JP2015229296A - Laminate and pouch - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of maintaining excellent laminate strength of each interlayer even used as a packaging material and volatile components such as drug effect components or perfume components or various volatile components containing volatile components have effects.SOLUTION: There is provided a laminate containing a laminate constitution containing of at least a polyester film (5)/a first adhesive layer (6)/a second adhesive layer (7)/a sealant layer (8), the first adhesive layer consists of an amine-containing polymer, the second adhesive layer consists of a diisocyanate monomer or a derivative of an adduct type-, a biuret type- or a trimer (isocyanate type)- diisocyanate and MOR value measured by a microwave transmission molecular orientation meter of the polyester film is 1.00 to 1.25.

Description

  The present invention relates to laminates and pouches, and particularly has strong penetrability in that the laminate strength does not decrease even when various strong penetrating contents including volatile components such as medicinal components and fragrance components act. It can be suitably used for the contents.

  Conventionally, as a packaging material for packaging foods and pharmaceuticals having an aluminum foil layer, for example, if the packaging form is a pouch, polyester layer / adhesive layer / aluminum foil layer / adhesive layer / polyester layer / adhesive layer / sealant A laminate in which layers such as layers are laminated has been widely used. As a method of laminating the laminate, a two-component curable polyurethane adhesive is usually used, and the adhesive layer is formed by dry lamination. And such a laminated body has moderate lamination strength, gas barrier property, etc., and is widely used as a packaging material for packaging foods and pharmaceuticals.

  However, many contents packed with packaging materials contain alkaline substances, fragrances, surfactants, high-boiling organic solvents, etc. When these strong penetrating contents are packaged, the adhesive layer adheres. The agent may be adversely affected, leading to a decrease in laminate strength in the laminate or peeling.

  In order to cope with this situation, various improvements have been made to the adhesive used for laminating, improving the resistance to highly alkaline contents, and further improving the adhesion to various plastic films. Various adhesives have been proposed (see, for example, Patent Document 1).

  However, when the contents to be packaged are a poultice or a bath preparation, since these contain volatile components, a laminate having the above-described configuration or a laminate obtained using the above adhesive is used. When used as a packaging material and packaging these contents, the strong penetration of volatile components causes the laminate strength between the polyester and sealant layers to decline over time, resulting in delamination. There was a problem.

  In order to cope with such a situation, a first adhesive layer composed of an amine-containing polymer and a diisocyanate monomer, or an adduct type, a burette type, or a trimer (isocyanurate) type of a diisocyanate monomer are formed on a polyester film substrate. There has been proposed a laminate in which an adhesive layer having a two-layer structure with a second adhesive layer made of any one of derivatives is provided, and a sealant layer is further provided on the second adhesive layer constituting the adhesive layer (for example, Patent Document 2). reference).

  However, when the contents such as poultices and bathing agents were packaged using the laminate, the laminate strength between the polyester layer and the sealant layer was not decreased over time. Depending on the type of film used, the polyester film may peel off, resulting in a significant decrease in laminate strength.

JP-A-10-130615 Japanese Patent No. 4306278

  This invention is made | formed in order to solve the said conventional problem, The place made into the subject is used as a packaging material, and includes volatile components and volatile components, such as a medicinal component and a fragrance | flavor component. An object of the present invention is to provide a laminate that can maintain excellent laminate strength between layers even when various strongly permeable contents act.

  The invention according to claim 1, which has been made to solve the above-mentioned problems, includes at least a laminated structure composed of a polyester film / first adhesive layer / second adhesive layer / sealant layer, and the first adhesive layer is an amine. Containing polymer, 2nd adhesive layer is either diisocyanate monomer, or adduct type, burette type, or trimer (isocyanurate) type derivative of diisocyanate monomer, measured with microwave transmission molecular orientation meter of polyester film The MOR value is 1.00 to 1.25.

  The invention according to claim 2 includes at least a laminated structure comprising an aluminum foil layer / adhesive layer / polyester film / first adhesive layer / second adhesive layer / sealant layer, wherein the first adhesive layer is an amine-containing polymer. The second adhesive layer is composed of either a diisocyanate monomer or an adduct type, burette type, or trimer (isocyanurate) type derivative of a diisocyanate monomer, and measured by a microwave transmission type molecular orientation meter of a polyester film. A laminate having a value of 1.00 to 1.25.

