JP5870587B2 - Packaging material and manufacturing method thereof - Google Patents

Description

  The present invention relates to a packaging material excellent in non-adsorbability and a method for producing the same.

  Conventionally, as a packaging material excellent in non-adsorbability with respect to the active ingredients of the contents (hereinafter referred to as non-adsorbent packaging material), a laminate including a metal foil or a laminate including a plastic film formed with a metal deposition layer is widely used. It is used by being molded into a bag-like container (for example, see Patent Documents 1 to 4). Here, as the metal, an aluminum foil is often used in terms of cost and workability.

However, when the thickness of the metal foil or metal deposition layer is non-adsorptive, it becomes opaque and obstructs visual recognition of the contents when used as a packaging material, and avoids metal contamination in the contents. For this reason, there is a drawback that it hinders metal detection.
Furthermore, it is difficult to provide a metal foil or metal vapor deposition layer on the innermost surface while maintaining the heat sealability of the non-adsorbable packaging material, so that the metal foil or metal vapor deposition layer has the maximum non-adsorption property. was difficult.

On the other hand, the acrylonitrile copolymer resin does not have the above-described problems and can be practically used as a non-adsorbing material. Therefore, it is generally used in the construction of non-adsorbing packaging materials. Furthermore, acrylonitrile copolymer is also known as an aroma retaining material that does not allow permeation of aroma components.
This acrylonitrile copolymer is provided, for example, as a film within a range of 20 μm or more to 30 μm or less, and is generally dry-laminated or sand-laminated with another base film to form a part of a packaging material. It is.

  Also, a method of coating an acrylonitrile copolymer in a solution has been proposed. However, since an acrylonitrile copolymer is not dissolved in a general solvent suitable for mass production, it is not easy to form a film by coating.

JP-A-11-170445 WO2003 / 043895 JP 2004-210356 A JP 2007-099324 A

As described above, acrylonitrile copolymer is used in a film state and is generally laminated with a base film to form a packaging material. However, in recent years, in order to reduce the number of processes, the base film and acrylonitrile copolymer are used. Attempts have been made to multi-layer coextrusion laminate with a plurality of resins containing polymers.
Generally, an acrylonitrile copolymer resin has a higher melt viscosity than a polyolefin resin or the like, and carbonizes and hardens when heated excessively to reduce the melt viscosity.

Therefore, it was difficult to co-extrude multiple types of resins including acrylonitrile copolymer resin, but as a result of repeated sincerity studies, by selecting the molecular weight of acrylonitrile copolymer, The present inventors have found a method for co-extrusion with high quality while maintaining sufficient adsorptivity.
An object of the present invention is to perform multilayer coextrusion with high quality while sufficiently maintaining the non-adsorption property of the acrylonitrile copolymer.

In order to achieve the object, the invention according to claim 1 is a packaging material in which a base film and a non-adsorptive sealant film are sequentially laminated, and the non-adsorptive sealant film comprises a polyolefin resin and an adhesive resin. , and are laminated in the order of acrylonitrile copolymer resin, the weight average molecular weight of the acrylonitrile copolymer resin state, and are within the range of 60000 or more 140 000 or less, the non-adsorbing sealant film, the polyolefin resin in packaging terms of being laminated to the base film, printed layer to a surface on which the non-adsorbing sealant film of the base film made of stretched film is laminated form, wherein Rukoto is there.

The invention according to claim 2 is the packaging material according to claim 1, wherein the adhesive resin is an acid-modified polyolefin resin .
Further, the invention according to claim 3 includes an anchor coat layer mainly composed of a polyurethane-based resin between the base film and the non-adsorptive sealant film in the invention according to claim 1 or 2 , The printed layer is a packaging material formed of an ink using a polyurethane-based resin as a vehicle .

  Moreover, the invention which concerns on Claim 4 is a manufacturing method of the packaging material of any one of Claim 1 thru | or 3, Comprising: The said non-adsorptive sealant film is the said polyolefin resin, the said adhesive resin, and It is a method for producing a packaging material, wherein the acrylonitrile copolymer resin is coextruded in the order, and the base film and the non-adsorptive sealant film are extrusion laminated.

