Description

  The present invention provides a laminate in which at least one adhesive layer and a sealant layer are provided in this order on a vapor deposition thin film layer of a laminate substrate in which a vapor deposition thin film layer made of an inorganic oxide is provided on at least one surface of a plastic substrate. In particular, the laminate strength between the vapor-deposited thin film layer and the sealant layer on the plastic substrate is lowered even when various strong penetrating contents having excellent laminate strength and containing volatile substances act. Further, the present invention relates to a laminate having a high gas barrier property.

  Conventionally, as a packaging material for packaging foods, pharmaceuticals, and the like, for example, laminates having a layer configuration of paper layer / polyethylene layer / aluminum foil layer / polyester layer / sealant layer have been widely used. The lamination of the polyester layer and the sealant layer of such a laminate is usually performed by applying a two-component curable polyurethane anchor coat agent on the polyester film and then extruding the sealant layer. . Such a laminate has an appropriate laminate strength and gas barrier property, and is widely used as a packaging material for packaging foods and pharmaceuticals.

  However, when a laminate having the above-described configuration is used as a packaging material and a volatile substance such as an acidic substance, an alkaline substance, a fragrance, a surfactant, or an organic solvent is packaged, the anchor is anchored by the strong osmotic force of the volatile substance. The coating agent was adversely affected, and the laminate strength between the plastic substrate and the sealant layer decreased with time, resulting in delamination.

  Such delamination is a two-component curable polyurethane in which an anchor coat agent used in the lamination process in the production process of a laminate having the above-described structure, for example, a main component such as polyester polyol and a curing agent composed of an isocyanate compound is blended. When the strongly penetrating contents as described above adversely affect the adhesive layer composed of the anchor coating agent of the system, the main component resin component of the adhesive layer is swollen or the molecular weight is lowered, and the cohesive force of the adhesive layer is reduced. It is thought to happen.

  Under such circumstances, in a laminate in which at least a sealant layer is provided on a plastic substrate via an adhesive layer, even if various strongly permeable contents containing a volatile substance act, There is a strong demand for the development of a laminate that can be suitably used for packaging materials, in which the laminate strength between the material and the sealant layer does not decrease.

  Various studies have been made on adhesives used in the laminating process during the manufacturing process of the laminate having the above-described configuration. For example, in a laminate in which an adhesive layer and a sealant layer are provided in this order on a plastic substrate made of polyester, nylon, polypropylene, etc., the adhesive layer is made of an isocyanate compound, which is superior to a plastic substrate. A laminate has been proposed in which the laminate strength is ensured and the laminate strength between the plastic substrate and the sealant layer does not decrease even when various strongly permeable contents containing volatile substances act (for example, , See Patent Document 1).

However, for example, a sealant layer is formed on the vapor-deposited thin film layer of a laminated substrate in which a vapor-deposited thin film layer made of an inorganic oxide such as aluminum oxide or silicon oxide is provided on a plastic substrate via an adhesive layer made of an isocyanate compound. In the provided laminate, the laminate strength between the vapor-deposited thin film layer and the adhesive layer composed of the isocyanate compound was not sufficient, and it was difficult to obtain a desired initial laminate strength. In addition, the urea bond formed by the reaction of the isocyanate group in this isocyanate compound with water has a very slow formation rate, so heat aging for several days is indispensable after laminating, but heat aging is performed for several days after laminating. However, sufficient laminate strength may not be exhibited.
JP 2005-335374 A

  The present invention has been made in order to solve the above-described conventional problems, and the object of the present invention is to provide a laminated substrate in which a vapor deposition thin film layer made of an inorganic oxide is provided on at least one surface of a plastic substrate. A laminated body in which an adhesive layer and a sealant layer are provided in this order on the vapor-deposited thin film layer of the material, and particularly, various strengths having excellent initial laminate strength and containing volatile substances. Even if the permeable contents act, the laminate strength between the vapor-deposited thin film layer and the sealant layer on the plastic substrate does not decrease, and it exhibits a high gas barrier property, and heating aging for several days after lamination is unnecessary. Another object of the present invention is to provide a laminate in which stable and sufficient laminate strength can be secured by room temperature aging for a short time.

