JP2009101589A - Preserving laminate sheet and preserving container for solution containing cationic disinfectant ingredient - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a preserving laminate sheet for a solution containing a cationic disinfectant ingredient which is reduced in an amount of the adsorption of the cationic disinfectant ingredient, and excellent in the suppression in the decrease of the solution containing the cationic disinfectant ingredient, and a preserving container. <P>SOLUTION: A first layer of the preserving laminate sheet for the solution containing the cationic disinfectant ingredient is composed of an aromatic polyester resin and a second layer which overlies the first layer is composed of a steam barrier resin. The preserving container is formed of the preserving laminate sheet, and the first layer is formed on the inside surface side of the preserving container. By this preserving container, the adsorption of the cationic ingredient is suppressed since the first layer located in the inside surface is formed of the aromatic polyester resin, and the suppression of the decrease of the solution stored in the preserving container can be achieved because it is possible to restrain the solution from oozing out in the form of steam out of the preserving container since the second layer is formed of the steam barrier resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminated sheet for storing a solution containing a cationic sterilizing component and a storage container.

  In general, a disinfectant-containing solution such as a contact lens disinfectant is filled with about 70 to 500 mL of a large-capacity container made of a single layer such as polypropylene and is manufactured and sold. In this way, when the amount of the solution stored in the container is large, the contact rate of the solution with the inner surface of the container is small, so that the disinfectant is also hardly adsorbed. In addition, since the large-capacity container is sufficiently thick, the weight change due to water vapor transmission is relatively suppressed.

However, since it is inconvenient to carry these large-capacity containers or carry them for a short trip, a small-capacity / light-weight type convenient for carrying is desired.
Patent documents 1 to 5 are publicly known.

  Patent Document 1 relates to a contact lens care product containing one or more surfactants and one or more antibacterial agents packaged in a PET (polyethylene terephthalate) container.

Patent Document 2 discloses a laminate for forming a sheet composed of easily moldable stretched polyester / first polypropylene / gas barrier resin / second polypropylene.
Patent Document 3 discloses a multilayer in which a gloss resin layer (A), a water vapor barrier layer (B), a gas barrier layer (C), and a support resin layer (D) are laminated in the order of ABCD from the outside. It relates to the sheet.

  Patent Document 4 relates to a medical device, in which at least a part of a container is made of a multilayer material, a first layer of the multilayer material is made of polyolefin or the like, and a second layer is made of polyester or the like.

Patent Document 5 relates to a sheet in which an amorphous unstretched polyethylene terephthalate resin layer is laminated on both sides of a polypropylene resin layer via an adhesive layer, and a thermal container made of the same. Patent Document 5 relates to containers for beverages such as juice and sake, and aims to enable heating in a microwave oven or the like without causing heat shrinkage in a high-temperature filling step.
Special table 2007-513654 gazette Japanese Patent Laid-Open No. 4-147858 (the third page of the lower left, lines 13 to 19) JP 2000-263730 A JP 2000-255642 A Japanese Patent Laid-Open No. 4-153022

  By the way, although the portable compact case for accommodating the disinfectant containing solution is sold conventionally, the small-capacity container and the storage case are not disposable. In addition, when using a portable compact case (small volume container), it is necessary to transfer the solution from the large volume container that contains the disinfectant-containing solution to the small volume container. There are also problems in hygiene, such as neglecting to clean the capacity container and the risk of contamination of the solution in the large capacity container by mistaken transfer operation. In view of hygiene and simplicity, it is desirable that the small-capacity container be a single use type.

  In this case, since the amount of liquid stored in the small-capacity container is as small as about 3 to 30 mL, the contact ratio of the solution to the inner surface of the container is increased. For this reason, when a disinfectant-containing solution such as a contact lens disinfectant is stored in a small-capacity container, there is a concern that cationic disinfectants and the like may be adsorbed onto the container during long-term storage. At the same time, when the liquid volume is as small as 3 to 30 mL, even if a disinfectant-containing solution is placed in a small-capacity container, the weight of the solution decreases due to water vapor permeation, thereby reducing the stability of the solution. There is a fear.

