JP2020040358A - Antibacterial packaging film and packaging material - Google Patents

Abstract

To provide an antibacterial packaging film not requiring a light control in a storage environment or a light shield package, capable of preventing deterioration of an antibacterial agent and suppressing decrease in antibacterial properties, while maintaining visibility.SOLUTION: An antibacterial packaging film is a film 1 in which at least a base material 10, an adhesion layer 20 and a thermofusion resin layer 30 are laminated in this order. The base material 10 is composed of a resin and an ultraviolet absorber. The ultraviolet absorber is included by 5-20 wt.% with regard to the weight of a base resin. The adhesion layer 20 includes a volatile antibacterial agent. A vaporization amount of the antibacterial agent is 0.1-1.5 g/mwhen the film 1 is heated for 20 minutes at 150°C.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an antibacterial packaging film and a packaging material formed using the same.

  In recent years, mold damage has occurred in various places such as food and living environment, and has become a social problem. On the other hand, a packaging material using an essential oil component as an antibacterial component has been proposed as a packaging material capable of spatial sterilization.

  However, some essential oil components, such as citral, are degraded by light.In packaging materials using such components, the antibacterial effect decreases with time if left for a long time under light irradiation. In some cases.

  The light irradiation environment includes, for example, storage of a film until use, display at a store, and the like. Deterioration of the antibacterial component during storage can be prevented by using a dark environment or light-shielding packaging, but there is a problem that the time and effort required to put the bag in each use and the storage environment are limited. In addition, such a method cannot prevent deterioration during use.

  Therefore, as a method of providing the light shielding function to the packaging material itself, a method of providing an aluminum layer or an aluminum vapor-deposited layer, or a method of applying or kneading a substance containing zinc oxide, titanium oxide, or the like as a main component to a substrate has been proposed. (See Patent Document 1). However, these materials have poor transparency and cannot be used for applications that require visibility of the contents.

Japanese Patent No. 2816402

  Accordingly, an object of the present invention is to provide an antibacterial packaging film that prevents deterioration of an antibacterial agent under light irradiation and suppresses a decrease in antibacterial activity while maintaining visibility.

In view of the above problems, the first invention of the present invention
At least a substrate, an adhesive layer, and a film laminated in the order of the heat-sealing resin layer, wherein the substrate includes a resin and an ultraviolet absorber, and the ultraviolet absorber is 5 to 5 parts by weight of the base resin. 20% by weight,
The adhesive layer contains a volatile antibacterial agent,
The antimicrobial packaging film is characterized in that the antimicrobial agent has a volatilization amount of 0.1 to 1.5 g / m ² when the film is heated to 150 ° C. for 20 minutes.

Further, the second invention of the present invention
At least a substrate, an adhesive layer, and a film laminated in the order of the heat-sealing resin layer, wherein the adhesive layer contains a resin, a volatile antibacterial agent and an ultraviolet absorber,
The ultraviolet absorber contains 5 to 20% by weight based on the weight of the adhesive layer resin, and
An antimicrobial packaging film, wherein the antimicrobial agent has a volatilization amount of 0.1 to 1.5 g / m ² when the film is heated to 150 ° C. for 20 minutes.

According to a third aspect of the present invention,
At least a substrate, an ultraviolet absorbing layer, an adhesive layer, and a film that is laminated in the order of the heat sealing resin layer,
The ultraviolet absorbing layer includes a resin and an ultraviolet absorbing agent, and the ultraviolet absorbing agent includes 5 to 20% by weight based on the weight of the ultraviolet absorbing layer resin.
The adhesive layer contains a volatile antibacterial agent, and
An antimicrobial packaging film, wherein the antimicrobial agent has a volatilization amount of 0.1 to 1.5 g / m ² when the film is heated to 150 ° C. for 20 minutes.

According to a fourth aspect of the present invention,
At least an ultraviolet absorbing layer, a substrate, an adhesive layer, and a film that is laminated in the order of the heat sealing resin layer,
The ultraviolet absorbing layer includes a resin and an ultraviolet absorbing agent, and the ultraviolet absorbing agent includes 5 to 20% by weight based on the weight of the ultraviolet absorbing layer resin.
The adhesive layer contains a volatile antibacterial agent, and
An antimicrobial packaging film, wherein the antimicrobial agent has a volatilization amount of 0.1 to 1.5 g / m ² when the film is heated to 150 ° C. for 20 minutes.

