JP2019119128A - Protective member and molded body - Google Patents

Abstract

To provide a protective member constituted by a laminate sheet, suitable for an application to contact with an aqueous liquid over a long time.SOLUTION: There is provided a protective member 10 used for an application to contact with an aqueous liquid continuously or intermittently over a long time, constituted by a laminate sheet having a resin layer 1, a barrier layer 3 and a thermoplastic resin layer 4 in this order, in which water vapor permeation rate as whole layer positioned closer to the resin layer 1 than the barrier layer 3 is 40 g/m/24 h or less. There is provided a protective member 10, preferably having an adhesive layer between the resin layer 1 and the barrier layer 3.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a protective member and a molded body.

  Conventionally, contents (for example, sensors (temperature, pressure, water flow, water pressure, etc.), wireless devices, power supplies, electronic components, heat exchange, etc. in places where there are many chances of contact with water, such as bathrooms, kitchens, inside of reservoirs, outdoors, etc. In order to prevent the contact of an object etc. with the aqueous liquid for a long period of time, a protective member formed of resin or metal is used.

  On the other hand, various sheet-like protective members for protecting the contents from water are known, and for example, as materials for protecting contents from water, light, etc., packaging materials for retort food are It is common.

  The packaging material for retort food has a structure in which a resin layer is disposed on both sides of a metal layer such as aluminum foil, and after heating the food to be sterilized by heating, the food as the content is protected from air and light. When cooking, it plays a role to prevent food from coming into direct contact with boiling water (see, for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 5-200894

  However, conventional retort food packaging materials are not premised to be in contact with water for a long period of time. Therefore, when the retort food packaging material is in contact with water for a long time, there is a problem that the resin layer on the outside of the metal layer peels off from the metal layer.

  As a result of investigations by the present inventors, such peeling of the resin layer is not only a factor due to the infiltration of water from the end where the resin layer and the metal layer are laminated, but the end is protected from water. Also in this case, it was revealed that moisture permeates from the surface of the resin layer and the peeling progresses.

  For this reason, the configuration of the conventional retort food packaging material is an application that prevents the contents from coming into contact with the aqueous liquid over a long period of time in a bathroom, kitchen, inside of a water tank, outside, etc. Was not suitable for

  Under such circumstances, according to the present invention, the reduction in the peel strength between the layers constituting the protective member is suppressed even when it is in contact with the aqueous liquid over a long period of time, and the application uses the aqueous liquid over a long period of time It is a main object of the present invention to provide a protective member composed of a laminated sheet, which is suitable for Furthermore, another object of the present invention is to provide a molded body obtained by molding the protective member.

The present inventors diligently studied to solve the above-mentioned problems. As a result, it is comprised from a lamination sheet provided with a resin layer, a barrier layer, and a thermoplastic resin layer at least in this order, and the water vapor transmission rate as the whole of the layer located in the resin layer side rather than the barrier layer. protective member but is not more than 40g / m ² / 24h, even when contacted with an aqueous liquid over a long period of time, decrease are suppressed in peel strength between the layers constituting the protective member, continuous over a long period of time or It has been found that it can be used particularly suitably for applications in which the aqueous liquid intermittently contacts.

Moreover, the present inventors are comprised from the lamination sheet provided with a resin layer, a barrier layer, and a thermoplastic resin layer at least in this order, and the water vapor transmission rate of a resin layer is 40 g / m < ² > / 24 h or less. When a protective member is in contact with an aqueous liquid over a long period of time, the decrease in peel strength between the layers constituting the protective member is suppressed, and the application in which the aqueous liquid contacts continuously or intermittently over a long period of time It has been found that it can be used particularly preferably.

  Furthermore, the present inventors are comprised from the lamination sheet provided with a resin layer, a barrier layer, and a thermoplastic resin layer in this order at least, and the temperature 120 degreeC, pressure 2 atm, and the environment of 100% of relative humidity 72. The tensile fracture stress retention ratio in the direction perpendicular to the laminating direction of the laminated sheet before and after being left for a time is 85% or more (that is, the protective member has an environment of 120 ° C., pressure 2 atm, relative humidity 100%) 72 The tensile failure stress in the direction perpendicular to the lamination direction of the laminated sheet after being left for a time is 85% or more of the tensile fracture stress in the direction perpendicular to the lamination direction of the laminated sheet before leaving. Even when in contact with the aqueous liquid over a period of time, the decrease in peel strength between the layers constituting the protective member is suppressed, and the aqueous continuously or intermittently for a long period of time Body found that can be used particularly preferably in contact applications.

  The present invention is an invention completed by repeating studies based on these findings.

That is, the present invention provides the inventions of the aspects listed below.
Item 1. A protective member used for applications in which an aqueous liquid contacts continuously or intermittently for a long period of time,
The protective member is composed of a laminated sheet provided with at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order,
The protective member whose water-vapor-permeation rate as the whole layer located in the said resin layer side rather than the said barrier layer is 40 g / m < ² > / 24 h or less.
Item 2. A protective member used for applications in which an aqueous liquid contacts continuously or intermittently for a long period of time,
The protective member is composed of a laminated sheet provided with at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order,
The water vapor permeability of the resin layer is not more than 40g / m ² / 24h, the protective member.
Item 3. A protective member used for applications in which an aqueous liquid contacts continuously or intermittently for a long period of time,
The protective member is composed of a laminated sheet provided with at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order,
The protective member has a tensile fracture stress retention rate of 85% or more in a direction perpendicular to the laminating direction of the laminated sheet before and after being left for 72 hours in an environment with a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100%. , Protection member.
Item 4. The protection member in any one of claim | item 1-3 which has an adhesive bond layer between the said resin layer and the said barrier layer.
Item 5. 5. The protective member according to item 4, wherein the resin constituting the adhesive layer has a polyolefin skeleton.
Item 6. Item 6. The protective member according to Item 4 or 5, wherein the adhesive layer contains an acid-modified polyolefin.
Item 7. 7. The protective member according to any one of Items 4 to 6, wherein when the adhesive layer is analyzed by infrared spectroscopy, a peak derived from maleic anhydride is detected.
Item 8. A resin composition, wherein the adhesive layer comprises the acid-modified polyolefin, and a curing agent having at least one selected from the group consisting of an oxygen atom, a heterocyclic ring, a C = N bond, and a C—O—C bond. Item 8. The protective member according to item 6 or 7, which is a cured product of
Item 9. A cured product of a resin composition, wherein the adhesive layer comprises the acid-modified polyolefin, and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound containing an epoxy group. 8. The protective member according to item 6 or 7.
Item 10. 5. The protective member according to item 4, wherein the resin constituting the adhesive layer is polyurethane.
Item 11. Item 11. The protective member according to any one of Items 1 to 10, wherein the barrier layer is an aluminum foil.
Item 12. Item 12. The protective member according to any one of Items 1 to 11, wherein the resin layer contains at least one selected from the group consisting of polyethylene naphthalate, polybutylene terephthalate, and polypropylene.
Item 13. The molded object by which the protection member in any one of claim | item 1-12 is shape | molded.
Item 14. The package whose content is accommodated using the protection member in any one of claim | item 1-12.
Item 15. What is claimed is: 1. A method of manufacturing a protective member for use in applications in which an aqueous liquid contacts continuously or intermittently for a long period of time, comprising:
And a step of laminating at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order to obtain the protective member composed of a laminated sheet,
Wherein the overall water vapor permeability of the layer located on the said resin layer side of the barrier layer of the protective member or less 40g / m ² / 24h, a manufacturing method of the protective member.
Item 16. What is claimed is: 1. A method of manufacturing a protective member for use in applications in which an aqueous liquid contacts continuously or intermittently for a long period of time, comprising:
And a step of laminating at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order to obtain the protective member composed of a laminated sheet,
A manufacturing method of a protection member which makes tensile fracture stress retention rate of a perpendicular direction 85% or more with a lamination direction of a lamination sheet before and after being left to stand in environment of temperature 120 ° C, pressure 2 atm, and relative humidity 100% for 72 hours.

  According to the present invention, the reduction in peel strength between the layers constituting the protective member is suppressed even when it is in contact with the aqueous liquid for a long period of time, and it is suitable for applications in which the aqueous liquid is in contact for a long period of time. A protective member composed of a laminated sheet can be provided. Further, according to the present invention, it is also possible to provide a molded body obtained by molding the protective member.

It is a schematic diagram which shows an example of the cross-section of the protection member of this invention. It is a schematic diagram which shows an example of the cross-section of the protection member of this invention. It is a schematic diagram which shows an example of the cross-section of the protection member of this invention. It is a schematic diagram which shows an example of the cross-section of the protection member of this invention.

The first protective member of the present invention is a protective member used for applications in which an aqueous liquid is in contact continuously or intermittently for a long period of time. The first protective member is composed of a laminated sheet including at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order, and water vapor as a whole of the layer located on the resin layer side with respect to the barrier layer transmittance equal to or less than 40g / m ² / 24h.

The second protective member of the present invention is also a protective member used for applications in which the aqueous liquid contacts continuously or intermittently for a long period of time. The second protective member comprises at least a resin layer, and the barrier layer is composed of a thermoplastic resin layer of a laminated sheet comprising in this order, a water vapor permeability of the resin layer is not more than 40 g / m ² / 24h It is characterized by

  Furthermore, the third protective member of the present invention is also a protective member used for applications in which the aqueous liquid contacts continuously or intermittently for a long time. The third protective member is composed of a laminated sheet provided with at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order, and the temperature is 120 ° C., the pressure is 2 atm, and the relative humidity is 100% for 72 hours. The tensile fracture stress retention ratio in the direction perpendicular to the lamination direction of the laminated sheet before and after being left is 85% or more.