  In Patent Document 1, a PET container and an antibacterial agent are disclosed, but the PET container is intended as a single-layer bottle, and there is no disclosure of a laminated sheet. Patent Document 2 discloses that a polyethylene terephthalate film is unsuitable as a material for forming a sheet and cannot be employed as an easily moldable stretched polyester. The multilayer sheet of Patent Document 3 was developed for foods and beverages, and is a multilayer sheet having hermeticity, heat resistance, transparency, and glossiness, and the surface in contact with the contents is the support resin layer (D) The glossy resin layer (PET) is positioned as a layer for obtaining transparency and glossiness of the appearance, and is completely different from the configuration of the present invention. In Patent Document 4, there is a description of polyester in the second layer, but the second layer is mainly intended for an adhesive layer, and aliphatic polyesters and polymerizable polyesters are preferred as adhesive components. However, it has no purpose as a polyester layer. In Patent Document 4, the same material is exemplified for the first layer and the third layer, and the second layer functions as an adhesive layer for the purpose of bonding these layers. And in patent document 4, it is related with the package which can carry out UV irradiation sterilization, and technical composition and the objective differ from this invention. In patent document 5, since the use is different from the present invention, the subject of the present invention is not raised. That is, Patent Document 5 does not mention prevention of adsorption of the bactericide and prevention of weight reduction of the contents, and is not a configuration intended to obtain these effects.

  In the present invention, by adhering the second layer made of the water vapor barrier resin to the first layer made of the aromatic polyester resin, the adsorption amount of the cationic sterilizing component is small, and the decrease in the solution containing the cationic sterilizing component is suppressed. It is an object of the present invention to provide a laminated sheet for storage of a solution containing a cationic sterilizing component excellent in the above and a storage container.

  SUMMARY OF THE INVENTION The present invention provides a laminated sheet for preserving a solution containing a cationic sterilizing component, wherein a second layer made of a water vapor barrier resin is laminated on a first layer made of an aromatic polyester resin. It is what.

In addition, a storage container may be constituted by the storage laminated sheet, and it is particularly preferable that the first layer is provided on the inner surface side of the storage container.
The aromatic polyester resin is preferably made of polyethylene terephthalate.

Further, the storage container preferably includes a base and a top. Moreover, it is preferable that the said base is equipped with a curvature prevention layer as a 3rd layer.
The water vapor barrier resin may be made of polyolefin.

The polyolefin is preferably polypropylene. In this case, the thickness of the polypropylene layer is preferably 50 to 100 μm.
Furthermore, the thickness of the polyethylene terephthalate layer is preferably 30 to 500 μm.

  According to the present invention, by laminating the second layer made of the water vapor barrier resin on the first layer made of the aromatic polyester resin, the adsorption amount of the cationic sterilizing component is small and the solution containing the cationic sterilizing component is reduced. The effect which was excellent in suppression of this.

Hereinafter, embodiments of the present invention will be described.
A laminated sheet for storing a solution containing a cationic sterilizing component is a laminated sheet in which a first layer made of an aromatic polyester resin and a second layer made of a water vapor barrier resin are laminated on the first layer. .

  As the aromatic polyester resin constituting the first layer, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTMT), polypropylene terephthalate (PPT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polybutylene A terephthalate (PBT) etc. can be mentioned. A particularly preferred material is polyethylene terephthalate (PET). The thickness of the polyethylene terephthalate layer is preferably 30 to 500 μm, and more preferably 50 to 200 μm. When the layer thickness is less than 30 μm, sheet formation cannot be performed. On the other hand, when the thickness of the layer exceeds 500 μm, the strength is excessively increased and the handling is deteriorated, and in the thermoforming, the heating time is increased and the moldability is also deteriorated. By comprising a 1st layer with an aromatic polyester resin, adsorption | suction of the below-mentioned cationic germicide contained in a solution is suppressed.

  Examples of the water vapor barrier resin constituting the second layer include polyolefins such as polyethylene (PE) and polypropylene (PP), polyvinyl chloride (PVC), and polyvinylidene chloride (PVDC). A particularly preferred material is polypropylene (PP). The thickness of the polypropylene layer is preferably 50 to 1000 μm. When the thickness of the polypropylene layer is less than 50 μm, a sufficient water vapor barrier function is not exhibited. As the thickness of the polypropylene layer increases, the water vapor barrier property is exhibited. However, when the thickness exceeds 1000 μm, the strength is excessively increased and the handling becomes worse.

Further, examples of the water vapor barrier resin include inorganic vapor-deposited PET (for example, alumina vapor-deposited PET, silica vapor-deposited PET, aluminum vapor-deposited PET, etc.) in addition to the above materials.
As a configuration of the laminated sheet, in addition to the first layer and the second layer, a warp preventing layer may be provided as a third layer on the opposite side of the second layer from the first layer. Due to the difference in material between the first layer and the second layer, there is a case where the sheet is warped at the time of sheet forming. Therefore, it is possible to prevent the laminated sheet from warping by laminating the third layer on the second layer. As the third layer, it is preferable to use the same material as the first layer or the same kind of material.

