JP6409253B2 - Nano thin film transfer sheet, method for producing nano thin film transfer sheet, and method for transferring nano thin film layer to adherend - Google Patents

Description

  The present invention relates to a nano thin film transfer sheet, a method for producing a nano thin film transfer sheet, and a method for transferring a nano thin film layer of a nano thin film transfer sheet to an adherend.

  In recent years, a nano thin film transfer sheet for attaching a nano thin film layer to an organ, skin or the like has attracted attention. For example, a nano thin film transfer sheet for medical use, which is affixed to the skin surface or organ wound surface as a wound dressing material, has been proposed (for example, see Non-Patent Document 1).

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

  When producing a conventional nano thin film transfer sheet, it tends to take time to form a nano thin film layer having a desired film thickness, shortening the work time, and producing the nano thin film transfer sheet more efficiently. Is desired.

  Therefore, the present invention provides a nano thin film transfer sheet having a nano thin film layer formed with high work efficiency, and a method for producing a nano thin film transfer sheet that can shorten the formation time of the nano thin film layer and has excellent transferability. For the purpose. Another object of the present invention is to provide a method for transferring a nano thin film layer of the nano thin film transfer sheet to an adherend.

The present invention relates to a nano thin film transfer sheet comprising: [1] a permeable base material that is a base material that can permeate or permeate a solvent; and a nano thin film layer containing plant chitosan.
The present invention also relates to a nano thin film transfer sheet comprising [2] a permeable base material that is a base material that can permeate or permeate a solvent, and a nano thin film layer containing chitosan containing β-glucan.
Further, according to the present invention, [3] the nano thin film layer has an A layer formed using a solution containing a polycation, and a B layer formed using a solution containing a polyanion, It relates to the nano thin film transfer sheet according to the above [1] or [2], wherein the cation contains plant chitosan or chitosan containing β-glucan.
The present invention also relates to the nanothin film transfer sheet according to the above [3], wherein the [4] nanothin film layer is a layer in which A layers and B layers are alternately laminated.
The present invention also relates to the nanothin film transfer sheet according to the above [1], [3] or [4], wherein [5] plant chitosan contains β-glucan.
Moreover, the present invention provides [6] the nano thin film according to any one of [3] to [5], wherein the polyanion is an anionic polymer having two or more carboxyl groups or carboxylate groups in one molecule. It relates to a transfer sheet.
Moreover, this invention is described in any one of said [1]-[6] provided with a [7] 1st permeable base material, a nano thin film layer, and a 2nd permeable base material in this order. The present invention relates to a nano thin film transfer sheet.
Moreover, this invention relates to the nano thin film transfer sheet in any one of said [1]-[7] further provided with the soluble support layer soluble in [8] solvent.
In addition, the present invention includes any one of the above [1] to [6], comprising [9] a permeable substrate, a soluble support layer soluble in a solvent, a nano thin film layer, and a cover film in this order. The present invention relates to a nano thin film transfer sheet as described above.
[10] The nano thin film transfer according to [8], wherein the nano thin film layer and the soluble support layer are provided between the first permeable substrate and the second permeable substrate. Regarding the sheet.
Moreover, this invention is equipped with a nano thin film layer and a soluble support layer in this order from the 1st permeable base material side between the [11] 1st permeable base material and the 2nd permeable base material. And the nanothin film transfer sheet according to [10] above.
In addition, the present invention includes [12] a soluble support layer and a nano thin film layer in this order from the first permeable substrate side between the first permeable substrate and the second permeable substrate. And the nanothin film transfer sheet according to [10] above.
The present invention also provides [13] a first soluble support layer, a nano thin film layer, and a second soluble support layer between the first permeable substrate and the second permeable substrate. It is related with the nano thin film transfer sheet as described in said [10] provided in this order from the 1st permeable base material side.
Moreover, this invention is [14] any one of said [10]-[13] from which a 1st permeable base material and a 2nd permeable base material mutually differ in the contact area with an adjacent layer. It relates to the described nano thin film transfer sheet.

[15] The nano-nano thin film transfer sheet according to any one of [1] to [14], wherein the [15] permeable substrate is a mesh sheet, a nonwoven fabric sheet, or a sheet having a porous structure. About.
The present invention also relates to the nanothin film transfer sheet according to any one of the above [8] to [15], wherein the [16] soluble support layer is a polymer layer soluble in water or alcohol.
Moreover, this invention relates to the nano thin film transfer sheet in any one of said [1]-[16] whose thickness of a [17] nano thin film layer is 1 nm-300 nm.
Moreover, this invention relates to the nano thin film transfer sheet in any one of said [1]-[17] whose [18] nano thin film layer is an object for skin sticking.
Moreover, this invention relates to the thin film transfer sheet in any one of said [1]-[18] whose [19] nano thin film layer is for cosmetics.