  Each of the protective members of the present invention is excellent in water resistance because it has the above-mentioned configuration, and the peel strength between the layers constituting the protective member even when in contact with an aqueous liquid for a long period of time The reduction is suppressed and it is suitably used for applications in contact with aqueous liquids over a long period of time. In addition, the 1st protection member, the 2nd protection member, and the 3rd protection member are put together, and it is called protection member of the present invention. Hereinafter, the protection member of the present invention will be described in detail.

  In addition, in this specification, the numerical range shown by "-" means "or more" and "or less." For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.

1. Laminated Structure, Physical Properties, Application of Protective Member The protective member of the present invention is constituted of a laminated sheet having at least a resin layer 1, a barrier layer 3 and a thermoplastic resin layer 4 in this order as shown in FIG. There is. In the protective member of the present invention, the resin layer 1 is on the outermost layer side, and the thermoplastic resin layer 4 is on the innermost layer. In protecting the contents by the protective member 10 of the present invention, the contents are protected from the contact of the aqueous liquid for a long period of time by accommodating the contents with the thermoplastic resin layer 4 inside. Can.

  In the present invention, the aqueous liquid means a liquid containing water, and the content of water in the aqueous liquid is, for example, 50 mass% or more, 70 mass% or more, 90 mass% or more, 99 % By mass, 100% by mass, and the like. Besides water, for example, an organic solvent may be mixed to adjust the freezing point or the boiling point. Examples of the organic solvent include ethylene glycol and the like.

  When the contents are accommodated with the thermoplastic resin layer 4 being on the inner side, for example, a molded article obtained by molding the protective member of the present invention is used, and the thermoplastic resin layers 4 located at the periphery of the contents are The contents can be sealed by sealing.

  The protective member of the present invention may be provided with an adhesive layer 2 between the resin layer 1 and the barrier layer 3 as shown in, for example, FIGS. Further, as shown in FIGS. 3 and 4, an adhesive layer 5 may be provided between the barrier layer 3 and the thermoplastic resin layer 4. Furthermore, as shown in FIG. 4, a surface coating layer 6 may be provided on the outer side of the resin layer 1 (the side opposite to the thermoplastic resin layer 4) as necessary.

In the first protection member of the present invention, overall water vapor transmission rate of the layer located on the resin layer 1 side of the barrier layer 3 is less than 40g / m ² / 24h. That is, for example, a resin layer 1 than the barrier layer 3 is located on the resin layer 1 side, the water vapor transmission rate of the sum of an adhesive layer 2 which is provided if necessary, at most 40g / m ² / 24h. From the viewpoint of further improving the water resistance over a long period of time, as the water vapor transmission rate of the entire layer located on the resin layer 1 side of the barrier layer 3, preferably not more than 36g / m ² / 24h, more preferably 20g / m ² / 24h or less and the like, more preferably include the following 15g / m ² / 24h. The lower limit of the water vapor transmission rate, for example, 0g / m ² / 24h or more, 0.1g / m ² / 24h or more, 1g / m ² / 24h or more and 3g / m ² / 24h or more. Also in the second protective member and the third protection member, it is preferable that the water vapor transmission rate is less than 40 g / m ² / 24h, more preferably at most ^{36g / m 2 / 24h, 20g} / more preferably m is ² / 24h or less, still more preferably not more than 15g / m ² / 24h. The range of the water vapor transmission rate of the entire layer located on the resin layer 1 side of the barrier layer 3, for example, 0~40g / m ² / 24h approximately, 0~36g / m ² / 24h approximately, 0～20G / m ² / 24h approximately, 0.1~40g / m ² / 24h approximately, 0.1~36g / m ² / 24h approximately, 0.1~20g / m ² / 24h approximately, 1~40g / m ² / about 24h, 1~36g / m ² / 24h approximately, 1~20g / m ² / 24h approximately, 3~40g / m ² / 24h approximately, 3~36g / m ² / 24h approximately, 3~20g / m ² / About 24 h.

In the first protection member of the present invention, in order to overall water vapor transmission rate of the layer located on the resin layer 1 side of the barrier layer 3 is below 40g / m ² / 24h, for example, as the resin layer 1 water vapor permeability (1 m ² (area of one side) per) can be mentioned a method of using the following about 40g / m ² / 24h. Moreover, if even a water vapor permeability of the resin layer 1 (1 m ² of (one side of the area) per) exceeds about 40g / m ² / 24h, between the resin layer 1 and the barrier layer 3, the adhesive layer by providing two such, it is also possible to set the water vapor permeability of the entire below 40g / m ² / 24h.

As described below, in the first protective member and the third protection member, it is preferable that water vapor permeability of only the resin layer 1 (1 m ² (one side of the area) per) of less than about 40g / m ² / 24h , more preferably less than about 36g / m ² / 24h, more preferably less than about 20g / m ² / 24h, more preferably not more than 15g / m ² / 24h. The lower limit of the water vapor transmission rate is 0g / m ² / 24h. The range of the water vapor transmission rate of only a resin layer 1, preferably 0~40g / m ² / 24h, more preferably about 0~36g / m ² / 24h or so, more preferably 0~20g / m ² / 24h approximately Can be mentioned.

Incidentally, as in the second protective member, the first protective member and the third protection member, by water vapor transmission rate of only a resin layer 1 is not more than 40 g / m ² / 24h, than the barrier layer 3 the water vapor transmission rate of the entire layer located on the resin layer 1 side, suitably can be set below 40g / m ² / 24h.

To the water vapor transmission rate of only a resin layer 1 below 40g / m ² / 24h, for example, the resin layer 1 is formed of a resin described later also preferably assumed to be described later for the thickness of the resin layer 1 .

In the present invention, 1 m ² (area of one side) water vapor transmission rate per the only resin layer ^{1 (g / m 2 / 24h} ) is a value measured by the following method. Water vapor transmission using a water vapor transmission rate measuring device by differential pressure method under a measurement condition of temperature 40 ° C., relative humidity 90%, measurement period 24 hours, measurement area 8 cmφ, adopting a method based on the provisions of ISO 15106-5 2008. Measure the rate. The water vapor transmission rate per 1 m ² is calculated by converting the water vapor transmission rate into 1 m ² . Water vapor transmission rate per 1 m ^2, specifically, it can be measured by the method described in Examples. In the present invention, the measurement of the water vapor transmission rate of the whole layer located closer to the resin layer than the barrier layer is also measured in the same manner. For example, a laminate of the resin layer 1 and the adhesive layer 2 is prepared, and the measurement is performed on the laminate in the same manner as the water vapor transmission rate of only the resin layer 1.

  The third protective member of the present invention is perpendicular to the laminating direction of the laminated sheet constituting the protective member before and after being left for 72 hours in an environment with a temperature of 120 ° C., a pressure of 2 atm and a relative humidity of 100%. The tensile fracture stress retention rate in the direction is 85% or more. From the viewpoint of further improving water resistance over a long period, the tensile fracture stress retention rate is preferably about 88% or more, more preferably about 90% or more. Also in the first protective member and the second protective member, it is preferable to satisfy the tensile fracture stress retention rate.

  The tensile fracture stress retention rate may be 85% or more in at least one direction of the direction perpendicular to the lamination direction of the laminated sheet constituting the protective member, preferably in the direction of MD (Machine Direction). Is preferably 85% or more (more preferably about 88% or more, more preferably about 90% or more), and more preferably 85% or more (more preferably about 88%) with respect to the direction of MD and the direction of TD (Transverse Direction). Or more, more preferably about 90% or more).

  In addition, in the lamination sheet which comprises the protection member, MD and TD in the manufacturing process can be normally discriminate | determined about the below-mentioned barrier layer. For example, in the case where the barrier layer is made of aluminum foil, in the rolling direction (RD: Rolling Direction) of the aluminum foil, linear streaks called so-called rolling marks are formed on the surface of the aluminum foil. Since the rolling marks extend along the rolling direction, the rolling direction of the aluminum foil can be grasped by observing the surface of the aluminum foil. In the process of manufacturing the laminated sheet, usually, the MD of the laminated sheet matches the RD of the aluminum foil, so the surface of the aluminum foil of the laminated sheet is observed to specify the rolling direction (RD) of the aluminum foil. Thus, the MD of the laminated sheet can be identified. Further, since the TD of the laminated sheet is perpendicular to the MD of the laminated sheet, the TD of the laminated sheet can also be specified.

  In the present invention, the tensile fracture stress retention before and after being left for 72 hours in an environment with a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100% conforms to JIS K7127: 1999, and the test piece has a rectangular shape. The size of the test piece is a value calculated from tensile fracture stress measured with a width of 15 mm × length of 150 mm and a test speed of 200 mm / min. The tensile breaking stress can be specifically measured by the method described in the examples.

  The third protective member of the present invention has a tensile breaking stress (initial tensile breaking stress) of about 10 to 200 MPa before being left for 72 hours in an environment of a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100%. Preferably it is about 20-180 MPa, and it is further more preferable that it is about 50-150 MPa. Also in the first protective member and the second protective member, it is preferable to satisfy the tensile breaking stress. In addition, these tensile breaking stress is a value measured in calculation of a tensile breaking stress retention.