In order to solve the above-mentioned problems, the invention according to claim 1 is characterized in that an adhesion is performed on a vapor deposition thin film layer of a laminated substrate in which a vapor deposition thin film layer made of an inorganic oxide is provided on at least one surface of a plastic substrate. The layer and the sealant layer are provided at least in this order, and the adhesive layer has a thickness of less than 1 μm, and the mixing ratio of the isocyanate compound having a bifunctional or higher functional isocyanic group and the metal alkoxide is 99: 1 to 60:40 ( A laminate comprising a constituent material containing 0.01 to 0.5% by weight of tri-n-propylamine or tri-n-butylamine with respect to 100% by weight of the mixture which is a weight ratio) ,
The laminate is a laminate having an initial laminate strength of 4.6 (N / 15 mm) or more when aged at 25 ° C. for 12 hours .

  The invention according to claim 2 is the laminate according to claim 1, wherein the isocyanate compound is a bifunctional isocyanate monomer, or a derivative of a trifunctional monomer of adduct, burette, or isocyanurate type. It is either of these.

  Furthermore, the invention described in claim 3 is the laminate according to claim 1, characterized in that the metal of the metal alkoxide is any one of silicon, aluminum, titanium, or zirconium.

  Furthermore, the invention according to claim 4 is the laminate according to claim 1, wherein the metal alkoxide is a silane coupling agent.

  The laminate of the present invention has at least a four-layer structure of a plastic substrate, a vapor-deposited thin film layer made of an inorganic oxide, an adhesive layer, and a sealant layer, and the adhesive layer is not affected by the strongly permeable content. In addition, since a very thin and dense layer is formed, the laminate strength is excellent with respect to the deposited thin film layer on the plastic substrate. Therefore, for example, even if it is used as a packaging material for storing various strongly permeable contents containing volatile substances such as acidic substances, alkaline substances, fragrances, surfactants, organic solvents, etc., a deposited thin film on a plastic substrate The laminate strength between the layer and the sealant layer does not decrease, and delamination does not occur. Moreover, since the laminated base material which has a vapor deposition thin film layer is used, it also has high gas barrier property. Furthermore, heat aging for several days after lamination is unnecessary, and stable and sufficient laminate strength can be secured by short-time room temperature aging.

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

  As a plastic base material provided with a vapor-deposited thin film layer made of an inorganic oxide constituting the laminate of the present invention, a polyester film normal type, a copolymer type, an easily adhesive type, a nylon film normal type, an easy type Various types such as an adhesive type, a non-static type of polypropylene film, and a static type can be used.

  Moreover, an aliphatic polyester film and an aliphatic aromatic polyester film can also be used. Furthermore, as a constituent material of the plastic substrate, a polymer mainly composed of lactic acid, for example, a homopolymer composed only of lactic acid, or a monomer other than lactic acid based on lactic acid, for example, oxyacids such as malic acid and glycolic acid, Copolymers obtained by copolymerizing 3-hydroxybutyrate, 3-hydroxyvalerate, caprolactone, dicarboxylic acids such as succinic acid and adipic acid and diols such as ethylene glycol and 1,4-butanediol, or mixtures thereof Can be used. In addition, copolymers of dicarboxylic acids such as succinic acid, adipic acid and terephthalic acid and diols such as ethylene glycol and 1,4-butanediol, such as polyethylene terephthalate-succinate with terephthalic acid, polybutylene adipate -Terephthalate, polytetramethylene adipate-terephthalate, etc. can also be used.

  And, it is more preferable that such a plastic substrate is subjected to surface treatment such as corona treatment or plasma treatment on one surface, and a vapor deposition thin film layer can be stably formed thereon. . Further, the thickness is not particularly limited.

  The vapor deposition thin film layer made of an inorganic oxide provided on such a plastic substrate is made of a vapor deposition thin film such as aluminum oxide, silicon oxide, magnesium oxide, tin oxide or a mixture thereof, and is a gas barrier against oxygen, water vapor, etc. It is a thin film having properties. Among these, a vapor-deposited thin film layer made of any one of aluminum oxide, silicon oxide, and magnesium oxide is preferable because it has excellent oxygen permeability and water vapor permeability, but is not limited to those made of the above-described constituent materials.