Furthermore, the present invention includes [20] a step of bringing a cover film into contact with a solution containing a polycation or a solution containing a polyanion, and forming a layer derived from the polycation or polyanion on the surface of the cover film; Contacting a layer derived from a cation with a polyanion solution to form a layer derived from a polyanion on a layer derived from a polycation; and (ii) contacting a solution containing a polycation with a layer derived from a polyanion. A step of repeatedly forming a layer derived from a polycation on a layer derived from a polyanion, a step of forming a first nanothin film layer, and a first dissolution on the first nanothin film layer. A first substrate which is a substrate capable of penetrating or permeating a solvent capable of dissolving the first soluble support layer on the first soluble support layer. And forming a-permeable substrate, a polycation contains chitosan containing vegetable chitosan or β-glucan, the method for producing a nano thin film transfer sheet.
In addition, the present invention provides [21] a side where the cover film is peeled off from the first nano thin film layer after the step of forming the first permeable substrate, and the cover film of the first nano thin film layer is peeled off. The nanothin film transfer according to the above [20], further comprising a step of laminating a laminate comprising the second permeable substrate, the second soluble support layer, and the second nanothin film layer in this order. The present invention relates to a sheet manufacturing method.
Moreover, this invention is the side by which the cover film of the 1st nano thin film layer was peeled from the 1st nano thin film layer after the process of forming a [22] 1st permeable base material. Furthermore, it is related with the manufacturing method of the nano thin film transfer sheet as described in said [21] which further includes the process of bonding a 2nd permeable base material.
[23] The nanothin film transfer according to any one of [20] to [22], further comprising a step of allowing the solvent to penetrate or permeate the permeable substrate and dissolving the soluble support layer. The present invention relates to a sheet manufacturing method.
Moreover, this invention is described in any one of said [20]-[23] which repeats step (i) and step (ii) 1 to 300 times alternately in the process of forming a [24] nano thin film layer. The present invention relates to a method for producing a nano thin film transfer sheet.
The present invention includes [25] a step of attaching the nano thin film transfer sheet according to any one of [1] to [19] to an adherend so that the nano thin film layer is in contact with the adherend. The present invention relates to a method for transferring a nano thin film layer to an adherend.

  According to the present invention, a nano thin film transfer sheet having a nano thin film layer formed with high work efficiency, and a method for producing a nano thin film transfer sheet that can shorten the formation time of the nano thin film layer and have excellent transferability are provided. Can do. Moreover, according to this invention, the transfer method to the to-be-adhered body of the nano thin film layer of the said nano thin film transfer sheet can be provided.

It is a schematic cross section which shows one Embodiment of a nano thin film transfer sheet. It is a schematic cross section which shows another embodiment of a nano thin film transfer sheet. It is a schematic cross section which shows another embodiment of a nano thin film transfer sheet. It is a schematic cross section which shows one Embodiment of the manufacturing method of a nano thin film transfer sheet.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. The dimensional ratio is not limited to the illustrated ratio.

  The nano thin film transfer sheet of this embodiment is characterized by comprising a permeable base material which is a base material that can permeate or permeate a solvent, and a nano thin film layer containing plant chitosan. Moreover, the nano thin film transfer sheet of this embodiment is characterized by comprising a permeable base material that is a base material that can permeate or permeate a solvent, and a nano thin film layer containing chitosan containing β-glucan.

  The nano thin film transfer sheet can comprise one or two permeable substrates. FIG. 1 is a schematic cross-sectional view showing an embodiment of a nano thin film transfer sheet. As shown in FIG. 1, the nano thin film transfer sheet 1 may include a first permeable substrate 2a, a nano thin film layer 3, and a second permeable substrate 2b in this order.

  (A), (b), and (c) of FIG. 2 are schematic cross-sectional views each showing another embodiment of the nano thin film transfer sheet. As shown in FIG. 2A, the nano thin film transfer sheet 11 includes a first permeable substrate 12a, a first soluble support layer 14a, a nano thin film layer 13, and a second soluble support layer. 14b and the second permeable base material 12b may be provided in this order. Further, as shown in FIG. 2B, the nano thin film transfer sheet 21 includes a first permeable base material 22a, a soluble support layer 24, a nano thin film layer 23, and a second permeable base material 22b. And may be provided in this order. Moreover, as shown in FIG.2 (c), the nano thin film transfer sheet 31 is the 1st permeable base material 32a, the nano thin film layer 33, the 2nd soluble support layer 34, and 2nd permeable property. The base material 32b may be provided in this order.

  FIG. 3 is a schematic cross-sectional view showing still another embodiment of the nano thin film transfer sheet. As shown in FIG. 3, the nano thin film transfer sheet 41 may include a permeable base material 42, a soluble support layer 44, a nano thin film layer 43, and a cover film 45 in this order.

[Nano thin film layer]
Since the nano thin film layer has the above-described configuration, it is excellent in handleability, toughness (mechanical strength), transparency and moisture retention, and has self-adhesiveness to an adherend (for example, skin). For this reason, sticking to an adherend is very easy, and further, the nano thin film layer after sticking to the adherend is hardly noticeable, and the uncomfortable feeling after sticking is reduced. In addition, as a material for forming the nano thin film layer, a material having high biodegradability or biocompatibility can be used. In this case, the nano thin film layer has an advantage that it is highly safe and hardly causes skin allergy.

  The nano thin film layer includes plant chitosan or chitosan containing β-glucan. Plant chitosan is a deacetylated product of plant chitin extracted from basidiomycetes such as mushrooms, enoki mushrooms, shiitake mushrooms, mitakeagaricus blazei, nameko, eringi, shimeji.

  The degree of deacetylation of plant chitosan is preferably in the range of 40 to 100%, more preferably in the range of 45 to 90%, because bioabsorbability and water solubility are more excellent. More preferably, it is in the range of 50 to 80%.

  One difference between plant chitosan and animal chitosan is that it contains a large amount of β-glucan. Therefore, as one method for identifying chitosan used in the present embodiment from the viewpoint of chemical structure, , Β-glucan can also be included. The plant chitosan used in this embodiment is preferably purified to a high purity, but usually contains a detectable amount of β-glucan.

  The nano thin film layer according to the present embodiment may include an A layer formed using a solution containing a polycation and a B layer formed using a solution containing a polyanion.

  The nano thin film layer is preferably a layer in which A layers and B layers are alternately laminated (alternate laminated thin film). By alternately laminating the A layer and the B layer, a nano thin film layer having superior mechanical strength and self-adhesiveness is obtained. In addition, it is not restricted to the case where A layer and B layer are laminated alternately, but it is not limited to the case where one layer A layer and one layer B layer are laminated alternately, a layer composed of a plurality of A layers, This includes the case where a plurality of B layers are alternately stacked.