  In the third protective member of the present invention, the tensile fracture stress retention ratio in the direction perpendicular to the laminating direction of the laminated sheet constituting the protective member before and after being left in water at a temperature of 98 ° C. for 30 days is also Is preferably 85% or more, more preferably 88%, and still more preferably 90%. The tensile fracture stress retention rate may also be 85% or more, preferably 85% or more in the MD direction, in at least one direction of the direction perpendicular to the lamination direction of the laminated sheet constituting the protective member. (More preferably about 88% or more, more preferably about 90% or more), more preferably 85% or more (more preferably about 88% or more, still more preferably about 90% or more) in both the MD direction and the TD direction Or more).

  In the present invention, the tensile fracture stress retention before and after being left in water at a temperature of 98 ° C. for 30 days is an environment with a pressure of 1 atm instead of leaving in an environment with a temperature of 120 ° C., a pressure of 2 atm and a relative humidity of 100%. With the value determined based on the tensile fracture stress retention before and after being left in the environment of temperature 120 ° C and relative humidity 100% for 72 hours except that the substrate is left in water at temperature 98 ° C for 30 days. Specifically, it can be determined by the method described in the examples.

  The third protective member of the present invention is also preferably about 10 to 200 MPa with respect to tensile fracture stress (initial tensile fracture stress) before being left in water at a temperature of 98 ° C. for 30 days, preferably 20 to 180 MPa. The degree is more preferably about 50 to about 150 MPa. Also in the first protective member and the second protective member, it is preferable to satisfy the tensile breaking stress. In addition, these tensile breaking stress is a value measured in calculation of a tensile breaking stress retention.

In the protective member of the present invention, the water vapor transmission rate of the entire layer located on the resin layer 1 side is equal to or less than 40g / m ² / 24h than the barrier layer 3, and a temperature of 120 ° C., pressure 2 atm, relative humidity It is particularly preferable that the tensile fracture stress retention ratio in the direction perpendicular to the laminating direction of the laminated sheet constituting the protective member is 85% or more before and after leaving in a 100% environment for 72 hours. That is, in the protective member of the present invention, excellent water resistance over a particularly long period of time is achieved by combining both the first protective member and the third protective member in the water vapor transmission rate and the tensile fracture stress retention rate. Sex is exhibited. The preferable values of the water vapor transmission rate and the tensile fracture stress retention rate are also as described above.

In the protective member of the present invention, before and after the water vapor permeability of the resin layer 1 is not more than 40g / m ² / 24h, and the temperature 120 ° C., is left for 72 hours at a pressure 2 atm, 100% relative humidity environment It is particularly preferable that the tensile fracture stress holding ratio in the direction perpendicular to the laminating direction of the laminated sheet in which the protective member is 85% or more. That is, in the protective member of the present invention, the water vapor transmission rate and the tensile fracture stress retention rate both have particularly high water resistance over a long period of time by combining both the second protective member and the third protective member. Sex is exhibited. The preferable values of the water vapor transmission rate and the tensile fracture stress retention rate are also as described above.

  Although the conventional retort food packaging materials are usually in contact with the aqueous liquid continuously or intermittently for several minutes, at most about 30 minutes, the protective member of the present invention has a long period of time It is a protection member used for the use which an aqueous fluid contacts continuously or intermittently. The protective member of the present invention is continuous or discontinuous for a long period of, for example, 2 hours or more, or for a long period of 12 hours or more, 24 hours or more, 72 hours or more, 7 days or more, 30 days or more, or 1 year or more. It may also be used in applications where aqueous liquids are in contact.

  The protective member of the present invention is used to protect the contents from contact with an aqueous liquid for a long period of time, and the specific application is not particularly limited. Content in kitchens, water reservoirs, outdoors, etc. (eg, sensors (temperature, pressure, water flow, water pressure, etc.), wireless devices, power supplies, electronic components, heat exchangers, etc.) Used for the purpose of preventing over a period of time. The protective member of the present invention is used, for example, for a long period of time to suppress decomposition or reaction of a heat-sensitive material such as a temperature sensor or a material to be heat-exchanged by direct contact with an aqueous liquid. . In particular, when the content is an electronic device, if the aqueous liquid contacts the electronic device, the electronic component is sealed with the protective member of the present invention, causing the electronic device to be continuous or intermittent for a long period of time. It can be suitably used for applications in which the aqueous liquid comes into contact with the

  In addition, in the protective member of the present invention, peeling between the resin layer and the barrier layer of the laminated sheet constituting the protective member before and after being left for 72 hours in an environment of temperature 120 ° C., pressure 2 atm and relative humidity 100%. The strength retention is preferably 20% or more, more preferably 50% or more, and still more preferably 80% or more. In the present invention, the peel strength retention is a value determined by the following method, and specifically, can be determined by the method described in the examples.

<Peeling strength retention rate>
The protective member is cut into a strip of width 15 mm × length 100 mm to form a test piece. First, to measure the initial peel strength T ₁ as follows. About 10 mm is peeled off in the length direction between the resin layer and the barrier layer of the test piece. Next, the resin layer and the barrier layer side of the test piece are respectively sandwiched by the upper and lower chucks, and pulled in the direction of 180 ° at a speed of 50 mm / min using a tensile tester to obtain the initial peel strength T ₁ of the test piece Measure N / 15 mm). Further, to measure the peel strength T ₂ in the following manner. The test piece is left for 72 hours in an environment at a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100%. Next, about 10 mm is peeled in the length direction between the resin layer of the test piece and the barrier layer. Next, the resin layer and the barrier layer side of the test piece are respectively sandwiched by the upper and lower chucks, and pulled in the direction of 180 ° at a speed of 50 mm / min using a tensile tester to separate the peel strength T _{2 of the} test piece (N Measure / 15 mm). The ratio (%) of the peel strength T ₂ to the peel strength T ₁ (T ₂ / T ₁ × 100) is calculated to be the peel strength retention.

  The thickness of the laminated sheet constituting the protective member 10 of the present invention is not particularly limited, but the thickness of the protective member is reduced to make the product containing the contents smaller while providing excellent water resistance over a long period of time In view of the above, the upper limit is, for example, about 200 μm or less, preferably about 180 μm or less, more preferably about 150 μm or less, and the lower limit is preferably about 50 μm or more, more preferably 60 μm or more. As a preferable range, about 50-200 micrometers, about 50-180 micrometers, about 50-150 micrometers, about 60-200 micrometers, about 60-180 micrometers, about 60-150 micrometers are mentioned.

  The protective member of the present invention is formed into a molded body by molding so as to be able to accommodate the contents, and is used for the purpose of protecting the contents. That is, according to the shape of the content as described above, the protective member of the present invention can be formed into a desired shape to form a molded body. For example, a molded body having a space for containing the contents can be obtained by molding using a mold or the like so as to project from the thermoplastic resin layer side of the protective member of the present invention to the resin layer side. . The protective member of the present invention can also be made into a bag-like molded body having a space for containing the contents, by heat-sealing the peripheral portions in a state where the thermoplastic resin layers are opposed to each other.

2. Each Layer Forming a Protective Member [Resin Layer 1]
In the protective member of the present invention, the resin layer 1 is a layer located on the outermost layer side.

In the first protection member, for the material for forming the resin layer 1, as long as the overall water vapor permeability of the layer located on the resin layer 1 side of the barrier layer 3 is less than 40g / m ² / 24h For example, it is not particularly limited. In the second protection member, as long as the water vapor transmission rate of the resin layer 1 becomes less than 40 g / m ² / 24h, not particularly limited. In the third protective member, tension in the direction perpendicular to the laminating direction of the laminated sheet constituting the protective member before and after being left for 72 hours in an environment of temperature 120 ° C., pressure 2 atm, relative humidity 100%. There is no particular limitation as long as the retention of fracture stress is 85% or more.

In the first protection member, the water vapor transmission rate of only a resin layer 1 is preferably not more than about 40g / m ² / 24h, more preferably less than about 36g / m ² / 24h, around 20 g / m still more preferably ² / 24h or less, and more preferably greater than about 15g / m ² / 24h.

In the second protection member, the water vapor transmission rate of only a resin layer 1, may not more than 40 g / m ² / 24h, preferably more than about 36 g / m ² / 24h, around 20 g / m still more preferably ² / 24h or less, still more preferably not more than 15g / m ² / 24h.

  On the other hand, in the third protective member, the water vapor transmission rate may not be the above value, but it is preferable to satisfy the value of the first protective member or the second protective member.

  In the protective member of the present invention, as a material for forming the resin layer 1, for example, polyester resin, polyolefin resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicone resin, phenol resin, polycarbonate, and the like Resin films, such as a mixture and a copolymer, are mentioned. Among these, preferred are polyester resins and polyolefin resins, and more preferred are polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, polybutylene naphthalate, copolyester, polypropylene and the like.

  From the viewpoint of effectively reducing the water vapor transmission rate, the resin layer 1 preferably contains at least one of polyethylene naphthalate, polybutylene terephthalate and polypropylene, and polyethylene naphthalate, polybutylene terephthalate and polypropylene It is more preferable that it is comprised by at least 1 sort (s) among these.

  The resin layer 1 may be formed of a resin film of one layer, but may be formed of a resin film of two or more layers in order to improve water resistance over a long period of time. Specific examples thereof include a multilayer structure in which a plurality of polyester films are laminated, and a multilayer structure in which a polyester film and a polypropylene film are laminated. Preferred specific examples of the multilayer structure include a multilayer structure in which two layers of polybutylene terephthalate film are laminated, a multilayer structure in which two layers of polyethylene naphthalate film are laminated, and a multilayer structure in which a polybutylene terephthalate film and a polyethylene naphthalate film are laminated. And a multilayer structure in which a polybutylene terephthalate film and a polypropylene film are laminated, and a multilayer structure in which a polyethylene naphthalate film and a polypropylene film are laminated. In the case where the resin layer 1 has a multilayer structure, the thickness of each layer is preferably about 2 to 25 μm.