  The invention according to claim 2 is a pouch characterized in that the sealant layers are heat sealed using the laminate of claim 1 or 2.

  The laminate of the invention according to claim 1 includes at least a laminated structure composed of polyester film / first adhesive layer / second adhesive layer / sealant layer, wherein the first adhesive layer is an amine-containing polymer, and the second adhesive layer is It consists of either a diisocyanate monomer, or an adduct type, burette type, or trimer (isocyanurate) type derivative of a diisocyanate monomer, and has a MOR value measured by a microwave transmission molecular orientation meter of a polyester film of 1.00 to 1.00. Since it is 1.25, each layer was excellent even when various strong penetrating contents including volatile components such as medicinal components and fragrance components and volatile components acted using this laminate as a packaging material. The laminate strength can be maintained.

  The laminate of the invention according to claim 2 includes at least a laminated structure composed of an aluminum foil layer / adhesive layer / polyester film / first adhesive layer / second adhesive layer / sealant layer, and the first adhesive layer contains an amine. The polymer and the second adhesive layer consisted of either a diisocyanate monomer or an adduct type, burette type, or trimer (isocyanurate) type derivative of a diisocyanate monomer, and measured with a microwave transmission type molecular orientation meter of a polyester film. Since the MOR value is 1.00 to 1.25, this laminate is used as a packaging material, and various strongly permeable contents including volatile components such as medicinal components and fragrance components and volatile components act. However, each layer can maintain excellent laminate strength, and the aluminum foil layer provides barrier and light shielding properties. An effect that is.

Since the pouch of the invention according to claim 3 uses the laminate of claim 1 or 2, various strongly permeable contents including volatile components such as medicinal components and fragrance components and volatile components act on it. In addition, each layer can maintain an excellent laminate strength. Further, when the laminate of claim 2 is used, it has an effect of being excellent in barrier properties and light shielding properties.

Sectional drawing which shows an example of the laminated structure of embodiment which concerns on this invention. Sectional drawing which shows another example of the laminated structure of embodiment which concerns on this invention.

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

  The embodiment according to the present invention is a laminate including at least a laminated structure composed of an aluminum foil layer / adhesive layer / polyester film / first adhesive layer / second adhesive layer / sealant layer. That is, as shown in FIG. 1, the laminate of the embodiment of the present invention includes at least an aluminum foil layer (3), an adhesive layer (4), a polyester film (5), a first adhesive layer (6), and a second layer. It is a laminated body including what laminated | stacked the contact bonding layer (7) and the sealant layer (8) in this order.

  As for the purity of the aluminum foil layer constituting the laminate of the embodiment according to the present invention, any purity can be used regardless of the numerical value, but the thickness is preferably 7 to 9 μm.

  Any adhesive layer between the aluminum foil layer and the polyester film constituting the laminate of the embodiment according to the present invention can be used regardless of the type, but a two-component curable urethane adhesive is suitable. Can be used for

  The polyester film constituting the laminate of the embodiment according to the present invention is specifically a biaxially stretched polyethylene terephthalate film, and a thickness of 7 to 16 μm can be suitably used.

  The adhesive layer between the polyester film and the sealant layer constituting the laminate of the embodiment according to the present invention has a two-layer configuration of the first adhesive layer and the second adhesive layer from the polyester film side, The first adhesive layer is made of an amine-containing polymer, and the second adhesive layer is made of an isocyanate compound.

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

  On the other hand, examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and hydrogenated products thereof. Various diisocyanate monomers can be used. 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.

  These first adhesive layer and second adhesive layer are composed of the above-mentioned amine-containing polymer, diisocyanate monomer, or adduct type, burette type, or trimer (isocyanurate) type derivative of diisocyanate monomer in a solid content ratio. Is applied with a coating solution containing 0.05 to 5 wt%, preferably 0.1 to 2 wt%, and the thickness when dried is about 0.1 μm to 2 μm. .