(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 and an ethylamino group; a dialkylamino group such as a dimethylamino group and a diethylamino group; an imino group and a guanidino group. The amino group may be —NH ₃ ⁺ in which a proton is coordinated.

  The polycation according to the present embodiment contains vegetable chitosan. When the polycation contains plant chitosan, it is possible to increase the thickness of the nano thin film layer and shorten the formation time of the nano thin film layer. The amino group in plant chitosan corresponds to the cationic group.

  Plant chitosan may be composed only of chitosan components, and may contain other components such as β-glucan and complex carbohydrates. The purity of the vegetable chitosan is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more.

  The molecular weight of plant chitosan is not particularly limited, but as the viscosity average molecular weight increases, the viscosity of the solution containing the polycation increases, so that it tends to be difficult to cast and stack when forming the nano thin film layer. . Further, when the adherend is a living body, if the viscosity average molecular weight of the plant chitosan is large, the bioabsorbability tends to be lowered. The viscosity average molecular weight of the vegetable chitosan is preferably in the range of 1,000 to 500,000, more preferably in the range of 10,000 to 400,000, and 50,000 to 200,000. More preferably within the range.

  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.

  The polycation may contain a polycation other than vegetable chitosan. A cationic polymer can be used as the polycation. 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, and polydivinylpyridine; and salts thereof (hydrochloride, acetate, etc.), polyethyleneimine, polyallylamine hydrochloride, polydiallyldimethylammonium chloride, and the like And derivatives thereof.

  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.

  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 weight compound having two or more cationic groups in one molecule include low molecular weight diamines and polyamines. Specific examples of such polycations include compounds having two amino groups in one molecule such as diaminoalkanes such as diaminoethane, diaminopropane, diaminobutane, diaminopentane, and diaminohexane, and the like. Of mono- or dilysylaminoalkanes such as-(lysyl) -diaminoethane, N, N '-(dilysyl) -diaminoethane, N- (lysyl) -diaminohexane, N, N'-(dilysyl) -diaminohexane Examples thereof include compounds having 3 to 4 amino groups in one molecule and compounds having 5 or more amino groups in one molecule.

(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 still more 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.

  A polycation other than vegetable chitosan (or chitosan containing β-glucan) may be used in combination with 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.

  As the solution containing a polycation, a solution obtained by dissolving a polycation in a solvent can be used as it is. For example, the pH of the solution containing the polycation can be 1.2 to 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.

  Examples of the derivative of acidic polysaccharide include alginic acid ethylene glycol ester, alginic acid propylene glycol ester, hyaluronic acid ethylene glycol ester and hyaluronic acid propylene glycol ester. 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 of acidic polysaccharide is preferably in the range of 40 to 100%, more preferably in the range of 45 to 90%, and in the range of 50 to 80%. Further preferred.

  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; and 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 containing the polyanion increases. Therefore, it tends to be difficult to cast and laminate when forming the nano thin film layer. Further, when the adherend is a living body, if the viscosity average molecular weight of the anionic polymer is large, the bioabsorbability tends to decrease. 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, and in the range of 50,000 to 200,000. More preferably, it is within.

  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.

(Solution containing polyanion)
The concentration of the polyanion in the solution containing the polyanion is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 2.0% by mass, and still more preferably 0.05 to 1.0% by mass.

  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.

  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 pH of the solution containing the polyanion is preferably 1.6 to 5.4, but is more preferably in the range of 1.8 to 5.0 because it is more excellent in solubility of the polyanion. More preferably, it is in the range of 0 to 4.5, and particularly preferably in the range of 2.5 to 4.0.

  The pH of the solution containing the polyanion can be adjusted, for example, by adding an organic acid such as acetic acid, propionic acid, succinic acid, malonic acid, oxalic acid or malic acid, or an inorganic acid such as hydrochloric acid, sulfuric acid or nitric 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. Specifically, 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.

  When the nano thin film layer is formed by alternately laminating the A layer and the B layer, the number of laminated layers is not particularly limited. Each of the A layer and the B layer is preferably 1 to 300 layers because it tends to ensure the transparency of the nano thin film layer. In addition, since the nano thin film layer tends to have a film thickness having self-adhesiveness, each of the A layer and the B layer is more preferably 10 to 100 layers, and preferably 20 to 80 layers. Is more preferable.

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

  The thickness of the nano thin film layer of this embodiment is not particularly limited. Since the properties such as self-adhesion, water absorption, and flexibility in a dry state become more excellent, the thickness of the nano thin film layer is preferably in the range of 1 to 300 nm, and preferably 40 to 300 nm. More preferably, it is particularly preferably in the range of 40 to 250 nm, and most preferably in the range of 40 to 200 nm.

  The said nano thin film layer can be used conveniently also as a nano thin film layer for skin sticking, a cosmetic nano thin film layer, or a nano thin film layer for cosmetic skin sticking.

[Solubility support layer]
In the present embodiment, the soluble support layer is not limited as long as it is soluble in a solvent, but considering the irritation to the skin, it is a layer made of a film formed from a polymer soluble in water or alcohol. It is preferable that The soluble support layer may be a layer soluble in a weakly alkaline or weakly acidic aqueous solution. That is, the soluble support layer is a soluble support membrane.

  Examples of polymers soluble in water or alcohol include polyelectrolytes such as polyacrylic acid and polymethacrylic acid; polyethylene glycol, polyacrylamide, polyvinyl alcohol, polyvinyl alcohol derivatives, polysaccharides such as starch and cellulose acetate, etc. Nonionic water-soluble polymers, such as novolac or poly (N-alkyl cyanoacrylate).

  The viscosity average molecular weight of the polymer forming the soluble support layer (soluble support film) is usually preferably from 1 to 1,000,000, more preferably from 5,000 to 500,000.

