JP2015217663A - Structure and manufacturing method of structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a structure whose total thickness is 100-300 nm, having a self-support property without a support medium, suppressing permeation of gas as low as possible, and a manufacturing method of the structure.SOLUTION: A structure 100 is obtained by sequentially laminating a first polymer base material 1, a gas barrier layer 2, and a second polymer base material 3. The total thickness of the structure is 100-300 nm. The first polymer base material and the second polymer base material are of polylactic acid or triacetyl cellulose. The gas barrier layer is a vapor-deposited layer of an inorganic substance, one of resin coating layers, or a combination of the layers.

Description

  The present invention relates to a structure and a method for manufacturing the structure.

  Since the functional thin film is insufficient in mechanical strength, the thin film is generally formed on the support and used together with the support. On the other hand, since the thin film itself has a high aspect ratio with respect to the surface area and thickness and the ability to follow the curved surface shape, a report on a nanometer-thick thin film having self-supporting properties has been made recently (Patent Document 1). ).

  Self-supporting means that the thin film maintains the form of the thin film even when the support is removed. For simplicity, the nanometer-thick thin film having the self-supporting property may be referred to as a nano thin film.

  The nano thin film has high gas permeability due to its thin film thickness, while its gas barrier property tends to be low. In order to improve the gas barrier property, a method such as coating an organic resin excellent in gas barrier property or depositing an inorganic compound such as diamond-like carbon or silicon oxide is required. A structure in which a gas barrier property is imparted to a self-supporting nanothin film that has been studied in recent years has not yet been reported.

  Known documents are shown below.

Japanese Patent No. 5207467

  The present invention has been made in view of the circumstances as described above, and has a total thickness of 100 nm to 300 nm and is self-supporting even without a support, and a method of manufacturing a structure and a structure that suppresses gas permeation as much as possible. It is an issue to provide.

  The present invention has been made in view of the above problems, and the invention of claim 1 is a structure in which a first polymer base material, a gas barrier layer, and a second polymer base material are sequentially laminated. Is a structure characterized by having a total thickness of 100 nm to 300 nm.

  The invention according to claim 2 of the present invention is characterized in that the gas barrier layer is any one of an inorganic deposition layer, a resin coating layer, or a combination thereof. It is a structure.

  The invention of claim 3 of the present invention is characterized in that the inorganic substance of the vapor deposition layer is magnesium oxide, calcium oxide, aluminum oxide, silicon oxide inorganic oxide, or diamond-like carbon. 2. The structure according to 2.

  The invention of claim 4 of the present invention is characterized in that the resin of the coating layer is one of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, and polyacrylonitrile. 3. The structure according to 3.

  The invention according to claim 5 of the present invention is characterized in that the first polymer substrate and the second polymer substrate are polylactic acid or triacetyl cellulose. It is a structure as described in.

  The invention according to claim 6 of the present invention is the method for producing a structure according to any one of claims 1 to 5, wherein the first polymer substrate, the gas barrier layer, and the second polymer are formed on the support. A structure manufacturing method is characterized in that a substrate is sequentially laminated to form a structure, and the structure is peeled off from the support.

  The invention according to claim 7 of the present invention is characterized in that the support is a film or sheet of any of glass, quartz, silicon wafer, mica, gold substrate, and resin. It is a manufacturing method.

  The invention according to claim 8 of the present invention is the method for producing a structure according to claim 6 or 7, wherein the surface of the support on which the structure is laminated is subjected to a liquid repellent treatment.

  The invention according to claim 9 of the present invention is characterized in that a removable sacrificial layer is provided on the surface of the support on which the structure is laminated, the sacrificial layer is removed, and the structure is peeled off. Item 8. The method for producing a structure according to Item 6 or 7.

  The structure of the present invention has a total thickness of 100 nm to 300 nm, has self-supporting properties even without a support, and suppresses gas permeation as much as possible. Moreover, according to the manufacturing method of the structure of this invention, this structure can be manufactured easily.

It is explanatory drawing which showed typically an example of the structure of this invention in the cross section. (A) (B) (C) It is typical sectional drawing explaining the manufacturing method of the structure of this invention.

Hereinafter, embodiments for carrying out the present invention will be described.
FIG. 1 is an explanatory view schematically showing a cross section of an example of the structure of the present invention.

