JP2015110294A - Sheet for adhesion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet for adhesion capable of adhering onto a living matter or a biomaterial with sufficient strength without using an adhesive component, difficult to separate even if adhered onto an uneven surface which moves, and excellent in water proofness.SOLUTION: A sheet for adhesion includes: a gel film; a protective layer formed at least on one surface of the gel film; and a support frame arranged at an outer periphery of the gel film and supporting the gel film. The total thickness of the gel film after desiccation and the protective layer is within a range of 100 nm-10 μm.

Description

  The present invention relates to an adhesive sheet suitable for use in medical use or cosmetic use.

  Affixing sheets that have been affixed to biological surfaces such as skin have been developed in the past, such as cosmetic sheet cosmetics and medical haptics. For example, Patent Document 1 discloses a sheet-shaped pack cosmetic based on a self-crosslinking alkylcellulose derivative hydrogel obtained by crosslinking an alkylcellulose derivative by irradiation with radiation.

  It is desirable not to use an adhesive on the surface in contact with the living body in the sheet for living body sticking. However, conventional bioadhesive sheets that do not use a pressure-sensitive adhesive do not have sufficient adhesion to the surface of the living body, and there is still room for improvement.

  On the other hand, Patent Document 2 discloses a method for producing a polymer self-supporting film by drying a foam film of an aqueous solution of a surface active polymer compound stretched on a frame. According to Patent Document 2, a polymer free-standing film having a thickness of nanometer order can be manufactured. In Patent Document 2, it is intended to use the produced polymer self-supporting membrane for applications such as a separation membrane, but the application to be applied to a living body is not studied at all.

  Patent Document 3 discloses that a thin film polymer structure (nanosheet) having a functional substance on both sides is stuck on the surface of the skin. Specifically, the thin polymer structure is applied to the skin while being supported on the surface of the soluble support membrane, and the soluble support membrane is dissolved after the application to leave the thin polymer structure on the skin. Technology is disclosed. This technique requires a complicated operation of dissolving the soluble support membrane.

  In Patent Document 4, a base film supporting hyaluronic acid or a derivative thereof and a support film that is a water-soluble polymer film or cloth are laminated, and the thickness of the base film is 10 to 500 nm. Thin film cosmetics are disclosed. In Patent Document 4, as a method of using a thin film cosmetic, a method in which a water-soluble polymer film is dissolved and removed immediately before application, and a base film carrying hyaluronic acid or a derivative thereof is applied to the skin, and wet skin A method is disclosed in which a thin film cosmetic is affixed to and a cloth is peeled off. The former method requires a complicated operation of dissolving the water-soluble polymer film. In the latter method, it is difficult to peel the cloth, or the base film may be damaged when the cloth is peeled off.

  In Patent Document 5, A layer formed using a solution containing polylysine or polylysine derivatives or salts thereof and B layer formed using a solution containing alginic acid or alginic acid derivatives or salts thereof are alternately used. A laminated thin film for skin bonding (a nanometer-size sheet) is disclosed. According to patent document 5, a thin film is manufactured by repeatedly laminating | stacking A layer and B layer on a base material. In addition, the thin film is peeled off from the substrate and then attached to the skin. Also in this case, since the thin film is very thin, it may be difficult to peel from the base material, or the thin film may be damaged when peeled from the base material.

  Patent Document 6 includes a base material and a thin film formed on the base material, the thin film includes an A layer formed using a solution containing a polycation, a polyanion, and a pH of 1. A thin film with a substrate having a B layer formed using a solution of 6 to 5.4 is disclosed. Patent Document 6 does not describe how to use the thin film with a base material, but the same problem arises if the thin film is peeled from the base material as in Patent Document 5.

  Patent Document 7 discloses a nano thin film transfer sheet comprising a permeable substrate, a soluble support layer, and a nano thin film layer, wherein the permeable substrate allows a solution that dissolves the soluble support layer to permeate or pass therethrough. A nano thin film transfer sheet is disclosed in which the nano thin film layer has an A layer formed using a solution containing a polycation and a B layer formed using a solution containing a polyanion. According to Patent Document 7, after the nano thin film layer is bonded to the skin, the nano thin film transfer sheet dissolves the soluble support layer while dripping water on the permeable base material, and then peels off the permeable base material. Thus, only the nano thin film layer can be transferred to the skin. This method requires a complicated operation of dissolving the soluble support layer.

Japanese Patent No. 4596774 JP 2011-143332 A International Publication No. 2008/050913 Pamphlet International Publication No. 2012/173198 Pamphlet JP 2013-71907 A International Publication No. 2012/153682 pamphlet JP2013-177385A JP 2013-223644 A JP 2013-224281 A

  The method for producing a thin film disclosed in Patent Document 2 in which a foam film of an aqueous solution of a surface active polymer compound such as gelatin is dried at room temperature is obtained when the concentration of the surface active polymer compound in the foam film is low. There is a problem that the foam film is broken and a thin film cannot be formed. In addition, the dry gel film produced by the method described in Patent Document 2 has a problem that adhesion and flexibility are not sufficient, and it tends to peel off on a moving uneven surface.

  Therefore, as a result of intensive studies, the inventors of the present invention formed a foam film from an aqueous solution containing a gel raw material and gelled the foam film in a state containing water, as described in Patent Documents 8 and 9, to thereby form a hydrogel film. Unlike the method described in Patent Document 2 in which the foam film is directly dried, the hydrogel film can be formed without breaking the foam film even when the gel raw material in the aqueous solution has a low concentration. It was found that even when the obtained hydrogel film was dried, the film was not broken. Furthermore, it has been found that the hydrogel film and the dried gel film obtained by this method have sufficient adhesion on the skin surface and are difficult to peel off even when applied to a moving uneven surface.

  However, as a result of further studies by the present inventors, the hydrogel film and the dried gel film as described above swell with water, so that they become easy to peel off when wet or the strength of the film decreases and is broken. It turns out that there is a problem of being loose. In addition, not only the above hydrogel film | membrane and a dry gel film | membrane but such a problem may arise if it is a gel film | membrane. For this reason, the adhesive sheet is required to have water resistance.

In Patent Documents 1 and 3 to 7, various sticking sheets have been proposed, but none have been studied for water resistance.
In particular, according to Patent Document 1, in a sheet-shaped pack cosmetic, hydrogel absorbs water and swells, thereby giving a feeling of adhesion and a feeling of fitting to improve the feeling of use. Seeking.
In Patent Document 3, a thin film polymer structure is applied to the skin while being supported on the surface of a soluble support membrane, and after application, the soluble support membrane is dissolved using water to dissolve the thin film polymer structure on the skin. It is said that a molecular structure can be left. In Patent Document 4, in a method in which a water-soluble polymer film is dissolved and removed immediately before application, and a base material film carrying hyaluronic acid or a derivative thereof is applied to the skin, the water-soluble polymer film is immersed in water. It is said that it can be melted. In Patent Document 7, it is said that only the nano thin film layer can be transferred to the skin by dissolving the soluble support layer while dropping water on the permeable substrate and peeling the permeable substrate. In these cases, water solubility and water permeability are required, and such a sheet does not have water resistance.

  The present invention has been made in view of the above problems, and can adhere to a living body or a biomaterial with sufficient strength without using an adhesive component and is attached to a moving uneven surface. However, it is an object of the present invention to provide a sticking sheet that is difficult to peel off and has good water resistance.

  To achieve the above object, the present invention provides a gel film, a protective layer formed on at least one surface of the gel film, and a support frame that is disposed on the outer edge of the gel film and supports the gel film. And a total thickness of the gel film and the protective layer after drying is in the range of 100 nm to 10 μm.

  According to the present invention, the total thickness of the gel film and the protective layer after drying is within a predetermined range and is very thin, and thus excellent in flexibility and adhesion to the skin and the like. Therefore, the adhesive sheet of the present invention can be adhered to a living body or a biomaterial with sufficient strength without using an adhesive component, and can be made difficult to peel even when applied to a moving uneven surface. . Moreover, according to this invention, the water resistance of the sticking sheet can be improved by forming the protective layer on the gel film. Therefore, even if it adheres to water after sticking the sticking sheet of this invention on skin etc., it can be hard to peel off and to be hard to tear. Furthermore, according to the present invention, since the gel film is supported by the support frame and the shape of the sticking sheet is held by the support frame, the handleability of the sticking sheet can be improved. Moreover, since the sticking sheet whose both surfaces are not in contact with the object can be obtained, the sticking sheet can be easily attached to the skin or the like.

  In the said invention, it is preferable that the said protective layer has hydrophobicity. The water contact angle on the surface of the protective layer is preferably 50 ° or more. Thereby, the penetration of water into the gel film can be suppressed.

  In the present invention, a functional layer is partially provided between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer. It may be formed automatically. In the portion where the functional layer is not formed, the adhesion of the gel film to the skin or the like can be increased.

  Further, the adhesive sheet of the present invention is formed between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer. The functional layer may be a fine particle layer in which fine particles are dispersed or a fluidized layer containing a fluid substance. If the functional layer is a fine particle layer or a fluidized bed, high adhesion of the gel film to the skin or the like can be maintained.

  Further, the adhesive sheet of the present invention is formed between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer. The gel layer after drying, the functional layer, and the protective layer may have a total thickness in the range of 100 nm to 10 μm. Even when a functional layer is formed on the gel film, if the total thickness of the gel film, functional layer and protective layer after drying is relatively thin, high adhesion of the gel film to the skin, etc. is maintained. can do.

  The sticking sheet of the present invention can be adhered to a living body or a biomaterial with sufficient strength without using an adhesive component, and has an effect that it is difficult to peel off even when stuck on a moving uneven surface. Moreover, in this invention, there exists an effect that the water resistance of the sheet | seat for sticking can be improved by forming the protective layer on a gel film.

It is the schematic plan view and sectional drawing which show an example of the sheet | seat for sticking of this invention. It is a schematic diagram which shows an example of the usage method of the sheet | seat for sticking of this invention. It is a schematic diagram which shows the other example of the usage method of the sheet | seat for sticking of this invention. It is process drawing which shows an example of the formation method of the gel film in this invention. It is process drawing which shows the other example of the formation method of the gel film in this invention. It is a schematic sectional drawing which shows the other example of the sheet | seat for sticking of this invention. It is a schematic sectional drawing which shows the other example of the sheet | seat for sticking of this invention. It is the schematic plan view and sectional drawing which show the other example of the sheet | seat for sticking of this invention. It is a schematic sectional drawing which shows the other example of the sheet | seat for sticking of this invention. It is a schematic sectional drawing which shows the other example of the sheet | seat for sticking of this invention. It is a schematic sectional drawing which shows the other example of the sheet | seat for sticking of this invention. It is a schematic sectional drawing which shows the other example of the sheet | seat for sticking of this invention. It is a schematic sectional drawing which shows the other example of the sheet | seat for sticking of this invention. It is a schematic sectional drawing which shows the other example of the sheet | seat for sticking of this invention. 2 is a photograph showing sheets for application in Example 1 and Comparative Example 2. FIG.

Hereinafter, the sticking sheet of the present invention will be described in detail.
The sticking sheet of the present invention has a gel film, a protective layer formed on at least one surface of the gel film, and a support frame that is disposed on the outer edge of the gel film and supports the gel film, The total thickness of the gel film and the protective layer after drying is in the range of 100 nm to 10 μm.

Here, the “gel film after drying” refers to a dried gel film when the gel film contains water, for example.
“The total thickness of the gel film and the protective layer after drying is in the range of 100 nm to 10 μm” means that, for example, when the gel film contains water, the total thickness of the dried gel film and the protective layer is The thickness may be within the above range, and the actual total thickness of the gel film and the protective layer may not be within the above range. In addition, when protective layers are formed on both sides of the gel film, the total thickness of the gel film and the protective layer after drying is the thickness of the gel film after drying and each protection formed on both sides of the gel film. Refers to the total thickness of the layers.

