JP6186741B2 - Laminated packaging material and packaging bag using the same - Google Patents

Description

  The present invention relates to a laminated packaging material suitable for packaging foods and drinks, pharmaceuticals or industrial products. More specifically, the present invention relates to a laminated packaging material suitable for packaging contents containing a volatile substance such as alcohol and fragrance, a surfactant, an acidic substance and an alkaline substance, and the like and a strong penetrating substance.

  Contents containing strong permeable substances such as volatile substances such as alcohol and fragrance, surfactants, acidic substances and alkaline substances, which have been stored in containers such as glass bottles, metal cans and plastic bottles, Due to increased awareness of environmental issues, packaging bags have been used for the purpose of reducing waste. Examples of the contents include alcohol-containing foods and drinks, pharmaceuticals, fragrances, deodorants, shampoos, rinses, and bathing agents. As a layer structure of the packaging bag, for example, a laminated packaging material comprising a film base layer / adhesive layer / sealant layer, paper layer / polyethylene layer / aluminum foil / adhesive layer / film layer / adhesive layer / adhesive resin layer / sealant Layered packaging materials composed of layers are used. In order to form a layer structure, these laminated packaging materials are bonded by a dry lamination method using an adhesive, or by extruding a polyethylene film while anchoring the adhesive, and bonding by a sand polylaminate method. It is done in

  Conventionally, polyurethane adhesives in combination with polyol compounds and polyisocyanate compounds and adhesives in combination with polyamine compounds and epoxy compounds are known as adhesives, and laminated packaging materials can be obtained using such adhesives. It has been.

  On the other hand, the contents have been expanded to retort foods and non-foods, and there is an increasing demand for laminated packaging materials that can stably store these contents for a long period of time.

  However, when packaging contents containing a strong osmotic substance as described above, the strong osmotic force of the strong osmotic substance penetrates the sealant layer and adversely affects the adhesive layer, reducing the adhesive strength, As a result, delamination may occur.

  Such delamination is considered to occur when the resin component of the adhesive layer swells due to the penetration of the strongly permeable substance, lowers the molecular weight, and decreases the cohesive force.

In order to improve such problems, an organic polyol compound, an organic polyisocyanate compound, a polyurethane resin having NH groups and NH ₂ groups obtained by reacting a chain extender, an excess amount of an organic polyisocyanate compound, There is a proposal of an alkali-resistant adhesive composition blended with (Patent Document 1).

  The contents containing alkaline substances are effective, but the contents containing volatile substances such as alcohol and fragrances and strong penetrating substances such as surfactants may decrease the adhesive strength.

There is also a proposal of a layer configuration that suppresses the penetration of a strongly permeable substance (Patent Document 2). A laminated packaging material in which a barrier base material layer, an adhesive layer, and a sealant layer made of a polyethylene resin are sequentially laminated, and for the purpose of sterically hindering the penetration, diffusion, and migration of volatile organic components. , Increased crystallization and aggregation density. That is, there is one provided with a copolymer of ethylene and an α-olefin which is produced using a metallocene catalyst and has a density of 0.935 to 0.975 g / cm ³ .

  However, even if the sealant layer tries to suppress the penetration of the strong permeable substance, there is a limit, and there is a possibility that the cohesive force of the adhesive layer is reduced and delamination occurs.

  Therefore, there is a demand for a laminated packaging material in which the adhesive strength does not decrease even when a strong penetrating substance acts.

JP-A-10-130615 JP 2008-44202 A

  In view of such problems, the present invention provides a laminated packaging material for packaging contents containing a strong osmotic substance, which can be stably stored for a long period of time without reducing adhesive strength. To do.

  In order to solve the above problems, the inventors have intensively studied and completed the present invention.

