JP6155543B2 - Thin film transfer sheet, manufacturing method thereof, and transfer method of thin film layer to adherend - Google Patents

Description

  The present invention relates to a thin film transfer sheet, a method for producing a thin film transfer sheet, a transfer method for transferring a thin film layer of a thin film transfer sheet to an adherend, and a method for effectively carrying an active ingredient on the thin film layer.

  In general, a person can be energetic and have a rich feeling by making the appearance beautiful. For those who are troubled by the appearance of the face and body, as well as for those who do not have such troubles, making the appearance beautiful with makeup can rejuvenate the heart and make you feel rich. Therefore, makeup is one of the important matters when people live a social life. Makeup can be said to be a work that brings out the energy of oneself. Therefore, various makeup has been performed since ancient times.

  In recent years, with the improvement of quality of life, cosmetic sheets aimed at improving skin gloss, moisture and whiteness, and preventing wrinkles have attracted attention. As such a decorative sheet, a wrinkle improving sheet obtained by pasting a moisturizer or the like on paper derived from wood fiber has been provided (for example, see Patent Document 1), but the base material is paper. It was easy to tear, poor adhesion to the skin, and uncomfortable when worn.

  Under such circumstances, use of natural raw materials derived from casein and silk has been studied as a cosmetic material such as a sheet pack. Non-Patent Document 1 describes a thin film layer in which chitosan and alginic acid are alternately laminated.

Japanese Patent No. 3215852

T. T. Fujie et al. , Adv. Funct. Mater. 2009, 19: 2560-2568.

  For example, in the cosmetics field, users are ordinary people, and it is desired to develop cosmetics that anyone can use easily.

  The thin film layer described in Non-Patent Document 1 can be bonded to the skin without the need for any adhesive, and is a cosmetic sheet, a moisturizing sheet, and a makeup auxiliary paste that holds cosmetics or cosmetic ingredients. The present invention relates to a thin film layer intended for use as a sheet and a decorative protective sheet. However, it is a film with a thickness of about 100 nm, and the film shrinks when it is applied to the skin, causing wrinkles, breakage, and falling off, which makes it difficult to handle uniformly. It was.

  Thus, the cosmetic thin film layer is required to be inconspicuous in the state of the patch itself applied to the skin, and not to have an uncomfortable feeling in the applied state. On the other hand, there is a need for a new thin film layer that anyone can easily use. Furthermore, a method for supporting an active ingredient on the thin film layer is also required.

  Accordingly, an object of the present invention is to provide a thin film transfer sheet that efficiently supports an active ingredient and that is very easy to be bonded to the skin, is not noticeable at the time of application, and has no sense of incongruity. Furthermore, the present invention also provides a method for producing a thin film transfer sheet that is very easy to be applied to the skin, is not noticeable at the time of application, and does not feel uncomfortable, and the thin film layer of the thin film transfer sheet is coated. It is an object of the present invention to provide a transfer method for transferring to a kimono.

The present invention is [1] a sheet comprising a substrate, a thin film layer, a soluble support layer, and a permeable substrate, wherein (a) a drug, (b) a cosmetic, and (c) a dye on the soluble support layer (D) The present invention relates to a thin film transfer sheet containing any of metal ions.
The present invention also relates to [2] the thin film transfer sheet according to the above [1], wherein the permeable substrate has a fibrous shape, a mesh, or a porous structure.
The present invention also relates to [3] the thin film transfer sheet according to the above [1] or [2], wherein the soluble support layer comprises a water-soluble or alcohol-soluble polymer.
The present invention also relates to [4] the thin film transfer sheet according to any one of [1] to [3], wherein the thin film layer has a thickness of 40 nm to 300 nm.
Moreover, this invention is described in any one of said [1]-[4] whose [5] thin film layer is what A layer containing a polycation and B layer containing a polyanion were laminated | stacked alternately. The present invention relates to a thin film transfer sheet.
In addition, the present invention provides [6] The above [5], wherein the thin film layer includes an A layer formed using a solution containing a polycation and a B layer formed using a solution containing a polyanion. It relates to the thin film transfer sheet described.
The present invention also relates to [7] the thin film transfer sheet according to the above [5] or [6], wherein the polycation is a cationic polymer having two or more amino groups in one molecule.
Moreover, this invention is [8] Any one of said [5]-[7] whose said polyanion is an anionic polymer which has a 2 or more carboxyl group or carboxylate group in 1 molecule. The present invention relates to a thin film transfer sheet.
Moreover, this invention relates to the thin film transfer sheet as described in any one of said [1]-[8] in which a [9] thin film transfer sheet is used for skin bonding.
Moreover, this invention relates to the thin film transfer sheet as described in any one of said [1]-[8] in which a [10] thin film transfer sheet is used for cosmetics.

The present invention comprises a permeable base material, a soluble support layer and a thin film layer on the base material, wherein the thin film layer is formed using a solution containing a polycation, and a solution containing a polyanion. A thin film transfer sheet having a B layer formed using
Since the thin film transfer sheet has the above-described configuration, it is easy to handle, tough (mechanical strength), excellent in transparency and moisture retention, and has self-adhesion to the skin. For this reason, when it is used by ordinary people, it is very easy to bond to the skin, and it is not easily noticeable at the time of application, and the uncomfortable feeling at the time of application is reduced. Further, since a material having high biodegradability or biocompatibility is used as the material, the thin film layer has an advantage that it is highly safe and hardly causes skin allergy.

  The thin film layer is preferably formed by alternately laminating the A layer and the B layer, and by mechanically laminating the A layer and the B layer, mechanical strength and self-adhesiveness are obtained. It becomes an excellent thin film layer. The A layer and the B layer are alternately stacked not only when the one A layer and the one B layer are alternately stacked, but the A layer composed of a plurality of layers, This includes the case where B layers composed of a plurality of layers are alternately laminated.

Furthermore, the present invention includes [11] a step of bringing a substrate into contact with a solution containing a polycation or a solution containing a polyanion to form a layer derived from the polycation or the polyanion on the surface of the substrate;
(I) contacting a polyanion solution with a layer derived from a polycation to form a layer derived from a polyanion on the layer derived from the polycation;
(Ii) a step of bringing a polycation-containing solution into contact with a layer derived from a polyanion to form a layer derived from a polycation on the layer derived from the polyanion; and the steps of (i) and (ii) A step of forming a thin film layer that is alternately laminated, a step of forming a soluble support layer on the thin film layer, and a step of forming a permeable base material on the soluble support layer. The present invention relates to a method for manufacturing a thin film transfer sheet.
[12] The thin film transfer sheet according to [11], wherein in the step of forming the thin film layer, the number of times that the steps (i) and (ii) are alternately repeated is 1 to 300 times. It relates to the manufacturing method.
In addition, the present invention provides [13] a step of bringing the thin film layer of the thin film transfer sheet according to any one of [1] to [10] into contact with an adherend, from the permeable substrate side. The invention relates to a method for transferring a thin film layer to an adherend, including a step of permeating and passing a solution for dissolving a soluble support layer, and a step of peeling a permeable substrate.