  When the resin layer 1 is formed of a multilayer resin film, two or more resin films may be laminated via an adhesive or an adhesive component such as an adhesive resin, and the type and amount of adhesive components used Is the same as in the case of the adhesive layer 2 described later. In addition, it does not restrict | limit especially as a method to laminate the resin film of two or more layers, A well-known method can be adopted, for example, a dry laminating method, a sandwich laminating method, etc. are mentioned, Preferably a dry laminating method is mentioned. When laminating by the dry lamination method, it is preferable to use a urethane type adhesive as an adhesive layer. At this time, the thickness of the adhesive layer is, for example, about 2 to 5 μm.

  About the thickness of the resin layer 1, in the 1st protection member, the above-mentioned water vapor transmission rate (water vapor transmission rate as the whole layer located in the resin layer 1 side rather than the barrier layer 3) should just be satisfied. Further, in the second protective member, it is sufficient that the above-described water vapor transmission rate of the resin layer 1 can be satisfied. Furthermore, in the third protective member, the tensile fracture stress holding ratio (a direction perpendicular to the laminating direction of the laminated sheet before and after being left for 72 hours in an environment of temperature 120 ° C., pressure 2 atm, relative humidity 100%) It is sufficient if the tensile fracture stress retention ratio of The thickness of the resin layer 1 is preferably about 3 to 50 μm, more preferably about 10 to 35 μm.

[Adhesive layer 2]
In the protective member 10 of the present invention, the adhesive layer 2 is a layer provided between the resin layer 1 and the barrier layer 3 as needed in order to bond the resin layer 1 and the barrier layer 3 firmly.

  The adhesive layer 2 is formed of an adhesive (resin) capable of adhering the resin layer 1 and the barrier layer 3. The adhesive used to form the adhesive layer 2 may be a two-part curable adhesive, or may be a one-part curable adhesive. Furthermore, the adhesive used to form the adhesive layer 2 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type, and the like.

  Specific examples of the adhesive component that can be used to form the adhesive layer 2 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, copolyester, etc .; Adhesives; Polyurethane adhesive; Epoxy resin; Phenolic resin resin; Polyamide resin such as nylon 6, nylon 66, nylon 12, copolymerized polyamide; Polyolefin resin such as polyolefin, carboxylic acid modified polyolefin, metal modified polyolefin Resin, polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; polycarbonate; amino resin such as urea resin, melamine resin; chloroprene rubber, nitrile rubber , Styrene - rubber such as butadiene rubber; and silicone resins. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, preferred are polyurethane adhesives or epoxy adhesives.

  Further, from the viewpoint of further improving the water resistance over a long period of time, it is preferable to use an adhesive component having excellent water resistance as an adhesive component that can be used for forming the adhesive layer 2. As an adhesive component excellent in water resistance, polyurethane, an epoxy resin, etc. are mentioned. Among these, as resin which comprises the adhesive bond layer 2, polyurethane is preferable. The polyurethane can be formed, for example, by a combination of a polyol compound and a polyisocyanate compound, a combination of a polyurethane compound having a hydroxyl group and a polyisocyanate compound, a combination of a polyurethane compound having an isocyanate group and a polyol compound, and the like. Each of these combinations can be used as a two-part polyurethane adhesive. In addition, a polyurethane compound having an isocyanate group may be cured by reaction with moisture such as in the air to form a polyurethane.

Moreover, as resin used for formation of the adhesive bond layer 2, polyolefin resin, such as polyolefin, cyclic polyolefin, acid-modified polyolefin, acid-modified cyclic polyolefin, can also be used suitably. That is, the resin constituting the adhesive layer 2 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The resin constituting the adhesive layer 2 can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, etc., as long as it contains a polyolefin skeleton, and there is no particular limitation on the analysis method. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

  From the viewpoint of further improving the water resistance over a long period while reducing the thickness of the protective member, the adhesive layer 2 preferably contains an acid-modified polyolefin. The acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of a polyolefin with an acid component such as a carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or anhydrides thereof. Moreover, as the polyolefin to be modified, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, etc .; homopolypropylene, block copolymer of polypropylene (for example, block copolymer of propylene and ethylene), polypropylene Polypropylenes such as random copolymers (e.g., random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like. Among these polyolefins, preferably polyethylene and polypropylene are mentioned.

  Among the acid-modified polyolefins in the adhesive layer 2, in particular, maleic anhydride-modified polyolefin and further maleic anhydride-modified polypropylene are preferable.

  Furthermore, from the viewpoint of further improving the water resistance over a long period while reducing the thickness of the protective member, the adhesive layer 2 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent. More preferable. As the acid-modified polyolefin, preferably, those described above can be exemplified.

  Hereinafter, various aspects in which the adhesive layer 2 is a cured product of a resin composition containing a curing agent will be described in detail.

  The adhesive layer 2 is a cured product of a resin composition containing an acid-modified polyolefin, and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group. Particularly preferred is a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group. In the case where a non-reacted substance of a curing agent such as a compound having an isocyanate group, a compound having an oxazoline group, or an epoxy resin remains in the adhesive layer 2, the presence of the non-reacted substance is, for example, infrared spectroscopy. It is possible to confirm by a method selected from Raman spectroscopy, time of flight secondary ion mass spectrometry (TOF-SIMS) and the like.

  The adhesive layer 2 preferably contains at least one selected from the group consisting of polyurethane, amide ester resin, and epoxy resin, and more preferably contains polyurethane and epoxy resin. The adhesive layer 2 is more preferably a cured product of a resin composition containing at least one of these resins and the acid-modified polyolefin.

  The adhesive layer 2 is a cured product of a resin composition containing a curing agent having at least one selected from the group consisting of oxygen atoms, heterocycles, C = N bonds, and C—O—C bonds. Is also preferred. As a curing agent which has a heterocyclic ring, the curing agent which has an oxazoline group, the curing agent which has an epoxy group, etc. are mentioned, for example. Moreover, as a curing agent having a C = N bond, a curing agent having an oxazoline group, a curing agent having an isocyanate group, and the like can be mentioned. Moreover, as a curing agent which has a C-O-C bond, the curing agent which has an oxazoline group, the curing agent which has an epoxy group, the combination which forms the above-mentioned polyurethane, etc. are mentioned. The adhesive layer 2 is a cured product of a resin composition containing these curing agents, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry ( It can confirm by methods, such as TOF-SIMS) and X-ray photoelectron spectroscopy (XPS).

  Although it does not restrict | limit especially as a compound which has an isocyanate group, Preferably a polyfunctional isocyanate compound is mentioned. The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and polymerizing or nucleating these. And mixtures thereof, and copolymers with other polymers.

  As content of the compound which has an isocyanate group, in the resin composition which comprises the adhesive bond layer 2, 0.1-50 mass%, 0.5-40 mass% is mentioned, for example. At this time, the said acid-modified polyolefin is mentioned as a remainder.

  The compound having an oxazoline group is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the compound having an oxazoline group include those having a polystyrene main chain, and those having an acryl main chain. Further, as a commercially available product, for example, Epocross series manufactured by Nippon Shokubai Co., Ltd. and the like can be mentioned.

  As a ratio of the compound which has an oxazoline group, in the resin composition which comprises the adhesive bond layer 2, 0.1-50 mass% and 0.5-40 mass% are mentioned, for example. At this time, the said acid-modified polyolefin is mentioned as a remainder.

  As a compound which has an epoxy group, an epoxy resin is mentioned, for example. The epoxy resin is not particularly limited as long as it is a resin capable of forming a cross-linked structure by an epoxy group present in the molecule, and a known epoxy resin can be used. The weight average molecular weight of the epoxy resin is preferably about 50 to about 2000, more preferably about 100 to about 1000, and still more preferably about 200 to about 800. In the present invention, the weight average molecular weight of the epoxy resin is a value measured by gel permeation chromatography (GPC), which is measured under the condition of using polystyrene as a standard sample.

  Specific examples of the epoxy resin include glycidyl ether derivative of trimethylolpropane, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether and the like. The epoxy resin may be used alone or in combination of two or more.

  As a ratio of the epoxy resin in the adhesive bond layer 2, 0.1-50 mass%, 0.5-40 mass% is mentioned in the resin composition which comprises the adhesive bond layer 2, for example. At this time, the said acid-modified polyolefin is mentioned as a remainder.

  As a ratio of the polyurethane in the adhesive bond layer 2, in the resin composition which comprises the adhesive bond layer 2, 0.1-50 mass%, 0.5-40 mass% is mentioned, for example. At this time, the said acid-modified polyolefin is mentioned as a remainder.

  In the present invention, in the resin composition, the adhesive layer 2 contains at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and an epoxy resin, and the acid-modified polyolefin. In the case of a cured product, the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the epoxy resin each function as a curing agent.