The invention according to claim 1 of the present invention is a laminated packaging material in which a base film layer / first adhesive layer / film layer / second adhesive layer / adhesive resin layer / sealant layer are laminated in this order from the outside,
The second adhesive layer comprises a mixture of a polyol compound of any one of polyester polyol, polyether polyol and acrylic polyol, and a polyisocyanate compound,
The mixing ratio of the polyol compound is 0 to 20% by weight with respect to the polyisocyanate compound,
Said film layer, Ri Do a polyamide film,
The first adhesive layer is a laminated packaging material comprising a polyester polyol compound .

The invention according to claim 2 of the present invention, the polyamide film is a laminated packaging material according to claim 1, wherein that you have a gas barrier property.

The invention according to claim 3 of the present invention is the laminated packaging material according to claim 1 or 2 , wherein the base film layer is a biaxially stretched polyester film.
The invention according to claim 4 of the present invention is the laminated packaging material according to any one of claims 1 to 3 , wherein the adhesive resin layer is a linear low-density polyethylene resin layer.
The invention according to claim 5 of the present invention is the laminated packaging material according to any one of claims 1 to 4 , wherein the polyisocyanate compound is isophorone diisocyanate.

The invention according to claim 6 of the present invention is a packaging bag using the laminated packaging material according to any one of claims 1 to 5 .

  The laminated packaging material of the present invention is suitable for packaging contents containing a strong osmotic substance and can be stored stably for a long period of time.

According to claim 1 of the present invention, the second adhesive layer comprises a mixture of a polyol compound of any one of polyester polyol, polyether polyol and acrylic polyol and a polyisocyanate compound, and the mixing ratio of the polyol compound is When the weight ratio with respect to the isocyanate compound is 0 to 20% by weight, a laminated packaging material that can be stably stored for a long period of time can be obtained without lowering the adhesive strength even when a highly permeable content is packaged. Since the adhesive layer made of polyurethane resin formed by urethanization reaction has strong cohesive force, the adhesive strength between the film layer and adhesive resin layer does not decrease, and a laminated packaging material that can be stored stably for a long time is obtained. It is done.

  When the polyol compound is any one of polyester polyol, polyether polyol and acrylic polyol, the adhesive layer made of polyurethane resin formed by urethanization reaction has a strong cohesive force and can provide strong adhesiveness. Thus, a laminated packaging material capable of stably storing contents containing a strong osmotic substance for a long period of time can be obtained.

  Laminate that can be stored stably for a long period of time with strong adhesiveness when the mixing ratio of the polyol compound is 0 to 20% by weight with respect to the polyisocyanate compound. A packaging material is obtained.

Further, according to claim 1 of the present invention, the film layer by a polyamide-based film, it is possible to more strongly bonding with the second adhesive layer.

According to claim 2 of the present invention, the polyamide-based film has gas barrier properties, whereby the contents can be stored for a long period of time. A laminated packaging material capable of stably storing contents containing a strong osmotic substance for a long period of time is obtained.

According to claim 6 of the present invention, the packaging bag using the laminated packaging material according to any one of claims 1 to 5 is stable for a long period of time even when the contents containing a strong osmotic substance are accommodated. Can be saved.

It is explanatory drawing which shows an example of the laminated constitution of the laminated packaging material of this invention. It is explanatory drawing which shows an example of the packaging bag using the laminated packaging material of this invention. It is explanatory drawing which shows another example of the packaging bag using the laminated packaging material of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described.

  FIG. 1 is an explanatory view showing an example of a layer structure of the laminated packaging material of the present invention. The laminated packaging material 50 comprises at least a base film layer 1 / first adhesive layer 2 / film layer 3 / second adhesive layer 4 / adhesive resin layer 5 / sealant layer 6 that are sequentially laminated.

  The base film layer 1 is made of a plastic film having heat resistance. For example, polyester film (PET), polyethylene film (PE), polypropylene film (PP), nylon film (ONy), polystyrene film (PS), polycarbonate film (PC), polyacrylonitrile film (PAN), polyimide film (PI) , Polyvinyl alcohol film (PVA), polyvinylidene chloride film (PVDC), and the like. There is no particular limitation as long as it has mechanical strength and dimensional stability. A biaxially stretched film is particularly preferable. The thickness of the base film layer is preferably in the range of 10 to 50 μm and more preferably in the range of 10 to 30 μm in consideration of workability.