  Since the said thin film layer has the above effects, it can be used conveniently as a thin film layer for skin bonding. Moreover, it can use suitably as a thin film layer for cosmetics. Furthermore, it can be suitably used as a thin film layer for cosmetic skin bonding.

  The thin film transfer sheet of the present invention has good handleability because it uses a permeable substrate. In addition, since it is a nanometer-sized thin film layer, it is suitable for wrinkles and fine irregularities (fine grooves) on the skin, and furthermore, since it is transparent, the sticking location does not stand out. Moreover, since it is a very thin thin film, there is no sense of incongruity at the time of sticking. Furthermore, since it has self-adhesiveness to the skin, it is not necessary to use an adhesive (pressure-sensitive adhesive), and there is no concern about rash or rough skin due to the adhesive. Furthermore, since a biodegradable or biocompatible polymer is used, skin allergies are less likely to occur when applied to the skin, and there is an advantage that it does not adversely affect the environment after disposal. In addition, by dissolving or dispersing the active ingredient in the soluble support layer, there is an advantage that the active ingredient penetrates into the thin film layer and the active ingredient can be supported in the thin film.

  In addition, the thin film transfer sheet of the present invention is a cosmetic sheet, a moisturizing sheet, a makeup auxiliary bonding sheet, and a cosmetic protective sheet that hold active ingredients, a sheet that enhances skin permeability of the cosmetic ingredients, and a cosmetic holding And can be suitably used as a reservoir sheet.

It is a figure showing a thin film transfer sheet in which a thin film layer (alternate laminated film of chitosan and alginic acid), a soluble support layer (polyvinyl alcohol + active ingredient dissolved or dispersed), and a permeable base material (polyethylene terephthalate mesh sheet) are sequentially laminated. is there. It is the photograph which stuck the thin film layer of Example 1 to skin (left), and is irradiating an ultraviolet-ray to it (right). 4 is a transmission electron micrograph of Example 3.

[Thin film layer]
The nano thin film layer according to the present embodiment includes an A layer formed using a solution containing a polycation and a B layer formed using a solution containing a polyanion.

[Polycation]
In this specification, the polycation refers to a compound having two or more cationic groups in one molecule, and the cationic group refers to a cationic group or a group that can be derived from a cationic group. Examples of the cationic group include an amino group; a monoalkylamino group such as a methylamino group or an ethylamino group; a dialkylamino group such as a dimethylamino group or a diethylamino group; an imino group; a guanidino group. The amino group may be —NH ₃ ⁺ in which a proton is coordinated.

  As the polycation, a cationic polymer is preferable. In the present specification, the cationic polymer refers to a polymer having two or more cationic groups in one molecule. The cationic polymer is preferably a polymer obtained by polymerizing a monomer having a cationic group.

  As a cationic polymer, a gel-like polyion complex can be formed with an anionic polymer, which will be described later, in the presence of water. Those with less are preferred. The cationic polymer is more preferably a bioabsorbable substance so that the affected tissue is healed and then biodegraded and absorbed into the living body.

  As the cationic polymer, those having hydrophilicity to such an extent that they can be dissolved or swollen in water and positively charged by the dissociation of the cationic group in water are preferably used. As the cationic polymer, a polymer having two or more amino groups in one molecule is particularly preferable.

  Preferred examples of the cationic polymer include basic polysaccharides such as collagen, polyhistidine, ionene, chitosan, and aminated cellulose; homopolymers of basic amino acids such as polylysine, polyarginine, and a copolymer of lysine and arginine. And copolymers; basic vinyl polymers such as polyvinylamine, polyallylamine, polydivinylpyridine; and their salts (hydrochloride, acetate, etc.), polyethyleneimine, polyallylamine hydrochloride, polydiallyldimethylammonium chloride .

  Furthermore, the crosslinked polymer obtained by bridge | crosslinking the above-mentioned cationic polymer can also be used. Any known method can be used as a method of crosslinking the cationic polymer. When the cationic polymer has an amino group, a method in which the amino group of the cationic polymer is subjected to a condensation reaction with a dicarboxylic acid is preferable.

  As the cationic polymer, a basic polysaccharide or a derivative thereof (for example, an acetylated product) or a salt thereof is suitable. In particular, chitosan is preferable as the basic polysaccharide. Chitosan is a deacetylated product of chitin, and its degree of deacetylation is preferably in the range of 40 to 100%, more preferably in the range of 45 to 90%, because it is more bioabsorbable and water-soluble. It is more preferable that it is in the range of 50 to 80%.

  The molecular weight of the cationic polymer is not particularly limited, but as the viscosity average molecular weight increases, the viscosity of the solution tends to increase during manufacture of the thin film layer with the base material, and casting and lamination tend to be difficult, and bioabsorption The viscosity average molecular weight of the cationic polymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 10,000 to 400,000. Preferably, it exists in the range of 50,000-200,000.

  In the present specification, the “viscosity average molecular weight” may be evaluated by a viscosity method which is a general measurement method. For example, it is calculated from an intrinsic viscosity number [η] measured based on JIS K 7367-3: 1999. can do.

  As the polycation, even a low molecular compound having two or more cationic groups in one molecule can be preferably used. Examples of the low molecular compound having two or more cationic groups in one molecule include low molecular diamines and polyamines. Specifically, for example, N- (lysyl) -diamino, a compound having two amino groups in one molecule such as diaminoalkanes such as diaminoethane, diaminopropane, diaminobutane, diaminopentane, and diaminohexane. One molecule such as mono- or dilysylaminoalkanes such as ethane, N, N ′-(dilysyl) -diaminoethane, N- (lysyl) -diaminohexane, N, N ′-(dilysyl) -diaminohexane, etc. The compound which has 3-4 amino groups in 1 and the compound which has 5 or more amino groups in 1 molecule can be mentioned.

[Solution containing polycation]
The concentration of the polycation in the solution containing the polycation is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 2.0% by mass, and particularly preferably 0.05 to 1.0% by mass. .

  The viscosity of the solution containing the polycation is preferably in the range of 0.1 to 1000 mPa · s, more preferably in the range of 0.5 to 500 mPa · s, and in the range of 1 to 100 mPa · s. More preferably. In the present specification, the viscosity is a value measured at a sample amount of 10 mL and 20 ° C. using a tuning fork type vibration viscometer SV-10 manufactured by A & D Co., Ltd.

  Two or more kinds of polycations may be used in combination in the solution containing the polycation.

  Any solvent can be used as the solvent for the solution containing the polycation as long as it can dissolve the polycation. However, since the amount of charge of the polycation can be increased, water or an aqueous solution of inorganic salts can be used. Is appropriate.

  The solution containing a polycation does not need to be adjusted in pH, and a solution obtained by dissolving a polycation in a solvent can be used as it is. For example, the pH can be 1.2-6.6.

[Polyanion]
In this specification, a polyanion means a compound having two or more anionic groups in one molecule, and an anionic group means an anion group or a group that can be derived from an anion group. Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfuric acid group, a sulfonic acid group, and a phosphoric acid group.