  In the present embodiment, it is more preferable to use polyvinyl alcohol or a derivative thereof as a polymer that is soluble in water or alcohol. When polyvinyl alcohol is used, the average degree of polymerization is preferably from 100 to 2,000, more preferably from 200 to 1,000, from the viewpoint of film-forming properties and solubility in a solvent. Here, the average degree of polymerization can be measured based on a method defined in JIS K 6726.

  In addition, the film thickness of the soluble support layer is preferably in the range of 1 to 100 μm, more preferably in the range of 2 to 50 μm, from the viewpoint of peelability from the nano thin film layer and bonding properties. More preferably, it is in the range of 5 to 20 μm.

[Penetration substrate]
The material of the permeable base material is not limited as long as it is selected from those insoluble in the solvent that dissolves the soluble support layer. However, the permeable base material is a base material having a function of permeating or permeating the solvent. The permeable substrate preferably has pores through which the solvent permeates or permeates, and more preferably has a nonwoven fabric, a fibrous shape, a mesh shape, or a porous structure. More preferably, the permeable substrate is a mesh cloth in which a thread-like material having a diameter of 100 μm or less is knitted in a lattice shape, or a composite product of a mesh cloth and a nonwoven fabric. The permeable substrate is preferably in the form of a sheet (film) from the viewpoint of handleability and availability.

  Examples of the mesh cloth include polyester mesh cloth, nylon mesh cloth, carbon mesh cloth, fluororesin mesh cloth, polypropylene mesh cloth, silk mesh cloth, and a composite product of these mesh cloth and nonwoven fabric. Among these, polyester mesh cloth, nylon mesh cloth, and polypropylene mesh cloth are preferable, and polyester mesh cloth is more preferable. Examples of the polyester mesh cloth include a polyethylene terephthalate mesh cloth.

Mesh cloth of the air gap, from the viewpoint of transferability, breathable by Frazier method described in JIS L 1096, is preferably 10~100000cc ^/ cm 2 · sec, at 100~50000cc ^/ cm 2 · sec More preferably, it is more preferably 1000 to 10000 cc / cm ² · sec.

  From the viewpoint of transferability, the mesh cloth opening is preferably 1 to 300 μm, more preferably 2 to 200 μm, and still more preferably 5 to 150 μm. Moreover, it is preferable that it is 5-45% from a viewpoint which permeate | transmits or permeate | transmits a solvent, and, as for the opening rate of a mesh sheet, it is more preferable that it is 5-40%.

  In the nano thin film transfer sheet, when the first permeable substrate and the second permeable substrate are used as the permeable substrate, the first permeable substrate and the second permeable substrate are adjacent to each other. The contact areas with the layers are preferably different from each other. In this case, when the nano thin film transfer sheet is used, the permeable substrate having the smaller contact area can be easily peeled from the nano thin film layer.

  The film thickness of the permeable substrate according to the present embodiment is preferably 1 to 500 μm, more preferably 3 to 300 μm, and further preferably 5 to 200 μm from the viewpoint of followability and handleability. preferable.

[Cover film]
The cover film is not particularly limited as long as it has a smooth surface, and may be a sheet shape or a roll shape. The cover film 8 may be either a thermoplastic resin or a thermosetting resin, such as polyethylene (high density, medium density or low density), polypropylene (isotactic or syndiotactic type), polybutene, ethylene. -Polypropylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyolefin such as ethylene-propylene-butene copolymer, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamide Acrylic resins such as imide, polycarbonate, poly- (4-methylbenten-1), ionomer, polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, Chill (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 precyclohexane terephthalate (PCT), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, others Various types of thermoplastic elastomers such as fluorine-based resin, styrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, fluororubber-based, chlorinated polyethylene-based, epoxy resin, phenolic resin, urea resin, melamine resin, unsaturated polyester, Examples thereof include cellulose resins such as silicone resin, polyurethane, nylon, nitrocellulose, cellulose acetate, and cellulose acetate propionate, and copolymers, blends, and polymer alloys mainly composed of these. One or two or more of these can be used in combination (for example, as a laminate of two or more layers).

  Among these resin films, plastic films such as polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PC) are preferably used. A polyethylene terephthalate (PET) film is more preferable because it is more excellent in the adhesion of the laminated film.

  Further, the surface of the cover film 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.

  In the cover film, a resin film, an inorganic film, or a film containing an organic material and an inorganic material (organic-inorganic film) may be laminated on the cover film. 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 cover film can also function as a base material for forming the nano thin film 6. The cover fill 8 may be formed as a multilayer nano thin film transfer sheet by forming the nano thin film 6 on both surfaces thereof, and providing the soluble support 4 and the permeable group 2 on each of the formed nano thin films 6. it can. This is convenient because the nano thin films 6 formed on both sides of the cover fill 8 can be used. Hereinafter, the cover film may be referred to as a “base material”.

  The film thickness of the cover fill 8 is preferably in the range of 1 to 500 μm, more preferably in the range of 3 to 300 μm, and still more preferably in the range of 5 to 200 μm.

[Production method of nano thin film transfer sheet]
The manufacturing method of the nano thin film transfer sheet of this embodiment is demonstrated. FIG. 4 is a schematic cross-sectional view showing an embodiment of a method for producing a nano thin film layer transfer sheet. The method for producing a nano thin film transfer sheet comprises a step of contacting a cover film with a solution containing a polycation or a solution containing a polyanion, and forming a layer derived from the polycation or polyanion on the surface of the cover film; Contacting a layer derived from a cation with a polyanion solution to form a layer derived from a polyanion on a layer derived from a polycation; and (ii) contacting a solution containing a polycation with a layer derived from a polyanion. A step of repeatedly forming a layer derived from a polycation on a layer derived from a polyanion, a step of forming a first nanothin film layer, and a first dissolution on the first nanothin film layer. A base material capable of permeating or permeating a solvent for dissolving the first soluble support layer on the first soluble support layer. And forming a permeable substrate, the.