The sticking sheet of the present invention will be described with reference to the drawings.
1A and 1B are a schematic plan view and a cross-sectional view showing an example of the sticking sheet of the present invention, and FIG. 1B is a cross-sectional view taken along line AA in FIG. As illustrated in FIGS. 1A and 1B, the sticking sheet 1 is disposed on the outer edge of the gel film 2, the protective layer 3 formed on the gel film 2, and the gel film 2. The gel film 2 is fixed in a state of being stretched on the support frame 12 so as to close the opening of the support frame 12. Further, the total thickness of the gel film 2 and the protective layer 3 after drying is within a predetermined range.

  According to the present invention, since the total thickness of the dried gel film and the protective layer is within a predetermined range, and the gel film is very thin, high adhesion to the surface of a living body or a biomaterial such as skin And has high flexibility. Therefore, the adhesive sheet of the present invention can be adhered to a living body or a biological material with sufficient strength without using an adhesive component. Therefore, it is possible to suppress irritation and rough skin due to the adhesive component at the time of application, and to reduce irritation to the skin and the like. Furthermore, the gel film has high unevenness followability, and even when the sticking sheet of the present invention is attached to a moving uneven surface, it can be made difficult to peel off.

  2A to 2C are schematic views showing an example of a method for using the sticking sheet of the present invention. As shown in FIGS. 2A to 2B, a sticking sheet 1 having a support frame 12, a gel film 2 held by the support frame 12, and a protective layer 3 formed on the gel film 2. Can be deformed along the surface shape of the object 30 whose surface is not flat. Also, as shown in FIG. 2B, the surface tension of the surface of the gel film 2 fixed to the support frame 12 of the sticking sheet 1 is applied to the surface of the adherend 30 such as skin moistened with water. Can be attached with sufficient contact. Since the periphery of the gel film 2 and the support frame 12 are weakly coupled to such an extent that they are separated when the support frame 12 is peeled off after the surface of the gel film 2 and the surface of the object 30 are adhered, FIG. As shown in c), the gel film 2 and the protective layer 3 can be left on the surface of the adherend 30.

  3A to 3B are schematic views showing an example of a state where the gel film and the protective layer of the sticking sheet of the present invention are stuck on the skin. First, in the same manner as in the example shown in FIGS. 2A to 2C, the gel film 2 of the adhesive sheet 1 is applied to the skin surface of the joint portion of the finger moistened with water while the finger is bent. These surfaces are adhered with surface tension and pasted, the support frame 12 is peeled off, and the gel film 2 and the protective layer 3 are pasted. In this case, as shown in FIGS. 3 (a) and 3 (b), the gel film 2 and the protective layer 3 may be deformed following the shape of the wrinkle even if the finger is stretched after the application and wrinkles are formed on the skin surface. it can. Further, the gel film 2 and the protective layer 3 are not easily peeled off even if the finger is repeatedly bent and stretched. That is, the sticking sheet of the present invention has excellent unevenness followability, and is difficult to peel even when attached to a fine uneven surface that moves like skin.

  In the present invention, since the gel film is supported by the support frame and the shape of the sticking sheet is held by the support frame, the handleability of the sticking sheet can be improved. Moreover, since the sticking sheet whose both surfaces are not in contact with the object can be obtained, the sticking sheet can be easily attached to the skin or the like. Furthermore, since a gel film whose both surfaces are not in contact with an object can be obtained by using a support frame when forming the gel film, a protective layer and a functional layer can be easily formed on the gel film.

  In the present invention, since the protective layer is formed on the gel film, water penetration into the gel film can be suppressed, so that the water resistance of the sticking sheet can be improved. Therefore, even if the sheet for sticking of the present invention is attached to the skin or the like and then wetted with water, it can be made difficult to peel off or torn easily.

In the present invention, the total thickness of the gel film and the protective layer after drying is in the range of 100 nm to 10 μm, preferably in the range of 100 nm to 5 μm, more preferably in the range of 100 nm to 3 μm. When the total thickness of the gel film and the protective layer after drying is too thick, the pastability and the unevenness followability deteriorate. Moreover, when the total thickness of the gel film after drying and a protective layer is too thin, it may be inferior to intensity | strength.
Here, when measuring the total thickness of the gel film and the protective layer after drying, prepare an adhesive sheet having the gel film and the protective layer, wet the cover glass surface with water, and apply the gel film to the glass surface with surface tension. Adhering, pasting the gel film and protective layer on the glass surface, vacuum drying for 1 hour to completely evaporate water, measuring the step between the film-air interface and the glass surface with an optical microscope, The total thickness of the protective layer. As an optical microscope, Olympus Nano Search Microscope OLS3500 can be used.

Moreover, the sticking sheet | seat of this invention should just have the area | region where the total thickness of the gel film after drying and a protective layer is in the said range. If the total thickness of the gel film and the protective layer after drying is within the above range, the adhesive sheet of the present invention can improve the adhesion of the gel film, and adheres firmly to the skin and the like. Can be made.
For example, as will be described later, when a gel film (hydrogel film 2a, dry gel film 2b) is formed using the foam film-forming support frame 20 as shown in FIGS. In some cases, the thickness of the gel film (hydrogel film 2a, dry gel film 2b) increases at the boundary between the hydrogel film 2a, dry gel film 2b) and the foam film-forming support frame 20. However, if there is a region where the total thickness of the gel film and the protective layer after drying is within the above range, the adhesive sheet of the present invention can be applied to the skin or the like.

  Hereinafter, each structure in the sheet | seat for sticking of this invention is demonstrated.

1. Gel film The gel film of the present invention has a predetermined thickness so that the total thickness of the dried gel film and the protective layer is within a predetermined range.

The gel film is not particularly limited as long as it has a predetermined thickness, and examples thereof include a hydrogel film and a dry gel film.
Here, the “hydrogel” refers to a gel in which a large amount of water is held in a network structure formed by combining polymers.
Hereinafter, the hydrogel film and the dry gel film will be described separately.

(1) Hydrogel film The hydrogel film in the present invention has a predetermined thickness so that the total thickness of the dried hydrogel film and the protective layer is within a predetermined range.

  The hydrogel film is not particularly limited as long as it has a predetermined thickness. However, it is preferably made of a biological material because it is highly safe for a living body. Examples thereof include proteins and polysaccharides. Specifically, macromolecular compounds such as collagen, hyaluronic acid, peptide hydrogel, laminin, chondronectin, glycosaminoglycan, proteoglycan, other extracellular matrix component proteins, gelatin, agarose, cellulose, oligonucleic acid, polynucleic acid, etc. The gel by. Moreover, it is not what was extracted from the living body, but artificially synthesized living body-derived material imitation material can also be used. Examples thereof include various artificial peptides and derivatives thereof, artificial oligopeptides and derivatives thereof, artificial polypeptides and derivatives thereof, artificial polysaccharides and derivatives thereof, and the like. Furthermore, water-soluble polymers such as polyethylene glycol and polyacrylamide can also be used.

  The method for forming the hydrogel film is not particularly limited as long as it is a method capable of forming a hydrogel film having a predetermined thickness as will be described later. For example, the hydrogel film is obtained by gelling a foam film. It may be. In this case, the hydrogel film is preferably prepared by gelling an aqueous foam film containing a gel raw material in a state containing water.

  In the above case, the gel raw material is not particularly limited as long as it has water solubility and exhibits surface activity and can form a foam film. Specifically, the above-described materials can be used. Of these, gelatin, collagen, and agarose are preferably used. Since gelatin, collagen, and agarose all have surface activity, it is thought that the molecules of these compounds are placed on both the front and back surfaces of the foam membrane so that the hydrophobic part is on the outside and the hydrophilic part is on the inside. It is done. Since the foam film has a homogeneous structure on the front and back, the gel film prepared from the foam film is homogeneous on the front and back and can be used without distinction between the front and back.

Although the origin of gelatin is not particularly limited, gelatin derived from porcine epidermis, porcine bone, bovine skin, bovine bone, fish and the like can be used.
The origin of collagen is not particularly limited, but collagen derived from pig skin, pig bone, cow skin, cow bone, fish and the like can be used.
The origin of agarose is not particularly limited, but agarose derived from seaweed or the like can be used.

  Moreover, the hydrogel film may contain a surfactant, an emulsification aid, a wetting agent and the like as appropriate. The surfactant, the emulsification aid, and the wetting agent are used for the purpose of stabilizing the foam film when forming the gel film.

  As the surfactant, surfactants with high safety to living bodies such as sucrose fatty acid esters are preferable.

  As the emulsification aid, emulsification aids with high safety to the living body such as methylcellulose, glycerin, polyethylene glycol, polyvinyl alcohol, sucrose, and polyglycerin are preferable. Volatilization of water from the foam film before gelation causes rupture of the foam film. The emulsification auxiliary agent has an action of suppressing volatilization of water from the foam film, that is, an action as a wetting agent for the foam film, and therefore can be added for the purpose of suppressing foam film rupture. In addition to the action as a wetting agent, an emulsification aid such as polyethylene glycol enters between the polymers constituting the gel film, and suppresses the formation of cross-links between the polymers to increase the flexibility of the film. Also have. For this reason, the gel film prepared from the aqueous solution containing the emulsification aid has an advantageous effect that it has high flexibility and high adhesion to the surface of a living body such as skin.

Furthermore, the hydrogel film may contain a desired component to be supplied to a living body such as skin, such as a component effective as a medicine or a component effective as a cosmetic. These components can be incorporated and retained in the polymer network in the gel film.
In addition, since the hydrogel film has a network structure of a polymer compound, it can permeate a desired component to be supplied to a living body such as skin, such as a component effective as a medicine or a component effective as a cosmetic. Is possible.

The thickness of the hydrogel film may be a thickness such that the total thickness of the hydrogel film and the protective layer after drying is within a predetermined range, and specifically, is within a range of 100 nm to 200 μm. Preferably, it is in the range of 1 μm to 200 μm, more preferably in the range of 1 μm to 100 μm. When the thickness of the hydrogel film is within the above range, the film is very flexible, so that the adhesion to a surface having fine irregularities such as skin is high, and the film is not easily peeled off after being applied.
Here, the thickness of the hydrogel film is a value measured by measuring the position of the film-air interface by focusing with an optical microscope. As an optical microscope, Olympus Nano Search Microscope OLS3500 can be used.

(2) Dry gel film The dry gel film in the present invention has a predetermined thickness so that the total thickness of the dry gel film and the protective layer is within a predetermined range.

  The dry gel film is not particularly limited as long as it has a predetermined thickness, and the same material as the hydrogel film can be used.

  The method for forming a dry gel film is not particularly limited as long as it is a method capable of forming a dry gel film having a predetermined thickness as described later. For example, a dry gel film gels a foam film. It may be made. In this case, the dry gel film is more preferably prepared by gelling and drying an aqueous foam film containing a gel raw material in a state containing water. The gel raw material is the same as that of the hydrogel film.

  Moreover, the dry gel film may contain a surfactant, an emulsification aid, a wetting agent, and the like as appropriate. The surfactant, emulsification aid, and wetting agent are the same as those in the hydrogel film.

Furthermore, the dry gel film may contain a desired component to be supplied to a living body such as skin, such as a pharmaceutical effective component or a cosmetic effective component. These components can be incorporated and retained in the polymer network in the gel film.
In addition, since the dry gel film has a network structure of polymer compounds, it penetrates desired components to be supplied to a living body such as skin, such as components effective as pharmaceuticals and components effective as cosmetics. Is possible.

