JP6592994B2 - Nano thin film transfer sheet and transfer method - Google Patents

Description

  The present invention relates to a nano thin film transfer sheet and a transfer method.

  In recent years, a nano thin film transfer sheet for attaching a nano thin film layer to skin or the like has attracted attention. For example, a cosmetic nano thin film transfer sheet in which a cosmetic component for the purpose of improving skin gloss, moisture, whiteness, wrinkle prevention, etc. is held in a nano thin film layer has been proposed (for example, Non-Patent Document 1). .

  In such a nano thin film transfer sheet, a nano thin film layer is usually provided on a substrate. And after arrange | positioning a nano thin film transfer sheet so that a nano thin film layer and a to-be-transferred body may contact, a nano thin film layer is transcribe | transferred to a to-be-transferred body by peeling a base material.

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

  On the other hand, since the nano thin film layer normally uses moisture at the time of transfer, the moisture of the nano thin film layer is used for the purpose of ensuring the sticking property of the nano thin film layer before peeling the substrate at the time of transfer. A process of removing is necessary. However, considering the convenience of the user, it is desirable that the number of steps for transferring the nano thin film layer is small.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a nano thin film transfer sheet and a transfer method capable of easily transferring a nano thin film layer.

  The nano thin film transfer sheet according to the present invention includes a water absorbing base material and a nano thin film layer laminated on the water absorbing base material.

  Since this nano thin film transfer sheet is provided with a water absorbing substrate, the water in the nano thin film layer is absorbed by the water absorbing substrate. Therefore, in this nano thin film transfer sheet, as long as the water-absorbing substrate is peeled off at the time of transfer, a step of removing moisture from the nano thin film layer becomes unnecessary. Therefore, according to the nano thin film transfer sheet, the nano thin film layer can be easily transferred.

The water-absorbing substrate is preferably a nonwoven fabric sheet having a basis weight of 20 g / m ² or more. In this case, the water-absorbing substrate can quickly absorb a larger amount of moisture.

  The water-absorbing substrate preferably contains particles of a water-absorbing polymer compound. In this case, the water-absorbing substrate can quickly absorb a larger amount of moisture.

  The nano thin film layer preferably contains fibroin. In this case, the biocompatibility of the nano thin film layer is improved.

  The nano thin film layer is preferably a layer in which A layers formed using a solution containing a polycation and B layers formed using a solution containing a polyanion are alternately laminated. In this case, the mechanical strength and self-adhesion of the nano thin film layer are improved.

  In the transfer method according to the present invention, the above-described nano thin film transfer sheet is disposed on the transfer target body so that the nano thin film layer side faces the transfer target body, and the nano thin film transfer sheet is pressed against the water absorbent substrate side. The nano thin film layer is transferred to the transfer target.

  In this transfer method, the nano-thin film layer is pressed onto the water-absorbing substrate side to transfer the nano-thin film layer to the transfer object, so that the followability and adhesion between the transfer object and the nano-thin film layer are improved. . Therefore, the nano thin film layer can be suitably transferred to the transfer target.

The load for pressing the water-absorbing substrate side of the nano thin film transfer sheet is preferably 10 to 1000 g / cm ² . In this case, it is possible to easily suppress the remaining of the nano thin film layer on the side of the water-absorbing substrate when the water-absorbing substrate is peeled off and the damage of the transferred material during transfer.

  ADVANTAGE OF THE INVENTION According to this invention, the nano thin film transfer sheet and transfer method which can transfer a nano thin film layer simply can be provided.

It is sectional drawing which shows one Embodiment of a nano thin film transfer sheet.

  Hereinafter, preferred embodiments of a nano thin film transfer sheet and a transfer method will be described in detail with reference to the drawings.

  FIG. 1 is a 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 includes a water absorbing substrate 2 and a nano thin film layer 3 laminated on the water absorbing substrate 2.