  As a method of laminating these first layer and second layer, or first layer, second layer, and third layer, known laminating methods such as coextrusion method, coextrusion laminating method, extrusion laminating method, dry laminating method, etc. Technology is used. Further, in order to bond these resins for lamination, an adhesive or adhesive resin suitable for each resin is used, but it may be unnecessary. Further, as a method for forming these multilayer sheets into a storage container, a vacuum forming method, a pressure forming method, a pressure vacuum forming method, and a cold working method are generally used.

  When forming as a storage container, the inner surface side of the container is used as the first layer, the outer surface side is used as the second layer or the third layer, and the first layer is in contact with the solution. Deploy. The shape of the storage container is not limited, and a blister case, a potion, etc. can be appropriately employed. An example of a storage container is a contact lens storage container including a base and a top.

  In the case of a laminated sheet or a storage container prepared from a laminated sheet, the first layer and the third layer are PET layers, the second layer is a PP layer, the first layer and the third layer are PEN layers, the second layer The layer may be a PP layer, the first and third layers may be a PET layer, the second layer may be a polyvinylidene chloride layer, and the like.

  The top may have the same two-layer or three-layer structure as the base, or may have a two-layer structure of a PET layer and an inorganic vapor-deposited PET layer. The top may be formed in a sheet shape or a film shape.

  In the present specification, a film means a film having a thickness of less than 0.2 mm, and a sheet means a film having a thickness of 0.2 mm or more. When the top is formed into a film, the PET layer may be formed as a PET sealant and an inorganic vapor-deposited PET layer may be laminated on the PET sealant, and the top may be adhered to the base by heat sealing, or an adhesive may be used. It may be used and glued to the base. In either case, the top PET layer will face the solution. In addition, when the top is formed of a laminated sheet having a three-layer structure, the PET layer is disposed on the side facing the solution, and is fitted to be removably fitted into the opening of the recessed region provided in the base. You may make it form a protrusion.

The base is a container body provided with a recessed region for storing contact lenses, solutions, and the like. The top is a lid that can seal the recessed region of the container body.
Examples of the cationic disinfectant contained in the solution stored in the storage container include polyhexamethylene biguanide (hereinafter referred to as PHMB), benzalkonium chloride, chlorhexidine hydrochloride, polyquaternium-4, and polyquaternium-22. However, it is not limited to these. Applications of the solution (solution) containing the cationic bactericide include various bactericides for hand washing, contact lens cleaning liquid, eye drops, cosmetics, and the like.

Now, according to said embodiment, there exist the following effects.
(1) According to this embodiment, the first layer of the laminated sheet for storage of a solution containing a cationic sterilizing component is composed of an aromatic polyester resin, and the second layer is made of a water vapor barrier resin with respect to the first layer. By laminating the layers, the adsorption amount of the cationic sterilizing component is small, and the reduction of the solution containing the cationic sterilizing component can be simultaneously suppressed.

  (2) Also, according to the present embodiment, the first layer is composed of an aromatic polyester resin and the second layer laminated on the first layer is stored from a laminated sheet composed of a water vapor barrier resin. A container is formed, and the first layer is provided on the inner surface side of the storage container. Thereby, even if the solution containing the cationic sterilizing component is stored in the storage container, the adsorption amount of the cationic sterilizing component is small, and the decrease in the solution containing the cationic sterilizing component can be suppressed at the same time. That is, since the first layer located on the inner surface of the storage container is an aromatic polyester resin, the adsorption of the cationic sterilizing component is suppressed, and the second layer is a water vapor barrier resin, so that the solution is Leakage to the outside of the storage container as water vapor can be suppressed, and reduction of the solution stored in the storage container can be suppressed.

  (3) Moreover, according to this embodiment, the aromatic polyester resin which comprises a 1st layer is comprised by PET, As a storage container, the adsorption amount of a cationic sterilization component can be decreased easily.

  (4) According to this embodiment, when the storage container is composed of the base and the top, the first layer of the base and the top is composed of the aromatic polyester resin, and the second layer is composed of the water vapor barrier resin. Become. Thereby, in the storage container composed of the base and the top, the adsorption amount of the cationic sterilizing component is small, and the reduction of the solution containing the cationic sterilizing component can be suppressed at the same time.

  (5) In this embodiment, the base is provided with a warp preventing layer as the third layer, so that it may warp during sheet molding due to the difference in material between the first layer and the second layer. The warpage can be prevented by laminating to the second layer.