  When a vapor-deposited thin film layer made of an inorganic oxide is provided on a plastic substrate, corona treatment, low-pressure plasma treatment, atmospheric pressure plasma treatment, flame treatment, ion treatment are performed as pre-treatments to improve adhesion to the vapor-deposited thin film layer. Surface treatment such as bombardment treatment, and further surface treatment such as chemical treatment and solvent treatment may be performed. Moreover, you may provide the thin film of the primer for vapor deposition which has an inorganic compound on the plastic base material as needed. Furthermore, a gas barrier coating layer having an inorganic compound may be provided on the vapor-deposited thin film layer in order to impart a high level of gas barrier properties comparable to that of a metal foil.

  In particular, for packaging applications of strong penetrating contents containing volatile substances with very high volatility, in order to improve the adhesion between the plastic substrate and the deposited thin film layer, It is preferable to use a laminated base material provided with a thin film of a deposition primer having an inorganic compound.

Adhesive layer laminated on the vapor deposition thin film layer, such as this has a thickness thinner than 1 [mu] m, the mixing ratio of the isocyanate compound and the metal alkoxide having two or more functional isocyanate groups 99: 1 to 60: 40 (weight The composition material is composed of 0.01 to 0.5% by weight of tri-n-propylamine or tri-n-butylamine with respect to 100% by weight of the mixture.

  Examples of the isocyanate compound constituting a part of such an adhesive layer include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-. Examples thereof include various diisocyanate monomers such as diphenylmethane diisocyanate and hydrogenated products thereof. In addition, adduct types obtained by reacting these diisocyanate monomers with trifunctional active hydrogen-containing compounds such as trimethylolpropane and glycerol, burette types obtained by reacting with water, and trimers utilizing self-polymerization of isocyanate groups ( A trifunctional derivative such as an isocyanurate type or a polyfunctional derivative higher than that may be used.

  Further, as the metal alkoxide, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, aluminum triisopropoxide, aluminum triethoxide, aluminum tri-n-butoxide, aluminum trimethoxide, titanium tetraisopropoxy , Titanium tetraethoxide, titanium tetra-n-butoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide and the like. Thus, there are various types of metal alkoxides, but silicon alkoxides are preferably used in consideration of handling properties, cost and the like. However, the present invention is not limited to this, and a silane coupling agent containing an isocyanate group, an epoxy group, an amino group, or the like may be appropriately selected and used. Examples of the metal of the metal alkoxide include silicon, aluminum, titanium, and zirconium.

  Tri-n-propylamine and tri-n-butylamine constituting the constituent material having the above-described composition are both tertiary amines, and when an isocyanate group in the isocyanate compound reacts with water to form a urea bond. This is a catalyst that promotes the formation of urea bonds in the adhesive layer and eliminates the need for heat aging for several days after laminating in the production of the laminate in the present invention. Works to ensure strength.

  Generally, a tin compound, a tertiary amine, or the like is used as a catalyst used for promoting the formation of a urea bond. Other tertiary amines include trimethylamine, triethylamine, N, N, N ′, N ′,-tetramethyl-1,3-butanediamine, 1,4-diazabicyclo [2,2,2] octane (tri Ethylenediamine) and the like are used. In the present invention, as described above, tri-n-propylamine and tri-n-butylamine are selected from among a number of catalysts used for promoting the formation of urea bonds, and have a bifunctional or higher functional isocyanic group. The mixing ratio of the isocyanate compound and the metal alkoxide is 0.01 to 0.5% by weight with respect to 100% by weight of the mixture of 99: 1 to 60:40 (weight ratio).

  An amount exceeding 0.5% by weight is not suitable because it is an amount sufficient to promote the formation of urea bonds, and an odor problem due to the amine odor of the resulting laminate may occur. About 0.01 to 0.1% by weight is more preferable.

Both tri-n-propylamine and tri-n-butylamine dissolve quickly and uniformly in ethyl acetate, which is widely used as a diluting solvent for adhesives used to form an adhesive layer, are inexpensive, and have a boiling point. As mentioned above, the mixing ratio of the isocyanate compound having a bifunctional or higher isocyanic group and the metal alkoxide is 99%, because the catalyst concentration in the adhesive is constant and the concentration of the catalyst is not lowered. : Volatilization of acidic substances, alkaline substances, fragrances, surfactants, organic solvents, etc. by including 0.01 to 0.5% by weight with respect to 100% by weight of the mixture of 1 to 60:40 (weight ratio) Even if various strongly permeable contents containing an active substance act on the laminate of the present invention, the cohesive force of the adhesive layer is not reduced, and the deposited thin film layer and the adhesive layer on the plastic substrate are not affected. Preliminary adhesive layer and without reducing the lamination strength of the sealant layers, both can be secured sufficient initial lamination strength and strong osmotic content resistance.