  About the sealant layer which comprises the laminated body of embodiment which concerns on this invention, a polyethylene-type resin or a polypropylene-type resin can use it conveniently. Specifically, ethylene resins such as high density polyethylene, low density polyethylene, medium density polyethylene, ethylene-α olefin copolymer, homo-block / random polypropylene resins, propylene-α olefin copolymer, etc. Propylene resin, ethylene-α, β unsaturated carboxylic acid copolymer such as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer, ethylene-methyl acrylate, ethylene-ethyl acrylate, ethylene-methacrylic Ethylene-α, β-unsaturated carboxylic acid copolymers such as methyl methacrylate and ethylene-ethyl methacrylate, ethylene-α, β-unsaturated carboxylic acid copolymer with carboxylic acid moiety cross-linked with sodium ion and zinc ion Ionic cross-linked products of polymers, ethylene-maleic anhydride graft copolymers and polymers Selected from acid anhydride-modified polyolefins typified by terpolymers such as tylene-ethyl acrylate-maleic anhydride, epoxy compound-modified polyolefins such as ethylene-glycidyl methacrylate copolymers, and ethylene-vinyl acetate copolymers It is provided by a single resin or a blend of two or more. Various additives (such as an antioxidant, a tackifier, a filler, and various fillers) may be added to these constituent materials as necessary.

  The MOR value obtained by the measurement with a microwave transmission type molecular orientation meter of the polyester film constituting the laminate of the embodiment according to the present invention is a numerical value indicating the anisotropy of the molecular orientation. In order to obtain a laminate in which the laminate strength does not decrease even when various strongly penetrating contents containing volatile components such as volatile components act, a polyester film having an MOR value of 1.00 to 1.25 is used. It can be used suitably. In the polyester film with MOR value exceeding 1.25, since the anisotropy of molecular orientation is too large, various strongly permeable contents including volatile components such as medicinal components and fragrance components and volatile components are acting. It is considered that a larger internal stress is generated inside, and the surface peeling of the polyester film is likely to occur, and as a result, a significant decrease in laminate strength is observed.

  As mentioned above, although the laminated body of embodiment which concerns on this invention was demonstrated, the laminated body of embodiment which concerns on this invention is not limited to the thing of the above structures, In consideration of the use as a packaging material, For the purpose of improving the rigidity and durability required as a packaging material, a configuration in which another layer is interposed may be used. In particular, the laminated body of the embodiment according to the present invention can be used in the following configuration example as an example with another layer interposed in the outer layer.

[Configuration example]
Outermost layer / adhesive layer / aluminum foil layer / adhesive layer / polyester film / first adhesive layer / second adhesive layer / sealant layer

  That is, as shown in FIG. 2, the laminated body of the embodiment according to the present invention having this configuration example includes an outermost layer (1), an adhesive layer (2), an aluminum foil layer (3), an adhesive layer (4), and a polyester. A film (5), a first adhesive layer (6), a second adhesive layer (7), and a sealant layer (8) are laminated in this order.

  For the outermost layer of this configuration example, a polymer film such as a stretched polyester film, a stretched nylon film, or a stretched polypropylene film can be selected.

Next, an example of the manufacturing method of the laminated body of the said structural example is described.
First, the polyester film (PET), aluminum foil layer, and PET, which are the outermost layers, are each laminated with a dry laminator using a two-component curable urethane adhesive, and PET / adhesive layer / aluminum foil layer / adhesive layer A laminate having a laminated structure of / PET is obtained. Thereafter, a gravure coating, a roll containing a coating liquid containing 0.05 to 5 wt%, preferably 0.1 to 2 wt% of an amine-containing polymer as a solid content ratio on the inner PET using this laminate. Coating is performed by a coating method such as coating, and the first adhesive layer is provided by sufficiently drying. Next, on the first adhesive layer, either a diisocyanate monomer or a diisocyanate monomer adduct type, burette type, or trimer (isocyanurate) type derivative is used in a solid content of 0.05 to 5 wt%. For example, a coating liquid containing 0.1 to 2 wt% is preferably applied at the anchor coating agent coating portion of the extrusion laminator to provide a second adhesive layer, dried in an oven, and then extruded from a T die. A laminate having a laminated structure of PET / adhesive layer / aluminum foil layer / adhesive layer / PET / first adhesive layer / second adhesive layer / sealant layer can be obtained by laminating a sealant layer made of polyethylene or the like. In addition, in order to obtain a laminate having better heat seal strength, linear low density polyethylene (LLDPE), which is the innermost layer from the sand shaft after drying in an oven after providing the second adhesive layer as described above. While extruding the film, an extruded resin made of, for example, polyethylene extruded from a T-die can be laminated to obtain a laminate in which the sealant layer becomes an extruded resin / LLDPE film.

