JP2019043896A - Thin film having support fixed thereon, the support capable of supporting aromatic molecules and of sustainedly releasing the supported aromatic molecules - Google Patents

Abstract

To provide a thin film that maintains an aromatic ability and/or a deodorant ability.SOLUTION: The present invention provides a thin film having a support fixed thereon, the support capable of supporting aromatic molecules and of sustainedly releasing the supported aromatic molecules.SELECTED DRAWING: Figure 8

Description

  The present invention relates to a thin film on which a carrier capable of supporting an aromatic molecule and capable of slow release of the supported aromatic molecule is immobilized.

  The smell is closely related to human life. Odor molecules are volatile low-molecular-weight organic compounds, and hundreds of thousands exist in the world. A large number of receptors have been identified since olfactory receptors were discovered. Even in humans with olfactory degeneration, about 10,000 odor molecules can be sniffed, and even if the concentration is pM to nM, they are detected with high sensitivity through olfactory receptors. Therefore, it is no exaggeration to say that the odor determines the first impression of the person, and the odor is a factor to be noted.

Recently, deodorants and air fresheners that erase unpleasant odors such as body odors and life odors and impart a desired smell to produce individuality are in full swing in the market.
Deodorants are odors such as age-related odor (causing compound: 2-nonenal), sweat odor (causing compound: ammonia, sebum oxide, etc.), feces and urine odor (causing compound: ammonia, 3-methylindole, etc.) Targeting and deodorizing methods include methods using cyclic oligosaccharides that capture hydrophobic molecules as physical adsorption methods (Non-Patent Document 1, Patent Document 1), and methods using water-absorbing polysaccharide microparticles (Patent Documents 2 and 3) ) And porous inorganic materials (activated carbon, zeolite, etc.) (Non-patent document 2, Patent documents 4 and 5), etc., and methods using metal complexes etc. as chemisorption method (Non-patent document 3, Patent document 6) And the like, and there is a method of using antibacterial silver nanoparticles as a biological method (Non-Patent Document 4, Patent Document 7) and the like.
Fragrances are representative of perfume-containing perfumes, and they are classified into a sensory deodorizing method that clogs offensive odors, and are often used in combination with the former.
These deodorants and fragrances are used as they are left in a room or the like. On the other hand, in recent years, liquid, gel-like, and powder-like forms have also become popular.

Patent No. 5497483 specification JP, 2005-87286, A JP 2005-523078 Gazette JP 2003-47648 Japanese Patent Application Laid-Open No. 2003-52799 Patent No. 5268128 specification Patent No. 4966763 specification

Lopedota, A. et al. Int. J. Cosmet. Sci. 37, 438 (2015) Mumpton, F. A. Proc. Natl. Acad. Sci. USA. 96, 463 (1999) Baxter, P. M. et al. Int. J. Cosmet. Sci. 5, 85 (1983) Nakane, T. et al. Int. J. Cosmet. Sci. 28, 299 (2006)

When the fragrance or deodorant is in the form of liquid, gel or powder and is applied to an exposed body surface such as skin, it is customary to apply or spray. However, the active ingredient flows with perspiration, etc., and the odor molecule is volatile, so that the effect fades immediately, and improvement of its fragrance ability and deodorizing ability is required. There is room.
An object of the present invention is to provide a thin film in which the aroma ability and / or the deodorizing ability is sustained.

  As a result of intensive studies to solve the above problems, the present inventors supported an aromatic molecule by immobilizing a carrier capable of supporting an aromatic molecule and capable of releasing the supported aromatic molecule in a thin film. At the same time, it was found that the aroma ability lasts. In addition, the present inventors are a carrier for slow release of an aromatic molecule, and the carrier having the aromatic molecule supported on the carrier is fixed to a thin film, for example, when the thin film is attached to a body surface or the like. It has been found that a deodorizing effect is exhibited by the gradual exchange of the odorous molecules in the pasted area and its peripheral area with the aromatic molecule, and an aromatic effect is exhibited by the liberated aromatic molecule. The present invention is as follows.