  (6) In this embodiment, since the water vapor barrier resin constituting the second layer is made of polyolefin, the storage container can be prevented from easily leaking out of the storage container as water vapor as a storage container. The reduction of the solution stored in the storage container can be suppressed.

  (7) According to this embodiment, since the water vapor barrier resin constituting the second layer is made of polypropylene as the polyolefin, a sufficient water vapor barrier function can be exhibited. Moreover, when the thickness of this polypropylene layer is in the range of 50 to 1000 μm, it is possible to provide a storage container that can exhibit a sufficient water vapor barrier function and is easy to handle.

  (8) According to the present embodiment, polyethylene terephthalate is used as the aromatic polyester resin constituting the first layer, and when the layer thickness is in the range of 30 to 500 μm, sheet formation can be facilitated and moderate. Strength is obtained and handling is not deteriorated, and there is an effect that moldability is improved during thermoforming of the storage container.

Next, examples and comparative examples of the present invention will be described.
The laminated sheets of Examples and Comparative Examples were produced by a co-extrusion method, and a container body having an opening at the top and having a flange as a storage container was produced by a vacuum forming method. And after storing 8 mL of the solutions of the following examples or comparative examples in the container body (base), the inorganic vapor-deposited PET layer on the PET sealant layer (PET layer: thickness 30 μm) as the top against the flange of the container body A film-shaped top (thickness: 42 μm) laminated with (thickness: 12 μm) was adhered by heat sealing to produce a container with the opening sealed.

  In Example 1, as the material of the container body, the first layer, the second layer, and the third layer were formed of PET, PP, and PET, respectively, and their thicknesses were set to 100 μm, 350 μm, and 100 μm, respectively. Moreover, the top inorganic vapor deposition PET layer of Example 1 was formed with alumina vapor deposition PET, and PHMB aqueous solution was put in the container main body.

  In Example 2, as the material of the container body, the first layer, the second layer, and the third layer were formed of PET, PP, and PET, respectively, and the thicknesses thereof were 100 μm, 100 μm, and 100 μm, respectively. The top inorganic vapor-deposited PET layer of Example 2 and the solution in the container body were the same as in Example 1.

In Example 3, the material and thickness of the container body and the solution in the container body were the same as in Example 1. Moreover, the top inorganic vapor deposition PET layer of Example 3 was formed by silica vapor deposition PET.
In Example 4, the material and thickness of the container body and the solution in the container body were the same as in Example 1. Moreover, the top inorganic vapor deposition PET layer of Example 4 was formed with aluminum vapor deposition PET.

  In Example 5, as the material of the container body, the first layer, the second layer, and the third layer were formed of PEN, PP, and PEN, respectively, and the thicknesses thereof were 100 μm, 350 μm, and 100 μm, respectively. Moreover, the top inorganic vapor deposition PET layer of Example 5 was formed with alumina vapor deposition PET, and PHMB aqueous solution was put in the container main body.

  In Example 6, as the material of the container body, the first layer, the second layer, and the third layer were formed of PET, polyvinylidene chloride, and PEN, respectively, and the thicknesses thereof were set to 100 μm, 350 μm, and 100 μm, respectively. Moreover, the top inorganic vapor deposition PET layer of Example 6 was formed with alumina vapor deposition PET, and PHMB aqueous solution was put in the container main body.

In Example 7, the material of the container body, the thickness, and the top inorganic vapor-deposited PET layer were the same as in Example 1. And the benzalkonium chloride solution was put in the container main body of Example 7.
In Example 8, the material and thickness of the container main body and the top inorganic vapor-deposited PET layer were the same as in Example 1. The chlorhexidine hydrochloride solution was placed in the container body of Example 8.

  In Comparative Example 1, as the material of the container body, the first layer, the second layer, and the third layer were formed of PET, PP, and PET, respectively, and the thicknesses thereof were 100 μm, 40 μm, and 100 μm, respectively. Moreover, the top inorganic vapor deposition PET layer of the comparative example 1 and the solution accommodated in a container main body were made the same as Example 1, respectively.

  In Comparative Example 2, the material of the container body was formed of a natural PP single layer, and the thickness was 600 μm. Moreover, the top inorganic vapor deposition PET layer of the comparative example 2 and the solution accommodated in a container main body were made the same as Example 1, respectively.

  In Comparative Example 3, the material of the container main body was formed of a PET single layer, and the thickness was 200 μm. Moreover, the top inorganic vapor deposition PET layer of the comparative example 3 and the solution accommodated in a container main body were made the same as Example 1, respectively.