  Moreover, what gave the gas barrier property to the base film layer can also be used. For example, a film in which an aluminum foil is laminated or an inorganic oxide such as silicon oxide or aluminum oxide is deposited can be used.

  The film layer 3 is laminated in order to improve the piercing property, rigidity and gas barrier property. For example, a nylon film (ONy), a polyester film (PET), or a polypropylene film (PP) can be used as long as the piercing property and rigidity are improved. If the gas barrier property is improved. For example, an ethylene-vinyl alcohol copolymer film (EVOH), a polyvinylidene chloride film (PVDC), a polyacrylonitrile film (PAN) are laminated, an aluminum foil, or an inorganic material such as silicon oxide, aluminum oxide, or magnesium oxide. A polyester film, a nylon film, a propylene film, or the like provided with an oxide vapor deposition layer or a PVDC resin coating layer can be laminated.

  Among the above films, the film layer 3 is preferably a polyamide-based film, that is, a nylon film, which can provide strong adhesion with the second adhesive layer. For example, by laminating a nylon film having gas barrier properties, strong adhesion to the second adhesive layer can be obtained, and puncture resistance and rigidity can be improved. Examples of the nylon film include MXD nylon, nylon 6, nylon 66, nylon 612, nylon 11, and nylon 12. Nylon films with gas barrier properties are, for example, nylon MXD6 film, three-layer coextruded film with nylon film laminated on both sides with nylon MXD6 film sandwiched, ethylene-vinyl acetate copolymer film (EVOH) on both sides with nylon film Examples thereof include a three-layer coextruded film in which nylon films are laminated, and a nylon film on which inorganic oxide is deposited.

  As the sealant layer 6, for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-methacrylic acid copolymer (EMAA), A film made of polyolefin resin such as ethylene-ethyl acrylate copolymer (EAA), ethylene-vinyl acetate copolymer (EVA), ionomer, polypropylene (PP) can be used. These resins can be used by forming a film with an extruder. A single layer or two or more types of the above resins can be used. The film thickness is preferably in the range of 10 to 100 μm, more preferably in the range of 15 to 70 μm.

  The adhesive resin layer 5 is a polyethylene film that is extruded by an extruder and formed by a sand polylaminate method in order to adhere the film layer and the sealant layer. The sealant layer is bonded through the adhesive resin layer while anchoring the second adhesive layer to the film layer. Adhesive resin layer is a polyolefin such as low density polyethylene, linear low density polyethylene, medium density polyethylene, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ionomer. A film made of a resin can be used.

  The second adhesive layer 4 is made of a mixture of a polyol compound and a polyisocyanate compound. Among them, a polyol compound composed of any one of polyester polyol, polyether polyol and acrylic polyol and a mixture of a polyisocyanate compound, and the mixing ratio of the polyol compound is from 0 to 20% by weight with respect to the polyisocyanate compound. As a result, the polyurethane resin formed by urethanization reaction has strong cohesive force, and even the contents containing strong permeable substances do not decrease the adhesive strength between the film layer and the adhesive resin layer, and are stable for a long time Thus, a laminated packaging material that can be stored is obtained.

  Examples of the polyisocyanate compound include isocyanate compounds containing two or more isocyanate groups, adducts, burettes, uretidiones, and isocyanurates of these isocyanate compounds. For example, aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate (IPDI), hydrogenated tri Alicyclic polyisocyanates such as diisocyanate, tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, xylene diisocyanate (XDI), triphenylmethane triisocyanate, tris (4-phenylisocyanate) ) Aromatic polyisocyanates such as thiophosphate. As an adduct body, for example, an adduct body obtained by reacting MDI, TDI, HDI, XDI, IPDI or the like with a dihydric or trivalent polyhydric alcohol, a buret body such as HDI or IPDI, a uretidione body such as TDI, TDI, Isocyanate bodies such as HDI and IPDI can be mentioned, and two or more of these compounds can also be mixed and used.