  As the polyanion, an anionic polymer is preferable. In the present specification, the anionic polymer refers to a polymer having two or more anionic groups in one molecule. The anionic polymer is preferably a polymer obtained by polymerizing a monomer having an anionic group.

  As an anionic polymer, a gel-like polyion complex can be formed with the above cationic polymer in the presence of water, and the polyion complex can exert an adhesive action on a living tissue, and has a harmful reaction to a living body. Less is preferred. The anionic polymer is more preferably a bioabsorbable substance so that the affected tissue is healed and then biodegraded and absorbed into the living body.

  As the anionic polymer, a polymer having a property of being hydrophilic enough to be dissolved or swollen in water and having a characteristic of being negatively charged when the anionic group is dissociated in water is preferably used. As the anionic polymer, a polymer having two or more carboxyl groups or carboxylate groups in one molecule is particularly preferable.

  Preferred examples of the anionic polymer include natural acidic polysaccharides having an anionic group such as a carboxyl group, a carboxylate group or a sulfate group such as alginic acid, hyaluronic acid, chondroitin sulfate, dextran sulfate, pectin and cherry, and derivatives thereof; Cellulose, dextran, starch, and other acidic polysaccharides and derivatives thereof that are artificially synthesized by binding anionic groups to polysaccharides that do not have anionic groups such as carboxyl groups, carboxylate groups, or sulfate groups in nature (for example, Carboxymethyl cellulose, carboxymethyl dextran, carboxymethyl starch, carboxymethyl chitosan, sulfated cellulose and sulfated dextran and their derivatives); polyglutamic acid, polyaspartic acid, glutamic acid and aspartic acid Homopolymers and copolymers of acidic amino acid such as a copolymer; acidic vinyl polymers such as polyacrylic acid; and salts thereof (e.g., alkali metal salts such as sodium salts).

  Examples of the derivatives of acidic polysaccharides include, for example, those obtained by reacting part or all of hydroxyl groups with acetic acid, nitric acid, sulfuric acid, phosphoric acid, etc .; and part of carboxyl groups or carboxylate groups such as ethylene glycol and propylene glycol. The compound esterified with the low molecular alcohol is mentioned.

  Specific examples of the derivative of acidic polysaccharide include alginic acid ethylene glycol ester, alginic acid propylene glycol ester, hyaluronic acid ethylene glycol ester, hyaluronic acid propylene glycol ester and the like. The degree of esterification in these derivatives is not particularly limited, but if the degree of esterification becomes too high, the proportion of carboxyl groups or carboxylate groups, that is, the anionicity decreases, and polyions formed with the cationic polymer The mechanical strength of the complex tends to decrease. Therefore, the degree of esterification in the derivative is preferably in the range of 40 to 100%, more preferably in the range of 45 to 90%, and still more preferably in the range of 50 to 80%.

  Examples of salts of acidic polysaccharides or derivatives of acidic polysaccharides include salts of these with monovalent ions, for example, alkali metal salts such as sodium salts and potassium salts; ammonium salts.

  Furthermore, the crosslinked polymer obtained by bridge | crosslinking the above-mentioned anionic polymer can also be used. Any known method can be used as a method of crosslinking the anionic polymer. In the case where the anionic polymer has a carboxyl group or a carboxylate group, a method in which the carboxyl group or the carboxylate group of the anionic polymer is subjected to a condensation reaction with a diamine is preferable.

  As the anionic polymer, acidic polysaccharides or derivatives thereof or salts thereof are suitable. In particular, since it is a natural polysaccharide, excellent in biocompatibility, and easily available, alginic acid or a derivative thereof (specifically, propylene glycol alginate, etc.) or a salt thereof (for example, sodium salt, etc.) Alkali metal salts) are preferred.

  The molecular weight of the anionic polymer is not particularly limited, but as the viscosity average molecular weight increases, the viscosity of the solution tends to increase during production of the thin film layer, and casting and lamination tend to be difficult, and bioabsorbability decreases. Therefore, the viscosity average molecular weight of the anionic polymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 10,000 to 400,000, More preferably, it is in the range of 000 to 200,000.

  As a polyanion, even a low molecular compound having two or more anionic groups in one molecule can be preferably used. Examples of the low molecular weight compound having two or more anionic groups in one molecule include compounds having two carboxyl groups or carboxylate groups in one molecule such as succinic acid and malonic acid.

  The combination of the cationic polymer and the anionic polymer may be any combination as long as it forms a polyion complex and gels when mixed in the presence of water. In particular, it is preferable that at least one of the cationic polymer and the anionic polymer is a bioabsorbable polymer because it is superior in safety.

  By bioabsorbable polymer is meant a polymer that can be biodegraded. Specific examples of the cationic polymer include chitosan, collagen, polylysine, polyarginine, polyhistidine, and ionene. Examples of the anionic polymer include alginic acid, hyaluronic acid, polyglutamic acid, chondroitin sulfate, and derivatives thereof. .

[Solution containing polyanion and having a pH of 1.6 to 5.4]
The concentration of the polyanion in the solution containing the polyanion and having a pH of 1.6 to 5.4 (hereinafter also referred to as “solution containing the polyanion”) is preferably 0.01 to 5.0% by mass, and 0.02 -2 mass% is more preferable, and 0.05-1.0 mass% is especially preferable.

  The viscosity of the solution containing the polyanion is preferably in the range of 0.1 to 1000 mPa · s, more preferably in the range of 1 to 500 mPa · s, and in the range of 10 to 100 mPa · s. Is more preferable.

  The pH of the solution containing the polyanion is 1.6 to 5.4, but it is preferably in the range of 1.8 to 5.0 because it is more excellent in solubility of the polyanion, and 2.0 to 4. More preferably, it is in the range of 5, more preferably in the range of 2.5 to 4.0.

  The pH of the solution containing the polyanion is, for example, malic acid, citric acid, acetic acid, propionic acid, succinic acid, malonic acid, oxalic acid, formic acid, butanoic acid, isobutyric acid, pentanoic acid, isovaleric acid, caproic acid, enanthic acid , Caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanoic acid, icosanoic acid, arachidonic acid, eicosapentaenoic acid, Docosanoic acid, docosahexaenoic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, salicylic acid, benzoic acid, phthalic acid, cinnamic acid, pyruvic lactic acid, tartaric acid, maleic acid, fumaric acid, malonic acid, succinic acid, aconitic acid, Organics such as glutaric acid, adipic acid, amino acids, L-ascorbic acid It can be adjusted by adding an inorganic acid such as acid, hydrochloric acid, sulfuric acid or nitric acid.

  Two or more kinds of polyanions may be used in combination in the solution containing the polyanions.

  As a solvent for the solution containing the polyanion, any solvent can be used as long as it can dissolve the polyanion. However, since the amount of charge of the polyanion can be increased, water or an aqueous solution of inorganic salts is suitable. is there.

  The thin film layer of the present embodiment includes an A layer formed using a solution containing a polycation, and a B layer formed using a solution containing a polyanion and having a pH of 1.6 to 5.4. Have. Moreover, it is preferable that the thin film layer of this embodiment is an alternately laminated thin film in which A layers and B layers are alternately laminated.