(Nano thin film layer formation process)
As shown in FIG. 4A, the nano thin film layer 3 a is formed on a base material that becomes the cover film 5. The nano thin film layer 3a includes, for example, a base material (cover film), a solution containing a polycation (hereinafter also referred to as “solution A”), and a solution containing a polyanion (hereinafter also referred to as “solution B”). From Langmuir, Vol. 13, pp. 6195-6203, (1997).

  Specifically, the manufacturing method of the nano thin film layer 3a according to the present embodiment is caused by bringing a base material that will later become the cover film 5 into contact with the solution A or the solution B, and originating from a polycation or a polyanion on the surface of the base material. A step of forming a layer (layer formation step), and (i) a step of bringing the solution B into contact with the layer derived from polycation to form a layer derived from polyanion on the layer derived from polycation; ii) contacting the solution A with the layer derived from the polyanion to form a layer derived from the polycation on the layer derived from the polyanion, and repeatedly forming a nano thin film layer. Is preferred. The polycation includes plant chitosan (or chitosan containing β-glucan).

  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 nano thin film 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 to bring the substrate into the surface of the substrate. A layer derived from a polyanion 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 step of forming the nano thin film layer, 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 process of forming the nano thin film layer, the number of times of repeating step (i) and step (ii) is not particularly limited, but is derived from polycation because it tends to ensure the transparency of the nano thin film layer. It is preferable to repeat until both the layer and the layer derived from the polyanion become 1 to 300 layers. In addition, since the nano thin film layer tends to have a film thickness that has a self-adhesive property, it is repeated until both the layer derived from the polycation and the layer derived from the polyanion become 10 to 100 layers. More preferably, it is particularly preferable to repeat until it becomes 20 to 80 layers. In addition, the film thickness of a nano thin film layer is controllable by controlling the repetition frequency in the process of forming a nano thin film layer.

  In the alternate lamination method, it is preferable that the step of forming the nano thin film layer ends with step (ii) rather than ends with step (i). Thereby, it becomes easy to express the antibacterial property which is the characteristic of chitosan used as a polycation.

  In the manufacturing method described above, the contact surface is rinsed after the contact between the substrate, the polycation-derived layer or the polyanion-derived layer, and the solution A or the solution B in the layer forming step or the nano thin film layer forming step. It is preferable to do. 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 production method described above, it is preferable to contact the substrate, the layer derived from the polycation or the layer derived from the polyanion by immersing them in the solution A or the solution B (hereinafter also referred to as “alternating immersion method”). . 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 step of forming the nano thin film layer, a layer derived from a polycation (or a layer derived from a polyanion) ) Is preferably contacted by immersing in solution B (or 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 by an alternate dipping method, J.A. 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 alternating 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 the case where the nano thin film layer is formed by using the alternate dipping method, the solution containing the polyanion preferably has a pH of 1.6 to 5.4 from the viewpoint that the alternate anodization can be efficiently performed.

  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 nano thin film layer of the present embodiment may be produced by forming an alternate laminated film by a spin coating method in which the solution A or the solution B is dropped or sprayed on a substrate. 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.

  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 reduced by removing the counter ion of the cation group or the anion group in the salt, a nano thin film layer is formed. Then, the mechanical strength of the nano thin film layer can be improved by removing the counter ions contained in the nano thin film layer. 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.

(Formation process of soluble support layer)
Next, as shown in FIG. 3B, a soluble support layer 4a is formed on the surface of the nano thin film layer 3a opposite to the surface on which the cover film 5 is provided.

  The soluble support layer 4a is obtained by applying a polymer solution dissolved in water or alcohol on the nano thin film layer 3a formed on the cover film 5, and usually 10 minutes to 24 hours, preferably 1 hour to 12 hours. It can be formed by removing water or alcohol by drying for a period of time.

  Examples of the method for applying the polymer solution onto the nano thin film layer 3a include, but are not limited to, a casting method and a spin coating method. The soluble support layer 4a can also be formed using a bar coater or a roll coater.

  Although there is no restriction | limiting in particular in the density | concentration of the polymer melt | dissolved in the said water or alcohol, 1-40 mass% is preferable from a coating property viewpoint, 2-30 mass% is more preferable, 5-20 mass% is still more preferable. 5-10 mass% is especially preferable.

  The soluble support layer (soluble support film) 4a can be peeled together with the nano thin film layer 3a from the cover film 5 using tweezers or the like. At this time, the nano thin film layer 3a is dissolved and supported at the same time as peeling by a secondary bonding force such as electrostatic interaction, hydrogen bonding, van der Waals force, etc. generated between the soluble support layer 4a and the nano thin film layer 3a. It becomes possible to transfer to the layer 4a.

(Formation process of permeable substrate)
As shown in FIG.4 (c), the permeable base material 2a can be formed by laminating | stacking the material which permeate | transmits or permeate | transmits the solvent which melt | dissolves the soluble support layer 4a on the soluble support layer 4a. Although the formation method of the permeable base material 2a is not specifically limited, Methods, such as a lamination, can be used. The permeable substrate 2a may be laminated on the soluble support layer 4a after removing the cover film 5.

  The nano thin film transfer sheet of this embodiment has good handleability because it uses a permeable substrate. In addition, since the nano thin film layer is a nanometer-sized thin film layer, the nano thin film layer is also suitable for fine grooves (for example, skin wrinkles or fine irregularities on the skin) of the adherend, and the nano thin film layer is pasted. The feeling of strangeness when attached can be reduced. Moreover, when a nano thin film layer is transparent, a sticking location becomes inconspicuous. When the adherend is skin, since it has self-adhesion to the skin, it is not necessary to use an adhesive (adhesive), and rash or rough skin due to the adhesive can be reduced. When a biodegradable or biocompatible polymer is used for the nano thin film layer, there is an advantage that skin allergy is hardly caused when it is applied to the skin, and it does not adversely affect the environment after disposal.