  The mixing ratio of the isocyanate compound and the metal alkoxide constituting the adhesive layer is such that when only the isocyanate compound is used, the laminate strength between the deposited thin film layer and the adhesive layer on the plastic substrate is weak and sufficient initial strength cannot be obtained. On the other hand, when only the metal alkoxide is used, the laminate strength between the adhesive layer and the sealant layer is weak and sufficient initial laminate strength cannot be obtained. Therefore, an isocyanate compound-rich adhesive layer should be formed in order to ensure strong adhesion to both the deposited thin film layer and the sealant layer on the plastic substrate, that is, an isocyanate compound and a metal alkoxide. The mixing ratio (weight ratio) to 99: 1 to 60:40, more preferably 99: 1 to 70:30, still more preferably 99: 1 to 80:20, and tri- By including n-propylamine or tri-n-butylamine, a sufficient initial laminate strength can be secured in both the vapor-deposited thin film layer and the adhesive layer on the plastic substrate, and between the adhesive layer and the sealant layer, and a volatile material. It can be set as the contact bonding layer which is not influenced by the various strongly permeable contents containing.

  In an adhesive layer made of a constituent material having such a composition, since an appropriate amount of metal alkoxide is added to the isocyanate compound, the affinity between the deposited thin film layer on the plastic substrate and the adhesive layer becomes better. Thus, a strong adhesive force can be obtained, and at the same time, the adhesive layer can be firmly adhered to the sealant layer. And it is provided between the vapor deposition thin film layer and the sealant layer, and the crosslinking reaction proceeds three-dimensionally until a reactive functional group disappears in the adhesive layer, thereby forming a network. At this time, since tri-n-propylamine or tri-n-butylamine is added, the network formation speed is increased, heating aging for several days after lamination is not required, and short-term room temperature aging is performed. Thus, a more stable and sufficient laminate strength can be obtained.

  For example, tri-n-propylamine or tri-n-butylamine is mixed with the above-described mixture of the isocyanate compound and the metal alkoxide on the above-described deposited thin film layer on the plastic substrate. It may be provided by coating with a coating solution diluted with ethyl acetate and having a solid content ratio of 0.05 to 5% by weight, preferably 0.1 to 2% by weight. Further, it is preferable that the thickness of the adhesive layer is thin. Specifically, the adhesive layer may be provided so that the thickness when dried is less than 1 μm. When the thickness is 1 μm or more, it takes time to dry the solvent, and the cross-linking reaction of the adhesive layer also takes time.

  On the other hand, the sealant layer laminated on the adhesive layer is a layer made of polyethylene resin or polypropylene resin. More specific constituent materials include high-density polyethylene, low-density polyethylene, medium-density polyethylene, ethylene-α-olefin copolymer and other ethylene resins, homo-block / random polypropylene resins, and propylene-α-olefins. Propylene-based resins such as copolymers, ethylene-α, β unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers, ethylene-methyl acrylate and ethylene-ethyl acrylate Ethylene-α, β-unsaturated, esterified product of ethylene-α, β-unsaturated carboxylic acid copolymer such as ethylene-methyl methacrylate or ethylene-ethyl methacrylate, carboxylic acid moiety crosslinked with sodium ion, zinc ion Ionic cross-linked product of carboxylic acid copolymer, ethylene-maleic anhydride Epoxy compound-modified polyolefins such as acid anhydride-modified polyolefins, ethylene-glycidyl methacrylate copolymers represented by terpolymers such as raft copolymers and ethylene-9 ethyl acrylate-maleic anhydride, ethylene-acetic acid Examples thereof include a single resin or a blend of two or more resins selected from vinyl copolymers.

  Also, aliphatic polyesters and aliphatic aromatic polyesters can be used. More specifically, a copolymer of a dicarboxylic acid such as succinic acid or adipic acid and a diol such as ethylene glycol or 1,4-butanediol (for example, polyethylene succinate, polybutylene succinate, polybutylene succinate). Nate-adipate), microbially produced polyhydroxybutyrate, polyhydroxybutyrate-valerate, polyhydroxybutyrate-hexanoate, polymers of oxyacids such as lactic acid, malic acid, glycolic acid or copolymers thereof, poly Caprolactone, polycaprolactone-butylene succinate, aliphatic polyester such as polyester having amide bond, polyester having carbonate bond, polyethylene terephthalate-succinate having terephthalic acid, polybutylene acrylate Pies - terephthalate, polytetramethylene adipate - terephthalate and alone or two or more of the blend of resin selected from the aliphatic-aromatic polyesters, and the like. To these constituent materials, various additives (such as an antioxidant, a tackifier, a filler, and various fillers) may be added as necessary.