The thickness of the dry gel film may be a thickness such that the total thickness of the dry gel film and the protective layer is within a predetermined range, and specifically, preferably within a range of 100 nm to 10 μm. More preferably, it is in the range of 200 nm to 1 μm. When the thickness of the dry gel film is within the above range, the film is very flexible, and thus has an excellent adhesion to a surface having fine irregularities such as skin, and the film is difficult to peel off after being applied. . In addition, when the thickness of the dried gel film is equal to or greater than the above lower limit value, the structural color due to light interference can be visually observed, so that the dried gel film can be visually observed without being colored by a coloring agent despite being extremely thin. Can be identified.
Here, when measuring the thickness of the dried gel film, the surface of the cover glass is wetted with water, the dried gel film is adhered to the glass surface with surface tension, vacuum-dried for 1 hour, and the water is completely volatilized. The level difference between the film-air interface and the glass surface was measured to determine the thickness of the dried gel film. As an optical microscope, Olympus Nano Search Microscope OLS3500 can be used.

(3) Gel Film Formation Method The gel film formation method is not particularly limited as long as it is a method capable of forming a gel film having a predetermined thickness. For example, a foam film forming support frame is used. Forming a foam film of an aqueous solution for forming a foam film containing a gel raw material and gelling the foam film (first method), or applying and applying a solution containing the gel raw material on a substrate having a hydrophilic surface A method of forming a film, placing a holding support frame on the coating film, gelling the coating film with the holding support frame placed, and peeling the gel film from the substrate together with the holding support frame (first 2 method).
Hereinafter, each method will be described.

(A) 1st method As a formation method of the hydrogel film in this aspect, what is necessary is just the method which can form the hydrogel film which gelatinized the foam film, for example. A hydrogel film forming method includes a foam film forming step of forming a foam film of a foam film forming aqueous solution containing a gel raw material in an opening of a foam film forming support frame, and the foam film is gelled in a state containing water. And a gelling step of forming a hydrogel film.
Moreover, as a formation method of the dry gel film | membrane in this aspect, what is necessary is just the method which can form the dry gel film | membrane which gelatinized the foam film | membrane, for example. A method for forming a dry gel film includes a foam film forming step of forming a foam film of a foam film forming aqueous solution containing a gel raw material at an opening of a foam film forming support frame, and gelling the foam film in a state containing water It is preferable to have a gelling process for forming a hydrogel film and a drying process for drying the hydrogel film.

  4 (a) to 4 (c) and FIGS. 5 (a) to 5 (e) are process diagrams showing an example of a gel film forming method in the present invention. First, as shown in FIGS. 4A and 5A, a foam film forming support frame 20 having at least one opening 21 is prepared. Next, as shown in FIG. 5B, the foam film-forming support frame 20 is dipped in the foam film-forming aqueous solution 22 and pulled up so as to close the opening 21 as shown in FIG. 5C. A foam film 23 of the aqueous solution for forming a foam film is formed. Next, as shown in FIGS. 4B and 5D, the hydrogel film 2 a is formed by gelling the foam film 23 in a state containing water. Subsequently, as shown in FIGS. 4C and 5E, the hydrogel film 2a is further dried to form a dry gel film 2b.

  Hereinafter, each step in the foam film forming support frame and the gel film forming method used for forming the gel film will be described.

(I) Foam film-forming support frame The material of the foam film-forming support frame for forming the foam film is not particularly limited as long as it can form a foam film of a foam film-forming aqueous solution containing a gel raw material. For example, resin, glass, metal, etc. can be mentioned. Also, the foam film forming support frame may or may not have flexibility. Especially, it is preferable that the support frame for foam film formation is a flexible film-like member.

What is necessary is just to select suitably the dimension and shape of the support frame for foam film formation. Area of the opening formed in the foam film forming support frame may as long as capable of forming a foam film, but is preferably in the range of 100mm ² ~40000mm ^2, within the range of 300mm ² ~2000mm ² More preferably. The shape of the opening is not particularly limited, and may be any shape such as a circle, a triangle, a polygon such as a quadrangle, etc., depending on the purpose. Among them, the shape of the opening is preferably a circle or a polygon with rounded corners. In the case of these shapes, since the stress applied to the periphery of the foam film can be reduced, the ease of handling of the foam film can be improved.

(Ii) Foam film formation process In a foam film formation process, the foam film of the foam film formation aqueous solution containing a gel raw material is formed in opening of the support frame for foam film formation.
Since the gel raw material has been described above, the description thereof is omitted here.
Formation of the foam film when the gel raw material is gelatin, agarose, or collagen is the same as the method described in JP2013-223644A.

  In addition, in the aqueous solution for forming a foam film, it is also possible to mix desired components to be supplied to a living body such as skin such as a component effective as a medicine or a component effective as a cosmetic. The components contained in the foam film-forming aqueous solution can be incorporated and retained in the polymer network structure in the hydrogel film and the dry gel film.

(Iii) Gelation process In a gelation process, a foam film is gelatinized in the state containing water, and a hydrogel film is formed.
In the gelation step, before the foam film dries, it gels in a state containing water to form a hydrogel. It is not essential that the gelling conditions are such that the moisture in the foam film is completely maintained, and any conditions may be used as long as a hydrogel film containing water is formed.
Gelation when the gel material is gelatin, agarose, or collagen is the same as the method described in JP2013-223644A.

(Iv) Drying step In the drying step, the hydrogel film is dried. The dried gel film can be prepared by further drying the hydrogel film.
The gelling step and the drying step do not need to be performed as separate steps, and the hydrogel membrane is processed from the foam membrane under the condition that the hydrogel membrane is subsequently dried, and the hydrogel membrane is processed as an intermediate product. It is also possible to obtain a dry gel film without obtaining
The drying conditions are the same as those described in JP2013-223644A.
The moisture in the dried gel film is not particularly limited, but is preferably dried until the moisture content is 10% by mass or less.

(V) Other Steps As a method for retaining a drug effective ingredient as a pharmaceutical or a cosmetic effective ingredient in a gel film, for example, a hydrogel film using a foam film-forming aqueous solution further added with the above components Or the method of forming a dry gel film | membrane, and the method of making the said component contact the obtained hydrogel film | membrane or dry gel film | membrane are mentioned. In the latter method, the contact of the above components is performed by an arbitrary method such as immersion of a hydrogel thin or dry gel film in a liquid containing the above components or application of a liquid containing the above components to a hydrogel film or a dry gel film. It can be carried out.

(B) Second method The base material used in this embodiment has a hydrophilic surface with a static water contact angle of 45 ° or less. Since such a base material has a sufficiently weak adhesive force with the gel film, even a very thin gel film can be recovered without being damaged at the time of peeling from the surface of the base material.

The hydrophilic surface can be obtained by forming a film of an organic compound having a carbon-oxygen bond on the surface of the substrate.
The base material is preferably a material capable of forming a film of an organic compound having a carbon-oxygen bond on the surface thereof. Specific examples include materials described in International Publication No. 2008/143149 pamphlet.

The hydrophilic surface can be formed by a hydrophilic film formed of an organic compound having a carbon-oxygen bond and having a static water contact angle of 45 ° or less.
Here, the carbon oxygen bond means a bond formed between carbon and oxygen, and is not limited to a single bond but may be a double bond. Examples of the carbon-oxygen bond include a C—O bond, a C (═O) —O bond, and a C═O bond.
Examples of the main raw material for the hydrophilic film include hydrophilic organic compounds such as water-soluble polymers, water-soluble oligomers, water-soluble organic compounds, surface active substances, and amphiphilic substances. These are physically or chemically cross-linked with each other and physically or chemically bonded to the substrate to form a hydrophilic film. Specific examples include materials described in International Publication No. 2008/143149 pamphlet.

  For the thickness of the substrate and the hydrophilic film and the method for forming the hydrophilic film on the substrate surface, International Publication No. 2008/143149 can be referred to.

  The holding support frame used in this embodiment can be the same as the above-described foam film forming support frame.

  In this embodiment, for example, a solution containing a gel raw material is applied on the hydrophilic film of the base material to form a coating film, the holding support frame is placed on the coating film, and the holding support frame is placed The coated film is gelled in the finished state. At this time, the gel film is detachably installed on the base material, and can be peeled from the base material by picking up the holding support frame using tweezers or the like.

2. Protective layer The protective layer in the present invention is formed on at least one surface of the gel film, and has a predetermined thickness so that the total thickness of the gel film and the protective layer after drying is within a predetermined range. It is what has. Further, the protective layer imparts water resistance to the sticking sheet of the present invention.
In the present invention, water resistance is exhibited by the presence of a protective layer on the gel film after the patch sheet has been applied to the skin or the like. Therefore, unlike patent documents 3-7, a protective layer is not peeled from a gel film after sticking of the sheet for sticking.

The protective layer is not particularly limited as long as the gel film can be prevented from swelling with water. For example, when the degree of swelling of the protective layer with respect to water is smaller than the degree of swelling of the gel film with respect to water, the penetration of water into the gel film can be suppressed. In addition, since the protective layer is very thin, it may be difficult to measure the degree of swelling of the protective layer in water, but the degree of swelling of the protective layer in water is the degree of swelling of the adhesive sheet including the protective layer in water. Can be evaluated. In this case, if the swelling degree of the adhesive sheet including the protective layer with respect to water is smaller than the swelling degree of the gel film with respect to water, it can be said that the swelling degree of the protective layer with respect to water is smaller than the degree of swelling of the gel film with respect to water. . Specifically, the degree of swelling of the adhesive sheet with respect to water is preferably in the range of 100% to 4000%, more preferably in the range of 100% to 2000%, and still more preferably in the range of 100% to 1000%. Within range.
Here, the degree of swelling is a ratio of “weight of the sticking sheet after moisture retention” to “weight of the sticking sheet after drying”, and is obtained by the following formula.
Swelling degree (%) = (weight of adhesive sheet after moisture retention) ÷ (weight of adhesive sheet after drying) × 100
Specifically, the weight of the dry laminate was measured with an electronic balance by applying a sheet for pasting to the entire area of both sides of a polyethylene film (Toyobo Co., Ltd., LIX-NP, 100 μm thick) and vacuum drying for 1 hour. The weight of the dried polyethylene film obtained by drying the polyethylene film alone is measured, and the difference between the weight of the dried laminate and the dried polyethylene film is defined as “weight of the sheet for pasting after drying”. Next, the weight of the moisture retaining laminate obtained by immersing the dried laminate in water at 23 ° C. for 5 seconds was quickly measured with an electronic balance so as not to dry, and the dried polyethylene film alone was similarly immersed in water. The weight of the moisture retaining polyethylene film is measured, and the difference in weight between the moisture retaining laminate and the moisture retaining polyethylene film is defined as “weight of the adhesive sheet after moisture retention”. Then, the degree of swelling is calculated by the above formula.

Moreover, it is preferable that a protective layer has hydrophobicity. Water can be repelled by the hydrophobic protective layer, and water penetration into the gel membrane can be suppressed.
Here, “hydrophobic” means that the water contact angle on the surface of the protective layer is 50 ° or more.
Specifically, the water contact angle on the surface of the protective layer is preferably in the range of 50 ° to 180 °, more preferably in the range of 70 ° to 180 °, and still more preferably in the range of 80 ° to 180 °. Is within. This is because when the water contact angle on the surface of the protective layer is within the above range, peeling and tearing of the adhesive sheet of the present invention can be effectively suppressed.