(Nano thin film transfer sheet forming process)
Then, as shown in FIG.4 (d), a cover film is removed from the laminated body obtained at the formation process of the permeable base material, the 1st permeable base material 2a, the 1st soluble support layer 4a. And a laminate including the first nano thin film layer 3a in this order, and a laminate including the second permeable substrate 2b, the second soluble support layer 4b, and the second nano thin film layer 3b in this order. To do. The nano thin film layers 3a and 3b of these laminates are bonded together. As a result, as shown in FIG. 4 (e), the first permeable substrate 2a, the first soluble support layer 4a, the nano thin film layer 3, the second soluble support layer 4b, Thus, a nano thin film layer transfer sheet 11 having two permeable base materials 2b in this order is obtained (FIG. 2A).

  In this step, only the second permeable substrate 2b is used instead of the laminate including the second permeable substrate 2b, the second soluble support layer 4b, and the second nano thin film layer 3b in this order. May be bonded to the first nano thin film layer 3a. In this case, the nano thin film transfer sheet 21 of FIG. 2B is obtained. Moreover, it replaces with the laminated body provided with the 1st permeable base material 2a, the 1st soluble support layer 4a, and the 1st nano thin film layer 3a in this order, and only the 1st permeable base material 2a is 2nd. It may be bonded to the nano thin film layer 3b. In this case, the nano thin film transfer sheet 31 of FIG. 2C is obtained.

(Removal process of soluble support layer)
Subsequently, as shown in FIG. 4F, the nano thin film transfer sheet is immersed in a solvent 6 such as water or alcohol for dissolving the soluble support layers 4a and 4b. Thereby, as schematically shown by arrows in FIG. 2 (f), the permeable base materials 2 a and 2 b permeate or permeate the solvent 6, so that the soluble support layers 4 a and 4 b are dissolved in the solvent 6. Therefore, the nano thin film transfer sheet 1 (FIG. 1) from which the soluble support layers 4a and 4b have been removed is obtained.

[Storage of nano thin film transfer sheet]
Since the nano thin film transfer sheet is desirably stored in an environment with little water vapor, it is desirable to store the nano thin film transfer sheet using a packaging material having a water vapor barrier property and a drying material.

(Packing material)
Even if the packaging material has a water vapor barrier property, it does not transmit water vapor at all, and a slight water permeation is inevitable, so it is more effective to keep the humidity inside the packaging material constant by adding a desiccant. It is.

  The performance of a packaging material having a water vapor barrier property is represented by a water vapor transmission rate. The smaller this value is, the better the water vapor barrier property is and it is suitable for packaging of the nano thin film transfer sheet, while the one having a low water vapor permeability is expensive.

Considering these, the water vapor transmission rate of the packaging material having a water vapor barrier property is 1.5 g / m ² · day (temperature 40 ° C., humidity 90% RH) or less, and the water vapor transmission rate of the nano thin film transfer sheet is 1 Packing is performed with a packing material having a water vapor barrier property of 5 g / m ² · day (temperature 40 ° C., humidity 90% RH) or less.

  If the water vapor transmission rate is larger than this, water penetration into the packing material increases, and it becomes difficult to suppress melting of the soluble support layer, and the burden on the desiccant increases, resulting in a deterioration in economic efficiency.

As a material satisfying such a water vapor transmission rate, an aluminum vapor deposition film (water vapor transmission rate of about 0.7 to 1.0 g / m ² · day (temperature 40 ° C., humidity 90% RH)), SiO vapor deposition film (water vapor transmission rate) Transmittance 0.1 to 0.7 g / m ² · day (temperature 40 ° C., humidity 90% RH)), alumina vapor deposition film (water vapor permeability 1.5 g / m ² · day (temperature 40 ° C., humidity 90%) RH) grade).

In addition, as a packaging material having a water vapor barrier property, a laminate film composed of a base film, a barrier layer, and a heat seal layer has been proposed. As the barrier layer, aluminum, nickel, titanium, magnesium are proposed. Etc. are used. In addition, the water-vapor-permeation rate of the polyethylene film which is an example of a base film is 10-20 g / m < ² > * day (temperature 40 degreeC, humidity 90% RH).

  In this embodiment, it is preferable that the nano thin film transfer sheet is packed in a plurality of layers with a plurality of packing materials, and a packing material having a water vapor barrier property is used for at least one other than the innermost layer.

(Dry material)
In the nano thin film transfer sheet product of the present embodiment, it is preferable to put a desiccant inside the packaging material having a water vapor barrier property. Moreover, it is preferable to maintain the humidity in the packaging material in an atmosphere of 70% RH or less.

  Examples of the desiccant to be put in the packing material include calcium chloride, quicklime, silica gel, and aluminosilicate. From the viewpoint of guaranteeing product quality, silica gel and aluminosilicate that do not cause deliquescence (liquefaction due to moisture absorption) are preferable.

  The amount of the desiccant used is determined according to the ability of the desiccant so as to absorb the amount of moisture permeation predicted from the hydrogen barrier property and the storage days of the packaging material to be combined.

  The operation of packing the nano thin film transfer sheet in a packing material is preferably performed in a low temperature and low humidity atmosphere, and the initial atmosphere in the packing material is preferably set to a low temperature and low humidity. A preferred atmosphere is specifically a temperature of 18 to 22 ° C. and a humidity of 30 to 50% RH. This is especially important when no desiccant is used.

[Other ingredients]
The nano thin film layer and the soluble support layer according to this 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 derivatives thereof, riboflavin sodium phosphate, riboflavin, hydroquinone, liponucleic acid and salts thereof , Amino acids and derivatives thereof, various plant extracts, and various animal-derived extracts.