なお、表１中、容器保体の欄における括弧内の数値は、厚さ（単位μｍ）を示している。

In Table 1, the numerical value in parentheses in the column of the container carrier indicates the thickness (unit: μm).

The test methods for the bactericidal agent reduction rate and the weight reduction rate in the examples and comparative examples produced as described above will be described below.
1. Bactericidal agent reduction rate 1-1. Calculation of bactericidal concentration in solution stored in container carrier Cationic bactericide (PHMB), benzalkonium chloride, and chlorhexidine hydrochloride in each adjusted solution prepared with each cationic bactericide Was determined, and the value was taken as the initial concentration. Regarding PHMB, a PHMB extract in a solution is prepared using a solid phase extraction method, and the absorbance at the maximum absorption wavelength (237 nm) in the ultraviolet region of the extract is measured. From the absorbance ratio with the standard solution, The initial concentration was calculated. For benzalkonium chloride and chlorhexidine hydrochloride, the initial concentration was calculated from the area ratio with the standard solution using a liquid chromatograph.

  The solution in which the cationic bactericidal agent was quantified was filled in the container of each example and each comparative example, and was stored at 40 ° C. for 3 months while being sealed with a top inorganic vapor-deposited PET layer. The cationic fungicide in each stored solution was quantified in the same manner as the initial concentration. This quantified value was used as the concentration after storage.

1-2. Calculation of bactericidal agent reduction rate The bactericidal agent reduction rate was calculated by the following formula.
Fungicide reduction rate [%] = ((initial concentration−concentration after storage) / initial concentration) × 100
2. Weight reduction rate Prepare a solution containing each cationic fungicide, fill each container with 8 mL (note that each solution has a specific gravity of 1), and measure its weight (ie, the total weight of the container and the solution) did. The value obtained by this measurement was used as the initial weight. The weight of each container after storage at 40 ° C. for 3 months (that is, the total weight of the remaining solution and the container) was measured. The measured value at this time was defined as weight after storage. Using these values, the weight loss rate was calculated by the following formula. In the following formula, the weight of the filling liquid is the weight of the solution filled in each container.

Weight reduction rate [%] = ((initial weight−weight after storage) / weight of filling liquid) × 100
3. Judgment criteria for ◯ In the examples and comparative examples, the bactericidal agent reduction rate was 0 for less than 10%, ◯ for 10-20%, and x for 20% or more.

  The weight reduction rate was 0 for less than 5%, ◯ for less than 5-10%, and x for 10% or more.

表２で分かるように、実施例１〜８は、殺菌剤減少率及び重量減少率の両者とも◎又は○の評価であり、同時に殺菌剤減少率及び重量減少率の抑制ができたレベルとなった。それに対して、比較例１〜３は、殺菌剤減少率又は重量減少率のいずれかが×の評価となり、両方の減少率の抑制を同時に満足するレベルまでのものはなかった。

As can be seen from Table 2, Examples 1 to 8 are both evaluations of 又 は or ○ for both the germicide reduction rate and the weight loss rate, and at the same time the levels of the germicide reduction rate and the weight loss rate can be suppressed. It was. On the other hand, in Comparative Examples 1 to 3, either the bactericidal agent reduction rate or the weight reduction rate was evaluated as x, and none of the levels satisfied the suppression of both reduction rates at the same time.

  From this result, in Examples 1-8, it was confirmed that the adsorption amount of the cationic sterilizing component is small, and that the container containing the cationic sterilizing component can be suppressed at the same time.

In addition, embodiment of this invention is not limited to the said embodiment, You may change a structure as follows.
In the above embodiment, the contact lens storage container is embodied. However, any storage container other than the contact lens may be embodied as long as it is a storage container that stores a solution containing a cationic sterilizing component. .

Claims (8)

  A laminated sheet for storing a solution containing a cationic sterilizing component, wherein a second layer made of a water vapor barrier resin is laminated on a first layer made of an aromatic polyester resin.   A storage container comprising the laminated sheet according to claim 1, wherein the first layer is provided on an inner surface side of the storage container.   The storage container according to claim 2, wherein the aromatic polyester resin is made of polyethylene terephthalate.   The storage container according to claim 2 or 3, comprising a base and a top.   The storage container according to claim 4, wherein the base includes a warp preventing layer as a third layer.   The storage container according to claim 2, wherein the water vapor barrier resin is a polyolefin.   The storage container according to claim 6, wherein the polyolefin is polypropylene, and the thickness of the polypropylene layer is 50 to 1000 μm.   The storage container according to claim 3, wherein the polyethylene terephthalate layer has a thickness of 30 to 500 μm.