  The thickness of the adhesive layer 2 is not particularly limited as long as it exhibits the function as a layer to be adhered, but it is preferable to use, for example, those exemplified as an adhesive component that can be used for forming the adhesive layer 2. About 1-10 micrometers, More preferably, about 1-5 micrometers are mentioned. Moreover, if it comprises with polyolefin resin, such as polyolefin and an acid-modified polyolefin resin, Preferably it is about 2-50 micrometers, More preferably, about 10-40 micrometers is mentioned. In the case of a cured product of a resin composition containing a curing agent, it is preferably about 30 μm or less, more preferably about 0.1 to 20 μm, and still more preferably about 0.5 to 5 μm. In the case where the adhesive layer 2 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 2 may be formed by applying the resin composition and curing it by heating or the like. it can.

[Barrier layer 3]
In the protective member of the present invention, the barrier layer 3 is a layer having a function to prevent water vapor, oxygen, light and the like from invading the inside of the protective member, in addition to the strength improvement of the protective member. The barrier layer 3 is preferably a metal layer, that is, a layer formed of a metal. Specifically as a metal which comprises the barrier layer 3, aluminum, stainless steel, titanium etc. are mentioned, Preferably aluminum is mentioned. The barrier layer 3 can be formed of, for example, a metal foil, a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, a film provided with these vapor deposition films, or the like. It is more preferable to form by aluminum alloy foil. From the viewpoint of preventing the occurrence of wrinkles and pinholes in the barrier layer 3 during the production of the protective member, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: 1994 A8079H It is more preferable to form by soft aluminum alloy foil, such as -O, JISH4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O).

  The thickness of the barrier layer 3 is not particularly limited as long as it can exhibit excellent water resistance over a long period of time, but preferably about 0.1 to 300 μm, more preferably about 10 to 100 μm, and still more preferably about 10 to 80 μm. It can be mentioned.

  In addition, it is preferable that at least one surface, preferably both surfaces, of the barrier layer 3 be subjected to chemical conversion treatment in order to stabilize adhesion, to prevent dissolution or corrosion, and the like. Here, the chemical conversion treatment means a treatment for forming an acid resistant film on the surface of the barrier layer. As the chemical conversion treatment, for example, chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium borate, chromium biphosphate, chromium acetate, acetyl acetate, chromium chloride, potassium chromium sulfate, etc .; Phosphoric acid treatment using phosphoric acid compounds such as sodium acid, potassium phosphate, ammonium phosphate, polyphosphoric acid and the like; using an aminated phenol polymer having repeating units represented by the following general formulas (1) to (4) And chromate treatment. In the aminated phenol polymer, repeating units represented by the following general formulas (1) to (4) may be contained singly or in any combination of two or more. It is also good.

In general formulas (1) to (4), X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. Also, R ¹ and R ² are the same or different and each independently represent a hydroxyl group, an alkyl group or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group, C1-C4 linear or branched alkyl groups, such as a tert- butyl group, are mentioned. Also, examples of the hydroxyalkyl group represented by X, R ¹ and R ² include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3- C1-C4 linear or branched with one hydroxyl group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group etc. substituted An alkyl group is mentioned. In the general formulas (1) to (4), the alkyl group and the hydroxyalkyl group represented by X, R ¹ and R ² may be identical to or different from each other. In the general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having repeating units represented by the general formulas (1) to (4) is, for example, preferably about 500 to 1,000,000, and about 1 to 20,000. More preferable.

  In addition, as a chemical conversion treatment method for imparting corrosion resistance to the barrier layer 3, a coating in which fine particles of aluminum oxide, titanium oxide, cerium oxide, metal oxide such as tin oxide, or barium sulfate are dispersed in phosphoric acid is coated; A method of forming an acid resistant film on the surface of the barrier layer 3 can be mentioned by carrying out the baking treatment at 150 ° C. or higher. In addition, on the acid resistant film, a resin layer may be further formed by crosslinking the cationic polymer with a crosslinking agent. Here, as the cationic polymer, for example, polyethylene imine, an ionic polymer complex composed of polyethylene imine and a polymer having a carboxylic acid, primary amine graft acrylic resin obtained by graft polymerizing a primary amine on an acrylic main skeleton, polyallylamine Or derivatives thereof, aminophenol and the like. As these cationic polymers, only 1 type may be used and you may use combining 2 or more types. Moreover, as a crosslinking agent, the compound which has an at least 1 sort (s) of functional group chosen from the group which consists of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, a silane coupling agent etc. are mentioned, for example. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.

  Moreover, as a method of specifically providing an acid resistant coating, for example, at least the surface on the inner layer side of an aluminum alloy foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method as one example. Degreasing treatment by a known treatment method such as acid activation method, and then the degreasing surface is treated with metal phosphate such as chromium phosphate, titanium phosphate, zirconium phosphate, zinc phosphate and the like Treatment solution (aqueous solution) mainly composed of a mixture of metal salts, or treatment solution (aqueous solution) mainly composed of a mixture of nonmetal phosphate and nonmetal salts thereof, or acrylic resin with these Or applying a treatment solution (aqueous solution) composed of a mixture with a phenolic resin or an aqueous synthetic resin such as a urethane resin by a known coating method such as a roll coating method, a gravure printing method, or an immersion method. Ri, it is possible to form the acid-resistant coating. For example, when treated with a chromium phosphate salt treatment liquid, it becomes an acid-resistant film composed of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc., and is treated with a zinc phosphate salt treatment liquid In the case of an acid resistant coating, the coating is made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride and the like.

  Moreover, as another example of the specific method of providing an acid resistant film, for example, at least the surface on the inner layer side of an aluminum alloy foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid resistant film can be formed by degreasing treatment by a known treatment method such as activation method and then applying known anodic oxidation treatment to the degreasing treatment surface.

  Moreover, phosphate-based and chromic acid-based films are mentioned as another example of the acid resistant film. Examples of phosphates include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate and chromium phosphate. Examples of chromic acid include chromium chromate.

  In addition, as another example of the acid-resistant film, a resin, such as a phosphate, a chromate, a fluoride, or a triazine thiol compound, is formed between the aluminum and the resin layer at the time of embossing by forming the acid-resistant film. Anti-lamination, dissolution and corrosion of aluminum surface, in particular, dissolution and corrosion of aluminum oxide present on the surface of aluminum are prevented, and adhesion (wettability) of aluminum surface is improved, and resin layer at the time of heat sealing The effect of preventing delamination between aluminum and aluminum and preventing delamination between the resin layer and aluminum during press molding is shown in the embossed type. Among the substances forming the acid resistant film, an aqueous solution composed of three components of a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is applied to the aluminum surface, and the treatment of dry baking is good.

  The acid resistant film further comprises a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent for crosslinking the anionic polymer, wherein the phosphoric acid or phosphate is any of the above-mentioned. About 1 to 100 parts by mass may be blended with 100 parts by mass of cerium oxide. It is preferable that the acid resistant film has a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.

  Furthermore, it is preferable that the said anionic polymer is a copolymer which has poly (meth) acrylic acid or its salt, or (meth) acrylic acid or its salt as a main component. Moreover, it is preferable that the said crosslinking agent is at least 1 sort (s) chosen from the group which consists of a compound which has a functional group in any one of an isocyanate group, glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.

  Moreover, it is preferable that the said phosphoric acid or phosphate is condensed phosphoric acid or condensed phosphate.

  For the chemical conversion treatment, only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion treatments may be performed in combination. Furthermore, these chemical conversion treatments may be performed using one type of compound alone, or may be performed using two or more types of compounds in combination. Among the chemical conversion treatments, a chromate treatment, a chemical conversion treatment in which a chromium compound, a phosphoric acid compound, and an aminated phenol polymer are combined, and the like are preferable. Among the chromium compounds, chromic acid compounds are preferred.

  Specific examples of the acid resistant coating include those containing at least one of phosphate, chromate, fluoride, and triazine thiol. In addition, an acid resistant film containing a cerium compound is also preferable. As a cerium compound, cerium oxide is preferable.

  Moreover, as a specific example of an acid resistant film, a phosphate type film, a chromate type film, a fluoride type film, a triazine thiol compound film, etc. are mentioned. The acid resistant coating may be one of these or a combination of two or more. Furthermore, as an acid resistant coating, after degreasing the surface of the aluminum alloy foil on the chemical conversion treatment, a treatment liquid comprising a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a nonmetallic phosphate and an aqueous synthetic resin It may be formed of a treatment liquid comprising

The analysis of the composition of the acid-resistant film can be performed using, for example, time-of-flight secondary ion mass spectrometry. Analysis of the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry detects, for example, a peak derived from at least one of Ce ⁺ and Cr ⁺ .

  It is preferable that the surface of the aluminum alloy foil is provided with an acid resistant film containing at least one element selected from the group consisting of phosphorus, chromium and cerium. In addition, it is confirmed using X-ray photoelectron spectroscopy that at least one element selected from the group consisting of phosphorus, chromium and cerium is contained in the acid-resistant film on the surface of the aluminum alloy foil of the protective member. Can. Specifically, first, in the protective member, the thermoplastic resin layer, the adhesive layer, and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is placed in an electric furnace, and the organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Thereafter, X-ray photoelectron spectroscopy of the surface of the aluminum alloy foil is used to confirm that these elements are contained.

The amount of acid-resistant coatings to be formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, for example, in the case of performing the above-mentioned chromate treatment, the surface 1 m ² per barrier layer 3, the chromium compound is chromium About 0.5 to 50 mg, preferably about 1.0 to 40 mg in conversion, about 0.5 to 50 mg of phosphorus compound in terms of phosphorus, preferably about 1.0 to 40 mg, and 1 to 200 mg of aminated phenolic polymer Desirably, it is desirable to be contained at a rate of about 5.0 to 150 mg.