  In the laminate of the present invention, when both the plastic substrate and the sealant layer on which the vapor-deposited thin film layer is formed are made of aliphatic polyester or aliphatic aromatic polyester, not only high gas barrier property and strong permeable content resistance but also biodegradation It will also have sexual function. At this time, the adhesive layer existing between the plastic substrate and the sealant layer provided with the vapor deposition thin film layer is not biodegradable. However, since the thickness of the adhesive layer is thinner than 1 μm, the biodegradation of the laminate is performed. Does not interfere with sex.

  The laminated body according to the present invention has been described above, but the laminated body of the present invention is not limited to the structure as described above, and the rigidity required as a packaging material in consideration of the use as a packaging material. For the purpose of improving the durability and the like, another layer may be interposed.

  A laminated body having such a configuration can be produced, for example, as follows. That is, on the vapor-deposited thin film layer on the plastic substrate, the mixture ratio of the isocyanate compound having a bifunctional or higher isocyanic group and the metal alkoxide is 99% to 60:40 (weight ratio). On the other hand, tri-n-propylamine or tri-n-butylamine is mixed in an amount of 0.01 to 0.5% and diluted with ethyl acetate to give a solid content of 0.05 to 5% by weight, preferably 0.8. A thin film is coated with a coating liquid of 1 to 2% by weight in a coating portion of an extrusion laminate so that the thickness is thinner than 1 μm, an adhesive layer is provided, dried in an oven, and then extruded from a T die. By laminating a sealant layer made of polyethylene or the like, a laminate having a laminated structure of plastic substrate / deposited thin film layer / adhesive layer / sealant layer can be obtained.

  According to the manufacturing method as described above, various strongly permeable contents including a good initial laminate strength between a vapor-deposited thin film layer and an adhesive layer on a plastic substrate, and an adhesive layer and a sealant layer, and containing a volatile substance. Even if an object acts, the laminate strength between the deposited thin film layer and the adhesive layer on the plastic substrate and between the adhesive layer and the sealant layer does not decrease, and it has a high gas barrier property, and the material is selected as described above. By doing so, a laminate having biodegradability can be produced. Furthermore, heating aging for several days after lamination is unnecessary, and it becomes possible to obtain a laminate having a sufficient and sufficient laminate strength by short-term room temperature aging.

  Examples of the present invention will be described below.

First, a laminated substrate in which a corona treatment was applied to one surface of a polyethylene terephthalate film having a thickness of 12 μm and an aluminum oxide vapor-deposited thin film layer was provided on the treated surface was prepared. Next, 0.01 weight of tri-n-propylamine is used with respect to 100 weight% of the mixture in which the mixing ratio of isophorone diisocyanate monomer and tetraethoxysilane is 95: 5 (weight ratio) using ethyl acetate as a diluent solvent. %, And a coating solution having a solid content ratio of 2% by weight was prepared. And using this coating liquid, after apply | coating a thin film on the vapor deposition thin film layer of an above-described lamination | stacking base material, after drying in oven, the low-density polyethylene layer whose thickness is 40 micrometers is 320 degreeC under die | dye temperature, Extrusion was carried out at a processing speed of 80 m / min by an extrusion laminating method, a sealant layer was laminated on the adhesive layer, and further subjected to aging at 25 ° C. for 12 hours to obtain a laminate according to Example 1. The thickness of the adhesive layer after drying was 0.24 μm.

  A nylon film having a thickness of 15 μm is used as the plastic substrate, and the mixing ratio of the adduct type of tolylene diisocyanate and aluminum triisopropoxide is 90:10 (weight ratio) as the coating liquid for forming the adhesive layer. A laminate according to Example 2 was obtained in the same manner as in Example 1 except that a coating liquid in which 0.3% by weight of tri-n-propylamine was added to 100% by weight of the mixture was used. The thickness of the adhesive layer after drying was 0.26 μm.