  In the laminated structure of the above laminated body, the inner PET has a MOR value of 1.00 to 1.25. The PET having the MOR value of 1.00 to 1.25 can be manufactured by making the stretching ratio in the vertical direction and the horizontal direction the same and stretching the film in the vertical and horizontal directions in the PET film manufacturing process. When the draw ratio is biased in either the longitudinal direction or the transverse direction, the MOR value exceeds 1.25.

  According to the production method as described above, a laminate having excellent laminate strength between layers is obtained even when various strongly permeable contents including volatile components such as medicinal components and fragrance components and volatile components act. It became possible.

  Examples of the present invention will be described below.

<Example 1>
The outermost layer 12 μm thick polyester film (PET), 7 μm aluminum foil, and 12 μm polyester film A (PET A) are each laminated with a dry laminator using a two-component curable urethane adhesive, A laminated body having a laminated structure of PET / adhesive layer / aluminum foil layer / adhesive layer / PET A was obtained.
Next, using this laminate, a coating liquid prepared by applying polyethyleneimine having a number average molecular weight of 50,000 to a solid content ratio of 1.0 wt% on the inner PET A was applied by a roll coater. The first adhesive layer was sufficiently dried and having a thickness of 0.5 μm.
Subsequently, an ethylene-methacrylic acid copolymer having a thickness of 50 μm was coated on the first adhesive layer while applying a coating solution prepared by isophorone diisocyanate monomer so that the solid content ratio was 2.0 wt%. Extrusion lamination is carried out by an extrusion laminating method at a processing speed of 50 m / min, and a second adhesive layer and a sealant layer are further provided. PET / adhesive layer / aluminum foil layer / adhesive layer / PET A / first adhesive layer / second adhesive layer / The laminated body which concerns on Example 1 used as the laminated structure of a sealant layer was obtained.
Next, the MOR value of PET A used for this laminate was measured with a microwave transmission type molecular orientation meter (manufactured by Shin-Oji Paper (currently Oji Scientific Instruments) MOA-5012A) and found to be 1.17.

<Example 2>
15 μm nylon film (Ny), polyester film B (PET B) for the outermost layer, primary amine graft acrylic polymer for the first adhesive layer, adduct type of tolylene diisocyanate for the second adhesive layer, and random polypropylene for the sealant layer Except for the above, a laminated body having a laminated structure of Ny / adhesive layer / aluminum foil layer / adhesive layer / PET B was obtained in the same manner as in Example 1, and further Ny / adhesive layer / aluminum foil layer / adhesive layer / PET. A laminated body according to Example 2 having a laminated structure of B / first adhesive layer / second adhesive layer / sealant layer was obtained.
The MOR value measured by the microwave transmission type molecular orientation meter of PET B used for this laminate was 1.25.

<Example 3>
A biaxially oriented polypropylene film (OPP) of 20 μm and polyester film C (PET C) are used for the outermost layer, and a primary amine-grafted acrylic polymer is used for the first adhesive layer. A laminated body having a laminated structure of aluminum foil layer / adhesive layer / PET C / first adhesive layer was obtained.
Next, on this first adhesive layer, a coating liquid prepared from hexamethylene diisocyanate burette type with a solid content ratio of 2.0 wt% was applied on the first adhesive layer, While feeding a 40 μm-thick linear low density polyethylene (LLDPE) film as an innermost layer, a 20 μm-thick low density polyethylene was extruded and laminated from a T die at a processing speed of 50 m / min, and a second adhesive layer and a sealant layer were formed. Further, a laminated body according to Example 3 having a laminated structure of OPP / adhesive layer / aluminum foil layer / adhesive layer / PET C / first adhesive layer / second adhesive layer / sealant layer was obtained.
The MOR value measured by the microwave transmission type molecular orientation meter of PET C used for this laminate was 1.02.

<Comparative Example 1>
A laminated body having a laminated constitution of PET / adhesive layer / aluminum foil layer / adhesive layer / PET D was obtained in the same manner as in Example 1 except that the polyester film D (PET D) was used. The laminated body which concerns on the comparative example 1 which becomes a laminated structure of layer / aluminum foil layer / adhesive layer / PET D / first adhesive layer / second adhesive layer / sealant layer was obtained. The MOR value measured with this PET D microwave transmission type molecular orientation meter was 1.31.