According to a fifth aspect of the present invention,
An antibacterial packaging film, wherein the antibacterial agent is citral.

According to a sixth aspect of the present invention,
The antibacterial packaging film, wherein the ultraviolet absorber is a benzophenone-based ultraviolet absorber.

According to a seventh aspect of the present invention,
An antibacterial packaging film, wherein a printing layer is provided between any layer between the layer containing the ultraviolet absorbent and the heat-sealing resin layer.

According to an eighth aspect of the present invention,
A packaging material comprising the antibacterial packaging film.

According to a ninth aspect of the present invention,
A packaging material comprising two or more laminated films, wherein at least one of the films is the antibacterial packaging film.

  By adopting the above configuration, the antibacterial packaging film of the present invention can prevent deterioration of the antibacterial agent under light irradiation and suppress a decrease in antibacterial activity by a layer containing a certain amount of an ultraviolet absorber while maintaining visibility. Further, by controlling the volatilization amount of the antibacterial agent to an appropriate amount, sufficient antibacterial properties can be exhibited.

FIG. 2 is a schematic sectional view showing first and second embodiments of the present invention. It is a schematic sectional view showing a 3rd embodiment of the present invention. It is a schematic sectional view showing a 4th embodiment of the present invention.

Hereinafter, the antibacterial packaging film of the present invention will be described in detail. However, the present invention is not limited to these embodiments, and other configurations belong to the present invention as long as they have similar technical features.

  In the embodiment according to the antibacterial packaging film of the present invention, at least a substrate, an adhesive layer, including a heat-fusible resin layer, the adhesive layer contains an antimicrobial agent, and the substrate, the adhesive layer, or between An ultraviolet absorber is contained in any of the layers, and 5 to 20% by weight based on the resin weight of the layer containing the ultraviolet absorber.

1 to 3 show schematic cross-sectional views of the antibacterial packaging film of the present embodiment.
FIG. 1 is a schematic sectional view showing the configuration of the first and second embodiments according to the present invention. The antibacterial packaging film 1 has an adhesive layer 20 and a heat-sealing resin layer 30 laminated on one surface of a substrate 10 in this order.

(First embodiment)
The first embodiment has a configuration as shown in FIG. 1, in which the substrate 10 contains at least a resin and an ultraviolet absorber, and contains the ultraviolet absorber in an amount of 5 to 20% by weight based on the weight of the base resin. The adhesive layer 20 contains at least a volatile antibacterial agent and an adhesive.

(Second embodiment)
The second embodiment also has a configuration as shown in FIG. 1, but the adhesive layer 20 includes an ultraviolet absorber, an antibacterial agent, and an adhesive made of resin.
In addition, the adhesive layer 20 contains 5 to 20% by weight of the ultraviolet absorbent based on the weight of the adhesive layer resin.

  FIG. 2 is a schematic sectional view showing the configuration of the third embodiment according to the present invention. The antibacterial packaging film 2 has an ultraviolet absorbing layer 40, an adhesive layer 20, and a heat-sealing resin layer 30 laminated on one surface of the substrate 10 in this order.

(Third embodiment)
The third embodiment has a configuration as shown in FIG. 2. The ultraviolet absorbing layer 40 contains at least a resin and an ultraviolet absorbing agent, and contains the ultraviolet absorbing agent in an amount of 5 to 20% by weight based on the weight of the ultraviolet absorbing layer resin.
The adhesive layer 20 contains at least a volatile antibacterial agent and an adhesive.

  FIG. 3 is a schematic sectional view showing the configuration of the fourth embodiment according to the present invention. The antibacterial packaging film 3 has a base material 10, an adhesive layer 20, and a heat-sealing resin layer 30 laminated in this order on one surface of an ultraviolet absorbing layer 40.