[1] A thin film on which a carrier capable of supporting an aromatic molecule and capable of slowly releasing the supported aromatic molecule is immobilized.
[2] A thin film in which a carrier capable of sustained release of an aromatic molecule is immobilized, and the carrier is supported on the carrier.
[3] The aromatic molecule is monoterpene hydrocarbons, sesquiterpene hydrocarbons, monoterpene alcohols, sesquiterpene alcohols, diterpene alcohols, terpene aldehydes, aromatic aldehydes, ketones, esters, The thin film according to [1] or [2], which is one or more selected from the group consisting of phenols, oxides, and lactones.
[4] The thin film according to any one of [1] to [3], wherein the carrier is one or more selected from the group consisting of cyclic oligosaccharides, polyacids, mesoporous silica particles, and silver nanoparticles.
[5] The thin film according to [4], wherein the cyclic oligosaccharide is γ-cyclodextrin.
[6] A kit for deodorant and aroma, comprising: (A) a thin film on which a carrier capable of supporting an aromatic molecule and capable of sustained release of the aromatic molecule is immobilized, and (B) the aromatic molecule.

  According to the present invention, it is possible to provide a thin film in which the aroma ability and / or the deodorizing ability is sustained.

It is a graph which shows the result of the experiment regarding support of linanol or trans -2- nonenal of a carrier (alone) in the reference example 1 of this invention. It is a graph which shows the result of the experiment which concerns on the exchange to linenal of linalor which a support | carrier (inside) supports in the reference example 2 of this invention. It is a flowchart which shows the manufacturing method of the thin film which fixed the cyclic oligosaccharide ((gamma) -cyclodextrin) in Example 1 of this invention. They are a visual image (a) of the thin film which fixed the cyclic oligosaccharide (gamma-cyclodextrin) in Example 2 of this invention, and an electron microscope image (b) of the surface (drawing substitute photograph). It is a graph which shows the relationship between the film thickness of the thin film which fixed the cyclic oligosaccharide ((gamma) -cyclodextrin) in Example 2 of this invention, and the rotation speed of the spin coat at the time of manufacture. It is a graph which shows the result of the infrared spectroscopy analysis of the thin film which fixed the cyclic oligosaccharide (gamma-cyclodextrin) in Example 2 of this invention. It is a graph which shows the result of the experiment regarding support of linanol of the cyclic oligosaccharide ((gamma) -cyclodextrin) fixed thin film in Example 3 of this invention. It is a graph which shows the result of experiment which concerns on sustained release of linanol of the cyclic oligosaccharide ((gamma) -cyclodextrin) fixed thin film in Example 4 of this invention.

The first embodiment of the present invention is a thin film on which a carrier capable of supporting an aromatic molecule and capable of slow release of the supported aromatic molecule is immobilized. The thin film according to the present embodiment is a thin film in a state in which an aromatic molecule is not supported on a fixed carrier. The thin film in a state where the aromatic molecule is supported on the immobilized carrier will be described later as another embodiment of the present invention.

  Examples of the aromatic molecules include known aromatic molecules, such as monoterpene hydrocarbons (limonene, δ-3-carene, γ-terpinene, α-pinene etc.), sesquiterpene hydrocarbons (camazulene etc.), mono Terpene alcohols (geraniol, citronellol, terpinen-4-ol, nerol, menthol, lavandurol, linalool etc.), sesquiterpene alcohols (santarol, nerolidol, bisabolol etc.), diterpene alcohols (sclareole etc.), terpenes Aldehydes (citral, citronellal, etc.), aromatic aldehydes (cuminaldehyde, etc.), ketones (camphor, thulon, mentone, etc.), esters (linalyl acetate, geranyl acetate, benzyl acetate, etc.), phenols (euge Lumpur, thymol, etc.), oxides (1,8-cineole), and the like lactones (furocoumarins, etc.) can be mentioned. In the present invention, one of these may be used, or two or more of these may be used.

  In addition, the malodor-emitting molecules described in the present specification include known molecules that emit malodor, for example, molecules causing aging odor (such as 2-nonenal), molecules causing sweat odor (Ammonia, sebum oxides such as fatty acid oxides, etc.), molecules (such as ammonia, 3-methylindole, etc.) that cause feces and urine odor, etc. may be mentioned. 2-Nonenal may be cis or trans.

  Also, the odor molecule described herein is a molecule that generates odor, and includes the above-mentioned aroma molecule and the above-mentioned molecule that emits malodor. The odor may be expressed as "scent", "scent", "aroma", etc. when it is felt preferable to humans and the like. On the other hand, when the odor is not felt favorably for humans etc. (for example, when it is felt unpleasant), it may be expressed as "smell" or "odor".