  As shown in the cross-sectional view of FIG. 1, the structure 100 of this example is a structure 100 in which a first polymer substrate 1, a gas barrier layer 2, and a second polymer substrate 3 are sequentially laminated, It has a multilayer structure with a thickness of 100 nm to 300 nm.

  The first polymer substrate 1 and the second polymer substrate 3 are preferably made of a polymer thin film such as polylactic acid or triacetylcellulose. These are preferably used from the viewpoint of film forming properties. The thicknesses of the first polymer substrate 1 and the second polymer substrate 3 are each preferably 10 nm to 100 nm.

  For the gas barrier layer 2, an inorganic vapor deposition layer or a resin coating layer is used. As an inorganic substance used for the vapor deposition layer, inorganic oxides such as magnesium oxide, calcium oxide, aluminum oxide, and silicon oxide, or diamond-like carbon can be used.

  As silicon oxide, a mixture of metal silicon and silicon dioxide is used as an evaporation material, and SiOn is set so that n is larger than 1 and smaller than 2, thereby achieving a balance between gas barrier properties and transparency. it can.

  In general, the thickness of the gas barrier layer 2 formed of the deposited layer is preferably in the range of 5 to 300 nm. However, since the gas barrier layer 2 of the present invention reduces the total thickness of the structure, It is desirable to be within a range of ˜100 nm.

  As the resin used for the coating film, resins such as polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN) can be used. The thickness of the gas barrier layer 2 of the present invention is preferably in the range of 5 to 100 nm, like the vapor deposition layer, in order to reduce the total thickness of the structure.

  In this way, the total thickness of the structure 100 composed of the first polymer base material 1, the gas barrier layer 2, and the second polymer base material 3 can be set to 100 nm to 300 nm. By doing in this way, it can have a self-supporting and flexible structure.

Hereafter, the manufacturing method of the structure of this invention is demonstrated.
2A, 2B, and 2C are schematic cross-sectional views illustrating a method for manufacturing a structure according to the present invention.

  The manufacturing method of the structure 100 first prepares the support 10. As the support 10, glass such as soda glass, quartz, silicon wafer, mica, gold substrate, resin film or sheet such as polyethylene terephthalate or polyethylene can be used.

  A polymer material such as polylactic acid or triacetyl cellulose used as the first polymer substrate 1 is coated on one surface of the support 10 by a known coating method such as a spin coater, bar coater, roll coater, die coater, or gravure coater. A film is formed.

  In the coating method, a spin coater is particularly preferable because it is suitable for forming a thin film. And it solidifies by drying, baking, light irradiation, etc., and forms the 1st polymeric base material 1 which consists of a coating film.

  Then, the gas barrier layer 2 is formed on the surface of the first polymer substrate 1. In order to provide a vapor deposition layer as the gas barrier layer 2, when an inorganic oxide is used as the vapor deposition layer, a vacuum vapor deposition method is preferably used. When diamond-like carbon is used as the vapor deposition layer, it can be formed by ionized vapor deposition.

  In order to provide a coating layer as the gas barrier layer 2, a resin such as polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), etc., is used. It can be formed by a method. A spin coater is most suitable and preferred.

  A polymer material such as polylactic acid or triacetyl cellulose is further applied to the surface of the gas barrier layer 2 of the laminate in which the first polymer base material 1 and the gas barrier layer 2 are provided on the support 10, and a spin coater, bar coater, roll A coating film is formed by a known coating method such as a coater, a die coater, or a gravure coater. In particular, a spin coater is suitable and preferable for forming a thin film. Furthermore, it is solidified by drying, baking, or light irradiation to form a second polymer base material 3 made of a coating film.

  In this manner, as shown in the cross-sectional view of FIG. 2A, the first polymer base material 1, the gas barrier layer 2, and the second polymer base material 3 of the structure 100 are laminated on the support body 10. Your body is ready. The single structure 100 can be obtained by physically peeling the structure 100 from the support 10. For example, the single structure 100 can be peeled off by making a handle by cutting with a razor between the support 10 and the structure 100.