(Fourth embodiment)
The fourth embodiment has a configuration as shown in FIG. 3, in which the ultraviolet absorbing layer 40 contains at least a resin and an ultraviolet absorbing agent, and contains 5 to 20% by weight of the ultraviolet absorbing agent with respect to the weight of the ultraviolet absorbing layer resin.
The adhesive layer 20 contains at least a volatile antibacterial agent and an adhesive.

Although not shown, a printing layer may be provided between any of the base material 10, the adhesive layer 20, the heat-sealing resin layer 30, and the ultraviolet absorbing layer 40.
Hereinafter, the contents of each layer will be described in detail.

(Base material 10)
The substrate 10 is desirably a film having excellent mechanical strength and excellent heat resistance. Further, it is desirable that the base material 10 be formed of a material having low permeability of the antimicrobial agent used.
Non-limiting examples of materials for forming the substrate 10 include polyamide (PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), and polyamides such as nylon (NY). PA) synthetic resin selected from the group consisting of:

  The base material 10 may have a single-layer structure or a multi-layer structure. The substrate 10 preferably has a thickness of 10 μm to 50 μm. By having a film thickness in the above-described range, good workability and handleability can be obtained. Optionally, substrate 10 may be any known in the art such as plasticizers, antioxidants, colorants, fillers, antistatics, antiblocking agents, flame retardants, thickeners, etc. It may contain additives.

  When blending the base material 10 with an ultraviolet absorber, it can be dispersed in the base material by mixing with a base resin and forming a melt-extruded film. In this case, the ultraviolet absorbent is contained in an amount of 5 to 20% by weight based on the weight of the base resin.

(Adhesive layer 20)
The adhesive layer 20 contains at least an antibacterial agent and an adhesive. The adhesive layer 20 has a function of storing and releasing the antibacterial agent, and a function of bonding the base material 10 and the heat-fusible resin layer 30 or the ultraviolet absorbing layer 40 and the heat-fusible resin layer 30.
Non-limiting examples of adhesives that can be used include polyester-based adhesives, polyurethane-based adhesives, polyether-based adhesives, acrylic-based adhesives, epoxy-based adhesives, ethylene-vinyl acetate-based adhesives, and vinyl chloride. Adhesives, silicone adhesives, and rubber adhesives. If desired, the adhesive layer 20 may contain any additives known in the art, such as colorants, fillers, thickeners, and the like.

  Non-limiting examples of antimicrobial agents included in the adhesive layer 20 include terpenes such as citral, limonene. Adhesive layer 20 may include one or more antimicrobial agents.

  The adhesive layer 20 preferably has a thickness of 1 μm to 10 μm. By having a film thickness in the above-described range, the adhesive strength between the adjacent layers can be sufficiently increased, and peeling (delamination) during use or distribution can be prevented. At the same time, workability when forming the adhesive layer 20 is improved.

  If necessary, the adhesive layer 20 may contain any additive known in the art such as a coloring agent, a filler, an ultraviolet absorber, a thickener, and the like.

(Heat fusion resin layer 30)
Desirably, the heat-fusible resin layer 30 exhibits excellent adhesion to an adherend when heated. The heat sealing resin layer 30 may be a self-supporting film or a non-self-supporting layer formed by coating or the like. The heat-sealing resin layer 30 may be selected according to the required antibacterial effect and the permeation amount of the used antibacterial agent.
Non-limiting examples of materials for forming the heat sealable resin layer 30 include PE, PP, and a synthetic resin selected from the group consisting of ethylene-vinyl acetate copolymer (EVA).

  The heat-sealing resin layer 30 may be a single layer or may have a multilayer structure of a plurality of layers. It is preferable that the heat-sealing resin layer 30 has a thickness of 10 μm to 100 μm. By having a film thickness in the above-mentioned range, good workability, handleability, openability, and thermal adhesion can be obtained. If necessary, the heat-sealing resin layer 30 may include an adhesion promoter, a plasticizer, an antioxidant, a coloring agent, a filler, an antistatic agent, an antiblocking agent, a flame retardant, a thickener, and an antifogging agent. And any additives known in the art such as slip agents.

  The formation of the heat-sealing resin layer 30 can be performed by any technique known in the art, such as extrusion lamination of a heat-sealing resin and dry lamination of a heat-sealing film.