The water-absorbing substrate 2 may be a known water-absorbing substrate that has been conventionally used as long as it can absorb moisture. The water-absorbing substrate 2 is preferably a substrate having a water absorption rate of 150% by mass or more. As used herein, “water absorption” refers to the mass M ′ after absorbing a water-absorbing substrate (mass M) having a predetermined size (for example, 10 cm × 10 cm) in 20 ° C. water for 1 minute. It means a water absorption A (mass%) measured and calculated by the following formula (1).
A = (M′−M) / M × 100 (1)

  Examples of the water-absorbing substrate 2 include a resin sheet made of a resin component such as polyacrylic acid, a fibrous sheet such as paper, knitted fabric, woven fabric, and non-woven fabric, and a composite sheet composed of a resin sheet and a fibrous sheet. A water-absorbent sheet is mentioned. Among these, a nonwoven fabric fibrous sheet (nonwoven fabric sheet) is more suitably used because it can absorb and diffuse a large amount of water quickly. Examples of fibers constituting the non-woven fibrous sheet (non-woven sheet) include natural fibers such as cotton, wool, hemp and pulp, semi-synthetic fibers such as rayon, and synthetic fibers such as polyvinyl alcohol and polyacrylic acid. be able to. These fibers are used singly or in combination of two or more. Among these, synthetic fibers such as polyvinyl alcohol and polyacrylic acid are particularly preferably used in consideration of mass production and availability.

The nonwoven fabric sheet may be a nonwoven fabric sheet produced by any of the spunbond method, spunlace method, needle punch method, resin bonding method, flash spinning method, melt blow method, air lay method and the like. The basis weight (mass per unit area) of the nonwoven fabric sheet is preferably 20 g / m ² or more, more preferably 25 g / m ² or more, from the viewpoint of being able to quickly absorb a large amount of moisture and easily suppressing a decrease in stickiness. More preferably, it is 30 g / m ² or more. The basis weight of the nonwoven fabric sheet is preferably 150 g / m ² or less, more preferably 130 g / m ² or less, still more preferably 100 g / m ² or less, from the viewpoint of excellent wearing feeling and use feeling.

  The water-absorbing substrate 2 may be a substrate in which particles of a water-absorbing polymer compound are further contained in the water-absorbing sheet from the viewpoint of being able to quickly absorb a larger amount of water. As such a water-absorbing polymer compound, known water-absorbing polymer compounds widely used in paper diapers and the like can be used. For example, sodium polyacrylate, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl Examples include pyrrolidone and polyvinyl methyl ether. The particle size (diameter) of the water-absorbing polymer compound may be, for example, 10 to 1000 μm.

  The thickness of the water-absorbing substrate 2 is preferably 100 μm to 10 mm, more preferably 300 μm to 5 mm, from the viewpoint of excellent usability.

  Since the thickness of the nano thin film layer 3 is more excellent in properties such as self-adhesion, water absorption, and flexibility in a dry state, the thickness during drying is preferably 1 to 300 nm, more preferably 40 to 300 nm. More preferably, it is 40-250 nm, Most preferably, it is 40-200 nm.

  The nano thin film layer 3 preferably contains fibroin (silk fibroin) from the viewpoint of excellent biocompatibility. Examples of fibroin include fibroin produced from natural silkworms such as rabbits, wild silkworms, and tengu, and transgenic silkworms.

  The nano thin film layer 3 preferably has an A layer formed using a solution containing a polycation and a B layer formed using a solution containing a polyanion. The A layer and the B layer It is more preferable that and are layers alternately stacked (alternate stacking). Thereby, the mechanical strength and self-adhesiveness of the nano thin film layer are improved. The layer in which the A layer and the B layer are alternately stacked (alternate stacking) may be a layer in which the A layer and the B layer are alternately stacked one by one. A layer formed by alternately laminating layers composed of B layers.

  When the nano thin film layer 3 is an alternate lamination of the A layer and the B layer, the transparency of the nano thin film layer 3 is easy to ensure, so the number of layers of the A layer and the B layer is 1 to 300 layers, respectively. Is preferred. Since the nano thin film layer 3 has suitable self-adhesiveness, the number of layers of the A layer and the B layer is more preferably 10 to 100, and further preferably 20 to 80, respectively.

  The layered structure of the A layer and the B layer in the nano thin film layer 3 is observed, for example, by IR, NMR, TOF-SIMS (time-of-flight secondary ion mass spectrometry, Time-of-Flight SIMS) or the like. This can be confirmed.

  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. 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; polyethyleneimine, polyallylamine hydrochloride, polydiallyldimethylammonium chloride, and salts (hydrochloride, acetate, etc.) and derivatives thereof Is mentioned. These polymers may form crosslinks.

  The polycation may be a low molecular compound having two or more cationic groups in one molecule. Examples of such low molecular weight compounds include compounds having two amino groups in one molecule such as diaminoalkanes such as diaminoethane, diaminopropane, diaminobutane, diaminopentane, and diaminohexane, and N- (lysyl) -diamino. 3-4 in one molecule such as mono or dilysylamino alkane such as ethane, N, N ′-(dilysyl) -diaminoethane, N- (lysyl) -diaminohexane, N, N ′-(dilysyl) -diaminohexane, etc. Examples thereof include compounds having one amino group and compounds having five or more amino groups in one molecule.