  Further, as shown in FIG. 2B, before laminating the first polymer base material 1 on the support 10, the liquid repellent layer 20 in which the surface of the support 10 has been subjected to a liquid repellent treatment to reduce the surface energy in advance. Can be provided. As a liquid repellent treatment method for providing the liquid repellent layer 20, any method may be used as long as it does not significantly erode the support 10 and the polymer substrate 1, for example, perfluorodecyltriethoxysilane. Alternatively, a self-assembled monolayer may be formed on the support using a silane coupling agent such as octadecyltriethoxysilane.

  Thus, the surface of the support 10 is subjected to a liquid repellent treatment to provide the liquid repellent layer 20, and as described above, the first polymer base 1, the gas barrier layer 2, and the second polymer base 3 are provided. Form body 100. The structure 100 can be peeled from the support 10 to obtain a single structure 100. At this time, since the surface of the support 10 is subjected to a liquid repellent treatment and the liquid repellent layer 20 is provided, the structure 100 can be easily peeled from the support 10.

  In addition, a sacrificial layer 30 that can be removed may be provided on the support 10 in advance. The method for providing and removing the sacrificial layer 30 may be any method as long as it does not damage the structure 100 of the present invention.

  As a material for forming the sacrificial layer 30, polyvinyl alcohol, polyhydroxystyrene, polystyrene sulfonate, a resist material for semiconductor, a thermally crosslinkable polymer, or the like can be used.

  The sacrificial layer 30 can be formed by dissolving these materials in a solvent and using the material as a coating solution. As a solvent to be used, a solvent that does not damage the structure 100 is preferable.

  As described above, the sacrificial layer 30 is provided on the surface of the support 10, the first polymer base material 1, the gas barrier layer 2, and the second polymer base material 3 are provided on the surface of the sacrificial layer 30. Form. Then, the sacrificial layer 30 is removed by dissolving with a solvent or the like, and the structure 100 is peeled from the support 10 as a self-supporting film.

  As described above, if the sacrificial layer 30 is provided on the surface of the support 10, the sacrificial layer 30 can be removed by dissolving it with a solvent or the like, so that the structure 100 is peeled from the support 10. But it can be done easily.

  The structure 100 manufactured as described above can be appropriately determined according to the application used in the range of the total thickness of 100 nm to 300 nm. By setting it as such a film thickness, it can have flexibility while having gas barrier property. And it can have self-supporting properties. Moreover, according to the above manufacturing method, the said structure 100 can be manufactured easily. The total thickness of the structure here is a thickness composed of the first polymer substrate 1, the gas barrier layer 2, and the second polymer substrate 3.

  As an application of the structure of the present invention, for example, it can be used as an application for covering a wound part of a human body and protecting the wound part from the outside. Moreover, in order to suppress dryness of the human skin, the structure can be attached to the dry part of the human body, thereby being used as an application to keep the dry part of the skin moist.

  Specific examples of the present invention will be described below.

<Example 1>
As the support 10, a soda glass substrate having a thickness of 0.7 mm and 10 cm × 10 cm was used. The glass substrate was immersed in a chloroform solution of perfluorodecyltriethoxysilane for 3 hours and dried at 120 ° C. for 1 hour to provide a liquid repellent treatment, and a liquid repellent layer was provided on the surface of the glass substrate of the support 10. .

  Subsequently, a 1% polylactic acid chloroform solution was formed on a glass substrate provided with a liquid repellent layer by spin coating, and dried at 70 ° C. for 1 hour. The thickness of the polylactic acid thin film of the first polymer substrate 1 formed in this way was about 100 nm.

  Next, a vapor deposition material made of metal silicon and silicon dioxide is prepared, and the mixed vapor deposition material is irradiated with an electron beam emitted from an electron gun by a vacuum vapor deposition apparatus of an electron beam heating method to evaporate the polymer substrate 1. A gas barrier layer 2 was formed thereon. The thickness of the gas barrier layer 2 was about 30 nm.

  The second polymer base material 3 was formed on the surface of the gas barrier layer 2 in the same manner as the first polymer base material 1 and dried at 70 ° C. for 1 hour to form the second polymer base material 3. . The thickness of the second polymer substrate 3 polylactic acid thin film was about 100 nm.

  A handle was made by cutting the structure 100 formed on the glass substrate of the support 10 with a razor, and the structure 100 was peeled off from the support 10. Thereby, the structure of Example 1 having a thickness of 230 nm was obtained.