  The water contact angle was 2 μl of water (pure water) dropped from a microsyringe on a protective layer placed horizontally in a dry state (23 ° C.-65% RH) to form a water droplet. It can be obtained by measuring after standing for 30 seconds. The water contact angle is an angle formed by a tangent to the surface of the water droplet at the point where the surface of the protective layer and the water droplet contact, and the surface of the protective layer. Say. For example, the water contact angle can be measured using a fully automatic contact angle meter (Kyowa Interface Chemical Co., Ltd. CA-Z type).

  As a material for the protective layer, it is preferable to satisfy the above characteristics, for example, silicone resin, fluorine resin, vinyl resin, conjugated diene copolymer resin, acrylic resin, polyurethane resin, polyester resin, epoxy resin, paraffin, Examples thereof include nitrocellulose. Further, a polymer gel layer in which a polymer is crosslinked may be used as the protective layer. As the polymer used for the polymer gel layer, the material used for the gel film can be applied.

  In addition, when a functional layer described later is formed between the gel film and the protective layer or on the surface opposite to the protective layer of the gel film, and the functional layer is colored, the protective layer is It is preferable to have transparency. Specifically, the transmittance of the protective layer with respect to the entire visible light wavelength range is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.

  The protective layer should just be formed so that at least one part of the said gel film may be covered. When affixing the adhesive sheet of the present invention to the skin or the like, the entire region of the gel film of the adhesive sheet is not necessarily applied, and a partial region of the gel film of the adhesive sheet may be applied. Therefore, if a protective layer is formed on the gel film in the region where the sticking sheet is stuck, water resistance can be exhibited. Among these, the protective layer is preferably formed on the entire surface of the gel film.

  The protective layer only needs to be formed on at least one surface of the gel film, and the protective layer 3 may be formed only on one side of the gel film 2 as illustrated in FIG. 1, as illustrated in FIG. Protective layers 3 a and 3 b may be formed on both sides of the gel film 2. Especially, it is preferable that the protective layer is formed only on one side of the gel film. In this case, the surface of the gel film of the sticking sheet can be used as the sticking face, and the adhesiveness of the sticking sheet to the adherend is excellent.

  The thickness of the protective layer may be a thickness such that the total thickness of the gel film after drying and the protective layer falls within a predetermined range, and specifically, it may be within a range of 10 nm to 10 μm. Preferably, it is in the range of 100 nm to 3 μm, more preferably in the range of 200 nm to 1 μm. If the thickness of the protective layer is within the above range, it is possible to maintain high adhesion of the gel film to the skin and the like and to form the protective layer on the gel film.

The method for forming the protective layer is not particularly limited as long as it can form the protective layer on the gel film, and is appropriately selected according to the type of material used for the protective layer. For example, a method for applying a protective layer forming composition on a gel film using a protective layer forming composition in which the above-described material is dissolved or dispersed in a solvent may be mentioned. The composition for forming a protective layer may be dried after coating.
The solvent is not particularly limited as long as it does not dissolve the gel film, and is appropriately selected according to the type of the above-described material.
The method for applying the composition for forming the protective layer is not particularly limited as long as it is a method that can be applied on the gel film, but is preferably a non-contact method, for example, a spin coating method, a spray coating method, etc. Can be mentioned. This is because the non-contact method can prevent the gel film from being damaged during application.
When the protective layer is a polymer gel layer, first, the protective layer-forming composition is applied on another substrate to form a coating film, and then, for example, the coating film is irradiated with ultraviolet rays or applied. By applying a cross-linking agent on the film, the polymer is cross-linked to form a polymer gel layer, and then the polymer gel layer is laminated on the gel film by transfer or the like. A gel layer can be placed.

  In the present invention, since the thickness of the protective layer is very thin, it is difficult to form only the protective layer without using a base material that supports the protective layer. Therefore, it is difficult to form a gel film on the protective layer.

3. Support frame The support frame in this invention is arrange | positioned in the outer edge of a gel film, and supports a gel film. That is, the shape of the sticking sheet of the present invention is held by the support frame. The support frame can improve the handleability of the sticking sheet. Moreover, since the sticking sheet whose both surfaces are not in contact with the object can be obtained, the sticking sheet can be easily attached to the skin or the like. Furthermore, since a gel film whose both surfaces are not in contact with an object can be obtained by using a support frame when forming the gel film, a protective layer and a functional layer can be easily formed on the gel film.

The support frame is not particularly limited as long as it can have a support frame when the sheet for application of the present invention is applied to the skin or the like.
Especially, it is preferable that a support frame is the support frame for foam film formation used at the time of foam film formation, or the support frame for holding used at the time of formation of a gel film. For example, as shown in FIGS. 4 and 5, the foam film forming support frame 20 used when forming the foam film can be used as a support frame without being separated from the gel film even after the gel film is formed. 4 and 5, the periphery of the hydrogel film 2 a or the dried gel film 2 b is bonded to the foam film forming support frame 20.

  Further, the gel film can be separated from the support frame for forming the foam film or the support frame for holding, and can be fixed to a separately prepared support frame. Even in this case, the gel film can be subjected to processing such as cutting to an appropriate size, addition of a desired component, formation of a protective layer and a functional layer, as required, at any stage.

  The material, dimensions, and shape of the support frame may be the same as those of the foam film forming support frame. Further, the shape of the support frame may be any shape as long as the support frame can be held when the sticking sheet of the present invention is applied. For example, the support frame may be a closed shape or an open shape. . For example, by opening the foam film-forming support frame 20 on which the hydrogel film 2a or the dry gel film 2b as shown in FIGS. 4B and 4C is formed at the center line, can do.

  The support frame is preferably a flexible film member. As shown in FIGS. 2A to 2C, a support frame 12 formed by a film-like member, a gel film 2 held by the support frame 12, and a protective layer 3 formed on the gel film 2 The surface of the gel film 2 in a state of being fixed to the support frame 12 of the adhesive sheet 1 can be deformed along the surface shape of the object to be applied 30 whose surface is not flat. In addition, it can be adhered and adhered to the surface of the object 30 such as skin moistened with water sufficiently with surface tension. Then, the support frame 12 can be peeled off, and the gel film 2 and the protective layer 3 can be left on the surface of the adherend 30.

4). Functional layer In the present invention, the adhesive property of the gel film is affected between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer. No functional layer may be formed. By forming a functional layer on the gel film, functionality can be imparted to the sheet for sticking. For example, the functional layer can be colored by using a colorant such as a pigment or a dye. In this case, unlike the case where the gel film contains a colorant, since the functional layer can be formed after the gel film is formed, for example, color control is easy. Furthermore, a pigment having a particle diameter equal to or larger than the thickness of the gel film can be applied without deteriorating the sticking property and feeling of use of the sticking sheet. The functional layer can also contain cosmetic ingredients, active pharmaceutical ingredients, and the like.

Here, “patchability” refers to the stickability to the surface of a living body or a biological material such as skin.
“Does not affect the adhesive properties of the gel film” means that the adhesive property of the gel film is maintained to the extent that it can be applied to the surface of a living body or biological material such as skin even after the functional layer is formed on the gel film. It means being.

As the arrangement of the functional layer, the functional layer 5 may be formed between the gel film 2 and the protective layer 3 as illustrated in FIG. 7A, and the protective layer as illustrated in FIG. 7B. The functional layer 5 may be formed on the surface opposite to the gel film 2 of FIG. 3, and when the protective layer 3 is formed only on one surface of the gel film 2 as illustrated in FIG. The functional layer 5 may be formed on the surface of the gel film 3 opposite to the protective layer 3. Especially, it is preferable that the functional layer is formed between the gel film and the protective layer. When the protective layer is on the outermost surface of the sticking sheet, the handleability of the sticking sheet can be improved. Further, when the functional layer is formed between the gel film and the protective layer, and the protective layer is formed only on one side of the gel film, the surface of the gel film of the adhesive sheet is applied to the adhesive surface. It is possible to improve the adhesion of the sticking sheet to the object to be stuck.
Moreover, when the protective layer is formed on both surfaces of the gel film, the functional layer may be formed only on one surface of the gel film.

  The functional layer can be roughly divided into three modes. Hereinafter, the description will be made separately for each aspect.

(1) 1st aspect The functional layer of this aspect is partially formed between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer. It is what is done.

  7A to 7C are schematic cross-sectional views showing other examples of the sticking sheet of the present invention. 7A includes a gel film 2, a functional layer 5 formed in a pattern on the gel film 2, a protective layer 3 formed on the functional layer 5, and a gel film. 2 and a support frame 12 that supports the gel film 2. 7B includes a gel film 2, a protective layer 3 formed on the gel film 2, a functional layer 5 formed in a pattern on the protective layer 3, and a gel film. 2 and a support frame 12 that supports the gel film 2. The sheet 1 for sticking illustrated in FIG. 7C is a gel film 2, a protective layer 3 formed on one surface of the gel film 2, and a function formed in a pattern on the other surface of the gel film 2. It has the layer 5 and the support frame 12 which is arrange | positioned at the outer edge of the gel film 2 and supports the gel film 2.

  In this embodiment, the functional layer is partially formed on the gel film, and there is a portion where the functional layer is not formed on the gel film. In such a portion where the functional layer is not formed on the gel film, the adhesion of the gel film can be enhanced, and the film can be firmly adhered to the skin or the like.

The functional layer may be formed in any position as long as the functional layer is partially formed on the gel film to such an extent that the adhesive sheet can be fixed to the surface of the object to be applied. For example, the functional layer 5 may be formed in a pattern at intervals as shown in FIGS. 7A to 7C, and the functional layer 5 may be formed as shown in FIGS. 8A and 8B. It may be formed only at the center of the gel film 2 and not formed at the end of the gel film 2. FIG. 8B is a cross-sectional view taken along line AA in FIG.
Especially, it is preferable that there are at least two portions where the functional layer is not formed on the gel film. This is because if the sticking sheet is brought into close contact with the surface of the article to be stuck, it can be fixed, and displacement of the sticking sheet can be suppressed.
Moreover, it is preferable that the functional layer is not formed in the edge part of a gel film. This is because it is possible to easily fix the sticking sheet to the surface of the article to be pasted and to prevent peeling of the sticking sheet. Especially, it is preferable that there are at least two portions where the functional layer is not formed at the end of the gel film. In particular, it is preferable that the functional layer is not formed over the entire area of the outer peripheral edge of the gel film. This is because the sticking sheet can be firmly adhered to the surface of the object to be stuck and peeling of the sticking sheet can be effectively prevented.

  The area ratio of the portion where the functional layer is not formed on the gel film with respect to the gel film is not particularly limited as long as it can fix the adhesive sheet to the surface of the object to be applied, and is appropriately determined depending on the purpose. Adjusted.

  The shape of the functional layer in plan view is not particularly limited as long as the functional layer is partially formed on the gel film, and can be an arbitrary shape. For example, a character, a figure, a pattern, etc. can be mentioned. Moreover, a dot shape may be sufficient. A plurality of types of functional layers such as CMYK (cyan, magenta, yellow, black) can be formed in a pattern and printed in color. Even when no colorant is used, a plurality of types of functional layers may be formed in a pattern.

  The material used for the functional layer is not particularly limited as long as the functional layer can be partially formed on the gel film, and materials used for cosmetics, medicines, and the like can be used. It is appropriately selected according to the purpose. For example, as the functional layer, those containing fine particles, those containing colorants such as pigments and dyes, those containing binders and fine particles, those containing binders and colorants, and binders and drugs, The thing containing an effective component as cosmetics can be mentioned. When the functional layer contains a desired component to be supplied to a living body such as skin such as a component effective as a medicine or a component effective as a cosmetic, the above component permeates the gel film and is supplied to the skin or the like be able to.