  The thickness of the acid-resistant coating is not particularly limited, but is preferably about 1 nm to 10 μm, more preferably about 1 to 100 nm, from the viewpoint of the cohesion of the coating and the adhesion to the barrier layer 3 and the thermoplastic resin layer. More preferably, about 1 to 50 nm can be mentioned. The thickness of the acid resistant coating can be measured by transmission electron microscopy or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy.

  In the chemical conversion treatment, the temperature of the barrier layer is 70 after the solution containing the compound used for forming the acid resistant coating is applied to the surface of the barrier layer by the bar coating method, roll coating method, gravure coating method, immersion method or the like. It is carried out by heating to about 200 ° C. In addition, before the chemical conversion treatment is performed on the barrier layer, the barrier layer may be subjected in advance to a degreasing treatment by an alkaline immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like. By performing the degreasing treatment in this manner, the chemical conversion treatment on the surface of the barrier layer can be performed more efficiently.

[Thermoplastic resin layer 4]
In the protective member of the present invention, the thermoplastic resin layer 4 corresponds to the innermost layer, and for example, when the contents are accommodated, the thermoplastic resin layers are thermally fused to seal the contents by the protective member. Can.

The resin component used for the thermoplastic resin layer 4 is not particularly limited as long as it can be heat-fused, but examples include polyolefins, cyclic polyolefins, acid-modified polyolefins, and acid-modified cyclic polyolefins. That is, the resin constituting the thermoplastic resin layer 4 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The resin constituting the thermoplastic resin layer 4 can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, etc., as long as it contains a polyolefin skeleton, and the analysis method is not particularly limited. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

  Specific examples of the polyolefin include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; homopolypropylene, block copolymers of polypropylene (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers of (e.g., random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like. Among these polyolefins, preferably polyethylene and polypropylene are mentioned.

  The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, isoprene and the like. . Moreover, as a cyclic monomer which is a constituent monomer of the cyclic polyolefin, for example, cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like can be mentioned. Among these polyolefins, preferred are cyclic alkenes, more preferably norbornene.

  The acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with an acid component such as a carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or anhydrides thereof.

  The acid-modified cyclic polyolefin is prepared by copolymerizing part of the monomers constituting the cyclic polyolefin with an α, β-unsaturated carboxylic acid or an anhydride thereof, or α, β- to the cyclic polyolefin. It is a polymer obtained by block polymerization or graft polymerization of unsaturated carboxylic acid or its anhydride. The cyclic polyolefin to be carboxylic acid modified is the same as described above. Moreover, as a carboxylic acid used for modification | denaturation, it is the same as that of the acid component used for modification | denaturation of the said polyolefin.

  Among these resin components, preferred are polyolefins such as polypropylene, carboxylic acid-modified polyolefins, and more preferably polypropylene and acid-modified polypropylenes.

  The thermoplastic resin layer 4 may be formed of one type of resin component alone, or may be formed of a blend polymer in which two or more types of resin components are combined. Furthermore, the thermoplastic resin layer 4 may be formed of only one layer, but may be formed of two or more layers of the same or different resin components.

  The thickness of the thermoplastic resin layer 4 is not particularly limited as long as it exhibits the function as a thermoplastic resin layer, but from the viewpoint of exhibiting excellent water resistance over a long period, it is preferably 100 μm or less, more preferably Is about 15 to 60 μm, and more preferably about 15 to 40 μm.

[Adhesive layer 5]
In the protective member of the present invention, the adhesive layer 5 is a layer which is optionally provided between the barrier layer 3 and the thermoplastic resin layer 4 in order to firmly bond them.

  The adhesive layer 5 is formed of a resin capable of adhering the barrier layer 3 and the thermoplastic resin layer 4. As the adhesive layer 5, the same adhesive component and resin as exemplified for the adhesive layer 2 can be used.

  Similar to the adhesive layer 2 described above, from the viewpoint of further improving water resistance over a long period of time, it is preferable to use an adhesive component having excellent water resistance as an adhesive component that can be used to form the adhesive layer 5. As an adhesive component excellent in water resistance, polyurethane, an epoxy resin, etc. are mentioned.

Moreover, as resin used for formation of the contact bonding layer 5, polyolefin resin, such as polyolefin, cyclic polyolefin, acid-modified polyolefin, acid-modified cyclic polyolefin, can also be used. That is, the resin constituting the adhesive layer 5 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. It is possible to analyze that the resin constituting the adhesive layer 5 contains a polyolefin skeleton, for example, by infrared spectroscopy, gas chromatography mass spectrometry, etc., and there is no particular limitation on the analysis method. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

  As in the case of the adhesive layer 2, the adhesive layer 5 preferably contains an acid-modified polyolefin from the viewpoint of making the protective member excellent in shape stability after molding while reducing the thickness of the protective member. The acid-modified polyolefin is as described for the adhesive layer 2 described above.

  Among the acid-modified polyolefins in the adhesive layer 5, in particular, maleic anhydride-modified polyolefin, and more preferably maleic anhydride-modified polypropylene are preferable.

  Further, from the viewpoint of making the protective member excellent in shape stability after molding while reducing the thickness of the protective member, the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent. Is more preferred. As the acid-modified polyolefin, preferably, those described above can be exemplified.

  The various aspects in which the adhesive layer 5 is a cured product of a resin composition containing a curing agent are the same as the adhesive layer 2 described above.

  The thickness of the adhesive layer 5 is not particularly limited as long as it exhibits a function as an adhesive layer, but for example, those exemplified as adhesive components that can be used for forming the adhesive layer 5 (that is, used for forming the adhesive layer 2) In the case of using a possible adhesive component), it is preferably about 1 to 10 μm, more preferably about 1 to 5 μm. Moreover, if it comprises with polyolefin resin, such as polyolefin and an acid-modified polyolefin resin, Preferably it is about 2-50 micrometers, More preferably, about 10-40 micrometers is mentioned. In the case of a cured product of a resin composition containing a curing agent, it is preferably about 30 μm or less, more preferably about 0.1 to 20 μm, and still more preferably about 0.5 to 5 μm. When the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing it by heating or the like.

[Surface covering layer 6]
In the protective member of the present invention, it is necessary on the resin layer 1 (the opposite side of the resin layer 1 to the barrier layer 3) as needed for the purpose of improving designability, abrasion resistance, moldability, etc. According to the above, the surface covering layer 6 may be provided. The surface covering layer 6 is a layer located on the outermost layer of the protective member of the present invention.

  The surface coating layer 6 can be formed of, for example, a fluorine resin, a silicone resin, polyvinylidene chloride, a polyester resin, a polyurethane, an acrylic resin, an epoxy resin, or the like. Among these, the surface coating layer 6 is preferably formed of a two-component curable resin. Examples of the two-component curable resin for forming the surface covering layer 6 include a two-component curable polyurethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Further, additives such as fine particles may be blended in the surface coating layer 6. Further, from the viewpoint of water resistance, fluorocarbon resin and silicone resin are preferable.

  Although it does not restrict | limit especially as a method to form the surface coating layer 6, For example, the method of apply | coating the two-component curable resin which forms the surface coating layer 6 on one surface of the resin layer 1 is mentioned. In the case of blending the additive, the additive may be added to and mixed with the two-component curable resin and then applied.

  The thickness of the surface coating layer 6 is not particularly limited as long as the above-described function as the surface coating layer 6 is exhibited, and for example, about 0.5 to 10 μm, preferably about 1 to 5 μm.

3. Method of Manufacturing Protective Member An example of the method of manufacturing the protective member of the present invention is as follows. First, a laminate (hereinafter sometimes referred to as “laminate A”) in which the resin layer 1, the adhesive layer 2, and the barrier layer 3 are sequentially laminated is formed. Specifically, the laminate A is formed by gravure coating a roll of an adhesive used for forming the adhesive layer 2 on the resin layer 1 or the barrier layer 3 whose surface has been chemically treated as required. It can carry out by the dry laminating method which makes the said barrier layer 3 or the resin layer 1 laminated | stacked, and hardens the adhesive layer 2 after apply | coating and drying by application methods, such as a method.

  Next, the adhesive layer 5 and the thermoplastic resin layer 4 are laminated in this order on the barrier layer 3 of the laminate A. For example, (1) a method of laminating the adhesive layer 5 and the thermoplastic resin layer 4 by coextrusion on the barrier layer 3 of the laminate A (co-extrusion laminating method), (2) separately, the adhesive layer 5 and the thermal layer A method of forming a laminated body in which the plastic resin layer 4 is laminated, and laminating the same on the barrier layer 3 of the laminated body A by thermal laminating method, (3) forming the adhesive layer 5 on the barrier layer 3 of the laminated body A The adhesive for forming is laminated by extrusion, solution coating, drying at high temperature and baking, etc., and the thermoplastic resin layer 4 previously formed into a sheet on the adhesive layer 5 is laminated by thermal lamination. Method (4) The laminate A is interposed between the barrier layer 3 of the laminate A and the thermoplastic resin layer 4 previously formed into a sheet, while the melted adhesive layer 5 is being poured. And the thermoplastic resin layer 4 Ri fit method (sandwich lamination method).

