JP6232788B2 - Sheet for sticking - Google Patents

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-like 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 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, the 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 a thin-film cosmetic is applied to wet skin, A method of peeling only the fabric is disclosed. The former method requires a complicated operation of dissolving the water-soluble polymer film. In the latter method, since the base film is very thin, 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.

Japanese Patent No. 4596774 JP 2011-143332 A International Publication No. 2008/050913 Pamphlet International Publication No. 2012/173198 Pamphlet JP 2013-71907 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 polymer compound in the foam film is low. There is a problem that 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.

  In addition, it is known that various components are added to the bioadhesive sheet in order to impart functionality. For example, Patent Document 1 discloses that the raw material alkyl cellulose derivative can be colored by blending various pigments, dyes, minerals and the like. Patent Document 4 discloses that a thin film cosmetic is colored using a dye, a pigment or the like. Patent Document 5 discloses that a thin film film holds a cosmetic colorant. However, color control may be difficult with such a method of adding a colorant to the thin film. In addition, when a pigment having a particle diameter equal to or greater than the thickness of the thin film is used, the adhesive sheet is easily peeled off or the feeling of use is deteriorated, so that such a pigment is difficult to apply.

  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 to provide a sticking sheet which is difficult to peel off and is provided with functionality.

  In order to achieve the above object, the present invention has a gel film which is a hydrogel film or a dry gel film in which a foam film is gelled, and the gel film which is formed on the gel film, and does not affect the pastability of the gel film. A sticking sheet comprising a functional layer is provided.

  According to the present invention, the gel film is a very thin film obtained by gelling the foam film, and thus has excellent flexibility and adhesion to the skin. The functional layer does not affect the pastability of the gel film. 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, functionality can be easily provided to the sheet | seat for sticking of this invention by forming the functional layer on a gel film | membrane.

  In the present invention, the functional layer is preferably a fine particle layer in which fine particles are dispersed or a fluidized layer containing a fluid substance. If the functional layer formed on the gel film is a fine particle layer or a fluidized layer, high adhesion of the gel film to the skin or the like can be maintained.

  Furthermore, in the present invention, it is also preferable that the functional layer is partially formed on the gel film. This is because the adhesiveness of the gel film to the skin or the like can be increased in the portion where the functional layer is not formed on the gel film.

  Moreover, in this invention, it is also preferable that the said gel film is the said dry gel film, and the thickness of the said sheet | seat for sticking exists in the range of 100 nm-10 micrometers. Furthermore, in this invention, it is also preferable that the said gel film is the said hydrogel film, and the thickness of the said sheet | seat for sticking exists in the range of 100 nm-200 micrometers. Even when the functional layer is formed on the gel film, the adhesiveness of the gel film to the skin or the like can be maintained if the thickness of the adhesive sheet is relatively thin.

  In the present invention, the functional layer includes a first functional layer formed on the gel film and a second functional layer formed on the first functional layer, and the gel film is dried. A fluidized bed that is a gel film, the total thickness of the gel film and the first functional layer is in the range of 100 nm to 10 μm, and the second functional layer contains a fine particle layer in which fine particles are dispersed or a fluid substance It is also preferable. Furthermore, in the present invention, the functional layer has a first functional layer formed on the gel film and a second functional layer formed on the first functional layer, and the gel film is the hydrogel. A total thickness of the gel film and the first functional layer is in the range of 100 nm to 200 μm, and the second functional layer is a fine particle layer in which fine particles are dispersed or a fluidized layer containing a fluid substance. It is also preferable that there is. Even when a functional layer having a two-layer structure is formed on the gel film, if the total thickness of the gel film and the first functional layer is relatively thin, the second functional layer is a fine particle layer or a fluidized layer. If it exists, the high adhesiveness to the skin etc. of a gel film can be maintained.

  In the present invention, the functional layer includes a first functional layer formed on the gel film and a second functional layer formed on the first functional layer, and the gel film is dried. It is also a gel film, the total thickness of the gel film and the first functional layer is preferably in the range of 100 nm to 10 μm, and the second functional layer is preferably partially formed on the first functional layer. . Furthermore, in the present invention, the functional layer has a first functional layer formed on the gel film and a second functional layer formed on the first functional layer, and the gel film is the hydrogel. It is also preferable that the total thickness of the gel film and the first functional layer is in the range of 100 nm to 200 μm, and the second functional layer is partially formed on the first functional layer. Even when a functional layer having a two-layer structure is formed on the gel film, the second functional layer is formed on the gel film if the total thickness of the gel film and the first functional layer is relatively thin. If there is an unexposed portion, the high adhesion of the gel film to the skin or the like can be maintained.

  The adhesive sheet of the present invention has an advantageous effect that it can be adhered to a living body or a biological material with sufficient strength without using an adhesive component, and is difficult to peel even when applied to a moving uneven surface. Play. Moreover, in this invention, there exists an effect that functionality can be provided easily by forming the functional layer on a gel film.

It is a schematic sectional drawing which shows an 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 diagram which shows an example of the usage method 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 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 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 diagram which shows the other example of the usage method 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 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. 2 is a photograph showing a sticking sheet of Example 1. FIG. 2 is a photograph showing a sticking sheet of Example 2. FIG.

Hereinafter, the sticking sheet of the present invention will be described in detail.
The sticking sheet of the present invention comprises a gel film that is a hydrogel film or a dry gel film obtained by gelling a foam film, and a functional layer that is formed on the gel film and does not affect the sticking property of the gel film. It is characterized by having.

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.

  The sticking sheet of the present invention can be roughly divided into three embodiments depending on the mode of the functional layer. In the following, each embodiment will be described separately.

A. First Embodiment A patch sheet of the present embodiment is formed on a gel film that is a hydrogel film or a dry gel film obtained by gelling a foam film, and affects the pastability of the gel film. The functional layer is a fine particle layer in which fine particles are dispersed or a fluidized layer 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.