  Note that the fine particles can be the same as the fine particles used in the fine particle layer in the second embodiment to be described later, and thus the description thereof is omitted here.

  As a binder used for a functional layer, what is used for cosmetics, a medicine, etc. can be used, and it is suitably selected according to the objective.

When the functional layer contains a binder and fine particles, the content of the binder in the functional layer is not particularly limited as long as it can exhibit the function as a binder, and is appropriately adjusted according to the purpose. And can be set within a range of 0.01% by mass to 99.9% by mass.
Further, the content of the fine particles in the functional layer is not particularly limited as long as the function required for the fine particles can be exhibited, and is appropriately adjusted according to the purpose, and is 0.01% by mass. It can be set within a range of ˜99.9% by mass.

When the functional layer contains a binder and a component effective as a medicine or cosmetic, the content of the binder in the functional layer is not particularly limited as long as it can exhibit the function as a binder, It adjusts suitably according to this, and can set it within the range of 0.01 mass%-99.9 mass%.
In addition, the content of an effective component as a pharmaceutical or cosmetic in the functional layer is not particularly limited as long as the characteristics of the active component can be obtained, and is appropriately adjusted according to the purpose. , 0.01% by mass to 99.9% by mass.

  When the functional layer contains fine particles, the fine particles may be uniformly dispersed in the functional layer, or the fine particles may be dispersed with a concentration gradient in the surface direction of the functional layer. In particular, the fine particles have a concentration gradient in the surface direction of the functional layer, and the functional layer 5 is formed only in the central portion of the gel film 2 as illustrated in FIGS. 8A and 8B. It is preferable that the content of the fine particles decreases from the center portion to the end portion of the functional layer 5. In this case, since the content of the fine particles is reduced at the end of the functional layer, the transparency can be improved and the sticking sheet can be made inconspicuous when sticking to the skin or the like.

  The thickness of the functional layer varies depending on the type of material used for the functional layer, but is preferably within a range of 1 nm to 100 μm, more preferably within a range of 10 nm to 50 μm, and even more preferably 100 nm to It is in the range of 20 μm. If the thickness of the functional layer is within the above range, the functional layer can be formed on the gel film. In this embodiment, even if the functional layer is thicker than the gel film, the adhesive sheet can be applied to the skin or the like. However, if the functional layer is too thick, the functional layer is formed on the gel film. It may be difficult to form the film, or the sticking property of the sticking sheet may be inferior.

  The functional layer may have a uniform thickness or may have a thickness gradient. In particular, when the functional layer has a thickness gradient, and the functional layer 5 is formed only in the central portion of the gel film 2 as illustrated in FIGS. It is preferable that the thickness decreases from the center to the end of the layer. In this case, since the thickness of the functional layer is reduced at the end portion of the functional layer, the transparency can be improved, and the sticking sheet can be made inconspicuous when sticking to the skin or the like.

The method for forming the functional layer is not particularly limited as long as the functional layer can be partially formed on the gel film, and is appropriately selected according to the type of material used for the functional layer. For example, there is a method in which a functional layer forming composition in which the above-described materials are dissolved or dispersed in a solvent is used, and this functional layer forming composition is partially applied onto a gel film. The composition for forming a functional layer may be dried after coating.
The solvent is not particularly limited as long as it does not dissolve the gel film, and is appropriately selected according to the type of the above-described material.
The method for applying the functional layer forming composition is not particularly limited as long as it is a method that can be partially applied onto the gel film, but is preferably a non-contact method, for example, an ink jet method or a dispenser method. And a spray method using a mask. This is because the non-contact method can prevent the gel film from being damaged during application. In addition, when the functional layer contains fine particles and the fine particles form a functional layer having a concentration gradient in the plane direction or when forming a functional layer having a thickness gradient, the functional layer forming composition As the coating method, an inkjet method or a dispenser method can be used.

  Examples of a method for containing a component effective as a pharmaceutical or a component effective as a cosmetic in the functional layer include, for example, a method of forming a functional layer using the functional layer forming composition further added with the above components, And the method of making the said component contact the obtained functional layer is mentioned. In the latter method, the contact of the component can be performed by any method such as immersion of the functional layer in a liquid containing the component, or application of a liquid containing the component to the functional layer.

(2) Second aspect The functional layer of this aspect is formed between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer, and the fine particles Is a fine particle layer dispersed or a fluidized bed containing a fluid substance.

Here, “fine particles are dispersed” means that the fine particles are not bonded or bound to each other. Note that “fine particles are dispersed” includes a case where the fine particles are aggregated.
A “fluid substance” refers to a substance that exhibits fluidity on a gel film.

  FIG. 9 is a schematic sectional view showing another example of the sticking sheet of the present invention. As illustrated in FIG. 9, the sticking sheet 1 includes a gel film 2, a fine particle layer 6 formed on the gel film 2 in which fine particles are dispersed, a protective layer 3 formed on the fine particle layer 6, a gel It has the support frame 12 which is arrange | positioned at the outer edge of the film | membrane 2 and supports the gel film | membrane 2. As shown in FIG.

  FIG. 10 is a schematic sectional view showing another example of the sticking sheet of the present invention. As illustrated in FIG. 10, the sticking sheet 1 includes a gel film 2, a fluidized layer 7 formed on the gel film 2 and containing a fluid substance, a protective layer 3 formed on the fluidized layer 7, It has the support frame 12 which is arrange | positioned at the outer edge of the gel film 2 and supports the gel film 2.

  In this embodiment, the fine particle layer is a particle in which fine particles are dispersed, and the fluidized bed contains a fluid substance, so that even if the fine particle layer or the fluidized layer is formed on the gel film. In addition, high adhesion of the gel film to the skin or the like can be maintained.

  Hereinafter, the description will be made separately for the fine particle layer and the fluidized bed.

(A) Fine particle layer The fine particle layer in this embodiment is one in which fine particles are dispersed.

  As the fine particles, those used in cosmetics, medicines and the like can be used, and are appropriately selected according to the purpose. For example, a pigment is mentioned. Further, the fine particles may be one kind or two or more kinds.

The average particle size of the fine particles is not particularly limited as long as it can be dispersed on the gel film, but is preferably in the range of 1 nm to 100 μm, more preferably in the range of 10 nm to 50 μm, and still more preferably. It is in the range of 100 nm to 20 μm. This is because if the particle size of the fine particles is small, the dispersibility is poor. In this embodiment, even if the particle diameter of the fine particle is large relative to the thickness of the gel film, the adhesive sheet can be applied to the skin or the like. However, if the fine particle diameter is too large, the fine particle is dispersed on the gel film. It may be difficult to apply, or the sticking property of the sticking sheet may be poor.
Here, an average particle diameter is an average particle diameter by microscopic observation. The average particle diameter by microscopic observation is obtained, for example, by performing microscopic observation at a magnification of 100, measuring 100 particle diameters of arbitrary fine particles with image processing software or the like, and averaging the number. The particle diameter refers to the average value of the major axis diameter and minor axis diameter of the fine particles.

  Since the fine particles are dispersed in the fine particle layer and the fine particles are not bonded or bound to each other, it is preferable that the fine particle layer does not contain a binder which is a binder or a binder. Note that a binder may be included as long as the amount of the gel film does not affect the pastability of the gel film.

  The fine particle layer may contain a dispersing agent such as a surfactant in order to improve the dispersibility of the fine particles.

  The content of the fine particles in the fine particle layer is preferably in the range of 50% by mass to 100% by mass.

  In the fine particle layer, fine particles may be dispersed. For example, the fine particles may be uniformly dispersed, or the fine particles may be dispersed with a concentration gradient in the surface direction of the fine particle layer. When the fine particles have a concentration gradient in the plane direction of the fine particle layer, it is preferable that the content of the fine particles decreases from the center to the end of the fine particle layer. In this case, since the content of the fine particles is reduced at the end of the fine particle layer, that is, the end of the gel film, the transparency can be improved, and the sticking sheet can be made inconspicuous when sticking to the skin or the like. . Moreover, the softness | flexibility of a gel film can be improved in the edge part of a gel film, and the adhesiveness to skin etc. can be improved.

  The thickness of the fine particle layer varies depending on the average particle size of the fine particles, but is preferably in the range of 1 nm to 100 μm, more preferably in the range of 10 nm to 50 μm, and still more preferably in the range of 100 nm to 20 μm. Is within. If the thickness of the fine particle layer is within the above range, the fine particle layer can be formed on the gel film. In this embodiment, even if the fine particle layer is thicker than the gel film, the sticking sheet can be applied to the skin or the like. However, if the fine particle layer is too thick, the fine particles are formed on the gel film. It may be difficult to form a layer or the sticking property of the sticking sheet may be inferior.

  The fine particle layer may have a uniform thickness or may have a thickness gradient. When the fine particle layer has a thickness gradient, it is preferable that the thickness decreases from the center to the end of the fine particle layer. In this case, since the thickness of the fine particle layer is reduced at the end of the fine particle layer, that is, at the end of the gel film, the transparency can be improved and the sticking sheet can be made inconspicuous when sticking to the skin or the like it can. Moreover, the softness | flexibility of a gel film can be improved in the edge part of a gel film, and the adhesiveness to skin etc. can be improved.

The method for forming the fine particle layer is not particularly limited as long as it is a method capable of forming the fine particle layer on the gel film, and is appropriately selected according to the kind of fine particles. For example, there is a method in which a fine particle dispersion in which fine particles are dispersed in a solvent is used and this fine particle dispersion is applied onto the gel film. The fine particle dispersion may be dried after coating.
The solvent is not particularly limited as long as it does not dissolve the gel film, and is appropriately selected according to the type of fine particles.
The method for applying the fine particle dispersion is not particularly limited as long as it is a method that can be applied onto the gel film, but is preferably a non-contact method, such as a spin coating method or a spray coating method. be able to. This is because if the non-contact method is used, the gel film can be prevented from being damaged during application. In addition, when forming a fine particle layer having a concentration gradient in the surface direction or when forming a fine particle layer having a thickness gradient, a dispenser method, an inkjet method, or the like may be used as a method for applying the fine particle dispersion. it can.

(B) Fluidized bed The fluidized bed in this aspect contains a fluid substance.

  The fluid substance may be any material that has fluidity on the gel film and does not dissolve the gel film, and can be used for cosmetics, medicines, etc. It is selected appropriately. For example, mineral oil, vegetable oil, alcohol, glycerin, polyethylene glycol and the like can be mentioned. Especially, it is preferable that a fluid substance has low volatility. The volatility of the flowable substance is preferably such that the flowable substance has a melting point such that the flowable substance contained in the fluidized bed has fluidity when the adhesive sheet is applied to the skin or the like. The flowable material preferably has a melting point of 37 ° C. or lower.

  The fluidized bed may further contain a desired component to be supplied to a living body such as skin, such as a component effective as a medicine or a component effective as a cosmetic. Since the gel film has a network structure of a polymer compound, it can penetrate the above components. Therefore, the said component permeate | transmits a gel film and can be supplied to skin etc.

The fluidized bed may contain colorants such as dyes and pigments. For example, an ink containing a fluid substance as a solvent and a colorant can be used for the fluidized bed.
The fluidized bed may contain fine particles. Since the fine particles can be the same as the fine particles used in the fine particle layer, description thereof is omitted here.

  The content of the fluid substance in the fluidized bed is preferably in the range of 50% by mass to 100% by mass.

  The thickness of the fluidized bed varies depending on the type of fluid substance, but is preferably in the range of 1 nm to 100 μm, more preferably in the range of 10 nm to 50 μm, and still more preferably in the range of 100 nm to 20 μm. Is within. If the thickness of the fluidized bed is within the above range, a fluidized bed can be formed on the gel film. In this embodiment, even if the fluidized layer is thicker than the gel membrane, the adhesive sheet can be applied to the skin or the like. However, if the fluidized layer is too thick, the fluidized layer flows on the gel membrane. It is difficult to form a layer.