(UV absorbing layer 40)
The ultraviolet absorbing layer 40 contains at least an ultraviolet absorbing agent. Non-limiting examples of the resin used for the ultraviolet absorbing layer 40 include one or more resins selected from the group consisting of polyester-based, polyurethane-based, acrylic-based, epoxy-based, silicone-based resins, and rubber-based resins. including.

  A known method can be used as a method of applying the adhesive layer 20 and the ultraviolet absorbing layer 40. Specific examples include a gravure coater, a dip coater, a reverse coater, a wire bar coater, and a die coater.

  Non-limiting examples of UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, cyanoacrylate UV absorbers, salicylic acid UV absorbers, and the like.

  It is preferable that the UV absorber is mixed in an amount of 5% by weight or more and 20% by weight or less based on the weight of the resin used in the layer containing the UV absorber. If the amount is less than 5% by weight, it is difficult to obtain a sufficient effect of suppressing the deterioration of the antibacterial agent. If the amount exceeds 20% by weight, the adhesiveness is reduced, and the material cannot be used practically. A plurality of ultraviolet absorbers may be used.

(Antibacterial effect)
In the antibacterial film of the present embodiment, the desired spatial antibacterial effect depends on the volatilization amount of the antibacterial agent. The antimicrobial film of the present invention can achieve a desired spatial antimicrobial effect by volatilizing an antimicrobial agent in an amount of 0.1 to 1.5 g / m ² when heated to 150 ° C. for 20 minutes. it can.

(Print layer)
The printing layer can be formed by a known printing method using ink. As a printing method, for example, it can be formed by a known method such as an offset printing method, a gravure printing method, a relief printing method, an intaglio printing method, a screen printing method, and an inkjet printing method.
As the inks used in these printing methods, inks and inks suitable for the printing method, such as offset inks, letterpress inks, gravure inks, letterpress inks, intaglio inks, and inkjet inks can be used as appropriate. For example, a resin ink, an oil-based ink, and a water-based ink can be used. Further, depending on the difference in the drying method, for example, an oxidation polymerization type ink, a penetration drying type ink, an evaporation drying type ink, and an ultraviolet curing type ink can be used. Some inks used in the printing layer may fade due to light deterioration, but the configuration of the present invention makes it possible to suppress the fading of the ink at the same time.

(Packaging material)
Non-limiting examples of packaging according to the present invention include bags (MA packaging, bags with zippers, etc.), sheets, cover films, and interior cardboard. The bag-shaped packaging material can be formed by bonding the antimicrobial film of the present invention and the second film by heating the peripheral portion with the heat-sealing resin layer 30 disposed inside. The second film is formed using any material known in the art, such as PE, PET, PEN, PP, and PA, provided that it can be bonded by the heated heat-sealing resin layer 30. can do.

Alternatively, the bag-shaped wrapping material may be formed by bonding two antibacterial films by heating the peripheral portion with the heat-sealing resin layer disposed inside.
Further, a so-called "gusset" bag may be formed with a third film interposed in the peripheral portion to be bonded. The bag-shaped packaging material may have any shape including a rectangle, a circle, and a triangle. The bag with a zipper according to the present invention is provided with a fitting portion that can be freely opened and closed at the opening of the bag-shaped packaging material by machining.

  Non-limiting examples of articles packaged using the packaging material of the present invention include food, shoes, clothing, cultural properties, futons, electronics, leather products, wood products, paper products (such as books), medical devices, And cosmetics.

  Many of the articles to be packaged cause poor appearance and quality deterioration due to light, and this packaging material can prevent the antibacterial agent from deteriorating and also prevent the contents from deteriorating. Further, depending on the type of antibacterial agent used, it is also possible to reduce the unpleasant odor generated by light degradation.

(Example 1)
First, a coating composition containing 30 parts by weight of a urethane adhesive (TM-320 / CAT-13B manufactured by Toyo Ink Co., Ltd.), 65 parts by weight of ethyl acetate, and 5 parts by weight of citral was prepared. The obtained coating composition is applied to a PET film substrate having a thickness of 12 μm containing 10% by weight of a benzophenone-based ultraviolet absorber (Uvinul manufactured by BASF Japan Co., Ltd.) and dried at a temperature of 80 ° C. to form an adhesive layer. Formed. Finally, a PE (LL-XMTD manufactured by Futamura Chemical Co., Ltd.) film having a thickness of 30 μm was bonded onto the adhesive layer to form a heat-sealing resin layer, thereby obtaining an antibacterial packaging film.