The sticking sheet of this embodiment will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a sticking sheet of this embodiment. As illustrated in FIG. 1, a sticking sheet 1 is formed on a gel film 2 which is a hydrogel film or a dry gel film in which a foam film is gelled, and on the gel film 2, and affects the sticking property of the gel film 2. It has a fine particle layer 3 in which fine particles are dispersed as a functional layer that is not provided.

  FIG. 2 is a schematic sectional view showing another example of the sticking sheet of this embodiment. As illustrated in FIG. 2, a sticking sheet 1 is formed on a gel film 2 that is a hydrogel film or a dry gel film in which a foam film is gelled, and on the gel film 2. It has the fluidized bed 4 containing a fluid substance as a functional layer which does not give.

  According to this embodiment, since the gel film is a gel film of the foam film, it is very thin, and thus has high adhesion to the surface of a living body or a biological material such as skin, And it has high flexibility. In the present embodiment, 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 on the gel film. However, the high adhesion of the gel film to the skin or the like can be maintained. Therefore, the adhesive sheet of this embodiment 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 this embodiment is attached to a moving uneven surface, it can be made difficult to peel off.

  3A to 3B are schematic views showing an example of a state in which the sticking sheet of this embodiment is stuck on the skin. First, with the finger bent, the surface of the gel film 2 of the application sheet 1 is adhered and adhered to the skin surface of the joint portion of the finger moistened with water by surface tension. In this case, even if a finger is stretched after sticking and wrinkles are formed on the skin surface, the sticking sheet 1 can also be deformed following the shape of the wrinkles. In addition, the sticking sheet 1 is hardly peeled off even when the finger is repeatedly bent and stretched. That is, the sticking sheet of the present embodiment has excellent unevenness followability, and is difficult to peel off even when attached to a fine uneven surface that moves like skin.

Moreover, in this embodiment, functionality can be provided to the sticking sheet by forming a fine particle layer or a fluidized bed as a functional layer on the gel film.
When the fine particle layer is formed as a functional layer on the gel film, for example, the fine particle layer can be colored by using a pigment or the like. In this case, unlike the case where fine particles such as pigment are contained in the thin film, the fine particle layer can be formed after the formation of the gel film, so that color control is easy, for example. Furthermore, fine particles having a particle size equal to or larger than the thickness of the gel film can be applied without degrading the sticking property and feeling of use of the sticking sheet.
When a fluidized bed is formed as a functional layer on the gel film, for example, the fluidized layer can be colored by using ink. In addition, the fluidized bed can contain components effective as cosmetics and medicines.

  FIG. 4 is a schematic sectional view showing another example of the sticking sheet of this embodiment. As illustrated in FIG. 4, when the functional layer is the fine particle layer 3 in the sticking sheet 1, a support 11 may be disposed on the fine particle layer 3. In this case, after sticking the surface of the gel film 2 of the sticking sheet 1 on the surface of the skin or the like, the support 11 can be peeled off. Since the support 11 is laminated on the gel film 2 via the fine particle layer 3, it is possible to make the support 11 difficult to contact the gel film 2. Therefore, although the gel film 2 has high adhesion, the support 11 can be peeled off. Moreover, the handleability of the sticking sheet 1 can be improved by arranging the support 11.

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

1. Gel film The gel film in the present embodiment is obtained by gelling a foam film, and is a hydrogel film or a dry gel film. Hereinafter, the hydrogel film and the dry gel film will be described separately.

(1) Hydrogel membrane The hydrogel membrane in this embodiment is a gelled foam membrane.
Here, the “hydrogel” refers to a gel in which a large amount of water is held in a network structure formed by combining polymers.
The hydrogel film is preferably prepared by gelling an aqueous foam film containing a gel raw material in a state containing water.

  The gel raw material is not particularly limited as long as it is water-soluble and exhibits surface activity and can form a foam film. Moreover, as a gel raw material, it is preferable that safety | security with respect to a biological body is high, for example, protein and polysaccharide can be mentioned. Specific examples include gelatin, collagen, agarose, hyaluronic acid, and cellulose. Water-soluble polymers such as polyethylene glycol and polyacrylamide can also 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 is not particularly limited, but 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 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 this embodiment is obtained by gelling a foam film. The dry gel film is preferably prepared by gelling and drying an aqueous foam film containing a gel raw material in a state containing water.
In addition, since it is the same as that of the said hydrogel film | membrane about a gel raw material, description here is abbreviate | omitted.

  Moreover, the dry gel film may contain a surfactant, an emulsification aid, a wetting agent, and the like as appropriate. Since the surfactant, the emulsification aid, and the wet are the same as those of the hydrogel film, the description thereof is omitted here.

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 dried gel film is not particularly limited, but is preferably in the range of 100 nm to 10 μm, and more preferably 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) Formation method of gel film The formation method of the gel film in this embodiment should just be a method which can form the hydrogel film which gelatinized the foam film, or the dry gel film. 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. The 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 the foam film containing water. It is preferable to have a gelling step of gelling to form a hydrogel film and a drying step of drying the hydrogel film.

  5 (a) to 5 (c) and FIGS. 6 (a) to 6 (e) are process diagrams showing an example of a method for forming a gel film in the present embodiment. First, as shown in FIGS. 5A and 6A, a foam film forming support frame 20 having at least one opening 21 is prepared. Next, as shown in FIG. 6 (b), 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. 6 (c). A foam film 23 of the aqueous solution for forming a foam film is formed. Next, as shown in FIGS. 5B and 6D, the hydrogel film 2 a is formed by gelling the foam film 23 in a state containing water. Subsequently, as shown in FIGS. 5C and 6E, the hydrogel film 2a is further dried to form a dry gel film 2b.