  As a carrier (it may be only described as a "carrier" in this specification) which can carry an aromatic molecule and can release the carried aromatic molecule according to this embodiment, for example, cyclic oligosaccharide (cyclo) Dextrin), polyacids, mesoporous silica particles, silver nanoparticles and the like.

  The amount of the carrier fixed to the thin film is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, in terms of occupancy relative to the surface area of the surface to which the carrier is fixed. Is usually 100% or less because it is preferable that more carrier be immobilized. The carrier may be fixed in a single layer on the thin film surface or may be fixed in a plurality of layers.

The amount of odor molecules carried on the carrier is preferably 10 pmol or more, more preferably 100 pmol or more, and preferably 10 mmol or less, as a total amount per 1 cm ² when measured as in Example 3 described later. More preferably, it is 1 mmol or less.

Here, when the carrier is a cyclic oligosaccharide, an α form (α-cyclodextrin), a β form (β-cyclodextrin), and a γ form (γ-cyclodextrin) are preferred. Β- and γ-forms are preferred, and γ-forms are more preferred, as they are more capable of supporting odor molecules, as shown in the case where they are not immobilized on a thin film, ie, in the case of the carrier alone.
In addition, as shown in Reference Example 2 described later (when the carrier is not immobilized on a thin film, ie, when the carrier is alone), the supported odor molecules are easily substituted by other odor molecules, and thus β-forms, The γ form is preferred, and the γ form is more preferred.
Further, from the viewpoint of sustained release, β-form and γ-form are preferable, and γ-form is more preferable.

One specific example of the present embodiment is an aspect in which a thin film is attached to a body surface such as skin for the purpose of aromatization.
In an environment where the area to which the thin film is attached does not contain a large amount of aromatic molecules and molecules that emit malodor, the support is attached to the thin film directly without supporting the aromatic molecules, and the aromatic molecules are directly supported on the carrier by spraying. It is preferable to That is, in an environment where the area to which the thin film is attached contains more aromatic molecules than the molecule that emits malodor, for example, in an environment where perfume etc. is sprayed before attaching the thin film, the carrier carries aromatic molecules on the carrier. It is preferable to apply a thin film without letting the carrier release aromatic molecules emitted from the body surface.
In this aspect, if the aromatic molecule is a first odor molecule, the first odor molecule may be a carrier that is easily substituted by a second odor molecule, or a carrier that is resistant to substitution. It is also good. Even if the first odor molecule is easily substituted by the second odor molecule, in this environment where the number of aromatic molecules is more than the odorous molecules, there is a high possibility that both will become odor molecules of the same kind, The effect of this will last longer.

Another embodiment of the present invention is a thin film in which a carrier capable of sustained release of an aromatic molecule is immobilized, and the carrier carries the aromatic molecule.
A specific example of the present embodiment is an aspect in which a thin film is attached to a body surface such as skin for the purpose of deodorization and aroma.
In an environment where the area to which the thin film is to be attached contains more molecules that give off malodor than aromatic molecules, it is preferable to support the aromatic molecule on the carrier and then to apply the thin film.
In this embodiment, if the odorous molecule is the first odor molecule and the aroma molecule is the second odor molecule, the carrier carries the first odor molecule, but the first odor molecule It is preferable that it is a carrier that is easily substituted by the second odor molecule.

  The thin film according to the present invention is usually a self-supporting thin film (in a state in which the support of the substrate is not required), which exhibits high adhesion, and physical adsorption without using reactive functional groups or adhesives. It can be attached to various interfaces (glass, plastics, living tissue, etc.) by itself.

The thin film may be nonporous or porous or may have a network structure.
Also, the thin film may be colorless or colored, but the thin film is preferably colorless because it may be stuck on the surface of a body such as skin, and even if it is colored, the thin film may be stuck It is preferable that the color is close to the skin and inconspicuous.
The thin film may be transparent or opaque, but the thin film is preferably transparent because it may be applied to a body surface such as skin, and even if it is opaque, the thin film may be applied. It is preferably opaque so as to be close to the color of the skin. The transmittance of the thin film is usually 80% or more, preferably 85% or more, more preferably 90% or more, when light having a visible light wavelength of 400 to 700 nm is used. On the other hand, the upper limit is preferably 100% or less because the larger one is preferable.