  When the A layer and the B layer are alternately laminated, the number of lamination is not particularly limited, but the A layer and the B layer tend to ensure the transparency of the thin film layer. It is preferable that each of 1 to 300 layers. In addition, since the thin film layer tends to have a film thickness that has self-adhesiveness, each of the A layer and the B layer is more preferably 10 to 100 layers, and more preferably 20 to 80 layers. Further preferred.

  The laminated structure of the A layer and the B layer in the thin film layer of the present embodiment is observed by, for example, IR, NMR, TOF-SIMS (time-of-flight secondary ion mass spectrometry, Time-Of-Flight SIMS)) This can be confirmed.

  Although the thickness of the thin film layer of the present embodiment is not particularly limited, it may be in the range of 1 to 300 nm because properties such as self-adhesion, water absorption, and flexibility in a dry state become more excellent. Preferably, it is 40 to 300 nm, more preferably within the range of 40 to 250 nm, and particularly preferably within the range of 40 to 200 nm.

(Solubility support layer)
In the present invention, the soluble support layer is not limited as long as it is soluble in a solvent. However, in consideration of irritation to the skin, a layer made of a polymer film soluble in water or alcohol is preferable. Those soluble in weakly alkaline and weakly acidic aqueous solutions are also included. The soluble support layer is composed of a polyelectrolyte such as polyacrylic acid or polymethacrylic acid, a polyethylene glycol, polyacrylamide, polyvinyl alcohol, or a nonionic water-soluble polymer such as a polysaccharide such as starch or cellulose acetate, a novolak or poly What is formed from resin, such as (N-alkyl cyanoacrylate), can be illustrated. In the polymer solution for producing the soluble support layer (soluble support membrane) or region, the molecular weight of the polymer is 1,000 to 1,000,000, preferably 5,000 to 500,000, and the concentration is 1 to 20% by mass, preferably 2 It is desirable that it is a 10 mass% solution. The soluble support layer (soluble support film) is formed on a substrate on which a thin film layer has been constructed and dried by drying for 10 minutes to 24 hours, preferably 1 to 12 hours.
Examples of the method for coating on the substrate include, but are not limited to, a casting method and a spin coating method. The soluble support layer (soluble support film) is peeled from the substrate together with the thin film layer using tweezers or the like. At this time, between the soluble support layer (soluble support film) and the thin film layer, the thin film becomes a support layer at the same time as peeling due to secondary bonding force such as electrostatic interaction, hydrogen bond, van der Waals force, etc. It can be transferred.

(Penetration substrate)
The material of the permeable base material is not limited as long as it is selected from those that do not dissolve in the solution that dissolves the soluble support layer. However, it has a function to penetrate and permeate the solution. Therefore, it is preferable to have pores that allow the solution to permeate and permeate, and are preferably fibrous, mesh, and porous. The permeable substrate is preferably in the form of a sheet (film) from the viewpoint of handleability and availability.

  Examples of materials that can be used as the permeable substrate include resins and non-woven fabrics. The shape of the permeable substrate can be any shape such as a film, a sheet, a plate, and a shape having a curved surface. Among these, considering mass productivity, a flexible resin film is preferable as the permeable substrate.

  Although there is no restriction | limiting in particular in the thickness of the resin film in the case of using the resin film which has flexibility, 5-500 micrometers is preferable from a practical viewpoint.

  Moreover, when using a mesh-shaped resin film, the mesh opening is preferably 1-1000 μm. From the viewpoint of peelability from the cover film and water permeability, 5-300 μm is more preferable. Furthermore, 10-100 micrometers is more preferable from the pasting to skin being easy.

The resin of the resin film having pores through which the solution permeates and permeates may be either a thermoplastic resin or a thermosetting resin, for example, polyethylene (high density, medium density or low density), polypropylene (isotactic type) Or syndiotactic type), polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-propylene-butene copolymer, etc., polyolefin, cyclic polyolefin, modified polyolefin, polyvinyl chloride, poly Vinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (me ) Acrylate copolymer, methyl (meth) acrylate-styrene copolymer, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET) ), Polybutylene terephthalate (PBT), ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, polyester such as poly-1,4-dimethylenecyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), Polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetra Fluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin, polyvinyl chloride, polyurethane, fluororubber, chlorinated polyethylene, and other thermoplastic elastomers, epoxy resins, phenol resins, urea resins, melamine Resin, unsaturated polyester, silicone resin, polyurethane, nylon, nitrocellulose, cellulose acetate, cellulose acetate such as cellulose acetate propionate, etc., or copolymers, blends, polymer alloys, etc. mainly comprising these These can be used alone or in combination of two or more (for example, as a laminate of two or more layers).
Among these resin films, a polyethylene terephthalate (PET) film is more preferable because of its good water permeability.

  As a nonwoven fabric, the nonwoven fabric which consists of fibers, such as a polyester resin, an acrylic resin, nylon, vinylon, glass, is mentioned, for example. The paper or the nonwoven fabric may have a strengthened interlayer strength between the fibers or another layer. Also, in order to prevent injuring or to suppress permeability, it may be added with resin such as acrylic resin, styrene butadiene rubber, melamine resin, urethane resin (impregnated with resin after paper making or embedded during paper making) Good.

〔Base material〕
The base material used by this invention functions as a support substrate at the time of manufacturing a thin film layer. Examples of the material that can be used as the substrate include resin and paper. The shape of the substrate can be any shape such as a film, a sheet, a plate, and a shape having a curved surface. Among these, considering mass productivity, a resin film having flexibility is preferable as the substrate.

  Although there is no restriction | limiting in particular in the thickness of the resin film in the case of using the resin film which has flexibility, 5-500 micrometers is preferable from a practical viewpoint.

The resin of the resin film may be either a thermoplastic resin or a thermosetting resin. For example, as described above, polyethylene (high density, medium density or low density), polypropylene (isotactic type or syndiotactic type) ), Polyolefins such as polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-propylene-butene copolymer, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, Polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer , Methyl (meth) acrylate-styrene copolymer, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene Polyester such as terephthalate (PBT), ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, poly-1,4-dimethylenecyclohexane terephthalate (PCT), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, poly Various thermoplastic elastomers such as vinylidene fluoride, other fluororesins, styrene, polyolefin, polyvinyl chloride, polyurethane, fluororubber, chlorinated polyethylene, epoxy resin, phenol resin, urea resin, melamine resin, Cellulosic resins such as unsaturated polyester, silicone resin, polyurethane, nylon, nitrocellulose, cellulose acetate, cellulose acetate propionate, etc., or copolymers, blends, polymer alloys, etc. mainly comprising these, etc. 1 type or 2 types or more can be used in combination (for example, as a laminate of two or more layers).
Among these resin films, a polyethylene terephthalate (PET) film is more preferable because it is more excellent in the adhesion of the laminated film.

  Examples of the paper include thin paper, kraft paper, high quality paper, linter paper, baryta paper, sulfuric acid paper, and Japanese paper.