  In the method of forming a foam film from an aqueous solution containing a gel raw material and gelling the foam film in a state containing water to obtain a hydrogel film, unlike the method described in Patent Document 2 in which the foam film is directly dried, Even when the gel raw material in the aqueous solution for forming a foam film has a low concentration, the hydrogel film can be formed without breaking the foam film. Further, even when the obtained hydrogel film is dried, the film is not broken. Furthermore, the hydrogel film and the dried gel film obtained by such a method have sufficient adhesion on the skin surface and are difficult to peel off even when applied to a moving uneven surface.

  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.

  When the gel raw material is gelatin, an aqueous gelatin solution is used as an aqueous solution for forming a foam film. The gelatin concentration in the gelatin aqueous solution is not particularly limited, but is preferably a low concentration, specifically, in the range of 0.1% by mass to 2.9% by mass, preferably 0.1% by mass to 2.5%. It is within the range of mass%, more preferably within the range of 1.0 mass% to 2.0 mass%. When the gelatin concentration is low, the foam film is thinner than when the gelatin concentration is high, and the produced hydrogel film and dry gel film are sufficiently flexible and difficult to peel off even on uneven surfaces. Therefore, it is preferable. Formation of a thin film from a low-concentration gelatin aqueous solution cannot be achieved by the method described in Patent Document 2.

  The gelatin aqueous solution contains the gelatin having the above-mentioned concentration in a non-gelled sol state at the stage of the foam film formation process. In order to maintain the sol state, the temperature is preferably in the range of 20 ° C to 40 ° C. The pH of the aqueous gelatin solution (measured at 23 ° C.) can be in the range of 6.0 to 8.0.

The thickness of the foam film prepared from the gelatin aqueous solution can be adjusted by adjusting the pulling rate of the foam film-forming support frame from the gelatin aqueous solution. In addition, after forming the foam film on the foam film forming support frame, the thickness of the gelatin film can be reduced by removing the gelatin aqueous solution from the foam film using a pipette or the like, or by adding the gelatin aqueous solution to the foam film. It is also possible. Typically, the thickness of the foam film formed by the aqueous gelatin solution is in the range of 1 μm to 200 μm, more preferably in the range of 10 μm to 100 μm.
The method for measuring the thickness of the foam film is the same as the method for measuring the thickness of the gel film.

  When the gel raw material is agarose, an agarose aqueous solution is used as the aqueous solution for forming a foam film. The agarose concentration in the agarose aqueous solution is not particularly limited, but is preferably a low concentration, specifically within the range of 0.1% by mass to 5.0% by mass, preferably 0.1% by mass to 2.0%. It is in the range of mass%, more preferably in the range of 0.5 mass% to 1.0 mass%. When the agarose concentration is low, the foam film is thinner than when the agarose concentration is high, and the produced hydrogel film and dried gel film are sufficiently flexible and difficult to peel off even on uneven surfaces. preferable. Formation of a thin film from a low-concentration agarose aqueous solution cannot be achieved by the method described in Patent Document 2.

  The agarose aqueous solution contains the agarose having the above-mentioned concentration in a sol state that is not gelled at the stage of the foam film formation process. In order to maintain the sol state, the temperature is preferably in the range of 20 ° C to 60 ° C. The pH of the agarose aqueous solution (measured value at 23 ° C.) can be in the range of 6.0 to 8.0.

The thickness of the foam film prepared from the agarose aqueous solution can be adjusted in the same manner as the gelatin aqueous solution. Typically, the thickness of the foam film formed by the agarose aqueous solution having the above-mentioned concentration is 1 μm to 200 μm, and more preferably 10 μm to 100 μm.
The method for measuring the thickness of the foam film is the same as the method for measuring the thickness of the gel film.

  When the gel raw material is collagen, an aqueous collagen solution is used as the aqueous solution for forming a foam film. The collagen concentration in the collagen aqueous solution is not particularly limited, but it is preferably a low concentration, specifically within the range of 0.1% by mass to 5.0% by mass, preferably 0.5% by mass to 5.0%. It is in the range of mass%, more preferably in the range of 1.0 mass% to 3.0 mass%. When the collagen concentration is low, the foam membrane is thinner than when the collagen concentration is high, and the produced hydrogel membrane and dry gel membrane are sufficiently flexible and difficult to peel off even on uneven surfaces. Therefore, it is preferable. Formation of a thin film from a low concentration collagen aqueous solution cannot be achieved by the method described in Patent Document 2.

The thickness of the foam film prepared from the collagen aqueous solution can be adjusted in the same manner as the gelatin aqueous solution. Typically, the thickness of the foam film formed by the collagen aqueous solution having the above-mentioned concentration is in the range of 1 μm to 200 μm, more preferably in the range of 10 μm to 100 μm.
The method for measuring the thickness of the foam film is the same as the method for measuring the thickness of the gel film.

  The collagen aqueous solution contains the above-mentioned concentration of collagen in a sol state that is not gelled at the stage of the foam film formation step. Unlike the gelatin aqueous solution and the agarose aqueous solution, the collagen aqueous solution is characterized in that it is in a sol state at a low temperature and a pH condition around pH 3.0, and is in a gel state at a high temperature and a pH condition around pH 7.0. In order to maintain the sol state, the temperature is preferably in the range of 4 ° C to 23 ° C. The pH of the aqueous collagen solution (measured value at 23 ° C.) is preferably in the range of 2.0 to 4.0 when the aqueous solution is prepared. The collagen aqueous solution is preferably adjusted to have a pH (measured value at 23 ° C.) in the range of 6.0 to 8.0 before forming the foam film. The pH can be adjusted by adding an alkali component such as sodium hydroxide.