  The material of the thin film is preferably insoluble in the liquid medium for dissolving the sacrificial layer during its production. In addition, since the thin film may be attached to the body surface such as the skin, the material does not adversely affect the body surface such as the skin, and is preferably not a material that stimulates the skin etc. or a material having toxicity. . For example, polysaccharides such as chitosan, alginic acid and hyaluronic acid; polylactic acid, copolymers of lactic acid and glycolic acid, biodegradable polymers such as polycaprolactone, etc. may be mentioned.

The thickness of the thin film is usually 20 nm or more, preferably 30 nm or more, more preferably 40 nm
The above is one, and it is usually 2000 nm or less, preferably 1500 nm or less, more preferably 1000 nm or less. The "thin film" of the present invention refers to a film in the film thickness range. When the film thickness is 20 nm or more, the thin film is easily handled. On the other hand, when the film thickness is 2000 nm or less, the adhesion of the thin film is improved, and it is preferable because it has no wearing feeling when attached to the skin.
The film thickness can be appropriately adjusted according to the conditions at the time of film formation. For example, adjustment can be made as appropriate by adjusting conditions such as the concentration of the material of the film, and the number of rotations and the rotation time when forming a film by spin coating. The film thickness can be measured by a known method and is not particularly limited. For example, as described in the examples to be described later, there is a method of scraping a part of the surface of a thin film produced on a silicon wafer with tweezers, exposing the silicon wafer, and measuring using a stylus type profilometer.

  The thin film according to the present invention may have a crosslinking agent (spacer) with the carrier. The crosslinking agent is not particularly limited as long as the material such as a polymer forming a thin film and the carrier do not have steric hindrance and can exhibit their original functions. For example, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, formaldehyde, glutaraldehyde, paraformaldehyde and the like can be mentioned. Those skilled in the art can select an appropriate crosslinking agent in consideration of both types, and the crosslinking can also be performed according to a conventional method.

Next, although the example of manufacture of the thin film concerning the present invention is described, it is not restricted to this.
For example, first, a polymer film to be a sacrificial layer is developed on a substrate having a smooth surface, and a thin film material layer is developed thereon. The substrate may be plate-like (ie, a substrate).
Examples of the material of the base include carbon materials such as silicon, silicone rubber, silica, glass, mica and graphite, polymer materials such as polyethylene, polypropylene, cellophane and elastomer, and calcium compounds such as apatite. The preferred material is silicon and the preferred substrate is a silicon wafer. Commercially available products can be used.

As the polymer to be the sacrificial layer, as described later, the material layer of the thin film is developed on it, and then it is immersed in the liquid medium to dissolve the sacrificial layer. It is not restricted. For example, when the liquid medium is an aqueous medium, polyelectrolytes such as polyacrylic acid and polymethacrylic acid; polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA); nonionic substances such as polysaccharides such as starch and cellulose acetate Water soluble polymers are mentioned. Commercially available products can be used.
There is no particular limitation on the method of developing the polymer film to be the sacrificial layer and the method of developing the material layer of the thin film thereon, and for example, it is possible to follow a conventional method such as spin coating. In addition, the film thickness can be appropriately adjusted according to the conditions at the time of film formation. For example, it can adjust suitably by adjusting conditions, such as density | concentration, rotation speed in the case of forming into a film by spin coat, and rotation time.

  After developing the thin film material layer, the carrier is fixed. At this time, the above-mentioned crosslinking agent may be used. The concentration of the solution containing the carrier and the reaction conditions can be appropriately adjusted as long as a sufficient amount of the carrier can be fixed to the material layer of the thin film, and the same applies when using a crosslinking agent.

  After the carrier is fixed, the carrier is immersed in a liquid medium in which only the sacrificial layer is dissolved, whereby the sacrificial layer is dissolved to obtain a thin film. Immersion in the liquid medium may be before or after separation of the substrate. As the liquid medium, for example, an aqueous medium is preferable, and when the sacrificial layer is cellulose acetate, acetone is preferable.

The obtained thin film can be stored in the liquid medium, and can be dried and stored. The drying method is not particularly limited, and examples thereof include natural drying, lyophilization and vacuum drying, all of which can be performed by a conventional method. As a further specific example, it can be attached to a silicon wafer and stored by drying in a desiccator.