<Example 2>
As the support 10, a polyethylene terephthalate film was used. A 1% aqueous solution of polyvinyl alcohol was formed as a sacrificial film 20 on this polyethylene terephthalate film by the bar coating method and dried at 70 ° C. for 1 hour.

  Subsequently, a 1% polylactic acid chloroform solution was formed as a first polymer substrate 1 on the surface of the sacrificial film 20 by a spin coating method and dried at 70 ° C. for 1 hour. The formed polylactic acid thin film had a thickness of about 100 nm.

  A vapor deposition material made of a mixture of metallic silicon and silicon dioxide is produced, and the first polymer base material is evaporated by irradiating the mixed vapor deposition material with an electron beam emitted from an electron gun by an electron beam heating type vacuum vapor deposition apparatus. A gas barrier layer 2 made of silicon oxide was formed on 1. The thickness of the gas barrier layer 2 was about 30 nm.

  On the gas barrier layer 2, the 2nd polymer base material 3 was formed by the method similar to the 1st polymer base material 1, and it dried at 70 degreeC for 1 hour. The formed polylactic acid thin film had a thickness of about 100 nm.

  The polyethylene terephthalate film on which the above structure is formed is immersed in water for 1 hour, peeled off at the peeled end of the structure 100 where the end is peeled off from the polyethylene terephthalate film by dissolution of polyvinyl alcohol, and has a thickness of 230 nm. The structure of Example 2 was obtained.

  Below, the comparative example of this invention is demonstrated.

<Comparative Example 1>
A structure of Comparative Example 1 having a thickness of 200 nm was obtained in the same manner as in Example 1 except that the gas barrier layer 2 was not formed.

<Test method>
The structures of Examples and Comparative Examples were tested and evaluated by the following methods.

<Moisture permeability>
Using the JIS-Z0208-1976 moisture-proof packaging material moisture permeability test method (cup method), the structures of Examples and Comparative Examples were permeated under conditions of a temperature of 40 ± 0.5 ° C. and a relative humidity of 90 ± 2%. Humidity was measured and gas barrier properties were evaluated. The results are summarized in Table 1.

以下に、実施例と比較例との比較結果について説明する。

Below, the comparison result of an Example and a comparative example is demonstrated.

<Comparison result>
The structures of Example 1 and Example 2 had a total thickness of 100 nm to 300 nm, had self-supporting properties, had lower moisture permeability than the structure of Comparative Example 1, and were given gas barrier properties.

DESCRIPTION OF SYMBOLS 100 ... Structure 1 ... 1st polymer base material 2 ... Gas barrier layer 3 ... 2nd polymer base material 10 ... Support body 20 ... Liquid-repellent layer 30 ... Sacrificial layer

Claims (9)

  A structure in which a first polymer substrate, a gas barrier layer, and a second polymer substrate are sequentially laminated, and the structure has a total thickness of 100 nm to 300 nm.   2. The structure according to claim 1, wherein the gas barrier layer is one of an inorganic vapor deposition layer, a resin coating layer, or a combination thereof.   The structure according to claim 2, wherein the inorganic substance of the vapor deposition layer is an inorganic oxide of any one of magnesium oxide, calcium oxide, aluminum oxide, and silicon oxide, or diamond-like carbon.   4. The structure according to claim 2, wherein the resin of the coating layer is a resin selected from polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, and polyacrylonitrile.   The structure according to any one of claims 1 to 4, wherein the first polymer base material and the second polymer base material are polylactic acid or triacetyl cellulose.   6. The method for producing a structure according to claim 1, wherein a structure is obtained by sequentially laminating a first polymer substrate, a gas barrier layer, and a second polymer substrate on a support. A method for producing a structure, comprising producing and peeling the structure from the support.   The method for manufacturing a structure according to claim 6, wherein the support is a film or sheet of any one of glass, quartz, silicon wafer, mica, gold substrate, and resin.   The method for producing a structure according to claim 6 or 7, wherein a surface of the support on which the structure is laminated is subjected to a liquid repellent treatment.   The structure according to claim 6 or 7, wherein a removable sacrificial layer is provided on a surface of the support on which the structure is laminated, the sacrificial layer is removed, and the structure is peeled off. Production method.

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