(Example 2)
An antibacterial packaging film was obtained by repeating the same procedure as in Example 1 except that the amount of the benzophenone-based ultraviolet absorber contained in the PET film substrate was changed to 5% by weight.

(Example 3)
An antibacterial packaging film was obtained by repeating the same procedure as in Example 1 except that the benzophenone-based ultraviolet absorber contained in the PET film substrate was changed to 20% by weight.

(Example 4)
The coating composition for the adhesive layer contains 30 parts by weight of a urethane adhesive, 62 parts by weight of ethyl acetate, 5 parts by weight of citral, and 3 parts by weight of a benzophenone-based ultraviolet absorber (the ultraviolet absorber is 10% by weight based on the resin). The antibacterial packaging film was obtained by repeating the same procedure as in Example 1 except that the PET film substrate did not contain an ultraviolet absorber.

(Example 5)
First, a coating composition containing 30 parts by weight of a polyurethane-based resin, 67 parts by weight of ethyl acetate, and 3 parts by weight of a benzophenone-based ultraviolet absorber (the amount of the ultraviolet absorber is 10% by weight based on the resin) is prepared as an ultraviolet absorbing layer. did. The obtained coating composition was applied to a PET film substrate having a thickness of 12 μm and dried at a temperature of 80 ° C. to form an ultraviolet absorbing layer. Next, a coating composition containing 30 parts by weight of a urethane adhesive, 65 parts by weight of ethyl acetate, and 5 parts by weight of citral was prepared and applied on the ultraviolet absorbing layer to form an adhesive layer. Finally, a PE (LL-XMTD manufactured by Futamura Chemical Co., Ltd.) film having a thickness of 30 μm was bonded onto the adhesive layer to form a heat-sealing resin layer, thereby obtaining an antibacterial packaging film.

(Example 6)
First, a coating composition containing 30 parts by weight of a polyurethane resin, 67 parts by weight of ethyl acetate, and 3 parts by weight of a benzophenone-based ultraviolet absorber as an ultraviolet absorbing layer was prepared. The composition was applied to a PET film substrate having a thickness of 12 μm and dried at a temperature of 80 ° C. to form an ultraviolet absorbing layer. Next, a coating composition containing 30 parts by weight of a urethane adhesive, 65 parts by weight of ethyl acetate, and 5 parts by weight of citral was prepared, and applied to the side of the substrate opposite to the ultraviolet absorbing layer side to form an adhesive layer. Finally, a PE (LL-XMTD manufactured by Futamura Chemical Co., Ltd.) film having a thickness of 30 μm was bonded onto the adhesive layer to form a heat-sealing resin layer, thereby obtaining an antibacterial packaging film.

(Comparative Example 1)
An antibacterial packaging film was obtained by repeating the same procedure as in Example 1 except that the PET film base did not contain an ultraviolet absorber.

(Comparative Example 2)
An antibacterial packaging film was obtained by repeating the same procedure as in Example 1 except that the amount of the benzophenone-based ultraviolet absorber contained in the PET film substrate was changed to 1% by weight.

(Comparative Example 3)
The same procedure as in Example 1 was repeated, except that the benzophenone-based ultraviolet absorber contained in the PET film base was changed to 40% by weight, but the adhesion to the adhesive layer was poor, and the antibacterial packaging film was used. Could not be obtained.

From the antibacterial packaging films obtained in Examples 1 to 6 and Comparative Examples 1 and 2, samples having an area of 10 cm ² were cut out. The sample was introduced into a 20 mL vial and heated to 150 ° C. for 20 minutes. 1 mL of the gas in the vial was collected and analyzed by gas chromatography to determine the volatilization amount of citral.

  Two films are cut out from the obtained antibacterial packaging film and bonded so that the heat-sealing resin layers 30 are opposed to each other to produce a pouch having an inner size of 10 cm × 10 cm. Stored under lamp illumination.