  As a method of supporting an aromatic molecule on a support fixed to a thin film, for example, as in Example 3, the thin film is put in a closed container in which a solution of aromatic molecule is sealed so as not to contact with the solution. The method of leaving still etc. is mentioned. Besides, the solution of the aromatic molecule may be directly dropped, sprayed, applied or the like. The concentration of the aromatic molecule solution, the dilution solvent, the application amount and the like can be appropriately selected or adjusted according to the application.

Another embodiment of the present invention is a kit for deodorant and aroma, comprising: (A) a thin film on which a carrier capable of carrying an aroma molecule and capable of sustained release of the aroma molecule is immobilized, and (B) the aroma molecule It is.
(A) may be stored in a liquid medium, or may be stored in a dry state. In addition, (B) may be appropriately concentrated before use, or may be appropriately diluted with water etc. immediately before use. For the other matters related to (A) and (B), the descriptions and preferred conditions described above apply.
In addition, the kit can further include an instruction or the like describing the above-described specific example of an embodiment in which the thin film is used by being attached to a body surface such as skin.

  EXAMPLES The present invention will be described below using examples, but the present invention is not limited to these examples.

[Reference Example 1: Support of odor molecule on carrier (alone)]
Three types of cyclic oligosaccharides (α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, manufactured by Wako Pure Chemical Industries, Ltd.) were used as a carrier. In addition, linalool (aromatic molecule, manufactured by Sigma-Aldrich) or trans-2-nonenal (molecule emitting malodor, manufactured by Tokyo Kasei Co., Ltd.) was used as an odor molecule.
Three cyclic oligosaccharides (0.88 mmol) were mixed with 10 mL each of distilled water / ethanol mixed solution (2/1, volume ratio) and dissolved using a stirrer. To each obtained cyclic oligosaccharide solution, an ethanol solution (1.1 mmol, 1.8 mL) of linalool or trans-2-nonenal was added and stirred (rt, 24 h). The precipitate obtained after stirring is centrifuged (3000 rpm, 10
The solution is purified in min) and vacuum-dried, and the cyclic oligosaccharide carries an odor molecule (this may be referred to as "cyclic oligosaccharide-odor molecular complex" or simply "complex"). It was collected. Each complex (about 5 mg) is dissolved in heavy water and subjected to nuclear magnetic resonance (NMR, AVANCE 500, manufactured by Bruker) analysis to calculate the molar ratio of the odor molecule supported by the cyclic oligosaccharide to the cyclic oligosaccharide. did.

The results are shown in FIG. As for linalool, it was revealed that α-cyclodextrin was not supported but both β- and γ-cyclodextrin were supported (Fig. 1a, molar ratio in the case of β-cyclodextrin: 1.01 ± 0.02, γ Molar ratio in the case of cyclodextrin: 1.08 ± 0.02). At this time, it was determined that a complex was formed because protons at the 3rd and 5th positions of the glucose unit were upfield-shifted.
Similar examination of trans-2-nonenal confirmed that both were supported (FIG. 1 b, molar ratio in the case of β-cyclodextrin: 0.80 ± 0.01, molar ratio in the case of γ-cyclodextrin: 1.10 ± 0.01).

[Reference Example 2: Exchange of linanol on a carrier (alone) for trans-2-nonenal]
The linalool-loaded cyclic oligosaccharides (β-cyclodextrin, γ-cyclodextrin) prepared according to Reference Example 1 were each dissolved in distilled water. Subsequently, 10 equivalents of trans-2-nonenal mixed solution of distilled water / ethanol (2/1 volume ratio) was added to each cyclic oligosaccharide and stirred at room temperature for 24 hours. The precipitate obtained after stirring was purified by centrifugation (3000 rpm, 10 min) and vacuum dried to recover the complex. Each complex (about 5 mg) was dissolved in heavy water and subjected to NMR analysis.

  The results are shown in FIG. When β-cyclodextrin was used as the carrier, the loading ratio of linalool was decreased by 22% by the addition of trans-2-nonenal, and it was confirmed that a complex of trans-2-nonenal was formed accordingly. This exchange reaction was found to occur more efficiently in γ-cyclodextrin (the loading ratio of linalool: decreased by 90%). Therefore, γ-cyclodextrin is considered to be a carrier that can efficiently capture malodorous molecule, trans-2-nonenal, and efficiently release linalool, an aromatic molecule previously supported.