The foam film-forming aqueous solution may contain other components as appropriate in addition to the gel raw material. Specifically, the aqueous solution for forming a foam film may contain a surfactant, an emulsification aid, a wetting agent, etc. for the purpose of stabilizing the foam film. Since the surfactant, the emulsification aid, and the wetting agent have been described above, the description thereof is omitted here.
The concentration of the surfactant in the aqueous solution for forming a foam film is not particularly limited, but can typically be in the range of 0.01% by mass to 1% by mass.
The concentration of the emulsification aid in the aqueous solution for forming a foam film is not particularly limited, but can typically be in the range of 0.01% by mass to 10% by mass.

  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 pharmaceutical and 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. The gel film forming method in this embodiment is different from the method described in Patent Document 2 in which the foam film is directly dried, and the foam film is broken even when the gel raw material in the aqueous solution for forming the foam film has a low concentration. It is possible to form a hydrogel film without drying, and it is also possible to dry the formed hydrogel film.

  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.

  When the gelatin aqueous solution having the above-mentioned concentration is used as the foam film-forming aqueous solution, gelation can be performed by cooling the foam film. Specifically, a gelatin hydrogel can be formed by cooling the foam film at a temperature of 1 ° C. to 19 ° C. for a short time, preferably 1 minute to 10 minutes.

  When an agarose aqueous solution having the above concentration is used as the foam film forming aqueous solution, gelation can be performed by cooling the foam film. Specifically, a hydrogel of agarose can be formed by cooling the foam film at a temperature of 1 ° C. to 19 ° C. for a short time, preferably 1 minute to 10 minutes.

  When the collagen aqueous solution having the above-mentioned concentration is used as the foam film-forming aqueous solution, the gelation can be performed by heating the foam film of the collagen aqueous solution adjusted to a pH condition near neutrality. Specifically, by heating a foam membrane formed from a collagen aqueous solution adjusted to pH 6.0 to 8.0 at a temperature of 32 ° C. to 37 ° C. for a short time, preferably 1 minute to 30 minutes, Collagen hydrogels can be formed.

  In order to suppress the volatilization of moisture in the gelation step, it is preferable to perform the gelation in a closed container adjusted to saturated humidity.

(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

  Although the conditions for drying are not specifically limited, Preferably it is made to dry at 19 degrees C or less for 2 hours or more. 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.

2. Functional layer The functional layer in this embodiment is formed on the gel film, and is a fine particle layer in which fine particles are dispersed or a fluidized layer containing a fluid substance.
Hereinafter, the description will be made separately for the fine particle layer and the fluidized bed.

(1) Fine particle layer The fine particle layer in the present embodiment is formed on the gel film, and has fine particles dispersed therein.

  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 size of the fine particles is large relative to the thickness of the gel film, a sticking sheet can be applied to the skin or the like. It may be difficult to disperse 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 adhesive sheet can be applied to the skin or the like. However, if the fine particle layer is too thick, In some cases, it is difficult to form a fine particle layer or the sticking property of the sticking sheet is poor.

  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.

(2) Fluidized bed The fluidized bed in this embodiment is formed on the gel film and 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 film, the adhesive sheet can be applied to the skin or the like. However, if the fluidized layer is too thick, It is difficult to form a fluidized bed.

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 an arbitrary method such as application to a flow of a liquid containing the components.

3. Supporting frame As illustrated in FIGS. 7A and 7B, the sticking sheet 1 of the present embodiment is preferably one in which the shape is held by the supporting frame 12. In this case, the gel film 2 is preferably fixed in a state of being stretched on the support frame 12 so as to close the opening 13 of the support frame 12. FIG. 7B is a cross-sectional view taken along line AA in FIG. The support frame can improve the handleability of the sticking sheet. Moreover, since a gel film in which both surfaces are not in contact with an object can be obtained by using a support frame when forming the gel film, a functional layer can be easily formed on one side of the gel film. The surface of the gel film that is preferable as the application surface (the other surface of the gel film) can be easily applied to the skin or the like.

  The support frame is preferably the foam film forming support frame used during the formation of the foam film. As shown in FIGS. 5 and 6, 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. 5 and 6, 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.

  Alternatively, the gel film may be separated from the foam film forming support frame used at the time of forming the foam film, and fixed to a support frame having one or more separately prepared openings so as to close the openings. Even in this case, the gel film can be subjected to a treatment such as cutting to an appropriate size, addition of a desired component, formation of a functional layer, etc., as required at an arbitrary stage.

  Note that the material, dimensions, and shape of the support frame are the same as those of the foam film forming support frame, and thus the description thereof is omitted here.

  The support frame is preferably a flexible film member. As shown in FIGS. 8A to 8C, a support frame 12 formed of a film-like member, a gel film 2 stretched so as to close the opening of the support frame 12, and a gel film 2 are formed. Further, the sticking sheet 1 including the functional layer (fine particle layer 3) can be deformed along the surface shape of the object to be stuck 30 whose surface is not flat. Further, as shown in FIG. 8B, the surface tension of the gel film 2 fixed to the support frame 12 of the sticking sheet 1 is applied to the surface of the object 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 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 functional layer (fine particle layer 3) can be left on the surface of the object 30 to be adhered.

4). Support In this embodiment, when the functional layer is a fine particle layer, a support 11 may be disposed on the fine particle layer 3 as illustrated in FIG. The shape of the sticking sheet 1 can be held by the support 11 and the handleability of the sticking sheet 1 can be improved.
The support can also be placed when the support frame is placed.

  When the support is arranged on the fine particle layer, although not shown in the figure, the surface of the gel film 2 of the sticking sheet 1 is pasted on the surface of the object to be pasted, and then the support 11 is peeled off, thereby the gel The film 2 and the fine particle layer 3 can be left on the surface of the adherend. Since the support 11 is laminated on the gel film 2 via the fine particle layer 3, it is possible to make the support 11 difficult to contact the gel film 2. Therefore, although the gel film 2 has high adhesion, the support 11 can be peeled off.