<Comparative Example 2>
A laminated body having a laminated structure of Ny / adhesive layer / aluminum foil layer / adhesive layer / PET E was obtained in the same manner as in Example 2 except that polyester film E (PET E) was used. The laminated body which concerns on the comparative example 2 used as the laminated structure of layer / aluminum foil layer / adhesive layer / PET E / first adhesive layer / second adhesive layer / sealant layer was obtained. The MOR value measured by this microwave transmission molecular orientation meter of PET E was 1.38.

<Comparative Example 3>
A laminated body having a laminated structure of OPP / adhesive layer / aluminum foil layer / adhesive layer / PET F / first adhesive layer was obtained in the same manner as in Example 3 except that polyester film F (PET F) was used, Furthermore, the laminated body which concerns on the comparative example 3 used as the laminated structure of OPP / adhesive layer / aluminum foil layer / adhesive layer / PET F / first adhesive layer / second adhesive layer / sealant layer was obtained. The MOR value measured by the PET F microwave transmission type molecular orientation meter was 1.27.

After performing aging at 40 ° C. for 3 days using each of the laminates of Examples 1 to 3 and Comparative Examples 1 to 3 obtained as described above, the sealant layers are heat sealed to produce a pouch. The contents are filled and sealed with poultice (containing methyl salicylate and menthol as volatile strong osmotic ingredients) and bathing agents (containing fragrance ingredients as volatile strong osmotic ingredients), respectively. Left in a constant temperature room.

  After the elapse of 3 months, these pouches were taken out from the thermostatic chamber, and the interlaminar laminate strength [N / 15 mm] of the polyester film A to F / first adhesive layer / second adhesive layer / sealant layer portion of each pouch was measured. Compared to the initial laminate strength in the pouch before entering the chamber. The measurement conditions for the laminate strength at this time were T-shaped 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. In addition, in the item of Table 1, an aluminum foil containing laminated base material means the laminated body of the laminated structure which consists of outermost layer / adhesive layer / aluminum foil layer / adhesive layer.

  As is clear from Table 1, the interlaminar laminate strength of the polyester films A to C / first adhesive layer / second adhesive layer / sealant layer portion of the pouch produced using the laminates according to Examples 1 to 3 However, even when a poultice containing a volatile strong penetrating component or a bath preparation was added and stored at 40 ° C. for 3 months, the initial laminate strength was sufficiently maintained.

  On the other hand, the interlaminar laminate strength of the polyester film D to F / first adhesive layer / second adhesive layer / sealant layer part of the pouch produced using the laminates according to Comparative Examples 1 to 3 is volatile. After a poultice containing a strong osmotic component and a bath preparation were stored at 40 ° C. for 3 months, a significant decrease was observed. Then, in order to confirm these peeling surfaces, as a result of analyzing by the X ray photoelectron spectroscopy, it turned out that it is surface layer peeling of the polyester films DF.

DESCRIPTION OF SYMBOLS 1 ... Outermost layer 2 ... Adhesive layer 3 ... Aluminum foil layer 4 ... Adhesive layer 5 ... Polyester film 6 ... 1st adhesive layer 7 ... 2nd adhesive layer 8 ... Sealant layer

Claims (3)

  At least a laminated structure comprising a polyester film / first adhesive layer / second adhesive layer / sealant layer, wherein the first adhesive layer is an amine-containing polymer, the second adhesive layer is a diisocyanate monomer, or an adduct type of a diisocyanate monomer, A laminate comprising either a burette type or a trimer (isocyanurate) type derivative, and having a MOR value of 1.00 to 1.25 measured by a microwave transmission type molecular orientation meter of a polyester film. body.   At least a laminated structure composed of an aluminum foil layer / adhesive layer / polyester film / first adhesive layer / second adhesive layer / sealant layer, wherein the first adhesive layer is an amine-containing polymer, the second adhesive layer is a diisocyanate monomer, or , A diisocyanate monomer adduct type, burette type, or a trimer (isocyanurate) type derivative, and a MOR value measured by a microwave transmission type molecular orientation meter of a polyester film is 1.00 to 1.25. A laminate characterized by being.   A pouch wherein the sealant layers are heat-sealed using the laminate of claim 1 or 2.

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