  Further, the surface of the substrate may be subjected to corona discharge treatment, glow discharge treatment, plasma treatment, ultraviolet irradiation treatment, ozone treatment, chemical etching treatment with alkali, acid or the like.

  The base material may be formed by laminating a resin film, an inorganic film, or a film containing an organic material and an inorganic material (organic-inorganic film) on the base material. The laminated structure consisting of these resin film layer, inorganic film layer, or organic-inorganic film layer only needs to cover a part of the substrate surface. Moreover, the film | membrane which is not located in an outermost surface layer in a laminated structure does not need to have a polar group.

  The base material can also function as a base material for forming a thin film layer. A thin film layer is formed on both surfaces of the base material, and a soluble support layer and a permeable base material are formed on each of the formed thin film layers. It can also be provided as a thin film transfer sheet. It is convenient because the thin film layers formed on both sides of the base material (cover film) can be used respectively.

[(A) Drug, (b) Cosmetics, (c) Dye, (d) Metal ion of soluble support layer]
In the soluble support layer according to the embodiment, any one of (a) a drug, (b) a cosmetic, (c) a pigment, and (d) a metal ion is contained and held. (A) drug, (b) cosmetics, (c) pigment, (d) metal ions diffused in the dissolvable support layer are diffused and reach the thin film layer adjacent to the dissolvable support layer, whereby the skin When affixed to (when used), (a) drug, (b) cosmetic, (c) pigment, (d) metal ions are gradually eluted from the thin film layer and can be gradually absorbed by the skin.

[(A) Drug]
The thin film layer and the soluble support layer according to this embodiment can hold a drug. This allows the drug to gradually elute from the thin film layer when applied to the skin (during use) and be gradually absorbed by the skin. Moreover, it can be set as the thin film layer with the effect of wound healing.
Examples of the drug include anti-inflammatory agents, hemostatic agents, vasodilators, thrombolytic agents, anti-arteriosclerotic agents and the like.

[(B) Cosmetics]
The thin film layer and the soluble support layer according to the present embodiment can also hold cosmetic ingredients such as moisturizing cream or cosmetic ingredients such as vitamin C. Thus, when applied to the skin (during use), the cosmetic and cosmetic ingredients are gradually eluted from the thin film and can be gradually absorbed by the skin.

  As cosmetics, general cosmetics used for skin care such as moisturizing cream, skin cream, whitening cream, milky lotion, lotion, cosmetic liquid, and cosmetic gel can be used. The cosmetic ingredient is not particularly limited as long as it is a cosmetically acceptable ingredient effective for the skin. Specifically, for example, ingredients used in cosmetics such as moisturizers, whitening ingredients, stain removal ingredients, antifungal ingredients, vitamins, anti-inflammatory ingredients, blood flow promoting ingredients, wetting ingredients, oils, and metal particulates. It can be used alone or in combination of two or more.

  Examples of such cosmetic ingredients include almond oil, alkyl acrylate copolymer, hemp cellulose, ashitaba extract, ascorbic acid, sodium ascorbate, xanthine, astaxanthin, asparagus extract, aspartic acid, azulene, acerola extract, adenosine three Phosphate 2Na, avocado oil, achacha extract, aminobutyric acid, alanine, allantoin, arginine, sodium alginate, argylline, altea extract, arnica extract, albumin, aloe vera extract-2-kidachi aloe extract, benzoate Na, ginkgo biloba extract, inositol, Turmeric extract, walrus extract, age extract, sodium chloride, oyster extract, gonon extract, duckweed extract, ginseng extract, licorice extract, orang Mustard extract, olive oil, oryzanol, sea salt, hydrolyzed keratin, collagen, hydrolyzed collagen, hydrolyzed conkylion, hydrolyzed silk, hydrolyzed egg shell membrane, hydrolyzed egg white, brown alga extract, caffeine, chamomile extract, calamine, karin extract , Carotene, carrot extract, arabesque extract, licorice extract, camphor, raspberry extract, kiwi extract, xylitol, chitosan, cucumber extract, quaternium-73, gardenia extract, kumazasa extract, clara extract, glycolic acid, glycine, glycerin, glycyrrhizic acid 2K , Stearyl glycyrrhetinate, glucose, glutathione, glutamic acid, grapefruit extract, clematis extract, chlorella extract, cape aloe extract, gentian extract, tea ex , Coenzyme Q10, coffee extract, corn starch, cocoyl hydrolyzed collagen K, cocoyl hydrolyzed collagen Na, cocobetaine, burdock extract, sesame oil, wheat starch, wheat germ extract, rice bran extract, cholesterol, comfrey extract, tocopherol acetate, retinol acetate, Sasanqua oil, safflower oil, salicylic acid, sodium salicylate, zinc oxide, titanium oxide, hawthorn extract, cyanocobalamin, shiitake extract, diau extract, diglycerin, shikon extract, shiso extract, dihydrocholesterol, diphenyldimethylmecon, shimotake extract, tartaric acid, ginger extract , Camphor root extract, silk, silk extract, hydrogenated lecithin, squalane, stearyl alcohol, glyceryl stearate, Sucrose stearate, ivy extract, mint extract, sage extract, cetanol, ceramide 3, serine, cellulose gum, sow extract, sorbitol, soybean extract, soybean fermented extract, evening primrose oil, dodami extract, tocopherol, trehalose, niacinamide, nicotine Acid tocopherol, lactic acid, sodium lactate, urea, bakuga extract, honey, papain, hamamelis extract, retinol palmitate, panthenol, hyaluronic acid Na, biotin, cypress extract, castor oil, sunflower oil, pyridoxine HCl, loquat leaf extract, buccal extract , Butcher bloom extract, grape extract, grape seed oil, placenta extract, pullulan, betaine, loofah extract, button extract, hop extract, jojoba Ile, Meadowfoam oil, Methoxy cinnamon octyl, Melissa extract, Merilot extract, Menthol, Peach leaf extract, Cornflower extract, Palm oil, Eucalyptus extract, Eucalyptus oil, Yukinoshita extract, Yuzu extract, Lily extract, Iodized garlic extract, Folic acid, Yokuinin Extract, mugwort extract, raspberry ketone, lactoferrin, lanolin, lavender extract, lysine, lysine HCl, linoleic acid, riboflavin, sodium sulfate, apple extract, litchi extract, lecithin, resorcin, lettuce extract, lemon extract, lemon oil, leucine, rose water , Rosehip oil, Rosemary extract, Roman chamomile extract, Royal jelly, Walnut extract, AHA, BG, DNA, PCA-Na, PCA-Na allantoin, PG, PPG 28 Butes-35, RNA-NA, t-butylmethoxydibenzoylmethane, α-arbutin, mucopolysaccharide, creatine, diacetylbordin, vitamin A and its derivatives, riboflavin sodium phosphate, riboflavin, hydroquinone, liponucleic acid and salts thereof Amino acids and derivatives thereof, various plant extracts, various animal-derived extracts, and the like.

[(C) Dye]
The thin film layer and the soluble support layer according to the present embodiment can also hold a dye. As a result, it is possible to confirm where it is pasted when it is stuck to the skin (during use). In addition, the presence of the thin film layer can be made inconspicuous in accordance with the color of the skin when attached to the skin (during use).