The method for forming the fluidized bed is not particularly limited as long as it is a method capable of forming a fluidized bed on the gel film, and examples thereof include a method of applying a fluid substance on the gel film.
The application method of the fluid substance is not particularly limited as long as it is a method that can be applied onto the gel film, but is preferably a non-contact method, and examples thereof include a spin coating method and a spray coating method. be able to. This is because if the non-contact method is used, the gel film can be prevented from being damaged during application.

  Examples of a method for adding a component effective as a pharmaceutical or a component effective as a cosmetic to the fluidized bed include, for example, a method of forming a fluidized bed using a fluid material further added with the above components, and The method of making the said component contact the obtained fluidized bed is mentioned. In the latter method, the contact of the components can be performed by any method such as application of a liquid containing the components to a fluidized bed.

(3) Third aspect The functional layer of this aspect is formed between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer and dried. It has a predetermined thickness so that the total thickness of the subsequent gel film, functional layer and protective layer is in the range of 100 nm to 10 μm.

  Here, “the total thickness of the dried gel film, functional layer and protective layer is in the range of 100 nm to 10 μm” means, for example, when the gel film contains water, the dried gel The total thickness of the film, the functional layer, and the protective layer may be within the above range, and the actual total thickness of the gel film, the functional layer, and the protective layer may not be within the above range. When protective layers are formed on both sides of the gel film, the total thickness of the dried gel film, functional layer and protective layer is the thickness of the dried gel film, the thickness of the functional layer and the gel. The total thickness of each protective layer formed on both sides of the film.

  FIG. 11 is a schematic sectional view showing another example of the sticking sheet of the present invention. As illustrated in FIG. 11, the sticking sheet 1 includes a gel film 2, a functional layer 5 formed on the gel film 2, a protective layer 3 formed on the functional layer 5, and an outer edge of the gel film 2. And a support frame 12 that supports the gel film 2. The total thickness of the gel film 2, the functional layer 5, and the protective layer 3 after drying is within a predetermined range.

  In this aspect, even when the functional layer is formed on the entire surface of the gel film by the total thickness of the gel film, the functional layer, and the protective layer after drying being within a predetermined range, High adhesion to skin or the like can be maintained.

  The material used for the functional layer is not particularly limited as long as it can form a functional layer having a predetermined thickness, and materials used for cosmetics and medicines can be used. It is appropriately selected depending on. For example, examples of the functional layer include those containing fine particles such as pigments, those containing binders and fine particles such as pigments, and those containing binders and components effective as pharmaceuticals and cosmetics. . When the functional layer contains a desired component to be supplied to a living body such as skin such as a component effective as a medicine or a component effective as a cosmetic, the above component permeates the gel film and is supplied to the skin or the like be able to.

  As a binder used for a functional layer, what is used for cosmetics, a medicine, etc. can be used, and it is suitably selected according to the objective.

  The fine particles can be the same as the fine particles used in the fine particle layer in the second aspect. The content of the binder, fine particles, and components effective as a medicine or cosmetic in the functional layer can be the same as in the functional layer in the second embodiment.

  When the functional layer contains fine particles, the fine particles may be uniformly dispersed in the functional layer, or the fine particles may be dispersed with a concentration gradient in the surface direction of the functional layer. In particular, when the fine particles have a concentration gradient in the surface direction of the functional layer, it is preferable that the content of the fine particles decreases from the center portion to the end portion of the functional layer. In this case, since the content of the fine particles is reduced at the end of the functional layer, the transparency can be improved and the sticking sheet can be made inconspicuous when sticking to the skin or the like.

  The thickness of the functional layer may be a thickness such that the total thickness of the gel film, the functional layer and the protective layer after drying is within a predetermined range. Although it varies depending on the type of the material used, it is preferably in the range of 10 nm to 10 μm, more preferably in the range of 100 nm to 10 μm, and still more preferably in the range of 100 nm to 5 μm. If the thickness of the functional layer is within the above range, it is possible to maintain high adhesion of the gel film to the skin and the like and to form the functional layer on the gel film.

  The functional layer may have a uniform thickness or may have a thickness gradient. Especially, when a functional layer has a thickness gradient, it is preferable that thickness becomes thin toward the edge part from the center part of a functional layer. In this case, since the thickness of the functional layer is reduced at the end of the functional layer, that is, the end of the gel film, the transparency can be improved and the sticking sheet can be made inconspicuous when sticking to the skin or the like. it can. Moreover, the softness | flexibility of a gel film can be improved in the edge part of a gel film, and the adhesiveness to skin etc. can be improved.

The method for forming the functional layer is not particularly limited as long as it can form a functional layer having a predetermined thickness on the gel film, and is appropriately selected according to the type of material used for the functional layer. The For example, there is a method in which a functional layer forming composition in which the above-described materials are dissolved or dispersed in a solvent is used, and this functional layer forming composition is partially applied onto a gel film. The composition for forming a functional layer may be dried after coating.
The solvent is not particularly limited as long as it does not dissolve the gel film, and is appropriately selected according to the type of the above-described material.
The method for applying the functional layer forming composition is not particularly limited as long as it is a method capable of forming a functional layer having a predetermined thickness on the gel film, but is preferably a non-contact method, for example, Examples thereof include a spin coating method and a spray coating method. This is because the non-contact method can prevent the gel film from being damaged during application. In addition, when the functional layer contains fine particles and the fine particles form a functional layer having a concentration gradient in the plane direction or when forming a functional layer having a thickness gradient, the functional layer forming composition As the coating method, an inkjet method or a dispenser method can be used.

The total thickness of the gel film, functional layer and protective layer after drying is in the range of 100 nm to 10 μm, preferably in the range of 100 nm to 5 μm, more preferably in the range of 100 nm to 3 μm. When the total thickness of the dried gel film, functional layer and protective layer is too thick, the unevenness followability deteriorates. Moreover, when the total thickness of the gel film after drying, a functional layer, and a protective layer is too thin, it may be inferior to intensity | strength.
Here, when the functional layer has a thickness gradient, the total thickness of the gel film, the functional layer, and the protective layer after drying refers to the maximum thickness.

  When the gel film is a hydrogel film, the total thickness of the dried hydrogel film, the functional layer, and the protective layer may be in the above range. Specifically, the total thickness of the hydrogel film, the functional layer, and the protective layer is preferably in the range of 100 nm to 200 μm, more preferably in the range of 1 μm to 200 μm, and still more preferably in the range of 1 μm to 150 μm. In particular, the thickness is preferably in the range of 10 μm to 100 μm. When the total thickness of the hydrogel film, the functional layer, and the protective layer is within the above range, high adhesion to the skin or the like of the hydrogel film can be maintained even if the functional layer is formed on the entire surface of the hydrogel film.

  When the gel film is a dried gel film, the total thickness of the dried gel film, the functional layer, and the protective layer is the same as the total thickness of the gel film, the functional layer, and the protective layer after drying. If the total thickness of the dry gel film, the functional layer and the protective layer is within the above range, even if the functional layer is formed on the entire surface of the dry gel film, high adhesion to the skin etc. of the dry gel film should be maintained. Can do.

  In this embodiment, the total thickness of the gel film, the functional layer, and the protective layer after drying may be within the above range. For example, the gel film may be thicker than the functional layer, and the functional layer may be thicker than the gel film. It may be thick.

(4) Fourth aspect The functional layer in this aspect is formed between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer. The first functional layer and the second functional layer are sequentially stacked from the film side, and the total thickness of the dried gel film, the first functional layer, and the protective layer is in the range of 100 nm to 10 μm. The bifunctional layer is a fine particle layer in which fine particles are dispersed or a fluidized layer containing a fluid substance.

  FIG. 12 is a schematic sectional view showing another example of the sticking sheet of the present invention. As illustrated in FIG. 12, the sticking sheet 1 includes a gel film 2, a functional layer 5 formed on the gel film 2, a protective layer 3 formed on the functional layer 5, and an outer edge of the gel film 2. The support frame 12 is disposed and supports the gel film 2. The functional layer 5 includes a first functional layer 8 formed on the gel film 2 and a fine particle layer 6 in which fine particles are dispersed as a second functional layer formed on the first functional layer 8. Moreover, the total thickness of the gel film 2, the first functional layer 8, and the protective layer 3 after drying is within a predetermined range.

  FIG. 13 is a schematic cross-sectional view showing another example of the sticking sheet of this embodiment. As illustrated in FIG. 13, the sticking sheet 1 includes a gel film 2, a functional layer 5 formed on the gel film 2, a protective layer 3 formed on the functional layer 5, and an outer edge of the gel film 2. The support frame 12 is disposed and supports the gel film 2. The functional layer 5 includes a first functional layer 8 formed on the gel film 2 and a fluidized layer 7 containing a fluid substance as a second functional layer formed on the first functional layer 8. . Moreover, the total thickness of the gel film 2, the first functional layer 8, and the protective layer 3 after drying is within a predetermined range.

  In this aspect, even if the first functional layer is formed on the entire surface of the gel film by the total thickness of the dried gel film, the first functional layer, and the protective layer being within a predetermined range, High adhesion of the gel film to the skin or the like can be maintained. The fine particle layer is a particle in which fine particles are dispersed, and the fluidized bed contains a fluid substance, so that the fine particle layer or the fluidized layer is formed as the second functional layer on the first functional layer. Even in this case, high adhesion of the gel film to the skin or the like can be maintained.

  The fine particle layer and the fluidized bed are the same as in the second embodiment, and the first functional layer is the same as the functional layer in the third embodiment. The total thickness of the gel film, the first functional layer, and the protective layer after drying can be the same as in the third embodiment.

  Further, the total thickness of the dried gel film, the first functional layer, and the protective layer may be in the above range. For example, the gel film may be thicker than the first functional layer, and the first functional layer is the gel film. It may be thicker.

(5) Fifth aspect The functional layer in this aspect is formed between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer, A first functional layer and a second functional layer laminated in order from the film side, the total thickness of the dried gel film, the first functional layer and the protective layer is in the range of 100 nm to 200 μm, The two functional layers are partially formed on the first functional layer.

  FIG. 14 is a schematic sectional view showing another example of the sticking sheet of the present invention. As illustrated in FIG. 14, the sticking sheet 1 includes a gel film 2, a functional layer 5 formed on the gel film 2, a protective layer 3 formed on the functional layer 5, and an outer edge of the gel film 2. The support frame 12 is disposed and supports the gel film 2. The functional layer 5 includes a first functional layer 8 formed on the gel film 2 and a second functional layer 9 partially formed on the first functional layer 8. Moreover, the total thickness of the gel film 2, the first functional layer 8, and the protective layer 3 after drying is within a predetermined range.

  In this aspect, even if the first functional layer is formed on the entire surface of the gel film by the total thickness of the dried gel film, the first functional layer, and the protective layer being within a predetermined range, High adhesion of the gel film to the skin or the like can be maintained. Moreover, the 2nd functional layer is partially formed on the 1st functional layer, and the part in which the 2nd functional layer is not formed exists on a gel film. In such a portion where the second functional layer is not formed on the gel film, the adhesion of the gel film can be enhanced.

  The first functional layer is the same as the functional layer in the third aspect, and the second functional layer is the same as the functional layer in the first aspect. The total thickness of the gel film, the first functional layer, and the protective layer after drying can be the same as in the third embodiment.

  Further, the total thickness of the dried gel film, the first functional layer, and the protective layer may be in the above range. For example, the gel film may be thicker than the first functional layer, and the first functional layer is the gel film. It may be thicker.