In this manner, at least the resin layer, the barrier layer, and the thermoplastic resin layer are laminated in this order to obtain the protective member made of the laminated sheet. If it is a 1st protection member, the water vapor transmission rate as the whole layer located in the resin layer side rather than the barrier layer of a protection member will be set as 40 g / m < ² > / 24 h or less. Further, if the second protective member, the water vapor permeability of the resin layer is set equal to or less than 40g / m ² / 24h. Furthermore, in the case of the third protective member, the tensile rupture stress retention ratio in the direction perpendicular to the lamination direction of the laminated sheet before and after being left for 72 hours in an environment of 120 ° C., 2 atm pressure and 100% relative humidity is 85 Set to% or more. The details of these setting methods are as described above.

  When the surface covering layer 6 is provided, the surface covering layer 6 is laminated on the surface of the resin layer 1 opposite to the barrier layer 3. The surface coating layer 6 can be formed, for example, by applying the above-mentioned resin that forms the surface coating layer 6 on the surface of the resin layer 1. The order of the step of laminating the barrier layer 3 on the surface of the resin layer 1 and the step of laminating the surface coating layer 6 on the surface of the resin layer 1 is not particularly limited. For example, after the surface covering layer 6 is formed on the surface of the resin layer 1, the barrier layer 3 may be formed on the surface of the resin layer 1 opposite to the surface covering layer 6.

  As described above, the surface covering layer 6 / resin layer 1 / optionally provided / adhesive layer 2 / optionally provided surface / the barrier layer 3 / optionally surface treated / optionally provided as described above A laminated sheet comprising the adhesive layer 5 / thermoplastic resin layer 4 to be provided is formed, but in order to strengthen the adhesiveness of the adhesive layer 2 or the adhesive layer 5, further, a heat roll contact system, a hot air system, a near surface It may be subjected to heat treatment such as infrared type or far infrared type. As conditions of such heat processing, 1 minute-5 minutes are mentioned at 150 degreeC-250 degreeC, for example.

  In the protective member of the present invention, each layer constituting the laminated sheet is, if necessary, for improving or stabilizing the film forming property, lamination processing, final product secondary processing (pouching, embossing) suitability and the like. The surface may be subjected to surface activation such as corona treatment, blast treatment, oxidation treatment, and ozone treatment.

4. Package The package of the present invention contains the contents using the protective member of the present invention. As described above, by forming the protective member so as to be able to accommodate the content using the protective member of the present invention, a molded body is formed having a space for accommodating the content, and the content is disposed in the space By thermally fusing the thermoplastic resin layers, the contents can be accommodated and sealed. The contents are as described above.

  Hereinafter, the present invention will be described in detail by showing Examples and Comparative Examples. However, the present invention is not limited to the examples.

<Manufacture of protective member>
Example 1
As a resin layer, a polybutylene terephthalate film (PBT, thickness 15 μm) having a water vapor transmission rate described in Table 1 was prepared. Further, an aluminum foil (JIS H4160: 1994 A8021 H-O, thickness 35 μm) was prepared as a barrier layer. Next, a resin composition containing an acid-modified polyolefin resin and an epoxy resin (DL1 in Table 2: epoxy adhesive) is applied to one surface of the aluminum foil, and an adhesive layer (thickness 1) is formed on the aluminum foil. .5 μm). Next, the adhesive layer on the aluminum foil and the resin layer were laminated by a dry lamination method, and then an aging treatment was performed to produce a laminate of resin layer / adhesive layer / aluminum foil. Both sides of the aluminum foil are subjected to chemical conversion treatment. The chemical conversion treatment of the aluminum foil is carried out on both sides of the aluminum foil by a roll coating method so that the coating amount of chromium is 10 mg / m ² (dry mass) with a treatment liquid consisting of a phenol resin, a chromium fluoride compound and phosphoric acid. It did by applying and baking.

  Next, on the chemical conversion treated surface of the barrier layer of the laminate obtained above, maleic anhydride modified polypropylene (PPa, thickness 15 μm) as an adhesive layer, random polypropylene (PP, thickness as a thermoplastic resin layer) 20 μm) was laminated by a co-extrusion lamination method, and an adhesive layer / thermoplastic resin layer was laminated on the barrier layer. Next, by aging the obtained laminated sheet, a protective member in which a resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained. The stack configuration is shown in Table 2.

Example 2
A resin layer was prepared in the same manner as in Example 1, except that a polyethylene naphthalate film (PEN, 12 μm thick) having a water vapor transmission rate described in Table 1 was used instead of the polybutylene terephthalate film as the resin layer. A protective member in which / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained. The stack configuration is shown in Table 2.

Example 3
A resin layer was prepared in the same manner as in Example 1, except that a non-stretched polypropylene film (CPP, thickness 30 μm) having a water vapor transmission rate described in Table 1 was used instead of the polybutylene terephthalate film as the resin layer. A protective member in which / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained. The stack configuration is shown in Table 2.

Example 4
As a resin layer, a polybutylene terephthalate film (PBT, thickness 15 μm) having a water vapor transmission rate described in Table 1 was prepared. Further, an aluminum foil (JIS H4160: 1994 A8021 H-O, thickness 35 μm) was prepared as a barrier layer. Next, a two-component polyurethane adhesive (a polyurethane compound having a hydroxyl group and a polyisocyanate compound) (DL2 in Table 2) is applied to one surface of an aluminum foil, and an adhesive layer (3 μm thick) on the aluminum foil Formed. Next, the adhesive layer on the aluminum foil and the resin layer were laminated by a dry lamination method, and then an aging treatment was performed to produce a laminate of resin layer / adhesive layer / aluminum foil. Both sides of the aluminum foil are subjected to chemical conversion treatment. The chemical conversion treatment of the aluminum foil is carried out on both sides of the aluminum foil by a roll coating method so that the coating amount of chromium is 10 mg / m ² (dry mass) with a treatment liquid consisting of a phenol resin, a chromium fluoride compound and phosphoric acid. It did by applying and baking.

  Next, on the chemical conversion treated surface of the barrier layer of the laminate obtained above, maleic anhydride modified polypropylene (PPa, thickness 15 μm) as an adhesive layer, random polypropylene (PP, thickness as a thermoplastic resin layer) 20 μm) was laminated by a co-extrusion lamination method, and an adhesive layer / thermoplastic resin layer was laminated on the barrier layer. Next, by aging the obtained laminated sheet, a protective member in which a resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained. The stack configuration is shown in Table 2.

Example 5
A resin layer was prepared in the same manner as in Example 4, except that a polyethylene naphthalate film (PEN, 12 μm thick) having a water vapor transmission rate described in Table 1 was used instead of the polybutylene terephthalate film as the resin layer. A protective member in which / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained. The stack configuration is shown in Table 2.

Example 6
A resin layer was prepared in the same manner as in Example 4, except that the unstretched polypropylene film (CPP, thickness 30 μm) having the water vapor transmission rate described in Table 1 was used instead of the polybutylene terephthalate film as the resin layer. A protective member in which / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained. The stack configuration is shown in Table 2.

Comparative Example 1
As a resin layer, a polyethylene terephthalate film (PET, 12 μm in thickness) having a water vapor transmission rate described in Table 1 was prepared. Further, an aluminum foil (JIS H4160: 1994 A8021 H-O, thickness 35 μm) was prepared as a barrier layer. Next, a two-component polyurethane adhesive (polyol compound and aromatic isocyanate compound) (DL described in Table 2) is applied to one side of the aluminum foil, and an adhesive layer (3 μm thick) is formed on the aluminum foil. Formed. Next, the adhesive layer on the aluminum foil and the resin layer were laminated by a dry lamination method, and then an aging treatment was performed to produce a laminate of resin layer / adhesive layer / aluminum foil. Both sides of the aluminum foil are subjected to chemical conversion treatment. The chemical conversion treatment of the aluminum foil is carried out on both sides of the aluminum foil by a roll coating method so that the coating amount of chromium is 10 mg / m ² (dry mass) with a treatment liquid consisting of a phenol resin, a chromium fluoride compound and phosphoric acid. It did by applying and baking.

  Next, on the chemical conversion treated surface of the barrier layer of the laminate obtained above, maleic anhydride modified polypropylene (PPa, thickness 15 μm) as an adhesive layer, random polypropylene (PP, thickness as a thermoplastic resin layer) 20 μm) was laminated by a co-extrusion lamination method, and an adhesive layer / thermoplastic resin layer was laminated on the barrier layer. Next, by aging the obtained laminated sheet, a protective member in which a resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained. The stack configuration is shown in Table 2.

Comparative example 2
In the formation of the adhesive layer for bonding the aluminum foil and the resin layer, instead of the two-component polyurethane adhesive (polyol compound and aromatic isocyanate compound) (DL described in Table 2), a modified polyolefin resin and Resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer are in this order in the same manner as in Comparative Example 1 except that a resin composition containing epoxy resin (DL1 in Table 2) is used. A laminated protective member was obtained. The stack configuration is shown in Table 2.

Comparative example 3
In the formation of the adhesive layer for bonding the aluminum foil and the resin layer, instead of the two-component polyurethane adhesive (polyol compound and aromatic isocyanate compound) (DL described in Table 2), a two-component polyurethane Resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin in the same manner as in Comparative Example 1 except that an adhesive (a polyurethane compound having a hydroxyl group and a polyisocyanate compound) (DL2 in Table 2) was used. The layer obtained the protective member laminated | stacked in this order. The stack configuration is shown in Table 2.