  Examples of pigments include naphthol dyes (azo dyes), mauve, para red, fluorescein, fuchsin, phenolphthalein, neutral red, phenazine derivative pigments, methylene blue, dihydrointol, congo red, eosin, indanthrene, aniline black, acridine, azo Dyes, azoic dyes, neocyanine, cryptocyanine, indocyanine green, hemoglobin, heme erythrin, pheoporphyrin, pheophorbide, cytochrome, bacteriochlorophyll, chlorophyllide, chlorophyll, melanin, catechin, anthocyan, anthrochlor, flavanone, flavones, flavonoids, lutein Lycopene, fucoxanthin, zeaxanthin, cryptoxanthine, xanthophylls, carotene, carotene Id, genistein, chlorocruoline, chlorin, crocetin, curcumin, xanthone machin, cartamine, erythrocruoline, urobilin, indigo, anthraquinone, anthocyanin, alizarin, bilirubin, biliverdin, phytochrome, phycoerythrin, phycobilin, phycocyanin, myoglobin, Porphine, porphyrin, hemocyanin, hemovanadine, rhodomatine, rhodoxanthine, rhodopsin, litmus, leghemoglobin, laminaran, morindin, horbilin, mangosteen, berberine, betacyanin, purpurin, bradylin, pinnaglobin, hypericin, bixin, tussine, tansine, tussine, tancine, tansine Commerinine, gossypol, cochineal and the like. Of these, ionic dyes are preferred because they dissolve in water and alcohol.

[(D) Metal ion]
The thin film layer and the soluble support layer according to the present embodiment can also hold metal ions. Thereby, when affixed to the skin (during use), the metal ions are gradually eluted from the thin film layer and can be gradually absorbed by the skin. Moreover, a metal ion can be used to form a thin film layer having effects such as antibacterial, sterilization, deodorization, and antiperspirant.

Examples of metal ions include alkaline metal ions such as lithium, sodium and potassium, alkaline earth metal ions such as magnesium, calcium and barium, transition metal ions such as gold, silver, copper, platinum and palladium, aluminum, lead and tin ions. Is mentioned. Among these, silver ions having antibacterial and deodorizing effects are more preferable.
The blending amount of these (a) to (d) varies depending on each active ingredient and is determined in consideration of the movement to the thin film layer, but in general, with respect to 100 parts by mass of the soluble support layer. 0.001 to 300 parts by mass, preferably 0.005 to 100 parts by mass, and more preferably 0.01 to 50 parts by mass.

  The thin film layer according to the present embodiment has, as a crosslinking agent, alkyldiimidates, acyldiazides, diisocyanates, bismaleimides, triazinyl, diazo compounds, glutaraldehyde, N-succinimidyl-3- (2-pyridyldithio) archio Nate, bromocyan, etc. may be used to crosslink with corresponding functional groups in the thin film layer.

  Furthermore, when the drug / cosmetic is hydrophobic, it is bonded to the hydrophobic region of the thin film layer by hydrophobic interaction. When the drug / cosmetic is hydrogen-bonded, the hydrogen-bonded region of the thin film layer A method of bonding by hydrogen bonding, or a method of bonding by electrostatic interaction to the oppositely charged region of the thin film layer may be used when the drug / cosmetic material has a charge.

  The thin film layer according to this embodiment can be used by applying a cosmetic ingredient such as a moisturizing cream or a cosmetic ingredient such as vitamin C to the skin and bonding a thin film thereon. In this case, the effect that the cosmetic and cosmetic ingredients are retained and is not easily peeled off can be obtained.

  The thin film layer which concerns on this embodiment can also be used so that a cosmetics or cosmetics component may be apply | coated on it, after bonding a thin film layer on skin. In this case, it is possible to make the skin with wrinkles, sagging, spots, bruises, freckles, pores, scars, acne scars, thermal scars, or discoloration due to skin diseases inconspicuous.

(Method for manufacturing thin film transfer sheet)
The thin film layer of the present embodiment includes, for example, a base material, a solution containing a polycation (hereinafter also referred to as “solution A”), a solution containing a polyanion and having a pH of 1.6 to 5.4 (hereinafter “ Also referred to as “Solution B”), from Langmuir, Vol. 13, pp. 6195-6203, (1997).

Specifically, in the method for producing a thin film layer of this embodiment, a base material to be a cover film later is brought into contact with the solution A or the solution B, and a layer derived from a polycation or a polyanion is formed on the surface of the base material. A layer forming step;
(I) contacting the solution B with the polycation-derived layer to form a polyanion-derived layer on the polycation-derived layer;
(Ii) a step of bringing the layer derived from the polyanion into contact with the solution A to form a layer derived from the polycation on the layer derived from the polyanion, and a lamination step.

  According to this alternate lamination method, the polycation and the polyanion are alternately formed by contacting the layer derived from the polycation formed on the substrate (or the layer derived from the polyanion) and the solution B (or solution A). A laminated film is formed by adsorption. Further, when the adsorption of polycation or polyanion proceeds by the above contact and the surface charge is reversed, further electrostatic adsorption does not occur, so the thickness of the layer formed by contact with solution A or solution B should be controlled. Can do.

  In the layer forming step, the substrate is brought into contact with the solution A to form a layer derived from a polycation on the surface of the substrate, or the substrate is brought into contact with the solution B and derived from a polyanion on the surface of the substrate. A layer to be formed is formed. The former is preferably performed when the surface of the substrate is negatively charged, and the latter is performed when the surface of the substrate is positively charged. Further, at least a part of the surface of the substrate may be brought into contact with the solution A or the solution B. The contact with the solution A or the solution B may be performed in two or more times.

  In the stacking process, the surface charge may be reversed in step (i) or step (ii). Moreover, the frequency | count of contact is not specifically limited. For example, in step (i), the contact with the solution B may be performed twice or more, and in the step (ii), the contact with the solution A may be performed twice or more.

  In the laminating process, there is no particular limitation on the number of times to repeat step (i) and step (ii), but since it tends to ensure transparency of the thin film layer, it is derived from the polycation-derived layer and the polyanion. It is preferable to repeat until all of the layers to become 1 to 300 layers. In addition, since the thin film layer tends to have a film thickness that has self-adhesiveness, it is more likely to repeat until both the layer derived from the polycation and the layer derived from the polyanion become 10 to 100 layers. It is particularly preferable to repeat until it becomes 20 to 80 layers. Note that the film thickness of the thin film layer can be controlled by controlling the number of repetitions in the stacking step.

  In the said manufacturing method, it is preferable to complete | finish a lamination process by step (ii) rather than ending by step (i). Thereby, the characteristic of the substance used as a polycation becomes easy to express. For example, when chitosan is used as the polycation, the antibacterial property that is the characteristic of chitosan is easily developed.

  In the said manufacturing method, it is preferable to rinse an adsorption surface after the contact with the solution A or the solution B in a layer formation process or a lamination process. Thereby, excess material can be removed from the adsorption surface.