[Example 1: Method for producing a thin film on which cyclic oligosaccharide (γ-cyclodextrin) is immobilized]
The schematic of the manufacturing method of the thin film which fixed cyclic oligosaccharide in FIG. 3 is shown.
(1) Production of thin film comprising chitosan: P-type silicon wafer (manufactured by KST World Inc., diameter: 100 ± 0.5 mm, thickness: 525 ± 25 μm, oxide film: 200 nm, crystal plane: 110) Was cut to a size of 20 × 20 mm and used (FIG. 3 a). A cellulose acetate solution (40 mg / mL, degree of acetylation: 55%, manufactured by Daicel) dissolved in 1,4-dioxane (manufactured by Wako Pure Chemical Industries, Ltd.) is spin-coated on a silicon wafer (4000 rpm, 40 s) , MS-A 100, manufactured by Mikasa Co., Ltd.), dried (50 ° C., 1 min), and used as a sacrificial film (FIG. 3 b). Then, a chitosan aqueous solution (10 mg / mL, manufactured by Nacalai Tesque, weight average molecular weight: 88,000) dissolved in 2% (v / v) acetic acid is spin-coated (3000 to 8000 rpm, 60 s) and dried. A thin film consisting of chitosan (50 ° C., 1 min) was produced on a silicon wafer (FIG. 3 c).
(2) Fixation of cyclic oligosaccharides An example of γ-cyclodextrin as cyclic oligosaccharides is shown. Dimethylformamide (DMF,
Mixed solution of methylene diphenyl 4,4'-diisocyanate (MDI, 15 mM, manufactured by Tokyo Chemical Industry Co., Ltd.) and γ-cyclodextrin (3.8 mM, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in Wako Pure Chemical Industries, Ltd. Triethylamine (2.5 mM) as a catalyst is added to 0.5 mL to make a solution, and this solution is added dropwise to the chitosan thin film prepared on the substrate in (1) and heated (70 ° C., 1 h), and then the solution is added. The surface was washed three times with excess DMF to produce a γ-cyclodextrin fixed chitosan film (FIG. 3 d).
(3) Peeling of thin film
The substrate obtained in (2) was immersed in an acetone solution to dissolve cellulose acetate in the sacrificial layer, and the γ-cyclodextrin fixed chitosan thin film was peeled off from the substrate (FIG. 3 e).

Comparative Example 1
Comparative Example 1 is the same as Example 1 except that γ-cyclodextrin is not immobilized on the chitosan thin film (with MDI crosslinking) in (2) of Example 1.

[Example 2: Evaluation of physical properties of thin film on which cyclic oligosaccharide (γ-cyclodextrin) is immobilized]
(1) Visual observation of thin film and electron microscope observation of thin film surface The results of the thin film spin-coated with an aqueous solution of chitosan at 6000 rpm and 60 s in (1) of Example 1 are shown in FIG. According to Example 2 (3), it was visually confirmed that the γ-cyclodextrin-immobilized chitosan thin film peeled off the substrate maintained the same size as the substrate and was transparent (FIG. 4 a). Further, the peeled thin film was skimmed on an aluminum oxide membrane filter (Anodisk (registered trademark) 25, pore diameter: 0.1 μm, diameter: 25 mm, manufactured by GE Healthcare Life Sciences), and dried in a desiccator. When the surface of the thin film was observed using a scanning electron microscope (FE-SEM S-4800, manufactured by Hitachi High-Technologies Corporation), it was confirmed that the surface was a smooth and defect-free thin film (FIG. 4 b).
(2) Film Thickness of Thin Film According to (3) of Example 1, the γ-cyclodextrin fixed chitosan thin film peeled from the substrate was attached to another silicon wafer and dried in a desiccator. A portion of the surface of the thin film was cut with tweezers to expose the silicon wafer. The difference in level between the silicon wafer and the thin film was measured using a stylus type profilometer (Dektak (registered trademark) DXT-E, manufactured by Bruker) to obtain a film thickness. As a result, it was confirmed that the film thickness of the γ-cyclodextrin fixed chitosan thin film after drying decreased with the increase of the rotation speed of the chitosan aqueous solution (FIG. 5, rotation speed: 3000 rpm, 4000 rpm, 6000 rpm, The film thickness is 125 ± 8 nm, 111 ± 9 nm, 83 ± 4 nm, 81 ± 10 nm, respectively, in the order of 8000 rpm. This means that the film thickness can be arbitrarily controlled by the number of revolutions.
(3) Infrared spectroscopy of thin film The γ-cyclodextrin fixed chitosan thin film is mixed with potassium bromide powder (about 130 mg) to make a disk for infrared spectroscopy, infrared spectroscopy (FTIR-4800, Shimadzu) (Made by Mfg.). The results are shown in FIG.