1 m ² of the resin layer 1 only water vapor transmission rate of (one side of the area) per (g / m ² / 24h) employs a method in accordance with the provisions of ISO15106-5 2008 year, the temperature 40 ° C., a relative humidity of 90 %, A measurement period of 24 hours, and under the measurement conditions of a measurement area of 8 cmφ, a value obtained by measuring a water vapor transmission rate using a water vapor transmission rate measuring apparatus by a differential pressure method. The water vapor transmission rate per 1 m ² is calculated by converting the water vapor transmission rate into 1 m ² . The water vapor transmission rate was measured using a water vapor transmission rate measuring apparatus PERMATRAN-W 3/33 manufactured by MOCON.

In the protective members of Comparative Examples 1 to 3, the water vapor transmission rate as a laminate of the resin layer and the adhesive layer (PET / DL1, PET / DL2, and PET / DL2 in Table 2) was measured. was also 44g / m ² / 24h.

<Tension fracture stress retention rate (72 hours in an environment with a temperature of 120 ° C and a relative humidity of 100%)>
Tension in the direction perpendicular to the thickness direction (MD direction) before and after being left for 72 hours in an environment with a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100% for each protective member obtained above The fracture stress was measured using a pressure cooker tester (trade name PC-422R8 manufactured by Hirayama Manufacturing Co., Ltd.) and in accordance with JIS K7127: 1999, the shape of the test piece was rectangular and the size of the test piece was 15 mm wide. The length of 150 mm and the test speed were measured as 200 mm / min, and the tensile fracture stress retention rate was calculated from the tensile fracture stress. As a tensile fracture stress measuring apparatus, a Tensilon universal material tester RTF manufactured by A & D Co., Ltd. was used. The results are shown in Table 2.

<Tension fracture stress retention rate (30 days in water at a temperature of 98 ° C)>
With respect to the protective member obtained in Comparative Example 1, the tensile fracture stress retention before and after being left in water at a temperature of 98 ° C. for 30 days was determined. The tensile fracture stress retention rate is not limited to standing at a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100% for 72 hours, but is maintained in water at a temperature of 98 ° C. for 30 days under a pressure of 1 atm. It calculated | required according to the method as described in above-mentioned <tensile fracture stress retention (72 hours in the environment of temperature 120 degreeC, 100% of relative humidity)>. As a result, the tensile fracture stress retention rate when left for 72 hours in an environment with a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100%, and the tensile fracture stress retention rate when left in water at a temperature of 98 ° C. for 30 days Are both 80%, it can be seen that they have a correlation.

<Peeling strength retention ratio (temperature 120 ° C., pressure 2 atm, relative humidity 100% environment 72 hours)>
Each protection member obtained above was cut into a strip of width 15 mm × length 100 mm to obtain a test piece. First, the peel strength was measured T ₁ as follows. About 10 mm was peeled in the length direction between the resin layer of the test piece and the barrier layer. Next, the resin layer and the barrier layer side of the test piece are respectively sandwiched by upper and lower chucks, and a tensile tester (trade name AGS-50D manufactured by Shimadzu Corporation) is used to move 180 ° at a speed of 50 mm / min. The tensile strength and the initial peel strength T ₁ (N / 15 mm) of the test piece were measured. Also, the peel strength was measured T ₂ in the following manner. The test piece was left for 72 hours in an environment of a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100%. Next, about 10 mm was peeled in the length direction between the resin layer and the barrier layer of this test piece. Next, the resin layer and the barrier layer side of the test piece are respectively sandwiched by upper and lower chucks, and a tensile tester (trade name AGS-50D manufactured by Shimadzu Corporation) is used to move 180 ° at a speed of 50 mm / min. The tensile strength and peel strength T ₂ (N / 15 mm) of the test piece were measured. The ratio (%) of peel strength T ₂ to peel strength T ₁ (T ₂ / T ₁ × 100) was calculated and used as the peel strength retention. The results are shown in Table 2.

  In Table 1, PBT means polybutylene terephthalate, PEN means polyethylene naphthalate, CPP means unstretched polypropylene film, and PET means polyethylene terephthalate. Also, DL, DL1 and DL2 respectively mean adhesive layers formed by the dry lamination method. ALM means aluminum foil, PPa means maleic anhydride modified polypropylene, and PP means random polypropylene.

As it is evident from the results shown in Table 2, the protective member of Examples 1 to 6 is a water vapor transmission rate of the resin layer is less 40 g / m ² / 24h, the layer positioned on the resin layer side of the barrier layer since the overall water vapor permeability of is equal to or smaller than 40g / m ² / 24h, high peel strength retention rate, is excellent in water resistance, it can be seen that are suitable for use in contact with an aqueous liquid over a long period of time. On the other hand, as described above, the water vapor permeability of as a laminate of a resin layer and the adhesive layer (Table 2 PET / DL1, PET / DL2, and PET / DL2) was both a 44 g / m ² / 24h The protective members of Comparative Examples 1 to 3 have extremely low peel strength retention compared to Examples 1 to 6, are inferior in water resistance, and are not suitable for use in contact with an aqueous liquid over a long period of time . Protection of Comparative Examples 1 to 3, during the measurement of the peel strength T _2, already peeled become ragged, because it was unmeasurable was expressed as 0% peel strength retention rate. In the protective members of Comparative Examples 1 to 3, it is considered that such a result is obtained because the base material after the test is brittle.

Further, the protective members of Examples 1 to 6 have a tensile fracture stress retention ratio in the direction perpendicular to the lamination direction of the laminated sheet before and after being left for 72 hours in an environment of temperature 120 ° C., pressure 2 atm, relative humidity 100%. Since it is 85% or more, the peel strength retention rate is high, the water resistance is excellent, and it can also be seen that it is suitable for use in contact with an aqueous liquid for a long time. On the other hand, the protective members of Comparative Examples 1 to 3 in which the tensile fracture stress retention rate is 80% or less have a remarkably low peel retention rate compared to Examples 1 to 6, and are inferior in water resistance, It can be seen that it is not suitable for applications in contact with liquids. As described above, the protection member of Comparative Examples 1 to 3, during the measurement of the peel strength T _2, already peeled become ragged, because it was unmeasurable was expressed as 0% peel strength retention rate. In the protective members of Comparative Examples 1 to 3, it is considered that such a result is obtained because the base material after the test is brittle.

DESCRIPTION OF SYMBOLS 1 ... Resin layer 2 ... Adhesive bond layer 3 ... Barrier layer 4 ... Thermoplastic resin layer 5 ... Adhesion layer 6 ... Surface coating layer 10 ... Protection member

Claims (16)

A protective member used for applications in which an aqueous liquid contacts continuously or intermittently for a long period of time,
The protective member is composed of a laminated sheet provided with at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order,
The protective member whose water-vapor-permeation rate as the whole layer located in the said resin layer side rather than the said barrier layer is 40 g / m < ² > / 24 h or less. A protective member used for applications in which an aqueous liquid contacts continuously or intermittently for a long period of time,
The protective member is composed of a laminated sheet provided with at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order,
The water vapor permeability of the resin layer is not more than 40g / m ² / 24h, the protective member. A protective member used for applications in which an aqueous liquid contacts continuously or intermittently for a long period of time,
The protective member is composed of a laminated sheet provided with at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order,
The protective member has a tensile fracture stress retention rate of 85% or more in a direction perpendicular to the laminating direction of the laminated sheet before and after being left for 72 hours in an environment with a temperature of 120 ° C., a pressure of 2 atm, and a relative humidity of 100%. , Protection member.   The protective member according to any one of claims 1 to 3, further comprising an adhesive layer between the resin layer and the barrier layer.   The protective member according to claim 4, wherein the resin constituting the adhesive layer has a polyolefin skeleton.   The protective member according to claim 4 or 5, wherein the adhesive layer contains an acid-modified polyolefin.   The protective member according to any one of claims 4 to 6, wherein when the adhesive layer is analyzed by infrared spectroscopy, a peak derived from maleic anhydride is detected.   A resin composition, wherein the adhesive layer comprises the acid-modified polyolefin, and a curing agent having at least one selected from the group consisting of an oxygen atom, a heterocyclic ring, a C = N bond, and a C—O—C bond. The protective member according to claim 6, which is a cured product of   A cured product of a resin composition, wherein the adhesive layer comprises the acid-modified polyolefin, and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound containing an epoxy group. The protection member according to claim 6 or 7.   The protection member according to claim 4, wherein the resin constituting the adhesive layer is polyurethane.   The protection member according to any one of claims 1 to 10, wherein the barrier layer is an aluminum foil.   The protective member according to any one of claims 1 to 11, wherein the resin layer contains at least one selected from the group consisting of polyethylene naphthalate, polybutylene terephthalate, and polypropylene.   The molded object by which the protection member in any one of Claims 1-12 is shape | molded.   The package which the content is accommodated using the protection member in any one of Claims 1-12. What is claimed is: 1. A method of manufacturing a protective member for use in applications in which an aqueous liquid contacts continuously or intermittently for a long period of time, comprising:
And a step of laminating at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order to obtain the protective member composed of a laminated sheet,
Wherein the overall water vapor permeability of the layer located on the said resin layer side of the barrier layer of the protective member or less 40g / m ² / 24h, a manufacturing method of the protective member. What is claimed is: 1. A method of manufacturing a protective member for use in applications in which an aqueous liquid contacts continuously or intermittently for a long period of time, comprising:
And a step of laminating at least a resin layer, a barrier layer, and a thermoplastic resin layer in this order to obtain the protective member composed of a laminated sheet,
A manufacturing method of a protection member which makes tensile fracture stress retention rate of a perpendicular direction 85% or more with a lamination direction of a lamination sheet before and after being left to stand in environment of temperature 120 ° C, pressure 2 atm, and relative humidity 100% for 72 hours.