  The nano thin film layer and the soluble support layer according to this embodiment can also hold a dye. Thereby, when it affixes on skin (at the time of use), an affixing position can be confirmed.

  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, Gossy Paul, Cochineal. Among these, ionic dyes are preferable because they dissolve in water and alcohol.

  Metal ions can also be held in the nano thin film layer and the soluble support layer according to the present embodiment. Thereby, when affixed to the skin (during use), the metal ions are gradually eluted from the nano thin film layer and can be gradually absorbed by the skin. In addition, by using metal ions, a nano thin film layer having effects such as antibacterial, sterilizing, deodorizing, and antiperspiring can be formed.

  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 nano thin film layer and the soluble support layer according to the present embodiment can also hold a drug. As a result, when applied to the skin (during use), the drug gradually elutes from the nano thin film layer and can be gradually absorbed by the skin. Moreover, it can be set as the nano 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.

  In the nano thin film layer according to the present embodiment, as a crosslinking agent, alkyldiimidates, acyldiazides, diisocyanates, bismaleimides, triazinyls, diazo compounds, glutaraldehyde, N-succinimidyl-3- (2-pyridyldithio) ) Alkionate, bromocyanide, etc. may be used to crosslink with the functional material and corresponding functional groups in the nanofilm layer.

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

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

  The nano thin film layer which concerns on this embodiment can also be used so that cosmetics or a cosmetics component may be apply | coated on it, after bonding a nano 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.

  Moreover, the nano thin film transfer sheet of the present invention can be suitably used as a cosmetic sheet, a moisturizing sheet, a makeup-assisting patch sheet, and a cosmetic protective sheet in which cosmetics or cosmetic ingredients are held.

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

[Example 1]
White mushroom-derived chitosan (manufactured by Sigma-Aldrich: viscosity average molecular weight 110,000-150,000, β-glucan content 2.9 mass%, concentration: 0.1 mass%) as the cationic polymer, alginic acid as the anionic polymer Sodium (manufactured by Kimika Co., Ltd .: viscosity average molecular weight 100,000, viscosity 6.7 mPa · s, concentration: 0.1% by mass), acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), malic acid (manufactured by Wako Pure) Yakuhin Kogyo Co., Ltd.) was used.

  As a solution containing a polycation, what dropped 1 mass part of acetic acid (1 mass% aqueous solution) with respect to 100 mass parts of 0.2 mass% chitosan aqueous solution was used. As a solution containing a polyanion, a solution obtained by adding 1 part by mass of malic acid (1% by mass aqueous solution) to 100 parts by mass of a 0.1% by mass sodium alginate aqueous solution was used.

  A polyethylene terephthalate film (trade name “A4100” manufactured by Toyobo Co., Ltd., 150 mm × 100 mm × 100 μm thickness) to be a cover film later is immersed in a solution containing (a) a polycation for 1 minute, and then an ultra-rinse for rinsing. The sample was immersed in pure water (specific resistance 18 MΩ · cm) for 1 minute, then immersed in a solution containing (b) polyanion for 1 minute, and then immersed in ultrapure water for rinsing for 1 minute.

  The procedure of performing steps (a) and (b) in turn is one cycle, and this cycle is repeated 15 times. On the polyethylene terephthalate film (cover film), a nanothin film layer consisting of a layer derived from mushroom chitosan and a layer derived from sodium alginate Formed. As a result of measuring the film thickness and the refractive index of the formed nano thin film layer by a model number F20 manufactured by Filmetris Co., Ltd., the film thickness was 88 nm and the refractive index was 1.52.

  Subsequently, using a 10% by mass aqueous solution in which polyvinyl alcohol 500 (manufactured by Kanto Chemical Co., Inc., average polymerization degree = 500) is dissolved in ultrapure water, the film thickness after drying is adjusted to 5 μm. Was applied by a bar coater to form a layer serving as a soluble support layer.

  Thereafter, a polyester mesh sheet (trade name “OKILON-SHA 2516”, manufactured by Daiki Shoji Co., Ltd.) as a permeable substrate is coated on the layer to be a soluble support layer, and moisture is added at room temperature (25 ° C.). Was evaporated. As a result, on the cover film (polyethylene terephthalate film), the nano thin film layer (alternate laminated film of chitosan-derived layer and alginic acid-derived layer), the soluble support layer (polyvinyl alcohol) and the permeable substrate (polyethylene terephthalate mesh) Sheets were sequentially laminated.

The cover film was peeled off, and a polyester mesh sheet (manufactured by Daiki Shoji Co., Ltd., trade name “OKILON HYBRID”, breathability 3600 cc / cm ² · sec by the fragile method described in JIS L 1096) was bonded. The ends were fixed, and the bonded sheets were immersed in water for 24 hours, and then water was evaporated at room temperature (25 ° C.).

As a result, on the permeable substrate (“OKILON HYBRID”), the nano thin film layer (alternate laminated film of chitosan-derived layer and alginic acid-derived layer), the permeable substrate (“OKILON-SHA 2516”, JIS L A nano thin film transfer sheet in which air permeability of 5850 cc / cm ² · sec) by the Frazier method described in 1096 was sequentially laminated was produced.

[Example 2]
The white polymer mushroom-derived chitosan (manufactured by Sigma Aldrich: viscosity average molecular weight 110,000-150,000, concentration: 0.1% by mass), which is a cationic polymer, is white mushroom-derived chitosan (manufactured by Sigma-Aldrich). The nano thin film transfer sheet was operated in the same manner as in Example 1 except that the viscosity average molecular weight was 60,000-120,000, the β-glucan content was 2.9 mass%, and the concentration was 0.1 mass%. Was made.