  Using a laminated base material with a corona treatment on one side of a polyethylene terephthalate film with a thickness of 12 μm and forming a vapor-deposited thin film layer made of silicon oxide on the treated surface, an adduct type of isophorone diisocyanate is used as the coating liquid. And 0.5% by weight of tri-n-propylamine to 100% by weight of a mixture in which the mixing ratio of titanium tetraethoxide is 85:15 (weight ratio). A laminate according to Example 3 was obtained in the same manner as in Example 1 except that an ethylene-methacrylic acid copolymer was used as a constituent material. The thickness of the adhesive layer after drying was 0.25 μm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 280 ° C.

  Using a laminated base material with a corona treatment on one side of a nylon film with a thickness of 15 μm and a vapor-deposited thin film layer made of silicon oxide formed on that side, the adduct type of xylylene diisocyanate and zirconium A material in which 0.01% by weight of tri-n-butylamine is added to 100% by weight of a mixture in which the mixing ratio with tetraisopropoxide is 80:20 (weight ratio) is used. A laminate according to Example 4 was obtained in the same manner as in Example 1 except that zinc ionomer was used. The thickness of the adhesive layer after drying was 0.24 μm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 300 ° C.

Using a plastic substrate that has been subjected to corona treatment on one surface of a polyethylene terephthalate film having a thickness of 12 μm, and applying and drying a primer solution thin film prepared as follows on the corona treatment surface, A vapor-deposited thin film layer made of aluminum oxide is formed, a thin film of a gas barrier coating agent prepared as described below is further applied thereon, dried, and a laminated base material provided with a gas barrier film layer is used for coating. As a working solution, 0.3 wt. Of tri-n-butylamine is added to 100 wt.% Of the mixture in which the mixing ratio of the hexamethylene diisocyanate burette type and the isocyanate silane coupling agent is 70:30 (weight ratio). %, And random polypropylene is used as the material for the sealant layer. Except in the same manner as in Example 1 to obtain a laminated body according to Example 5. The thickness of the adhesive layer after drying was 0.22 μm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 275 ° C.
[Preparation of primer solution]
It mixed so that the isocyanate group of the following B liquid might become equivalent with respect to the hydroxyl group of the acrylic polyol of the following A liquid, and diluted so that the solid content ratio of this mixed solution might be 2 weight%.
<Liquid A>
A mixed solution in which 1% by weight of γ-isocyanatopropyltrimethylsilane and 10% by weight of acrylic polyol are mixed in a diluting solvent (ethyl acetate).
<Liquid B>
7: 3 (weight ratio) mixture of XDI and IPDI which are isocyanate compounds.
[Preparation of gas barrier coating agent]
The following C liquid and the following D liquid were mixed at 60:40 (weight ratio).
<C liquid>
A hydrolyzed solution in which 89.6 g of 0.1N hydrochloric acid was added to 10.4 g of tetraethoxysilane, and the mixture was stirred for 30 minutes for hydrolysis to give a solid content of 3% by weight (in terms of SiO ₂ ).
<D liquid>
Polyvinyl alcohol 3 wt% water / isopropyl alcohol solution (water: isopropyl alcohol = 90: 10, weight ratio).

  A laminated base material having the same structure as in Example 5 except that a polylactic acid film was used as the plastic base material and the vapor-deposited thin film layer on one side thereof was a vapor-deposited thin film layer made of silicon oxide. Added 0.5% by weight of tri-n-butylamine to 100% by weight of a mixture in which the mixing ratio of the isocyanurate type of hexamethylene diisocyanate and the epoxy silane coupling agent was 60:40 (weight ratio). The laminate according to Example 6 was obtained in the same manner as in Example 1 except that polybutylene succinate was used as the sealant layer. The thickness of the adhesive layer after drying was 0.25 μm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 280 ° C.

  Example for comparison in the same manner as in Example 1 except that a mixture of adduct type of tolylene diisocyanate and tetraethoxysilane in a mixing ratio of 30:70 (weight ratio) was used as the coating liquid. A laminate according to 7 was obtained. The thickness of the adhesive layer after drying was 0.27 μm.

  Using a laminated base material with a corona treatment on one side of a nylon film with a thickness of 15 μm and an aluminum oxide vapor-deposited thin film layer provided on that side, the adduct type of isophorone diisocyanate and aluminum triisopropoxy are used as the coating liquid. A mixture with a mixing ratio of 20:80 (weight ratio) with a silica was used, an ethylene-methacrylic acid copolymer was used as a constituent material of the sealant layer, and aging was at 50 ° C. for 5 days. In the same manner as in Example 1, a laminate according to Example 8 for comparison was obtained. The thickness of the adhesive layer after drying was 0.26 μm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 280 ° C.