  The material of the support is not particularly limited as long as it can be disposed on the fine particle layer, and examples thereof include a resin and glass. In addition, the support may or may not have flexibility. Among them, the support is preferably a flexible film member. As in the case of the support frame, when the support is a flexible film-like member, even if the surface of the adherend is not flat, the sticking sheet is placed on the surface of the adherend. It is possible to attach the adhesive sufficiently.

  The thickness of the support is not particularly limited as long as the shape of the sticking sheet can be maintained, but it is preferable that the support has flexibility, for example, 10 μm to It is preferably within the range of 10 mm.

5. Protective layer In this embodiment, when the functional layer is a fluidized bed, a protective layer may be disposed on the fluidized bed. The protective layer can facilitate the handling of the sticking sheet and can suppress volatilization of the fluid substance contained in the fluidized bed.

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

  The material of the protective 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, and examples thereof include resins and glass. it can. Moreover, the protective layer may or may not have flexibility. Especially, it is preferable that a protective layer is a flexible film-like member similarly to the case of said support body.

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

6). Sheet for sticking In the present embodiment, when the functional layer is a fine particle layer, the surface of the gel film of the sticking sheet may be the sticking face, or the face of the fine particle layer may be the sticking face. Especially, it is preferable to make the surface of a gel film into a sticking surface. This is because the adhesiveness of the sticking sheet to the adherend is excellent. On the other hand, when the surface of the fine particle layer is used as the sticking surface, for example, 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 thickness of the fine particle layer is By making it have a gradient, it is possible to ensure the adhesion of the sticking sheet to the object to be stuck.

  In this embodiment, 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 this embodiment can also be used for the purpose of protecting the surface of a living body or a biomaterial.

  The sticking sheet of this embodiment 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. The sticking sheet of this embodiment can also be used as a decorative seal such as a nail seal or a tattoo seal.

B. Second Embodiment A patch sheet according to this embodiment includes a gel film that is a hydrogel film or a dry gel film, and a functional layer that is formed on the gel film and does not affect the pastability of the gel film. The functional layer is partially formed on the gel film.

The sticking sheet of this embodiment will be described with reference to the drawings.
FIG. 9 is a schematic cross-sectional view showing an example of the sticking sheet of this embodiment. As illustrated in FIG. 9, the sticking sheet 1 is formed in a pattern on the gel film 2, which is a hydrogel film or a dry gel film obtained by gelling a foam film, and the sticking property of the gel film 2. And a functional layer 5 that does not affect the function.

  According to this embodiment, since the gel film is obtained by gelling a foam film, the thickness is very thin, so that high adhesion to the surface of a living body or a biomaterial such as skin and high flexibility are achieved. Have. Furthermore, 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. Therefore, the sticking sheet of this embodiment can be adhered to a living body or a biomaterial with sufficient strength without using an adhesive component, and it is difficult to peel off even when pasted on a moving uneven surface. Can do.

Moreover, in this embodiment, functionality can be provided to the sheet | seat for sticking by forming the functional layer on the gel film | membrane.
For example, the functional layer can be colored by containing a colorant such as a pigment or dye. In this case, unlike the case where the colorant is contained in the thin film, the functional layer can be formed after the gel film is formed, and thus, 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.

  FIG. 10 is a schematic cross-sectional view showing another example of the sticking sheet of this embodiment. As illustrated in FIG. 10, in the sticking sheet 1, a support 11 may be disposed on the functional layer. In this case, the support 11 can be peeled off after the surface of the gel film 2 of the sticking sheet 1 is stuck on the surface of a living body or biomaterial such as skin. Since the support 11 is laminated on the gel film 2 via the functional layer 5, it is possible to make the support 11 difficult to contact the gel film 2. Therefore, although the gel film 2 has high adhesion, the support 11 can be peeled off. Moreover, the handleability of the sticking sheet 1 can be improved by arranging the support 11.

  Since the gel film is the same as that in the first embodiment, description thereof is omitted here. Hereinafter, the other structure in the sheet | seat for sticking of this embodiment is demonstrated.

1. Functional layer The functional layer in the present embodiment does not affect the sticking property of the gel film and is partially formed on the gel film.

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, as shown in FIG. 9 and FIG. 10, the functional layer 5 may be formed in a pattern at intervals, and the functional layer 5 is formed of the gel film 2 as shown in FIGS. It may be formed only at the center and not at the end of the gel film 2.
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.

  Since the fine particles can be the same as the fine particles used in the fine particle layer in the first embodiment, 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, when 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. 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 thickness is thick with respect to the thickness of the gel film, it is possible to apply the adhesive sheet 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 at 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. Support Frame The sheet 1 for sticking according to the present embodiment is preferably one in which the shape is held by the support frame 12 as illustrated in FIGS. 11 (a) and 11 (b). In addition, FIG.11 (b) is the sectional view on the AA line of Fig.11 (a).
The support frame is the same as that in the first embodiment, and a description thereof is omitted here.

3. Support In this embodiment, the support 11 may be disposed on the functional layer 5 as illustrated in FIG.
The support is the same as that in the first embodiment, and a description thereof is omitted here.

4). Sheet for pasting In the present embodiment, the surface of the gel film of the sheet for pasting may be the pasting surface, and the surface of the functional layer may be the pasting surface. Especially, it is preferable to make the surface of a gel film into a sticking surface. This is because the adhesiveness of the sticking sheet to the adherend is excellent. On the other hand, when the surface of the functional layer is used as the pasting surface, for example, by increasing the area ratio of the portion where the functional layer is not formed on the gel film, the adhesiveness of the pasting sheet to the object to be pasted is increased. Can be secured.

  In addition, since it is the same as that of the said 1st embodiment about other points, such as a usage method and a use of a sticking sheet, description here is abbreviate | omitted.