5. Cover layer In the present invention, when the functional layer is a fluidized bed and the fluidized layer is formed on the surface of the protective layer opposite to the gel film, the cover layer is disposed on the fluidized layer. May be. The cover layer can facilitate the handling of the sticking sheet and suppress volatilization of the fluid substance contained in the fluidized bed.

When the cover layer is disposed on the fluidized bed, the cover layer may or may not be peeled after the sticking sheet is stuck. When the cover layer is not peeled off, stickiness of the sticking sheet after sticking and volatilization of the fluid substance can be suppressed.
When the cover layer is peeled off, the gel film surface of the sticking sheet is stuck on the surface of the object to be pasted, and then the gel layer and the fluidized layer are left on the surface of the object to be pasted by peeling the cover layer. Can do. Since the cover layer is laminated on the gel film via the fluidized bed, the cover layer can be prevented from contacting the gel film. Therefore, the gel film has high adhesion, but the cover layer can be peeled off.

  The material of the cover layer is not particularly limited as long as it can be disposed on the fluidized bed and is not dissolved in the fluid substance contained in the fluidized bed. Examples thereof include resins and glass. it can. Moreover, the cover layer may or may not have flexibility. Especially, it is preferable that a cover layer is a flexible film-like member similarly to the case of said support frame.

  The thickness of the cover layer is not particularly limited as long as it can protect the fluidized bed, but it is preferable that the cover layer has flexibility, for example, in the range of 10 μm to 10 mm. It is preferable.

6). Sheet for pasting In the present invention, when a protective layer is formed only on one side of the gel film, the side of the gel film is used as the pasting surface. Moreover, when the protective layer is formed on both surfaces of the gel film, the surface of one of the protective layers is used as the pasting surface. Especially, it is preferable that the protective layer is formed only on one side of the gel film, and the surface of the gel film is the pasting surface. This is because the adhesiveness of the sticking sheet to the adherend is excellent. On the other hand, even when the surface of the protective layer is used as the sticking surface, the thickness of the protective layer is very thin, so that the adhesion of the sticking sheet to the object to be stuck can be ensured.

  In the case where the functional layer is formed and the functional layer 5, the gel film 2 and the protective layer 3 are laminated in this order as illustrated in FIG. It can be a sticking surface. For example, when the functional layer is partially formed, the adhesiveness of the adhesive sheet to the object to be adhered is ensured by increasing the area ratio of the part where the functional layer is not formed on the gel film. be able to. For example, when the functional layer is a fine particle layer, the content (density) of the fine particles is reduced, the fine particles have a concentration gradient in the surface direction of the fine particle layer, or the fine particle layer has a thickness gradient. By doing so, the adhesiveness of the sticking sheet to the object to be stuck can be ensured. For example, when the functional layer has a predetermined thickness, the adhesiveness of the sticking sheet to the object to be stuck can be ensured by making the functional layer have a thickness gradient.

  When using the adhesive sheet of the present invention, moisten the skin or the like with water or wet the adhesive surface of the adhesive sheet with water, and adhere the adhesive surface of the adhesive sheet to the surface of the skin or the like with surface tension. Can be affixed.

  In the present invention, after use of the adhesive sheet, it can be easily washed away with water or the like, depending on the type of gel film.

  The sticking sheet of the present invention can also be used for the purpose of protecting the surface of a living body or a biomaterial.

  The sticking sheet of the present invention is useful for cosmetic use or medical use. Specifically, makeup cosmetics such as concealers for unevenness correction and color correction, cosmetic pack materials, wound dressings for protecting wounds on the skin surface, and procedures for applying a drug transcutaneously. A skin-absorbing preparation, affixed to the surface of an organ or tissue in a living body, can be used for applications such as a protective sheet that protects the surface of an organ or tissue or prevents adhesion to other organs or tissues. Further, the sticking sheet of the present invention can also be used as a decorative seal such as a nail seal or a tattoo seal.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Reference example]
1. Preparation of Support Frame A 4 cm × 4 cm, 250 μm thick SUNDIC polystyrene film was cut out to form a 3.2 cmφ true circular opening at the center to prepare a support frame having an opening.

2. Preparation of aqueous solution (1) Aqueous solution 1-a, 1-b
Aqueous solutions prepared by dissolving Sigma-Aldrich gelatin in pure water to a concentration of 2% by mass or 6% by mass were referred to as “aqueous solution 1-a” and “aqueous solution 1-b”, respectively.
(2) Aqueous solution 2-a, 2-b
Aqueous solutions prepared by dissolving Sigma Aldrich Agarose in pure water to a concentration of 2% by mass or 6% by mass were designated as “Aqueous Solution 2-a” [Aqueous Solution 2-b], respectively.
(3) Aqueous solution 3-a, 3-b
Aqueous solutions prepared by adjusting the concentration of collagen Cellmatrix Type I-A manufactured by Nitta Gelatin Co. to 2% by mass (pH = 3) or 6% by mass (pH = 3) were obtained as “Aqueous solution 3-a” [Aqueous solution 3]. -B].

3. Formation of Gelatin Hydrogel Film and Dry Gel Film The support frame is immersed in the aqueous solution 1-a in a sol state at 37 ° C. for 1 second, and then the support frame is removed from the aqueous solution so that the support frame is parallel to the vertical direction. It was lifted up so that a foam film of an aqueous solution was formed in the opening. Immediately after the lifting, the support frame was exposed to a temperature condition of 4 ° C. for 10 minutes to gel the foam film of the aqueous solution, thereby preparing a hydrogel film 1-a having a thickness of about 10 μm.
Next, the hydrogel film was dried at 4 ° C. for 120 minutes to obtain a dried gel film 1-a having a thickness of about 400 nm.

  Further, the aqueous solution 1-b is also gelled after forming a foam film with the aqueous solution by the same method to produce a hydrogel film 1-b having a thickness of about 10 μm, and dried to a dried gel film 1 having a thickness of 1.2 μm. -B was produced.

4). Formation of hydrogel film and dry gel film of agarose The support frame is immersed in an aqueous solution 2-a in a sol state at 50 ° C. for 1 second, and then the support frame is removed from the aqueous solution so that the support frame is parallel to the vertical direction. It was lifted up so that a foam film of an aqueous solution was formed in the opening. Immediately after the lifting, the support frame was exposed to a temperature condition of 4 ° C. for 10 minutes to gel the foam film of the aqueous solution, thereby preparing a hydrogel film 2-a having a thickness of about 10 μm.
Next, the hydrogel film was dried at 4 ° C. for 120 minutes to obtain a dried gel film 2-a having a thickness of about 400 nm.

  Also for the aqueous solution 2-b, a foam film was formed with an aqueous solution and gelled by the same method to produce a hydrogel film 2-b having a thickness of about 10 μm, and dried to a dried gel film 2-b having a thickness of 1.2 μm. Was made.

5. Formation of collagen hydrogel membrane and dry gel membrane At 4 ° C., the aqueous solution 3-a was adjusted to pH = 7 with sodium hydroxide and immersed in an aqueous solution in a sol state at 4 ° C. for 1 second. The support frame was lifted from the aqueous solution so as to be parallel to the base plate so that a foam film of the aqueous solution was formed in the opening of the support frame. Immediately after the lifting, the support frame was exposed to a temperature condition of 37 ° C. for 30 minutes to gel the foam film of the aqueous solution, thereby preparing a hydrogel film 3-a having a thickness of about 10 μm.
Next, the hydrogel film was dried at 23 ° C. for 120 minutes to obtain a dried gel film 3-a having a thickness of about 400 nm.

  Also for the aqueous solution 3-b, a foam film is formed with an aqueous solution and gelled by the same method to produce a hydrogel film 3-b having a thickness of about 10 μm, and dried to a dried gel film 3-b having a thickness of 1.2 μm. Was made.

[Comparative Example 1]
1. Formation of Gelatin Hydrogel Film and Dry Gel Film Aqueous solution 1-a was subjected to a drying treatment at a temperature of 23 ° C. without gelation after forming a foam film with an aqueous solution by the same method as in Example 1. The foam film was broken.

2. Formation of Agarose Hydrogel Film and Dry Gel Film Aqueous solution 2-a was subjected to a drying treatment at a temperature of 23 ° C. without gelation after forming a foam film with an aqueous solution by the same method as in Example 1. The foam film was broken.

3. Formation of collagen hydrogel membrane and dry gel membrane For aqueous solution 3-a, the aqueous solution 3-a was adjusted to pH = 7 at 4 ° C. by the same method as in Example 1 to form a foam film and gelled. When the drying process was performed at a temperature of 23 ° C., the foam film was broken.

[Comparative Example 2]
An aqueous solution prepared by dissolving Sigma Aldrich Agarose in pure water to a concentration of 1% by mass was designated as “Aqueous Solution 4”. The hydrogel film 4 was formed by coating the aqueous solution 4 in a sol state at 50 ° C. on a glass substrate so as to have a thickness of 1 mm and gelling. Since this hydrogel film is strong, it can be peeled off from the substrate with tweezers and handled.

[Evaluation]
1. Evaluation of Hydrogel Film Adhesion to Human Skin For each of the hydrogel films 1-a, 2-a, and 3-a prepared above, the support frame portion of the support frame on which the hydrogel film was formed was grasped and wetted with water. When the hydrogel film was brought into contact with the human skin, the hydrogel film adhered to the skin due to surface tension, and when the support frame part was moved away from the skin, the hydrogel film separated from the support frame part, and only the hydrogel film could be applied to the skin. . In addition, since the hydrogel film is very thin, it can be applied to curved or refracted parts, and all of the hydrogel film follows the curved shape when it is brought into contact with a finger joint moistened with water with the finger bent. The film was in close contact with the skin due to surface tension, and the hydrogel film did not peel off while sticking to the skin even during refraction of the finger after application, and the appearance after application was hardly noticeable.

  The hydrogel membranes 1-b, 2-b, and 3-b could also be attached by bringing the finger joints into close contact with a finger joint moistened with water with surface tension. However, compared with the hydrogel films 1-a, 2-a, and 3-a, the adhesion to the skin is weak, and the hydrogel film tends to be displaced from the skin during finger refraction. In addition, the appearance after sticking tends to be noticeable.

  On the other hand, when the hydrogel film 4 is brought into contact with the bent finger joint, a part of it floats, and the adhesion of the hydrogel film deviates from the skin when the finger is refracted, and the appearance after application is also conspicuous. .

2. Evaluation of application of dry gel film to human skin For each of the dry gel films 1-a, 2-a, and 3-a prepared above, the support frame portion of the support frame on which the dry gel film is formed is grasped, When the dried gel film is brought into contact with the human skin wetted with, the dried gel film is very thin, so it is flexible and adheres to the skin with surface tension so as to follow the fine shape of the skin, and the support frame is moved away from the skin. The dried gel film peeled off from the support frame, and only the dried gel film could be applied to the skin. In addition, since the dry gel film is very thin, it can be applied to curved or refracted parts. When the finger is bent and touched with a finger joint moistened with water, the dry gel film follows the curved shape. All of these adhered to the skin by surface tension, and even when the finger was refracted after application, the dried gel film did not peel off while being adhered to the skin, and the appearance after application was hardly noticeable.

  The dried gel films 1-b, 2-b, and 3-b could also be attached by bringing them into close contact with a finger joint moistened with water with surface tension while the fingers were bent. However, the adhesiveness to the skin is weak compared with the adhesive sheet having the dry gel films 1-a, 2-a, and 3-a, and the dry gel film tends to be displaced from the skin during finger refraction. . In addition, the appearance after sticking tends to be noticeable.