  After one month, a bacterial solution containing Aspergillus niger at a concentration of 1.0 × 10 2 cfu / mL was applied to a circular medium having a diameter of 5 cm and stored in a pouch. The medium contained in the pouch was cultured at 25 ° C. for 3 days. The state of the medium at the end of the culture was evaluated as antibacterial. A case where the growth of Aspergillus niger was not visually observed was evaluated as “○”, and a case where the growth was visually observed was evaluated as “×”.

  Table 1 shows the evaluation results of the obtained antibacterial packaging films.

From the above results, in Examples 1 to 6, even if the antibacterial packaging film was stored under a fluorescent lamp for one month, the used antibacterial agent did not deteriorate and exhibited antibacterial properties.
However, in Comparative Example 1, since no ultraviolet absorber was used, the antibacterial agent deteriorated and no antibacterial property was obtained. In Comparative Example 2, the amount of the ultraviolet absorber added was small and the ultraviolet absorption amount was not sufficient, so that deterioration of the antibacterial agent could not be suppressed, and antibacterial properties could not be obtained. Furthermore, in Comparative Example 3, since the amount of the ultraviolet absorber added was too large, the adhesion of the film was poor, and it was difficult to form the film.

1, 2, 3 Antibacterial packaging film 10 Base material 20 Adhesive layer 30 Heat-fusible resin layer

Claims (9)

At least a substrate, an adhesive layer, and a film that is laminated in the order of the heat sealing resin layer,
The base material includes a resin and an ultraviolet absorber, and the ultraviolet absorber includes 5 to 20% by weight based on the weight of the base resin,
The adhesive layer contains a volatile antibacterial agent,
The antimicrobial packaging film, wherein the amount of the antimicrobial agent volatilized when the film is heated to 150 ° C. for 20 minutes is 0.1 to 1.5 g / m ² . At least a substrate, an adhesive layer, and a film that is laminated in the order of the heat sealing resin layer,
The adhesive layer contains a resin and a volatile antibacterial agent and an ultraviolet absorber,
The ultraviolet absorber contains 5 to 20% by weight based on the weight of the adhesive layer resin, and
An antimicrobial packaging film, wherein the antimicrobial agent has a volatilization amount of 0.1 to 1.5 g / m ² when the film is heated to 150 ° C. for 20 minutes. At least a substrate, an ultraviolet absorbing layer, an adhesive layer, and a film that is laminated in the order of the heat sealing resin layer,
The ultraviolet absorbing layer includes a resin and an ultraviolet absorbing agent, and the ultraviolet absorbing agent includes 5 to 20% by weight based on the weight of the ultraviolet absorbing layer resin.
The adhesive layer contains a volatile antibacterial agent, and
An antimicrobial packaging film, wherein the antimicrobial agent has a volatilization amount of 0.1 to 1.5 g / m ² when the film is heated to 150 ° C. for 20 minutes. At least an ultraviolet absorbing layer, a substrate, an adhesive layer, and a film that is laminated in the order of the heat sealing resin layer,
The ultraviolet absorbing layer includes a resin and an ultraviolet absorbing agent, and the ultraviolet absorbing agent includes 5 to 20% by weight based on the weight of the ultraviolet absorbing layer resin.
The adhesive layer contains a volatile antibacterial agent, and
An antimicrobial packaging film, wherein the antimicrobial agent has a volatilization amount of 0.1 to 1.5 g / m ² when the film is heated to 150 ° C. for 20 minutes.   The antibacterial packaging film according to any one of claims 1 to 4, wherein the antibacterial agent is citral.   The antibacterial packaging film according to any one of claims 1 to 5, wherein the ultraviolet absorber is a benzophenone-based ultraviolet absorber.   The antibacterial packaging film according to any one of claims 1 to 6, wherein a printing layer is provided between any of the layers between the layer containing the ultraviolet absorbent and the heat-sealing resin layer. .   A packaging material comprising the antibacterial packaging film according to claim 1.   A packaging material comprising two or more films bonded together, wherein at least one of the films is the antibacterial packaging film according to any one of claims 1 to 7.

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