C. Third Embodiment A patch sheet according to the present embodiment includes a gel film that is a hydrogel film or a dry gel film, and a functional layer that is formed on the gel film and does not affect the pastability of the gel film. The thickness of the sticking sheet is within a predetermined range. The thickness of the sticking sheet varies depending on whether the gel film is a hydrogel film or a dry gel film. When the gel film is a hydrogel film, the thickness of the patch sheet is in the range of 100 nm to 200 μm. On the other hand, when the gel film is a dry gel film, the thickness of the sticking sheet is in the range of 100 nm to 10 μm.

The sticking sheet of this embodiment will be described with reference to the drawings.
FIG. 12 is a schematic cross-sectional view showing an example of the sticking sheet of this embodiment. As illustrated in FIG. 12, the adhesive sheet 1 is formed on a gel film 2 that is a hydrogel film or a dry gel film in which a foam film is gelled, and on the gel film 2. And a functional layer 5 not provided. The sticking sheet 1 has a predetermined thickness.

  According to this embodiment, since the gel film is obtained by gelling a foam film, the thickness is very thin, so that high adhesion to the surface of a living body or a biomaterial such as skin and high flexibility are achieved. Have. Furthermore, the adhesive sheet of the present embodiment has a predetermined thickness, so that high adhesion to the skin of the gel film is maintained even when the functional layer is formed on the entire surface of the gel film. be able to. Therefore, the sticking sheet of this embodiment can be adhered to a living body or a biomaterial with sufficient strength without using an adhesive component, and it is difficult to peel off even when pasted on a moving uneven surface. Can do.

Moreover, in this embodiment, functionality can be provided to the sheet | seat for sticking by forming the functional layer on the gel film | membrane.
For example, the functional layer can be colored by containing a colorant such as a pigment or dye. In this case, unlike the case where the colorant is contained in the thin film, the functional layer can be formed after the gel film is formed, and thus, 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.
In addition, the functional layer may contain components effective as cosmetics or pharmaceuticals.

  Since the gel film is the same as that in the first embodiment, description thereof is omitted here. Hereinafter, the other structure in the sheet | seat for sticking of this embodiment is demonstrated.

1. Functional layer The functional layer in the present embodiment does not affect the pastability of the gel film. The functional layer has a predetermined thickness so that the sticking sheet of this embodiment has a predetermined thickness.

  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 first embodiment. 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 first 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 is not particularly limited as long as the thickness of the adhesive sheet is within a predetermined range, and varies depending on the thickness of the gel film, the type of material used for the functional layer, and the like. It is preferably within the range of 10 nm to 10 μm, more preferably within the range of 100 nm to 10 μm, and even more preferably within 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.

2. Support Frame As illustrated in FIG. 13, it is preferable that the sticking sheet 1 of the present embodiment has a shape held by the support frame 12.
The support frame is the same as that in the first embodiment, and a description thereof is omitted here.

3. Sheet for pasting In this embodiment, when the gel film is a hydrogel film, the thickness of the sheet for pasting is in the range of 100 nm to 200 μm, preferably in the range of 1 μm to 200 μm, more preferably 1 μm to 150 μm. In the range of 10 μm to 100 μm. If the thickness of the sticking sheet is within the above range, even if the functional layer is formed on the entire surface of the hydrogel film, high adhesion of the hydrogel film to the skin or the like can be maintained. On the other hand, if the thickness of the sticking sheet is too thick, the unevenness followability deteriorates. Moreover, when the thickness of the sticking sheet is too thin, the strength may be inferior.

Moreover, in this embodiment, when the gel film is a dry gel film, the thickness of the adhesive sheet 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. It is. If the thickness of the sticking sheet is within the above range, high adhesion to the skin or the like of the dry gel film can be maintained even if the functional layer is formed on the entire surface of the dry gel film. On the other hand, if the thickness of the sticking sheet is too thick, the unevenness followability deteriorates. Moreover, when the thickness of the sticking sheet is too thin, the strength may be inferior.
Here, when the functional layer has a thickness gradient, the thickness of the sticking sheet is the maximum thickness.

  Moreover, in this embodiment, the thickness of the sheet | seat for sticking should just be in the above-mentioned range, for example, a gel film may be thicker than a functional layer, and a functional layer may be thicker than a gel film.

  In this embodiment, the surface of the gel film of the sticking sheet may be the sticking surface, and the surface of the functional layer may be the sticking surface. Especially, it is preferable to make the surface of a gel film into a sticking surface. This is because the adhesiveness of the sticking sheet to the adherend is excellent. On the other hand, when the surface of the functional layer is a pasting surface, for example, the adhesiveness of the pasting sheet to the object to be pasted can be ensured by making the functional layer have a thickness gradient.

  In addition, since it is the same as that of the said 1st embodiment about other points, such as a usage method and a use of a sticking sheet, description here is abbreviate | omitted.

D. Other Embodiments The sticking sheet of the present invention has other embodiments in addition to the above-described embodiments. Each embodiment will be described below.

1. Fourth Embodiment A patch sheet of the present embodiment is a patch having a gel film that is a hydrogel film or a dry gel film, and a functional layer that is formed on the gel film and does not affect the pastability of the gel film. The functional layer includes a first functional layer formed on the gel film and a second functional layer formed on the first functional layer, the gel film and the first The total thickness of one functional layer is within a predetermined range, and the second functional layer is a fine particle layer in which fine particles are dispersed or a fluidized layer containing a fluid substance. The total thickness of the gel film and the first functional layer varies depending on whether the gel film is a hydrogel film or a dry gel film. When the gel film is a hydrogel film, the total thickness of the gel film and the first functional layer is in the range of 100 nm to 200 μm. On the other hand, when the gel film is a dry gel film, the total thickness of the gel film and the first functional layer is in the range of 100 nm to 10 μm.