  Moreover, the invention which concerns on Claim 5 is a manufacturing method of the packaging material of any one of Claim 1 thru | or 3, Comprising: The said non-adsorptive sealant film is polyolefin resin, the said adhesive resin, and the said It is a method for producing a packaging material, wherein the film is coextruded in the order of acrylonitrile copolymer resin, and the base film and the non-adsorbing sealant film are neel laminated.

According to the present invention, while maintaining the non-adsorption property of the acrylonitrile copolymer, there is provided a plurality of types of resins including the acrylonitrile copolymer, which do not have a decrease in strength of the sealant film, a wrapping phenomenon, a poor appearance of extrusion such as neck-in. A non-adsorbing sealant film formed by multilayer coextrusion can be obtained.
In addition, according to the present invention, the base film is a stretched film, and the printed layer is formed on the surface of the base film on which the non-adsorptive sealant film is laminated. It becomes a suitable packaging material.

  Further, according to the present invention, in the packaging material manufacturing method, the base film and the non-adsorptive sealant multilayer co-extruded film are co-extruded laminated or knee-laminated in the same step. There is no need to laminate the adhesive sealant film in a separate process, and the manufacturing cost of the packaging material can be reduced.

It is sectional drawing which shows the structural example of the non-adsorptive packaging material of this embodiment. It is a figure which shows the result of having measured the heat seal intensity | strength of the packaging material of Examples 1, 2, and 3 and the comparative example 1. FIG. It is a figure which shows the result of having measured the amount of flurbiprofen adsorption of the packaging materials of Examples 1, 2, and 3 and Comparative Examples 1 and 2. It is a figure which shows the result of having measured the flurbiprofen adsorption amount of the packaging material of Examples 1, 2, and 3 and the comparative example 1. FIG.

Embodiments of the present invention will be described below with reference to the drawings.
This embodiment is a non-adsorbing packaging material to which the present invention is applied.
FIG. 1 is a diagram illustrating a configuration example of the non-adsorbing packaging material 1 of the present embodiment.
As shown in FIG. 1, the non-adsorbing packaging material 1 is a packaging material in which a base film 2 and a non-adsorbing sealant film 3 are sequentially laminated.

  The base film 2 is a main layer of the packaging material, and gives the packaging material 1 properties such as mechanical strength, tear properties, slip properties, and heat resistance. As a preferable material, a material excellent in mechanical strength such as a polyester film such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, a polyamide film such as 6-nylon and 6,6-nylon, or a polypropylene film can be used. . In particular, it is preferable to use these uniaxial or biaxially stretched films. Moreover, a well-known additive, for example, an antistatic agent, a slip agent, an antifogging agent, a ultraviolet absorber, etc. can be added to these films as needed. Moreover, a well-known process, for example, a corona discharge process, an ozone process, a flame process etc., can be performed as needed.

The thickness of the base film 2 is not particularly limited, but is preferably in the range of 12 μm to 40 μm.
Moreover, although the printing layer 7 is normally formed in the packaging material 1, as shown in FIG. The method for forming the print layer 7 is not particularly limited, and may be appropriately selected from various printing methods such as offset printing, gravure printing, flexographic printing, silk screen printing, ink jet printing, and pad printing. Moreover, in FIG. 1, 8 shows an adhesive bond layer or an anchor coat layer.

In addition, the base film 2 is made of a two-layer structure in which paper or non-woven fabric is laminated on the outer surface side or inner surface side of the film for the purpose of imparting a texture or rigidity, or aluminum for the purpose of preventing chemical reaction of contents. It is good also as a 2 layer structure which laminates | stacks foil.
The non-adsorptive sealant film 3 laminated on the base film 2 is composed of a polyolefin resin 4, an adhesive resin 5, and an acrylonitrile copolymer resin 6. Specifically, the non-adsorptive sealant film 3 is formed by coextrusion in the order of the polyolefin resin 4, the adhesive resin 5, and the acrylonitrile copolymer resin 6.