  As the rinsing liquid used for rinsing, water, an organic solvent, or a mixed solvent of water and a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include methanol, ethanol, propanol, acetone, dimethylformamide, acetonitrile and the like.

  In the said manufacturing method, it is preferable to contact by immersing the base material, the layer derived from a polycation, or the layer derived from a polyanion in the solution A or the solution B. For example, in the layer formation step, it is preferable to contact the substrate by immersing it in solution A or solution B. In the lamination step, a layer derived from a polycation (or a layer derived from a polyanion) is added to solution B ( Or it is preferable to contact by immersing in the solution A). Thereby, it becomes easier to produce industrially more and it can be set as the manufacturing method which can be used still more widely.

  As an apparatus for forming a laminated film, J.I. Appl. Phys. , Vol. 79, pp. 7501-7509, (1996), Japanese Patent Application No. 2000-568599 (Japanese Patent No. 4302321), or the like may be used. When the dipper is used, the arm to which the substrate is fixed automatically moves, and the substrate or the like can be sequentially immersed in the solution A, the solution B, or the rinse solution according to the program.

  According to the method of alternately dipping (hereinafter also referred to as “alternative dipping method”), the film formation can be continued as long as the surface charge is reversed. Therefore, the film thickness uniformity of the thin film formed by the alternate dipping method is higher and the film thickness controllability is higher than the normal dip coating method.

  In addition, according to the alternate dipping method, even if a part or all of the substrate has a shape such as a cylinder, a thread, a fiber, and a foam, the solution can enter by dipping. Since the laminated film is formed on the surface, it can be used. Moreover, even if the surface of the substrate has an uneven shape, a laminated film can be formed following the surface structure. Furthermore, even if the substrate surface has a nanometer scale or submicron scale structure, a laminated film can be formed following the structure.

  The thin film layer of this embodiment may be manufactured by forming a laminated film by a spin coating method in which the solution A or the solution B is dropped or sprayed on a base material. At that time, the rinsing liquid may be supplied by dripping, spraying or showering, or a combination thereof. The base material may perform movements such as conveyance and rotation. However, the spin coating method has a demerit that the amount of the solution A, the solution B, etc. used is large and the film is formed one by one, so that the mass productivity is not excellent.

  In any of the production methods, any solvent can be used as the solvent for the solution A or the solution B as long as it can dissolve the polycation or the polyanion. However, the charge amount of the polycation or the polyanion can be used. Therefore, water or an aqueous solution of an inorganic salt is suitable. The concentration of the polycation or polyanion in the solution is not particularly limited, and may be appropriately set according to each production method.

  Furthermore, when at least one of the polycation and the polyanion is a salt, and the solubility of the polycation or the polyanion in water is lowered by removing the counter ion of the cation group or the anion group in the salt, a thin film layer was formed. By removing counter ions contained in the thin film layer later, the mechanical strength of the thin film layer can be improved. The removal of the counter ions can be performed by, for example, a method of increasing the number of washing steps or immersing in a pH adjusting solution.

A soluble support layer further comprising (a) a drug, (b) a cosmetic, (c) a dye, or (d) a metal ion is formed on the thin film layer formed on the substrate, and the soluble support layer A thin film transfer sheet can be produced by providing a permeable substrate on the substrate. (A) Drug, (b) Cosmetics, (c) Dye, (d) Metal ions blended in the soluble support layer immediately after production are diffused into the adjacent thin film layer, and the concentration of the blended substance increases with time. When used, the concentration is constant.
The method for transferring a thin film layer to an adherend of the present invention includes a step of peeling the substrate of the thin film transfer sheet, exposing the thin film layer, and contacting the thin film layer so as to face the adherend; A step of permeating and passing a solution for dissolving the soluble support layer from the side of the permeable substrate, and a step of peeling the permeable substrate. The sheet from which the thin film transfer sheet substrate is peeled and the thin film layer is exposed has a certain degree of rigidity because the thin film layer is supported by the adjacent soluble support layer and permeable substrate. It can be easily brought into contact with the adherend and pasted. Then, the solution is brought into contact with the surface of the permeable substrate so that the solution reaches the soluble support layer using a solution such as water or alcohol from the mesh-shaped resin film side which is the permeable substrate, and the soluble support layer Is dissolved and the permeable substrate is peeled off. When the soluble support layer swells in the solution and peels off at the interface of the thin film layer, it can be peeled off as it is. In addition, when the soluble support layer is dissolved in the solution, the dissolved solution in which the soluble support layer is dissolved is attached from the permeable substrate side using a tissue, cotton, etc., and the solution is further dissolved from the permeable substrate side. The thin film layer can be transferred to the adherend by removing the soluble support layer and the permeable substrate by supplying the soluble support layer, dissolving the soluble support layer, and removing the dissolved solution. . In this case, if the soluble support layer dissolves in the solution to some extent and the permeable substrate can be peeled off, after removing the permeable substrate, remove the soluble support layer adhering to the thin film layer as necessary. You can also

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a reference example, this invention is not limited to this.

  Chitosan aqueous solution (manufactured by Kimika Co., Ltd .: viscosity average molecular weight 90,000, viscosity 12.5 mPa · s (25 ° C.), concentration: 0.3% by mass) as the cationic polymer, sodium alginate aqueous solution (Kimika Co., Ltd.) as the anionic polymer Product: Viscosity average molecular weight 100,000, viscosity 6.7 mPa · s (25 ° C., concentration: 0.1% by mass), malic acid (manufactured by Wako Pure Chemical Industries, Ltd.), acetic acid (Wako Pure Chemical Industries, Ltd.) as the acid component Manufactured by), hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) or nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.).

[Example 1]
The chitosan aqueous solution used was prepared by dropping 3 parts by mass of acetic acid (1% by mass aqueous solution) with 100% by mass of the 0.3% by mass chitosan aqueous solution. As the sodium alginate aqueous solution, one obtained by dropping 1 part by mass of malic acid (1% by mass aqueous solution) into the sodium alginate aqueous solution with respect to 100 parts by mass of the 0.1% by mass sodium alginate aqueous solution was used.
A polyethylene terephthalate film (Toyobo Co., Ltd., A4100, 150 mm × 100 mm × 125 μm thickness) as a base material was immersed in (a) chitosan aqueous solution for 1 minute, and then rinsed ultrapure water (specific resistance 18 MΩ · cm) ) For 1 minute, (a) immersed in an aqueous sodium alginate solution for 1 minute, and then immersed in ultrapure water for rinsing for 1 minute.
The procedure in which (a) and (b) were performed in turn was one cycle, and this cycle was repeated 15 times to obtain a thin layer of chitosan and sodium alginate on a polyethylene terephthalate film (PET film). The film thickness of the obtained thin film layer was measured by the film metrisk. As a result, the film thickness was 75 nm. Subsequently, riboflavin sodium phosphate (coenzyme-type vitamin B2, skin) as a cosmetic in a 10% by mass aqueous solution of polyvinyl alcohol (manufactured by Kanto Chemical Co., Ltd., weight average molecular weight 22000) dissolved in ultrapure water as a soluble support layer. (Mucous membrane health maintenance / recovery) 0.1 parts by mass dissolved was applied onto the thin film layer by a bar coater so as to be 5 μm after drying. Thereafter, as a permeable substrate, a polyethylene terephthalate mesh sheet (PET mesh, manufactured by Semitex Co., Ltd., PES45) was coated, and water was evaporated at room temperature (25 ° C.). As a result, on the base material (polyethylene terephthalate), a thin film layer (alternate laminated film of chitosan and alginic acid), a soluble support layer (a solution of sodium riboflavin phosphate in polyvinyl alcohol), a permeable base material (polyethylene terephthalate mesh) A thin film transfer sheet in which sheets were sequentially laminated was formed. From this sheet, the PET film of the substrate was peeled off, the thin film layer was exposed, brought into contact with the skin surface, and bonded. Thereafter, polyvinyl alcohol, which is a soluble support layer, was dissolved while dripping water onto the PET mesh. After 3 minutes of wiping off the water, when the PET mesh was peeled off, only the thin film layer was transferred to the skin surface. When the transferred thin film layer was irradiated with ultraviolet rays (256 nm), the nano thin film layer was shined, and the portion where the nano thin film layer was stuck was easily observed.