  The solution containing a polycation is obtained by dissolving one or more of the above-described polycations in a solvent such as water. The concentration of the polycation in the solution 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.

  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. Preferred examples of the anionic polymer include natural acidic polysaccharides having an anionic group such as carboxyl group, carboxylate group or sulfate group such as alginic acid, hyaluronic acid, chondroitin sulfate, dextran sulfate, pectin and cherry, and derivatives thereof; Acidic polysaccharides obtained by binding anionic groups to natural polysaccharides such as cellulose, dextran, starch and derivatives thereof (for example, carboxymethylcellulose, carboxymethyldextran, carboxymethyl starch, carboxymethylchitosan, sulfated cellulose and sulfuric acid) Dextran and their derivatives); homopolymers and copolymers of acidic amino acids such as polyglutamic acid, polyaspartic acid, copolymers of glutamic acid and aspartic acid; acidic vinyl polymers such as polyacrylic acid Mer; and their salts (e.g., alkali metal salts such as sodium salts). 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. These polymers may form crosslinks.

  The polyanion may be a low molecular compound having two or more anionic groups in one molecule. Examples of such low molecular weight compounds include compounds having two carboxyl groups or carboxylate groups in one molecule such as succinic acid and malonic acid.

  The solution containing a polyanion is obtained by dissolving one or more of the above polyanions in a solvent such as water. The concentration of the polyanion in the solution 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 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. From the standpoint of safety, at least one of the cationic polymer and the anionic polymer is preferably a bioabsorbable polymer. By bioabsorbable polymer is meant a polymer that can be biodegraded. Examples of the bioabsorbable cationic polymer include chitosan, collagen, polylysine, polyarginine, polyhistidine, and ionene. Examples of the bioabsorbable anionic polymer include alginic acid, hyaluronic acid, polyglutamic acid, chondroitin sulfate, and derivatives and salts thereof (for example, alkali metal salts such as sodium salts).

  The nano thin film layer 3 may contain a functional substance (for example, a substance that exhibits functionality in a transfer target such as an organ or skin). Examples of the functional substance include cosmetics, pigments, metal ions, drugs and the like. A functional substance is used individually by 1 type or in combination of 2 or more types.

  The nano thin film layer 3 can be suitably used as a thin film for skin application, a thin film for cosmetic use, or a thin film for skin application for cosmetic use. The nano thin film layer 3 can be suitably used as a medical thin film.

  As described above, since the nano thin film transfer sheet 1 includes the water absorbent base material 2, the water of the nano thin film layer 3 and the water used for pasting are absorbed by the water absorbent base material 2. Therefore, in the nano thin film transfer sheet 1, as long as the water-absorbing substrate 2 is peeled off at the time of transfer, a process of removing moisture from the nano thin film layer 3 becomes unnecessary. Therefore, according to this nano thin film transfer sheet 1, the nano thin film layer 3 can be simply transferred.

The nano thin film transfer sheet 1 is manufactured by, for example, the following steps.
(1) A nano thin film layer is formed on the main surface of a supporting substrate formed of a thermoplastic resin, a thermosetting resin, or the like.
(2) A soluble support layer is formed on the opposite side of the nano thin film layer from the support substrate. The soluble support layer is formed of a compound that dissolves in a solvent such as water or alcohol.
(3) A permeable base material is laminated on the opposite side of the soluble support layer from the nano thin film layer by lamination or the like.
(4) A support base material is peeled off to obtain a first laminate including a permeable base material, a soluble support layer, and a nano thin film layer in this order.
(5) A water-absorbing substrate is bonded to the nano thin film layer of the first laminate to obtain a second laminate.
(6) The second laminate is dipped in a solvent (for example, water) for dissolving the soluble support layer, and the soluble support layer is dissolved, whereby the water-absorbing substrate, the nano thin film layer, and the permeable substrate are separated from each other. A third laminated body provided in order is obtained.
(7) The nano thin film transfer sheet 1 provided with a water absorbing base material and a nano thin film layer is obtained by peeling the permeable base material from the third laminate.