In the present embodiment, the non-adsorbable packaging material 1 is obtained by coextruding laminate or knee laminating the non-adsorbent sealant film 3 on the base film 2.
Here, the polyolefin resin 4 is preferably a low-density polyethylene or a linear low-density polyethylene in consideration of coextrusion suitability with the acrylonitrile copolymer resin 6 and adhesiveness with the base film 2. .

As the adhesive resin 5, it is preferable to employ a maleic anhydride-modified polyolefin adhesive resin that has good adhesion between the polyolefin resin 4 and the acrylonitrile copolymer resin 6.
And in this embodiment, it is preferable that the average molecular weights of the acrylonitrile copolymer resin 6 are in the range of 60000 or more and 140000 or less.

  This is because, when the average molecular weight of the acrylonitrile copolymer resin 6 is smaller than 60000, the melt viscosity is lowered and the suitability for coextrusion film formation with a polyolefin resin or the like is improved, but the film strength as a sealant film is lowered. This is because the original non-adsorption property of the acrylonitrile copolymer cannot be sufficiently exhibited. On the other hand, when the average molecular weight of the acrylonitrile copolymer resin 6 exceeds 140000, the melt viscosity is extremely increased, and the consistency of the melt viscosity with other resins cannot be maintained during the co-extrusion film formation. This is because film cracking occurs and the film cannot be formed satisfactorily.

In addition, as described above, in the production of the non-adsorbable packaging material 1, by applying a co-extrusion laminate or a knee laminate, only the adhesion of each film such as a dry laminate that has been widely performed conventionally is intended. The process can be omitted, and therefore the manufacturing cost of the packaging material can be suppressed.
Prior to lamination, an anchor coating agent can be applied to the laminated surface, and pretreatment such as corona treatment or ozone treatment can be performed as necessary.

  Moreover, you may add a well-known additive, for example, an antistatic agent, a slip agent, an antifogging agent, etc. to each layer of the non-adsorptive sealant film 3 as needed. Moreover, a well-known process, for example, a corona discharge process, an ozone process, a flame process etc., can be performed as needed. In particular, in the present embodiment, the non-adsorptive sealant film 3 is laminated by coextrusion lamination or kneelam lamination, and therefore, depending on the type of resin used for the base film 2 or the non-adsorptive sealant film 3, the non-adsorptive sealant film 3 is laminated. Adhesion improving treatment such as corona discharge treatment or ozone treatment for the sealant film 3 is required.

  Further, the film thicknesses of the non-adsorbing sealant film 3, the polyolefin resin 4, the adhesive resin 5 and the acrylonitrile copolymer resin 6 are not particularly limited, but the polyolefin resin 4 has an adhesive property within the range of 10 μm to 20 μm. The resin 5 is in the range of 3 μm to 10 μm, the acrylonitrile copolymer resin 6 is in the range of 10 μm to 20 μm, and the non-adsorptive sealant film 3 as a laminate is in the range of 23 μm to 50 μm. It is preferable.

  Although the embodiments of the present invention have been specifically described above, the scope of the present invention is not limited to the illustrated and described exemplary embodiments, and effects equivalent to those intended by the present invention. All embodiments that provide are also included. Further, the scope of the present invention is not limited to the combination of features of the invention defined by claim 1 but can be defined by any desired combination of specific features among all the disclosed features. .

Specific examples of the non-adsorbing packaging material of the present invention will be described below, but the present invention is not limited to these examples.
Example 1
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm was used as the base film, and a printing layer was formed on the base film with an ink using a polyurethane resin as a vehicle. On this printed layer, an anchor coating agent composed mainly of a polyurethane resin was applied at a coating amount of 4 g / m ² . Further, by using a three-type three-layer coextrusion machine, an acrylonitrile copolymer resin a having a linear low density polyethylene resin of 15 μm as a polyolefin resin, an acid-modified polyolefin resin as an adhesive resin of 5 μm, and an average molecular weight of 100,000 is used. A coextruded non-adsorptive sealant film was formed at an extrusion temperature of 200 ° C. so as to be 10 μm. Thereafter, the base film and the non-adsorptive sealant film are laminated by kneelam lamination so that the linear low-density polyethylene resin surface of the non-adsorptive sealant film is laminated to the base film, A non-adsorbing packaging material in the form was obtained.