  FIG. 14 is a schematic cross-sectional view showing an example of the sticking sheet of this embodiment. As illustrated in FIG. 14, a sticking sheet 1 is formed on a gel film 2 that is a hydrogel film or a dry gel film in which a foam film is gelled, and on the gel film 2. And a functional layer 5 not provided. The functional layer 5 includes a first functional layer 6 formed on the gel film 2 and a fine particle layer 3 in which fine particles are dispersed as a second functional layer formed on the first functional layer 6. The total thickness of the gel film 2 and the first functional layer 6 is within a predetermined range.

  FIG. 15 is a schematic cross-sectional view showing another example of the sticking sheet of this embodiment. As illustrated in FIG. 15, the sticking sheet 1 is formed on the gel film 2, which is a hydrogel film or a dry gel film in which a foam film is gelled, and affects the sticking property of the gel film 2. And a functional layer 5 not provided. The functional layer 5 includes a first functional layer 6 formed on the gel film 2 and a fluidized layer 4 containing a fluid substance as a second functional layer formed on the first functional layer 6. . The total thickness of the gel film 2 and the first functional layer 6 is within a predetermined range.

  According to this embodiment, since the gel film is obtained by gelling a foam film, the thickness is very thin, so that high adhesion to the surface of a living body or a biomaterial such as skin and high flexibility are achieved. Have. Moreover, in this embodiment, even if the first functional layer is formed on the entire surface of the gel film because the total thickness of the gel film and the first functional layer is within a predetermined range, the skin of the gel film It is possible to maintain high adhesion to the like. Furthermore, 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 the fine particle layer or the fluidized layer is provided as the second functional layer on the first functional layer. Even if it is formed, high adhesion of the gel film to the skin or the like can be maintained. Therefore, the sticking sheet of this embodiment can be adhered to a living body or a biomaterial with sufficient strength without using an adhesive component, and it is difficult to peel off even when pasted on a moving uneven surface. Can do.

  Moreover, in this embodiment, functionality can be provided by the functional layer being formed on the gel film.

  In addition, about the usage method of a gel film, a fine particle layer, a fluidized bed, a support frame, a support body, a protective layer, a sticking sheet, an application, etc., it is the same as that of the said 1st embodiment. The first functional layer is the same as the functional layer in the third embodiment. The total thickness of the gel film and the first functional layer can be the same as the thickness of the sticking sheet in the third embodiment.

  In the present embodiment, the total thickness of the gel film and the first functional layer may be within the above-described range. For example, the gel film may be thicker than the first functional layer, and the first functional layer is larger than the gel film. May be thick.

2. Fifth Embodiment A patch sheet of this embodiment is a patch having a gel film that is a hydrogel film or a dry gel film, and a functional layer that is formed on the gel film and does not affect the pastability of the gel film. The functional layer includes a first functional layer formed on the gel film and a second functional layer formed on the first functional layer, the gel film and the first The total thickness of one functional layer is within a predetermined range, and the second functional layer is partially formed on the first functional layer. The total thickness of the gel film and the first functional layer varies depending on whether the gel film is a hydrogel film or a dry gel film. When the gel film is a hydrogel film, the total thickness of the gel film and the first functional layer is in the range of 100 nm to 200 μm. On the other hand, when the gel film is a dry gel film, the total thickness of the gel film and the first functional layer is in the range of 100 nm to 10 μm.

  FIG. 16 is a schematic cross-sectional view showing an example of the sticking sheet of this embodiment. As illustrated in FIG. 16, the sticking sheet 1 is formed on the gel film 2, which is a hydrogel film or a dry gel film obtained by gelling a foam film, and affects the sticking property of the gel film 2. And a functional layer 5 not provided. The functional layer 5 has a first functional layer 6 formed on the gel film 2 and a second functional layer 7 partially formed on the first functional layer 6. The total thickness of the gel film 2 and the first functional layer 6 is within a predetermined range.

  According to this embodiment, since the gel film is obtained by gelling a foam film, the thickness is very thin, so that high adhesion to the surface of a living body or a biomaterial such as skin and high flexibility are achieved. Have. Moreover, in this embodiment, even if the first functional layer is formed on the entire surface of the gel film because the total thickness of the gel film and the first functional layer is within a predetermined range, the skin of the gel film It is possible to maintain high adhesion to the like. Furthermore, in this embodiment, 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. Therefore, the sticking sheet of this embodiment can be adhered to a living body or a biomaterial with sufficient strength without using an adhesive component, and it is difficult to peel off even when pasted on a moving uneven surface. Can do.

  Moreover, in this embodiment, functionality can be provided by the functional layer being formed on the gel film.

  In addition, about the usage method, a use, etc. of a gel film, a support frame, a support body, a protective layer, and a sticking sheet, it is the same as that of the said 1st embodiment. The first functional layer is the same as the functional layer in the third embodiment, and the second functional layer is the same as the functional layer in the second embodiment. The total thickness of the gel film and the first functional layer can be the same as the thickness of the sticking sheet in the third embodiment.

  In the present embodiment, the total thickness of the gel film and the first functional layer may be within the above-described range. For example, the gel film may be thicker than the first functional layer, and the first functional layer is larger than the gel film. May be thick.

3. Sixth Embodiment The adhesive sheet of this embodiment has a single adhesive property, and is formed on the single layer film that does not contain an adhesive and an adhesive, and affects the adhesive property of the film. And a functional layer not provided.

Here, “patchability” refers to the stickability to the surface of a living body or a biological material such as skin.
The phrase “having a sticking property as a single substance” means that the film can be stuck on the surface of a living body or a biological material such as skin.
“Does not affect the adhesiveness of the membrane” means that the adhesiveness of the membrane is maintained to the extent that it can be applied to the surface of a living body or biomaterial such as skin even after the functional layer is formed on the membrane. Say.

  The film used in this embodiment may be a single layer that has a sticking property, does not include an adhesive and an adhesive, and is a single layer. For example, from the first embodiment to the fifth embodiment In addition to the gel film in the adhesive sheet, the films described in Patent Documents 1 and 3 to 5 described above, rubber sheets, and the like can be given.