As a method for forming the second adhesive layer, for example, a sand polylaminate method is used. A 2nd adhesive agent is apply | coated to a film layer, a polyethylene film is extruded from an extruder, drying, and it bonds together with a sealant layer through an adhesive resin layer. The adhesive may be cured at room temperature or under heating. The amount of adhesive applied is preferably about 1 to 10 g / m ² (dry). What is necessary is just to determine suitably with adhesive strength. The second adhesive layer formed in this way has a strong cohesive force, and obtains a strong initial adhesive strength, without causing a decrease in adhesive strength or delamination even in contents containing strong permeability. The adhesive strength can be maintained stably for a long time.

  The first adhesive layer 2 is used for bonding the base film layer and the film layer together. It is preferable to use an aliphatic adhesive. For example, an adhesive composed of an aliphatic polyol compound and an aliphatic polyisocyanate compound is preferable. By using an aliphatic adhesive, it is possible to suppress yellowing due to light (ultraviolet rays) or heat and a decrease in adhesive strength even when stored for a long period of time.

  Examples of the aliphatic polyol compound include an aliphatic polyether polyol compound, an aliphatic polyester polyol compound, and a polycarbonate polyol compound. Examples of the aliphatic isocyanate include butane diisocyanate, pentane diisocyanate, hexanemethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and the like. The urethane resin layer produced by the urethanization reaction of these aliphatic polyol compounds and aliphatic polyisocyanate compounds can suppress yellowing and cohesive force reduction due to heat and light (ultraviolet rays).

As a method for forming the first adhesive layer, a dry laminating method can be used. The amount of adhesive applied is preferably about 1 to 10 g / m ² (dry). What is necessary is just to determine suitably with adhesive strength.

  The laminated packaging material obtained in this way is heat-sealed to produce bags according to the purpose, such as three-side sealed packaging bags, four-side sealed packaging bags, standing packaging bags, gusset packaging bags, and has strong permeability. The contents can be sealed and packaged. The laminated packaging material of the present invention can be stably stored for a long period of time even if the contents containing strong permeability are hermetically packaged.

  FIG. 2 is an explanatory view showing an example of a packaging bag using the laminated packaging material of the present invention. FIG. 2-1 shows the three-side sealed packaging bag 10. FIG. 2-2 shows the four-side sealed packaging bag 20.

  FIG. 3 is an explanatory view showing another example of a packaging bag using the laminated packaging material of the present invention. FIG. 3A shows the standing packaging bag 30. FIG. 3-2 shows the standing packaging bag 40 with a stopper. A plug 41 is provided.

  The packaging bag can be a gusset packaging bag, a polygonal packaging bag or the like in addition to the packaging bag as described above. Further, the laminated packaging material of the present invention can be used for a laminated tube container, a composite container with paper, a lid material, and the like.

  The contents containing strong osmotic substances include foods and drinks containing volatile substances such as alcohol and fragrances, pharmaceuticals, fragrances, deodorants, surfactants, shampoos and rinses containing acidic substances and alkaline substances. Examples thereof include bathing agents and poultices.

  Hereinafter, an example of the manufacturing method of the laminated packaging material of the present invention will be described.

  A polyester film is used as the base film layer. For example, a gravure printing layer is provided on one side of the polyester film. Next, as a film layer, a nylon film on which an inorganic oxide is vapor-deposited is bonded to the surface of the printing layer via a first adhesive layer by a dry laminating method. In addition, the vapor deposition surface of an inorganic oxide is arranged on the bonding surface side. The first adhesive layer is formed of an aliphatic adhesive.

  Next, the polyethylene resin is extruded from an extruder while the second adhesive layer is applied to the surface of the nylon film, and the linear low-density polyethylene film of the sealant layer is bonded while sandwiching the extruded polyethylene film. The second adhesive layer is a mixture of a polyol compound of any one of polyester polyol, polyether polyol and acrylic polyol and a polyisocyanate compound, and the mixing ratio of the polyol compound is 0 to 20 by weight ratio to the polyisocyanate compound. It should consist of% by weight. In this way, a laminated packaging material is formed.