(Example 2)
In Example 1, except that the acrylonitrile copolymer resin a was changed to the acrylonitrile copolymer resin b having an average molecular weight of 50000, it was the same as Example 1, and the non-adsorbing packaging material of the above-described embodiment was obtained. .
(Example 3)
In Example 1, except that the acrylonitrile copolymer resin a was changed to the acrylonitrile copolymer resin c having an average molecular weight of 150,000, it was the same as Example 1, and the non-adsorbent packaging material of the above-described embodiment was obtained. .

(Comparative Example 1)
A printing layer was formed on a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm with an ink using a polyurethane resin as a vehicle. On this printed layer, an anchor coating agent mainly composed of a polyurethane resin is applied in an amount of 4 g / m ² , and an acrylonitrile copolymer film (Tamapoly Co., Ltd. Hytron BX) having a thickness of 30 μm is pasted as a sealant. A combined dry laminate film was obtained.

(Comparative Example 2)
A printing layer was formed on a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm with an ink using a polyurethane resin as a vehicle. On this printed layer, an anchor coating agent mainly composed of a polyurethane-based resin was applied at a coating amount of 4 g / m ^{2, and} a linear low density polyethylene film having a thickness of 30 μm (Fujimura Chemical Co., Ltd. XMTN) as a sealant layer. ) To obtain a dry laminate film.

<Appearance inspection>
The non-adsorbent packaging materials obtained in Examples 1, 2, and 3 were examined for appearance and cross-sectional thickness in the width direction.
As a result, in Examples 1 and 2, no abnormality was observed in both appearance and film thickness, and good visibility was maintained for the printed layer of the base film. However, in Example 3, because of the wrapping phenomenon of the polyethylene resin, the acrylonitrile copolymer resin c approaches the center in the film width direction, the polyethylene resin escapes to the outer periphery, and the film thickness distribution in the width direction becomes non-uniform, Distortion also occurred in the printed layer of the base film. Furthermore, film cracks occurred in some places, and satisfactory quality packaging materials could not be obtained.

<Heat seal strength>
Subsequently, a heat seal strength test was performed on the packaging materials of Examples 1, 2, and 3 and Comparative Example 1. The strength was measured using a tensile / compression tester (AandD Tensilon Co., Ltd.) based on the JIS-Z0238 test method. The result is shown in FIG.
As is clear from the results of FIG. 2, compared with Comparative Example 1 obtained by dry-laminating an acrylonitrile copolymer film, Example 1 using acrylonitrile copolymer a having an average molecular weight of 100,000 and an average molecular weight of 150,000 Example 3 using acrylonitrile copolymer c shows an equivalent strength to the heat seal strength, but the heat seal strength of Example 2 using acrylonitrile copolymer b having an average molecular weight of 50000 is comparative example 1. It was inferior to the strength.

<Non-adsorptive>
Subsequently, the packaging materials of Examples 1, 2, and 3 and Comparative Examples 1 and 2 were used to carry out actual packaging and storage tests for the purpose of evaluating non-adsorbability.
The packaging materials of Examples 1, 2, and 3 and Comparative Examples 1 and 2 were cut into a predetermined size, and the sealant film was opposed to the inner surface to heat-seal the three sides into a bag shape. Seven patches (Mikasa Pharmaceutical Co., Ltd. Zepolus tape) containing 20 mg of flurbiprofen were inserted, and the openings were sealed by heat sealing. Furthermore, after storing them at 40 ° C. and 75% RH for 1 month, the amount of flurbiprofen adsorbed per unit area of the bag was measured by HPLC (liquid chromatography). The results are shown in FIGS.