[Example 2]
The same operation as in Example 1 was performed except that the process was changed to a step of dissolving methylene blue as a pigment in the soluble support layer. As a result, it was possible for methylene blue to penetrate from the soluble support layer to the thin film layer and to color the thin film in blue.

Example 3
The same operation as in Example 1 was performed except that the process was changed to a step of dissolving silver nitrate as metal ions in the soluble support layer. Thereafter, when the thin film layer was irradiated with ultraviolet rays, silver ions in the thin film were reduced to form fine particles (such as a wound dressing), and the thin film layer was colored yellow. A TEM (transmission electron microscope) photograph of this thin film layer is shown in FIG.

[Comparative Example 1]
Except for the step of coating a polyethylene terephthalate mesh sheet (PET mesh, manufactured by Semitex Co., Ltd., PES45), a thin film layer (chitosan, alginic acid) was formed on the substrate (polyethylene terephthalate substrate) in the same manner as in Example 1. An alternating laminated film) and a soluble support layer (polyvinyl alcohol in which riboflavin sodium phosphate was dissolved) were sequentially laminated to form a sheet. From this sheet, the PET film of the substrate was peeled off, the thin film layer was exposed, brought into contact with the skin surface, and bonded. Then, it was made to melt | dissolve, dripping water on the polyvinyl alcohol layer which is a soluble support layer which faced the surface. After 3 minutes, a part of the thin film layer was transferred to the skin surface, but most of the thin film layer fell off the skin surface together with the polyvinyl alcohol layer.

[Comparative Example 2]
The same operation as in Example 1 was performed except that the step of dissolving riboflavin sodium phosphate in the soluble support layer was omitted.

"Evaluation method (confirmation of thin film layer by UV irradiation)"
The thin film layer transferred onto the skin was irradiated with ultraviolet rays (256 nm), and if the state of light emission from the thin film layer could be confirmed, it was evaluated as “◯”, and otherwise it was evaluated as “X”.

"Evaluation method (confirmation of thin film layer by visual inspection)"
If the thin film layer transferred onto the skin could be confirmed visually, it was evaluated as “◯”, and if not, it was evaluated as “x”.
Tables 1 and 2 summarize the evaluation results of Examples 1 and 2 and Comparative Example 2.

  Example 1 is an example in which sodium riboflavin phosphate is blended as a cosmetic, and Comparative Example 2 is an example in which no riboflavin is blended. In any example, it is difficult to visually confirm, but in Example 1 in which riboflavin sodium phosphate was blended, its presence can be confirmed by applying ultraviolet rays. Thus, it can be made inconspicuous at the time of sticking, but it is inconvenient to know its existence. Presence after pasting when other active ingredients are blended with this can be confirmed by ultraviolet irradiation as shown in this Example. FIG. 2 shows photographs of Example 1 before and after UV irradiation. The thin film layer can be confirmed by ultraviolet irradiation.

  Example 2 is an example in which a very small amount of methylene blue is blended as a pigment, and Comparative Example 2 is an example in which no blending is performed. In Example 1, an ultraviolet irradiation device is required for confirming the thin film layer, but in Example 2 in which a pigment is blended, it is not noticeable, but since it is colored light blue, its presence should be visually confirmed everywhere. Can do. By adjusting the blending, a thin film layer that is less noticeable, uncomfortable, and can be visually confirmed can be obtained.

Claims (11)

A sheet comprising a substrate, a thin film layer, a soluble support layer, and a permeable substrate, wherein the soluble support layer comprises a water-soluble or alcohol-soluble polymer film, and the thin film layer comprises a polycation. and a layer comprising, and a B layer comprising a polyanion, wherein the soluble support layer (a) a drug, (b) a cosmetic, (c) dye, viewed contains any of (d) a metal ion, the thin film A thin film transfer sheet having a layer thickness of 1 to 300 nm .   The thin film transfer sheet according to claim 1, wherein the permeable substrate has a fibrous, mesh, or porous structure.   The thin film transfer sheet according to claim 1 or 2, wherein the thin film layer has a thickness of 40 nm or more and 300 nm or less.   The thin film transfer sheet according to any one of claims 1 to 3, wherein the thin film layer is formed by alternately laminating A layers containing polycations and B layers containing polyanions.   The thin film as described in any one of Claims 1-4 in which a thin film layer has A layer formed using the solution containing a polycation, and B layer formed using the solution containing a polyanion. Transfer sheet.   The thin film transfer sheet according to any one of claims 1 to 5, wherein the polycation is a cationic polymer having two or more amino groups in one molecule.   The thin film transfer sheet according to any one of claims 1 to 6, wherein the polyanion is an anionic polymer having two or more carboxyl groups or carboxylate groups in one molecule.   The thin film transfer sheet according to any one of claims 1 to 7, which is used for skin bonding.   The thin film transfer sheet according to any one of claims 1 to 7, which is used for makeup. Contacting the substrate with a solution containing a polycation or a solution containing a polyanion to form a layer derived from the polycation or polyanion on the surface of the substrate;
(I) contacting a polyanion solution with a layer derived from a polycation to form a layer derived from a polyanion on the layer derived from the polycation;
(Ii) a step of bringing a polycation-containing solution into contact with a layer derived from a polyanion to form a layer derived from a polycation on the layer derived from the polyanion; and the steps of (i) and (ii) A step of forming a thin film layer that is alternately laminated, a step of forming a soluble support layer on the thin film layer, and a step of forming a permeable base material on the soluble support layer. Including
The soluble support layer is made of a water-soluble or alcohol-soluble polymer film, and the soluble support layer is any one of (a) a drug, (b) a cosmetic, (c) a dye, and (d) a metal ion. unrealized, the thickness of the thin film layer is 1 to 300 nm, a manufacturing method of the thin film transfer sheet.   The method for producing a thin film transfer sheet according to claim 10, wherein in the step of forming the thin film layer, the number of times of repeating the steps (i) and (ii) alternately is 1 to 300 times.

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