  The produced laminated packaging material is made into a packaging bag according to the purpose, and a sealed packaging bag can be produced by filling the content containing a strong osmotic substance. A packaging bag containing contents containing a strongly permeable substance can be created.

  Hereinafter, specific examples of the present invention will be described.

  The following materials were used to prepare a laminated packaging material in which a base film layer / first adhesive layer / film layer / second adhesive layer / adhesive resin layer (EX-PE) / sealant layer were sequentially laminated.

<Material>
-As a base film layer, the biaxially stretched polyester film whose thickness which gave the corona treatment to one side is 12 micrometers is used.
・ A biaxially stretched nylon film with a thickness of 15 μm is used as the film layer.
-A linear low density polyethylene film 80 μm is used as the sealant layer.
-Adhesive resin layer (EX-PE) uses a 20 μm film obtained by extruding a linear low density polyethylene resin with an extruder.

<Adhesive>
The first adhesive layer uses a mixture of polyester polyol compound / curing agent (isophorone diisocyanate (IPDI)) / solvent (toluene / methyl ethyl ketone = 1/1) in a weight ratio of 8/1 / 11.6. The first adhesive layer was applied at a coating amount of 5.0 g / m ² . Bonding was performed by a dry laminating method.

The second adhesive layer was formed in a weight ratio of polyester polyol compound / curing agent (isophorone diisocyanate (IPDI)) = 0/100 at an application amount of 3.0 g / m ² (dry). In addition, while applying the second adhesive layer to the nylon film, the linear low density polyethylene resin of the adhesive resin layer (EX-PE) is extruded by an extruder, and is laminated with the sealant layer while sandwiching the extruded film. A packaging material was prepared.

  Using the above laminated packaging material, a standing packaging bag with a height of 250 mm, a width of 120 mm, and a bottom fold of 35 mm is made, and filled with an alcohol disinfectant (alcohol concentration 55%) as the contents, and sealed packaging Created a bag.

Example 1 except that the second adhesive layer was bonded at a weight ratio of polyester polyol compound / curing agent (isophorone diisocyanate (IPDI)) = 5/95 at a coating amount of 3.0 g / m ² (dry). In the same manner as above, a sealed packaging bag was prepared.

Example 1 except that the second adhesive layer was bonded at a weight ratio of polyester polyol compound / curing agent (isophorone diisocyanate (IPDI)) = 20/80 at a coating amount of 3.0 g / m ² (dry). In the same manner as above, a sealed packaging bag was prepared.

Except that the second adhesive layer was bonded at a weight ratio of polyether polyol compound / curing agent (isophorone diisocyanate (IPDI)) = 0/100 at an application amount of 3.0 g / m ² (dry). A sealed packaging bag was prepared in the same manner as in Example 1.

Example 2 except that the second adhesive layer was bonded at a weight ratio of acrylic polyol compound / curing agent (isophorone diisocyanate (IPDI)) = 0/100 at an application amount of 3.0 g / m ² (dry). 1 was performed and a sealed packaging bag was prepared.

  A sealed packaging bag was produced in the same manner as in Example 2 except that a nylon film having a thickness of 30 nm deposited with 30 nm of aluminum oxide was used as the film layer. The bonding surface with the second adhesive layer was a nylon film surface.

  Hereinafter, comparative examples of the present invention will be described.

<Comparative Example 1>
Example 1 except that the second adhesive layer was bonded at a weight ratio of polyester polyol compound / curing agent (isophorone diisocyanate (IPDI)) = 30/70 and an application amount of 3.0 g / m ² (dry). In the same manner as above, a sealed packaging bag was prepared.

<Comparative example 2>
A sealed packaging bag was prepared in the same manner as in Example 1 except that the second adhesive layer was bonded using the same adhesive as the first adhesive layer and the sealant layer was 100 μm. In addition, the adhesive resin layer was not used and it bonded together by the dry lamination method. The coating amount was 5.0 g / m ² .