As is apparent from the results of FIG. 3, Examples 1, 2, and 3 and Comparative Example 1 using an acrylonitrile copolymer as a sealant film were compared with Comparative Example 2 using polyethylene as a sealant film. Excellent non-adsorbability for biprofen.
On the other hand, as is clear from the results of FIG. 4, compared with Comparative Example 1 obtained by dry laminating an acrylonitrile copolymer film, Example 1 using acrylonitrile copolymer a having an average molecular weight of 100,000, and average molecular weight Example 2 using 150,000 acrylonitrile copolymer c shows non-adsorbability equal to or higher than flurbiprofen, but Example 2 using acrylonitrile copolymer b having an average molecular weight of 50000 The non-adsorbability of flurbiprofen was inferior to that of Comparative Example 1.

  From the above, the non-adsorbing packaging material 1 of this embodiment is a packaging material in which a base film and a non-adsorbing sealant film are sequentially laminated, and the non-adsorbing sealant film is a polyolefin resin or an adhesive resin. And the acrylonitrile copolymer resin is laminated in this order, and the average molecular weight of the acrylonitrile copolymer resin is within the range of 60000 or more and 140,000 or less, while sufficiently maintaining the non-adsorbability of the acrylonitrile copolymer, It is possible to obtain a non-adsorbing sealant film obtained by multilayer coextrusion film formation of a plurality of types of resins including an acrylonitrile copolymer, which does not have a decrease in strength of the sealant film, an enveloping phenomenon, or a poor extrusion appearance such as neck-in.

In addition, the base film and non-adsorptive sealant multi-layer coextrusion film are processed in the same process while maintaining non-adsorptiveness equivalent to or better than non-adsorptive packaging material in which the base film and non-adsorptive sealant film are laminated in separate processes. The manufacturing cost of the packaging material can be reduced by coextrusion lamination or knee lamb lamination.
In addition, by forming a base film as a stretched film and forming a print layer on the surface of the base film on which the non-adsorptive sealant film is laminated, the print layer is protected and a packaging material suitable for packaging of pharmaceuticals and the like is obtained. be able to. Furthermore, since it prints on the smooth stretched film surface, a printing layer with high designability can be formed.

  DESCRIPTION OF SYMBOLS 1 ... Nonadsorbent packaging material, 2 ... Base film, 3 ... Nonadsorbent sealant film, 4 ... Polyolefin resin, 5 ... Adhesive resin, 6 ... Acrylonitrile co-polymer Combined resin, 7 ... print layer, 8 ... adhesive layer (anchor coat layer)

Claims (5)

A packaging material in which a base film and a non-adsorptive sealant film are sequentially laminated,
The non-adsorptive sealant film is laminated in the order of polyolefin resin, adhesive resin, and acrylonitrile copolymer resin,
The weight average molecular weight of the acrylonitrile copolymer resin state, and are within the range of 60000 or more 140 000 or less,
The non-adsorptive sealant film has a surface of the polyolefin resin laminated to the base film,
Packaging said non-adsorbing sealant film of the substrate film consisting of stretched film, characterized in Rukoto printing layer is formed on the surface to be laminated. The packaging material according to claim 1, wherein the adhesive resin is an acid-modified polyolefin resin. Between the base film and the non-adsorptive sealant film, an anchor coat layer mainly comprising a polyurethane-based resin is provided,
The packaging material according to claim 1, wherein the printing layer is formed of an ink using a polyurethane-based resin as a vehicle. A method for manufacturing a packaging material according to any one of claims 1 to 3,
The non-adsorptive sealant film is co-extruded in the order of the polyolefin resin, the adhesive resin, and the acrylonitrile copolymer resin;
A method for producing a packaging material, comprising: extrusion laminating the base film and the non-adsorbing sealant film. A method for manufacturing a packaging material according to any one of claims 1 to 3,
The non-adsorptive sealant film, the polyolefin resin, the adhesive resin, and are co-extruded film formation in the order of the acrylonitrile copolymer resin,
A method for producing a packaging material, comprising: laminating the base film and the non-adsorptive sealant film.

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