  In addition, about a functional layer, since it can be set as the same as the functional layer in the sheet | seat for sticking from the 1st embodiment to the 5th embodiment, description here is abbreviate | omitted.

  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
An aqueous solution 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) was 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 lifting, the support 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 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 was exposed to a temperature condition of 37 ° C. for 30 minutes to gel the foam film of the aqueous solution, thereby producing 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.

[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.

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 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 to prepare a sticking sheet. A photograph of the obtained sticking sheet is shown in FIG.

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 functional 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. The photograph at the time of sticking the sticking sheet on the skin is shown in FIGS.

[Comparative Example 2]
A dry gel film was formed in the same manner as in Example 1.
A solution prepared by dissolving butyral resin as a binder in toluene was prepared. This solution was dropped onto a dry gel film to form a functional layer so as to have a thickness of 11.5 μm, and a sheet for pasting was prepared.
When the adhesive sheet was brought into close contact with water moistened with water in the same manner as in Example 1, the adhesive property was inferior, such as being easily peeled off after application.

[Example 2]
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 100 μl of mineral oil was dropped on the dried gel film, the dried gel film was tilted to uniformly spread the mineral oil to form a fluidized layer, and a patch sheet was prepared.
3. Evaluation When the surface of the dry gel film of the patch sheet was brought into close contact with the skin moistened with water by surface tension, only the dry gel film and the functional layer could be applied to the skin, and the follow-up to wrinkles was confirmed, The same result as in Example 1 was obtained.

[Example 3]
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 onto the dried gel film in a pattern to form a functional layer pattern, thereby preparing a sticking sheet. A photograph of the obtained sticking sheet is shown in FIG.
3. Evaluation When the surface of the dry gel film of the patch sheet is adhered to the skin moistened with water by surface tension, only the dry gel film and the functional layer can be applied to the skin while maintaining the pattern shape of the functional layer. Following wrinkles was also confirmed, and the same results as in Example 1 were obtained. The photograph at the time of sticking the sticking sheet on the skin is shown in FIGS.

[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 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 is spin-coated on a dry gel film to form functional layers having various thicknesses, and the total thicknesses are (a) 2.8 μm, (b) 3.2 μm, (c) 5.8 μm, (D) Four types of 12.0 μm sticking sheets were prepared.

3. 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 and the functional layer were applied to the skin for (a), (b), and (c). Although it was able to be affixed, (d) was inferior in affixability, such as being easily peeled off after affixing.

[Example 5]
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 6]
A sticking sheet was produced in the same manner as in Example 2 except that the support frame used in Example 5 was used.
With this sticking sheet, the same results as in Example 2 were obtained.

[Example 7]
A sticking sheet was produced in the same manner as in Example 3 except that the support frame used in Example 5 was used.
With this sticking sheet, the same results as in Example 3 were obtained.

[Example 8]
A sticking sheet was produced in the same manner as in Example 4 except that the support frame used in Example 5 was used.
With this sticking sheet, the same results as in Example 4 were obtained.

DESCRIPTION OF SYMBOLS 1 ... Sheet for sticking 2 ... Gel film 3 ... Fine particle layer 4 ... Fluidized layer 5 ... Functional layer 6 ... 1st functional layer 7 ... 2nd functional layer

Claims (6)

A hydrogel film obtained by gelling a foam film that is a thin film that can constitute a foam or a gel film that is a dry gel film;
A functional layer that is formed on the gel film and does not affect the pastability of the gel film;
The sticking sheet, wherein the functional layer is a fine particle layer in which fine particles are dispersed. A hydrogel film obtained by gelling a foam film that is a thin film that can constitute a foam or a gel film that is a dry gel film;
A functional layer that is formed on the gel film and does not affect the pastability of the gel film;
Sticking sheet, wherein the functional layer is partially formed on the gel film. A hydrogel film obtained by gelling a foam film that is a thin film that can constitute a foam or a gel film that is a dry gel film;
A functional layer that is formed on the gel film and does not affect the pastability of the gel film;
The functional layer has a first functional layer formed on the gel film and a second functional layer formed on the first functional layer,
The gel film is the dry gel film, and the total thickness of the gel film and the first functional layer is in the range of 100 nm to 10 μm;
Sticking seat the second functional layer, characterized in that the fine particles are fine particle layer are dispersed. A hydrogel film obtained by gelling a foam film that is a thin film that can constitute a foam or a gel film that is a dry gel film;
A functional layer that is formed on the gel film and does not affect the pastability of the gel film;
The functional layer has a first functional layer formed on the gel film and a second functional layer formed on the first functional layer,
The gel film is the hydrogel film, and the total thickness of the gel film and the first functional layer is in the range of 100 nm to 200 μm;
Sticking seat the second functional layer, characterized in that the fine particles are fine particle layer are dispersed. A hydrogel film obtained by gelling a foam film that is a thin film that can constitute a foam or a gel film that is a dry gel film;
A functional layer that is formed on the gel film and does not affect the pastability of the gel film;
The functional layer has a first functional layer formed on the gel film and a second functional layer formed on the first functional layer,
The gel film is the dry gel film, and the total thickness of the gel film and the first functional layer is in the range of 100 nm to 10 μm;
Sticking sheet, wherein the second functional layer is partially formed on the first functional layer. A hydrogel film obtained by gelling a foam film that is a thin film that can constitute a foam or a gel film that is a dry gel film;
A functional layer that is formed on the gel film and does not affect the pastability of the gel film;
The functional layer has a first functional layer formed on the gel film and a second functional layer formed on the first functional layer,
The gel film is the hydrogel film, and the total thickness of the gel film and the first functional layer is in the range of 100 nm to 200 μm;
Sticking sheet, wherein the second functional layer is partially formed on the first functional layer.