[Comparative Example 3]
The cationic polymer “chitosan derived from white mushrooms (manufactured by Sigma Aldrich: viscosity average molecular weight 110,000-150,000, concentration: 0.1 mass%)” is referred to as “chitosan derived from crabs (manufactured by Nacalai Tesque: viscosity). An average molecular weight of 80,000, concentration: 0.1% by mass) was performed in the same manner as in Example 1 except that a nano thin film transfer sheet was prepared.

  Table 1 shows the film thickness and refractive index of the nano thin film layers of Examples 1 and 2 and Comparative Example 1.

  1,11,21,31,41 ... nano thin film layer transfer sheet, 2a, 2b, 12a, 12b, 22a, 22b, 32a, 32b ... permeable substrate, 3, 3a, 3b, 13, 23, 33, 43a ... nano thin film layer, 4a, 4b, 14a, 14b, 24, 34, 44a ... soluble support layer, 5, 45 ... cover film, 6 ... solvent.

Claims (24)

A permeable substrate that is a substrate that is permeable or permeable to water or alcohol ;
A nano thin film transfer sheet comprising: a nano thin film layer containing plant chitosan and having a thickness of 1 nm to 300 nm. A permeable substrate that is a substrate that is permeable or permeable to water or alcohol ;
A nano thin film transfer sheet comprising a chitosan containing β-glucan and a nano thin film layer having a thickness of 1 nm to 300 nm. The nano thin film layer has an A layer formed using a solution containing a polycation, and a B layer formed using a solution containing a polyanion,
The nano thin film transfer sheet according to claim 1 or 2, wherein the polycation contains the plant chitosan or chitosan containing β-glucan.   The nano thin film transfer sheet according to claim 3, wherein the nano thin film layer is a layer in which the A layer and the B layer are alternately laminated.   The nano thin film transfer sheet according to claim 1, 3 or 4, wherein the plant chitosan contains β-glucan.   The nano thin film transfer sheet according to any one of claims 3 to 5, wherein the polyanion is an anionic polymer having two or more carboxyl groups or carboxylate groups in one molecule.   The nano thin film transfer sheet according to any one of claims 1 to 6, comprising the first permeable substrate, the nano thin film layer, and the second permeable substrate in this order. The nano thin film transfer sheet according to any one of claims 1 to 7, further comprising a soluble support layer soluble in water or alcohol . The nano according to any one of claims 1 to 6, comprising the permeable base material, a soluble support layer soluble in water or alcohol , the nano thin film layer, and a cover film in this order. Thin film transfer sheet.   The nano thin film transfer sheet according to claim 8, comprising the nano thin film layer and the soluble support layer between the first permeable substrate and the second permeable substrate.   The nano thin film layer and the soluble support layer are provided in this order from the first permeable substrate side between the first permeable substrate and the second permeable substrate. The nano thin film transfer sheet according to 1.   The said soluble support layer and the said nano thin film layer are provided in this order from the said 1st permeable base material side between the said 1st permeable base material and the 2nd said permeable base material. The nano thin film transfer sheet according to 1.   Between the first permeable substrate and the second permeable substrate, the first soluble support layer, the nano thin film layer, and the second soluble support layer are disposed in the first penetration. The nano thin film transfer sheet according to claim 10 provided in this order from the conductive substrate side.   The nano thin film transfer sheet according to any one of claims 10 to 13, wherein the first permeable substrate and the second permeable substrate have different contact areas with adjacent layers.   The nano thin film transfer sheet according to any one of claims 1 to 14, wherein the permeable substrate is a mesh-like sheet, a nonwoven fabric sheet, or a sheet having a porous structure.   The nano thin film transfer sheet according to any one of claims 8 to 15, wherein the soluble support layer is a polymer layer soluble in water or alcohol.   The nano thin film transfer sheet according to any one of claims 1 to 16, wherein the nano thin film layer is for skin application.   The nano thin film transfer sheet according to claim 1, wherein the nano thin film layer is for cosmetic use. Contacting the cover film with a solution containing a polycation or a solution containing a polyanion, and forming a layer derived from the polycation or polyanion on the surface of the cover film;
(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) contacting a solution containing a polycation with a layer derived from a polyanion to form a layer derived from a polycation on the layer derived from the polyanion, and repeating the step of forming the first nano thin film layer. Forming, and
Forming a first soluble support layer on the first nanofilm layer;
Forming a first permeable base material on the first soluble support layer, which is a base material that can permeate or permeate a solvent that dissolves the first soluble support layer.
The method for producing a nano thin film transfer sheet according to any one of claims 1 to 18, wherein the polycation contains plant chitosan or chitosan containing β-glucan.   After the step of forming the first permeable substrate, the cover film is peeled off from the first nano thin film layer, and the second nano thin film layer is peeled off on the side where the cover film is peeled off. The manufacturing method of the nano thin film transfer sheet of Claim 19 which further includes the process of bonding the laminated body which comprises a permeable base material, a 2nd soluble support layer, and a 2nd nano thin film layer in this order. After the step of forming the first permeable substrate, the cover film is peeled off from the first nano thin film layer, and the second nano thin film layer is peeled off on the side where the cover film is peeled off. The manufacturing method of the nano thin film transfer sheet of Claim 19 which further includes the process of bonding the permeable base material of this.   The method for producing a nano thin film transfer sheet according to any one of claims 19 to 21, further comprising a step of allowing the solvent to permeate or permeate the permeable substrate and dissolving the soluble support layer.   23. The production of a nano thin film transfer sheet according to any one of claims 19 to 22, wherein in the step of forming the nano thin film layer, the step (i) and the step (ii) are alternately repeated 1 to 300 times. Method.   A nano thin film transfer sheet according to any one of claims 1 to 18, comprising a step of affixing the nano thin film layer to an adherend so that the nano thin film layer is in contact with the adherend. Transcription method.

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