3. Effect of film flexibility by addition of polyethylene glycol 1 ml each of a solution containing 2% by weight of gelatin and 0%, 1%, 2% or 6% by weight of polyethylene glycol on a 3 cm × 3 cm bare glass The solution is made into a sol state at 37 ° C., uniformly coated, exposed to a temperature condition of 4 ° C. for 10 minutes to gel the solution, and dried at 4 ° C. for 24 hours to be applied onto the raw glass. A dry film was formed. Then, when the hardness of the dry film | membrane was measured using Picodenter HM500 by Fischer Instruments, the value of the Martens hardness of the film | membrane became low and the flexibility increased with the increase in the amount of polyethylene glycol. The results are shown in the table below.

[Example 1]
1. Formation of Dry Gel Film A polystyrene plate having a size of 4 cm × 4 cm and a thickness of 1 mm was cut out so that a true circular opening of 3.2 cmφ was formed at the center to prepare a support frame having an opening.
Further, an aqueous solution containing 1.5% by mass of gelatin manufactured by Sigma-Aldrich and 1.0% by mass of polyethylene glycol was prepared.
By a method similar to that of the reference example, a foam film was formed with an aqueous solution, gelled, and dried to form a dry gel film having a thickness of 500 nm.

2. Formation of protective layer A silicone resin was applied on the gel film to a thickness of 300 nm to form a protective layer. The water contact angle on the surface of the obtained protective layer was 90 °.

3. Evaluation Holding the support frame of the adhesive sheet and bringing the dry gel film into contact with human skin moistened with water, the dry gel film adheres to the skin due to surface tension, and the dry gel film is supported when the support frame is moved away from the skin. Separated from the frame, only the dried gel film and protective layer could be applied to the skin. The appearance after sticking was hardly noticeable. Also, since the dry gel film is very thin, it has good unevenness followability. Even if wrinkles are applied to the skin after application, the dry gel film adheres to the skin so that it will follow the uneven shape, and the dry gel film adheres to the skin. It was not peeled off.
Further, when the sticking sheet was pasted and dried, and then wetted with water, as shown in FIG. 15 (a), water repellent and water resistance were high, and it was not peeled off even when rubbed with a finger.
Further, the swelling degree of the adhesive sheet including the dried gel film and the protective layer with respect to water was measured and found to be 300%. Compared to Comparative Example 3 described later, it is considered that the penetration of water into the gel film is suppressed and the swelling of the gel film is suppressed because the protective layer is formed.

[Comparative Example 3]
A patch sheet was prepared in the same manner as in Example 1 except that the protective layer was not formed.
When the surface of the dry gel film of the adhesive sheet was brought into close contact with the skin moistened with water by surface tension, only the dry gel film could be applied to the skin.
On the other hand, when the adhesive sheet was applied and dried and then wetted with water, as shown in FIG. 15B, the adhesive sheet was swollen with water and poor in water resistance, and easily peeled off when rubbed with a finger. .
Moreover, when the swelling degree with respect to the water of the sticking sheet | seat containing only a dry gel film | membrane was measured, it was 4100%.

[Comparative Example 4]
1. Formation of Dry Gel Film A dry gel film having a thickness of 500 nm was formed in the same manner as in Example 1.
2. Formation of Protective Layer A silicone resin was applied on the dried gel film to a thickness of 11 μm to form a protective layer. The water contact angle on the surface of the obtained protective layer was 90 °.
3. Evaluation When the surface of the dry gel film of the sticking sheet was brought into close contact with the skin moistened with water by surface tension, the sticking property was inferior, such as easy peeling after sticking.

[Comparative Example 5]
1. Formation of Dry Gel Film A dry gel film having a thickness of 50 nm was formed in the same manner as in Example 1.
2. Formation of Protective Layer A silicone resin was applied on the dried gel film to a thickness of 30 nm to form a protective layer. The water contact angle on the surface of the obtained protective layer was 90 °.
3. Evaluation The obtained sticking sheet was weak and torn.

[Example 2]
A sticking sheet was prepared in the same manner as in Example 1 except that the following support frame was used.
A polystyrene film having a size of 4 cm × 4 cm and a thickness of 200 μm was cut out so that a true circular opening of 3.2 cmφ was formed at the center to prepare a support frame having an opening.
With this sticking sheet, the same results as in Example 1 were obtained.

[Example 3]
1. Formation of dry gel film (production of substrate having hydrophilic surface)
39.0 g of toluene and 0.8 g of TSL8350 (GE Toshiba Silicone) were mixed, and 450 μl of triethylamine was added while stirring. After stirring at room temperature for several minutes, the whole amount was transferred to a glass dish. A 10 cm square glass substrate that had been cleaned with UV was immersed therein and allowed to stand at room temperature for 16 hours. Thereafter, the glass substrate was washed with ethanol and water and dried by nitrogen blowing. Next, 25 μl of concentrated sulfuric acid was added dropwise while stirring 50 g of tetraethylene glycol (TEG). After stirring for several minutes, the whole amount was transferred to a glass dish. The above substrate was immersed therein and reacted at 80 ° C. for 20 minutes. After the reaction, the substrate was thoroughly washed with water and dried by nitrogen blowing. Thereby, the membrane | film | coat containing TEG was formed in the glass substrate surface. The surface static water contact angle was approximately 30 °. This substrate was cut into a size of 25 mm × 15 mm and used as a base material having a hydrophilic surface.

(Formation of gel film)
As the support frame, a polyethylene terephthalate film (thickness 16 μm, outer size 25 mm × 15 mm, inner size 20 mm × 9 mm, Teijin DuPont film) was used. A collagen solution was prepared to a final concentration of 2.4 mg / ml on ice using a collagen gel culture kit (Cellmatrix IA, Nitta Gelatin). 40 μl of this was added onto the substrate and gelled together with the support frame at 37 ° C. for 1 hour, and then dried in a clean bench for 3 hours to produce a collagen thin film.
As a result of measuring the thickness of the collagen thin film with a stylus type surface shape measuring instrument (Dektak FPD-650, Japan Vacuum Technology), it was 770 nm ± 191 nm. The collagen thin film thus prepared was adhered to the substrate even after PBS was added and hydrated.

  An appropriate amount of water was added to the laminate in which the collagen thin film and the support frame were arranged on the base material, and the collagen thin film held by the support frame was desorbed and recovered from the base material by picking and lifting the support frame with tweezers after hydration. .

2. Formation of protective layer A protective layer was formed on the collagen thin film in the same manner as in Example 1.

3. Evaluation When the surface of the collagen thin film of the patch sheet was brought into close contact with the skin wetted with water by surface tension, only the collagen thin film and the protective layer could be adhered to the skin, and the follow-up to wrinkles was also confirmed.
Further, when the sheet for pasting was pasted and dried, and then wetted with water, water repelling and water resistance were high, and it did not peel off even when rubbed with a finger.

[Example 4]
1. Formation of dried gel film A dried gel film was formed in the same manner as in Example 1.
2. Formation of Functional Layer (Fine Particle Layer) A dispersion liquid in which fine particles mainly composed of mica were dispersed in isopropyl alcohol was prepared. The average particle size of the fine particles was 5 μm. A functional layer was formed by applying the dispersion liquid dropwise onto a dry gel film.
3. Formation of protective layer A protective layer was formed on the functional layer in the same manner as in Example 1.
4). Evaluation When the surface of the dry gel membrane of the patch sheet is brought into close contact with the skin wetted with water by surface tension, only the dry gel membrane, functional layer and protective layer can be affixed to the skin, and follow-up to wrinkles has also been confirmed. It was done.
Further, when the sheet for pasting was pasted and dried, and then wetted with water, water repelling and water resistance were high, and it did not peel off even when rubbed with a finger.

[Comparative Example 6]
1. Formation of dried gel film A dried gel film was formed in the same manner as in Example 1.
2. Formation of functional layer A solution was prepared by dissolving butyral resin as a binder in toluene. This solution was dropped on the dry gel film to form a functional layer so as to have a thickness of 11.5 μm.
3. Formation of protective layer A protective layer was formed on the functional layer in the same manner as in Example 1.
4). Evaluation When the surface of the dry gel film of the sticking sheet was brought into close contact with the skin moistened with water, the sticking property was inferior, such as easy peeling after sticking.

[Example 5]
1. Formation of dried gel film A dried gel film was formed in the same manner as in Example 1.
2. Pattern formation of functional layer A commercially available oil-based ink in which a dye was dissolved in toluene was prepared. This oil-based ink was dropped on the dried gel film in a pattern to form a functional layer pattern.
3. Formation of protective layer A protective layer was formed on the functional layer in the same manner as in Example 1.
4). Evaluation When the surface of the dry gel film of the adhesive sheet is brought into close contact with the skin moistened with water by surface tension, only the dry gel film, functional layer and protective layer are applied to the skin while maintaining the pattern shape of the functional layer. It was possible to follow the wrinkles.
Further, when the sheet for pasting was pasted and dried, and then wetted with water, water repelling and water resistance were high, and it did not peel off even when rubbed with a finger.

[Example 6]
1. Formation of dried gel film A dried gel film was formed in the same manner as in Example 1.

2. Formation of Functional Layer An ink was prepared so that the weight ratio of dye: butyral resin: toluene: methyl ethyl ketone was 4.2: 3.3: 46.25: 46.25. This ink was spin-coated on a dry gel film to form functional layers having various thicknesses. At this time, the functions were such that the total thickness of the dry gel film, the functional layer, and the protective layer was (a) 2.8 μm, (b) 3.2 μm, (c) 5.8 μm, and (d) 12.0 μm, respectively. The layer thickness was adjusted.

3. Formation of protective layer A protective layer was formed on the functional layer in the same manner as in Example 1.

4). Evaluation When the surface of the dry gel film of the patch sheet was adhered to the skin moistened with water by surface tension, only the dry gel film, the functional layer and the protective layer were used for (a), (b) and (c). Was able to be applied to the skin, but (d) was inferior in application properties, such as being easily peeled off after application.

DESCRIPTION OF SYMBOLS 1 ... Sheet for sticking 2 ... Gel film 3, 3a, 3b ... Protective layer 5 ... Functional layer 6 ... Fine particle layer 7 ... Fluidized layer 8 ... 1st functional layer 9 ... 2nd functional layer 12 ... Support frame

Claims (6)

Gel film,
A protective layer formed on at least one surface of the gel film;
A sticking frame disposed on an outer edge of the gel film and supporting the gel film, wherein the total thickness of the gel film and the protective layer after drying is in the range of 100 nm to 10 μm Sheet.   The adhesive sheet according to claim 1, wherein the protective layer has hydrophobicity.   The adhesive sheet according to claim 1 or 2, wherein a water contact angle on the surface of the protective layer is 50 ° or more.   Between the gel film and the protective layer, a functional layer is partially formed on the surface of the protective layer opposite to the gel film or on the surface of the gel film opposite to the protective layer. The sticking sheet according to any one of claims 1 to 3, wherein the sticking sheet is provided.   A functional layer formed between the gel film and the protective layer, on the surface of the protective layer opposite to the gel film, or on the surface of the gel film opposite to the protective layer; 4. The sticking sheet according to claim 1, wherein the functional layer is a fine particle layer in which fine particles are dispersed or a fluidized layer containing a fluid substance.   Further comprising a functional layer formed between the gel film and the protective layer, the surface of the protective layer opposite to the gel film, or the surface of the gel film opposite to the protective layer, and drying The total thickness of the said gel film, the said functional layer, and the said protective layer after that exists in the range of 100 nm-10 micrometers, The sticking sheet in any one of Claim 1 to 3 characterized by the above-mentioned.