<Comparative Example 3>
Except that the first adhesive layer was a mixture of ester resin / curing agent (xylene diisocyanate (XDI)) / solvent (toluene / methyl ethyl ketone = 1/1) in a weight ratio of 8/1 / 11.6, A sealed packaging bag was prepared in the same manner as in Example 2.

<Comparative Example 4>
A biaxially stretched nylon film having a thickness of 15 μm was used as the base film layer. As the film layer, a biaxially stretched polyester film having a thickness of 12 μm was used. Other than that was carried out similarly to Example 2, and created the sealed packaging bag.

<Evaluation method>
The prepared sealed packaging bag was stored at 50 ° C. for 3 months. The adhesive strength and seal strength of each adhesive part of the sealed packaging bag were measured. Compared to the initial value. The measurement conditions were a sample width of 15 mm, T-type peeling, and a peeling speed of 300 mm / min. The average value of N = 3 is shown.

  The evaluation results are shown in Tables 1 and 2.

ポリオール化合物と硬化剤（イソシアネート化合物）との重量比では、実施例１〜３では、５０℃・３ヶ月保存後で接着強度の低下は観られず、十分な接着強度を維持していた。しかし、比較例１では、実施例１〜３に比べて、５０℃・３ヶ月保存後で、接着強度が低下していた。

With respect to the weight ratio of the polyol compound and the curing agent (isocyanate compound), in Examples 1 to 3, a decrease in adhesive strength was not observed after storage at 50 ° C. for 3 months, and sufficient adhesive strength was maintained. However, in Comparative Example 1, the adhesive strength decreased after storage at 50 ° C. for 3 months as compared with Examples 1 to 3.

  In Examples 4 and 5, even when the polyol compound was a polyether polyol compound or an acrylic polyol compound, sufficient adhesive strength was maintained.

  In Example 6, even when nylon having gas barrier properties was used, sufficient adhesive strength was maintained.

  In Comparative Example 2, a decrease in adhesive strength was observed after storage at 50 ° C. for 3 months.

  In Comparative Example 3, the first adhesive layer turned yellow after storage at 50 ° C. for 3 months, and a slight decrease in adhesive strength was observed.

  Comparative Example 4 shows the evaluation results in Table 2. The initial adhesive strength between PET / PE and the adhesive strength after storage at 50 ° C. for 3 months were low.

  It has been found that the laminated packaging bag of the present invention is suitable for packaging a content containing a strong osmotic substance.

1: base film layer 2: first adhesive layer 3: film layer 4: second adhesive layer 5: adhesive resin layer 6: sealant layer 10: three-side seal packaging bag 20: four-side seal packaging bag 30: standing packaging bag 40: Standing packaging bag 50 with spout: Laminated packaging material

Claims (6)

A laminated packaging material in which a base film layer / first adhesive layer / film layer / second adhesive layer / adhesive resin layer / sealant layer are laminated in this order from the outside,
The second adhesive layer comprises a mixture of a polyol compound of any one of polyester polyol, polyether polyol and acrylic polyol, and a polyisocyanate compound,
The mixing ratio of the polyol compound is 0 to 20% by weight with respect to the polyisocyanate compound,
Said film layer, Ri Do a polyamide film,
The laminated packaging material , wherein the first adhesive layer contains a polyester polyol compound .   The laminated packaging material according to claim 1, wherein the polyamide-based film has gas barrier properties. The laminated packaging material according to claim 1 or 2 , wherein the base film layer is a biaxially stretched polyester film. The laminated packaging material according to any one of claims 1 to 3 , wherein the adhesive resin layer is a linear low-density polyethylene resin layer. The laminated packaging material according to any one of claims 1 to 4 , wherein the polyisocyanate compound is isophorone diisocyanate. A packaging bag using the laminated packaging material according to any one of claims 1 to 5 .

Images