  When the nano thin film layer 3 contains fibroin, the nano thin film layer 3 is formed by applying a fibroin aqueous solution onto a supporting substrate by, for example, a cast method, a spin coating method, a spray coating method, or a die coating method. As a method for obtaining a fibroin aqueous solution, any known method may be used.For example, after fibroin is dissolved in a high concentration lithium bromide aqueous solution, a method for obtaining a fibroin aqueous solution through desalting by dialysis and concentration by air drying is available. Convenient. In this case, the concentration of the lithium bromide aqueous solution is preferably 8 to 10M, more preferably 8.5 to 9.5M. When the concentration of the lithium bromide aqueous solution is within the above range, the fibroin aqueous solution is hardly gelled, and the nano thin film layer 3 having a uniform film thickness can be obtained stably. The fibroin concentration in the fibroin aqueous solution is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and still more preferably 0.1 to 1.0% by mass.

  When nano thin film layer 3 has A layer formed using the solution containing polycation, and B layer formed using the solution containing polyanion, formation method of nano thin film layer 3 Is obtained by bringing a support substrate into contact with a solution containing a polycation (hereinafter also referred to as “solution A”) or a solution containing a polyanion (hereinafter also referred to as “solution B”). A step of forming a layer containing layer (A layer) or a layer containing polyanion (B layer), and (i) contacting the solution B with the A layer to form the B layer on the A layer; ii) It is preferable to be an alternate lamination method including a step of forming the nano thin film layer 3 by repeating the step of bringing the solution A into contact with the B layer and forming the A layer on the B layer.

  According to the alternate lamination method, when the A layer (or B layer) and the solution B (or solution A) are in contact, the polycation and the polyanion are alternately adsorbed to form a laminated film. In the alternate lamination method, when the adsorption of the polycation or polyanion proceeds and the surface charge is reversed, further electrostatic adsorption does not occur. Therefore, the thicknesses of the A layer and the B layer formed by contact with the solution A and the solution B, respectively. Is controlled.

  Using the nano thin film transfer sheet 1 described above, the nano thin film layer 3 can be transferred to an object to be transferred such as an organ or skin. As a transfer method, the nano thin film transfer sheet 1 is placed on the transfer target body so that the nano thin film layer 3 side faces the transfer target body, and the nano thin film transfer sheet 1 is pressed by pressing the water absorbent substrate 2 side. A method of transferring the thin film layer 3 to the transfer target is preferable. In this method, in order to transfer the nano thin film layer 3 to the transferred body by pressing the water absorbent base material 2 side of the nano thin film transfer sheet 1 in a state where the water absorbent base material 2 covers the nano thin film layer 3, The followability and adhesion between the transferred object and the nano thin film layer are improved. Therefore, in this method, for example, the method of transferring the nano thin film layer 3 to the transfer object after peeling off the water-absorbing substrate 2 in advance, or the method of transferring the nano thin film layer 3 to the transfer object without pressing. Compared to the above, the nano thin film layer 3 can be transferred suitably.

  In this transfer method, it is preferable to apply a substantially uniform pressure to the entire surface of the water absorbent substrate 2 when pressing against the water absorbent substrate 2. The pressing is performed more easily and suitably by using a jig such as a roller.

The load when pressing the water-absorbing substrate 2 side of the nano thin film transfer sheet 1 is preferably 10 to 1000 g / cm ² , more preferably 30 to 900 g / cm ² , and still more preferably 50 to 800 g / cm ² . . It can suppress easily that the nano thin film layer 3 remains in the water-absorbing base material 2 side when peeling the water-absorbing base material 2 as a load is more than a lower limit. On the other hand, when the load is equal to or lower than the upper limit value, it is possible to easily suppress damage to the transferred body such as skin.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to an Example.

<Example>
First, 150 g of high-pressure squeezed chopped wood (silk fibroin, manufactured by Nagasuna Coffee Co., Ltd.) was added to 1000 mL of a 9M lithium bromide aqueous solution and dissolved by stirring at room temperature (25 ° C.) for 6 hours. Subsequently, after centrifugation (rotation speed: 12000 rpm, 5 minutes) and removing the precipitate by decantation, a dialysis tube (Spectra / Por (registered trademark) 1 Dialysis Membrane, MWCO 6000-8000, manufactured by Spectrum Laboratories, Inc.). ), And dialysis for 12 hours was repeated 5 times against 5 L of ultrapure water collected from ultrapure water production equipment (PRO-0500 and FPC-0500 (model number), manufactured by Organo Corp.) to obtain a silk fibroin solution. An aqueous solution was obtained.

  2 mL of the obtained aqueous solution for silk fibroin solution was dispensed into an aluminum container and weighed. Then, it heat-dried. The obtained dried product was taken out from the dryer and weighed, and the silk fibroin concentration (unit: g / L) in the aqueous solution for silk fibroin solution was determined from the mass reduction.