  A laminated base material with a corona treatment on one side of a polyethylene terephthalate film with a thickness of 12 μm and a silicon oxide vapor-deposited thin film layer formed on that side is used. The coating liquid is solid with an adduct type of tolylene diisocyanate. A laminate according to Example 9 for comparison was obtained in the same manner as in Example 1 except that a component having a fraction of 2% by weight was used and random polypropylene was used as a constituent material of the sealant layer. The thickness of the adhesive layer after drying was 0.23 μm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 275 ° C.

  As a coating solution, the same method as in Example 1 was used except that a coating solution in which the adduct type of tolylene diisocyanate and tetraethoxysilane was 70:30 (weight ratio) was used for comparison. A laminate according to Example 10 was obtained. The thickness of the adhesive layer after drying was 0.25 μm.

  A pouch was prepared using each of the laminates of Examples 1 to 6 and 8 obtained by the manufacturing method as described above, in which the initial laminate strength was sufficiently ensured, and a poultice (volatile) as the contents. Filled with a salicylate or menthol as a strong osmotic substance and a bath agent (containing a fragrance component as a volatile strong osmotic substance), sealed, and left in a constant temperature room at 40 ° C.

  After 3 months, these pouches were taken out from the temperature-controlled room, and the laminate strength [N / 15 mm] between each base material and the sealant layer of each pouch was measured and compared with the initial laminate strength in the pouch before entering the temperature-controlled room. . The measurement conditions of the laminate strength at this time were T-type peeling with a sample width of 15 mm and a peeling speed of 300 mm / min. Table 1 summarizes the measurement results of the laminate strength before and after the constant temperature input.

表１からも明らかなように、実施例１〜６に係る積層体の各積層基材とシーラント層間における初期のラミネート強度は、シーラント切れを示すほど強固であった。また、揮発性物質を含む湿布薬や浴用剤を入れて４０℃で３ヶ月間保存したパウチにおいてもラミネート強度に変化はなく、初期のラミネート強度を十分に保っていた。

As is clear from Table 1, the initial laminate strength between each laminate substrate and the sealant layer of the laminates according to Examples 1 to 6 was so strong that the sealant was cut. Further, even in the pouch stored with a poultice containing a volatile substance and a bath agent and stored at 40 ° C. for 3 months, the laminate strength did not change, and the initial laminate strength was sufficiently maintained.

  In contrast, the initial laminate strength between the laminate base material and the sealant layer of the laminates according to Examples 7, 9, and 10 was not sufficiently obtained.

  In addition, the initial laminate strength between the laminate base material and the sealant layer of the laminate according to Example 8 was strong enough to show a sealant breakage by performing sufficient heat aging at 50 ° C. for 5 days. In a pouch that has been stored for 3 months at 40 ° C with a poultice or bathing agent containing volatile substances, the laminate strength is significantly reduced, and the packaging material for the contents containing volatile substances such as poultices and bathing agents It turned out to be unsuitable for use.

Claims (4)

At least one adhesive layer and a sealant layer are provided in this order on the vapor-deposited thin film layer of the laminated base material provided with the vapor-deposited thin film layer made of an inorganic oxide on at least one side of the plastic substrate, and the thickness of the adhesive layer is Tri-n-propylamine with respect to 100% by weight of a mixture in which the mixing ratio of the isocyanate compound having a bifunctional or higher functional isocyanic group and the metal alkoxide is less than 1 μm and 99: 1 to 60:40 (weight ratio), Or a laminate comprising a constituent material containing 0.01 to 0.5% by weight of tri-n-butylamine ,
The laminate has an initial laminate strength of 4.6 (N / 15 mm) or more when subjected to aging at 25 ° C. for 12 hours .   The laminate according to claim 1, wherein the isocyanate compound is any one of a bifunctional isocyanate monomer or a derivative of a trifunctional monomer of adduct, burette, or isocyanurate type.   The laminate according to claim 1, wherein the metal of the metal alkoxide is any one of silicon, aluminum, titanium, or zirconium.   The laminate according to claim 1, wherein the metal alkoxide is a silane coupling agent.