  Glycerin and ultrapure water were added to the silk fibroin solution for which the concentration was measured, and the silk fibroin solution (silica fibroin nanofilm preparation solution. Silk fibroin: glycerin = 1: 1) with a silk fibroin concentration of 10 g / L and glycerin 0.3% by volume. 0.3 (mass ratio)) was prepared.

(Preparation of silk fibroin nanofilm)
A silk fibroin solution was coated on a PET film (polyethylene terephthalate film, manufactured by Toyobo Co., Ltd., trade name “A4100”, 150 mm × 100 mm × 100 μm thickness) as a supporting substrate using an applicator. Then, it dried at 100 degreeC for 1 hour, and formed the silk fibroin nano thin film. As a result of measuring the film thickness of the silk fibroin nano thin film by a model number F20 manufactured by Filmetris Co., Ltd., the film thickness of the silk fibroin nano thin film was 100 nm.

  Subsequently, a 10 mass% aqueous solution in which polyvinyl alcohol 500 (manufactured by Kanto Chemical Co., Inc., average polymerization degree: 500) is dissolved in ultrapure water is placed on the silk fibroin nano thin film layer so that the film thickness after drying becomes 5 μm A soluble support layer was formed by coating with a bar coater.

Thereafter, as a permeable base material, a polyethylene terephthalate mesh sheet (PET mesh, manufactured by Daiki Shoji Co., Ltd., trade name “OKILON-SHA 2516”, air permeability 5850 cc / cm ² · sec by fragile method described in JIS L 1096) , Thickness: 80 μm) was laminated on the soluble support layer, and water was evaporated at room temperature (25 ° C.). As a result, a nano thin film layer containing silk fibroin, a soluble support layer (polyvinyl alcohol), and a permeable substrate (polyethylene terephthalate mesh sheet) were laminated in this order on a support substrate (polyethylene terephthalate film). Body A was obtained.

The support base material is peeled off from the laminate A, and a water-absorbing base material (Miracle Cotton Spunlace, manufactured by Marusan Sangyo Co., Ltd., basis weight: 30 g / m ² ) is bonded and immersed in water for 24 hours with the ends fixed. did. Thereafter, water was evaporated at room temperature (25 ° C.).

  As a result, a nano thin film transfer sheet was obtained in which a silk fibroin nano thin film layer and a permeable base material (“OKILON-SHA 2516”) were laminated in this order on a water absorbent base material (miracle cotton spunlace).

<Comparative example>
The same operation as in the example was performed except that the water-absorbing substrate (Miracle Cotton Spunlace) was changed to the permeable substrate (“OKILON-SHA HYBRID”).

<Evaluation of adhesiveness>
When the nano thin film layer was applied to the skin, the skin was previously wetted with moisture. After the permeable substrate (“OKILON-SHA 2516”) is peeled off, the nano thin film transfer sheet is placed on the transferred body so that the nano thin film layer side faces the transferred body. The nano thin film layer was transferred to the transfer object by pressing the water-absorbing substrate side and the permeable substrate (“OKILON-SHA HYBRID”) side of the comparative example. In the examples, the water-absorbing base material absorbs wet moisture, so that it can be easily applied. However, in the comparative example, a process for removing moisture is necessary, and one extra application process is required. .

  DESCRIPTION OF SYMBOLS 1 ... Nano thin film transfer sheet, 2 ... Water absorbing base material, 3 ... Nano thin film layer.

Claims (4)

A water-absorbing substrate, and a nano thin film layer laminated on the water-absorbing substrate ,
The water-absorbent substrate is a nonwoven fabric sheet having a basis weight of 20 g / m ² or more,
The nano thin film layer is a layer containing fibroin, or an A layer formed using a solution containing a polycation and a B layer formed using a solution containing a polyanion are alternately laminated. Nano-thin film transfer sheet , which is a layer formed . The nano thin film transfer sheet according to claim 1 , wherein the water absorbing substrate contains particles of a water absorbing polymer compound. The nano thin film transfer sheet according to claim 1 or 2 is arranged on the transfer target body so that the nano thin film layer side faces the transfer target body, and the water absorbing substrate side of the nano thin film transfer sheet is pressed. A transfer method in which the nano thin film layer is transferred to a transfer target. The transfer method according to claim 3 , wherein a load when pressing the water-absorbing substrate side of the nano thin film transfer sheet is 10 to 1000 g / cm ² .

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