[Comparative Example 2-1, Comparative Example 2-2, Comparative Example 2-3]
Comparative Example 2-1 was the same as (3) in Example 2 except that the chitosan thin film (with MDI crosslinking) to which γ-cyclodextrin was not immobilized which was prepared in Comparative Example 1 was used. And The results are shown in FIG.
What was carried out similarly to (3) of Example 2 except having used MDI powder was set as Comparative Example 2-2. The results are shown in FIG.
What was carried out similarly to (3) of Example 2 except having used the chitosan powder was set as Comparative Example 2-3. The results are shown in FIG. 6a.

In the case of the chitosan thin film not immobilized with γ-cyclodextrin shown in FIG. 6 c (with MDI crosslinking), as in the case of the MDI powder shown in FIG. 6 b, the isocyanate group (N = C = O) is derived from 2260 cm ⁻¹ The peak of the stretching vibration of was observed (Fig. 6b, arrow in Fig. 6c). This indicates that an isocyanate group is present in the thin film. As shown in FIG. 6 d, when it was bound to γ-cyclodextrin, the peak of stretching vibration derived from the isocyanate group disappeared. This supports that the thin film surface is modified with γ-cyclodextrin through MDI.

[Example 3: Evaluation of Linanol loading of cyclic oligosaccharide (γ-cyclodextrin) -fixed thin film]
According to Example 1 (3), the γ-cyclodextrin-immobilized chitosan thin film peeled off the substrate was attached to another silicon wafer and dried in a desiccator. The obtained thin film was placed in a closed vessel (volume 350 mL) so as not to be in direct contact with linalool (200 μL), and allowed to stand (rt, 15 h). Thereafter, the thin film is immersed in deuterated dimethyl sulfoxide (DMSO-d6, 0.8 mL, manufactured by Sigma-Aldrich) to extract the loaded linalool, and benzyl alcohol (100 μL / mL in DMSO-d6, as an internal standard substance is extracted. 10 μL (manufactured by Sigma Aldrich) was added, and subjected to nuclear magnetic resonance (NMR, AVANCE 500, manufactured by Bruker) analysis. Specifically, the integral value of protons derived from the methyl group of linalool (1.6 ppm) and the position 1 of benzyl alcohol (4.5
By comparing the integral value of the proton peak of ppm), the loading amount of linalool per unit area of the thin film was calculated.

[Comparative Example 3-1, Comparative Example 3-2]
A sample obtained in the same manner as Example 3 was used as Comparative Example 3-1 except that a chitosan thin film (with MDI crosslinking) to which γ-cyclodextrin was not fixed was used.
The thing similar to Example 3 was set as Comparative Example 3-2 except having used only the chitosan thin film.

The results are shown in FIG. In the case of chitosan thin film alone, linalool was not supported at all. γ-
Chitosan thin film (but with MDI cross-linking) to which cyclodextrin was not fixed was slightly supported by linalool (0.56 ± 0.28 nmol / cm ² ), compared with that of chitosan thin film fixed to γ-cyclodextrin, It was found to support linalool significantly (3.32 ± 0.63 nmol / cm ² ). This means that the immobilization of γ-cyclodextrin could impart an odor molecule carrying ability.

[Example 4: Linanol Slow Release Evaluation]
According to (3) of Example 1, the γ-cyclodextrin-fixed chitosan thin film peeled off from the substrate was attached to a polyethylene substrate (thickness 1 mm, manufactured by As One Corporation) cut into a circle with a diameter of 10 mm. 10 μL of a 30% linalool solution in ethanol was dropped on the thin film surface, and the solution was allowed to stand under constant temperature and humidity (22 ° C., RH: 40%). The substrate was taken out over time, placed in a 10 mL sample bottle, and sealed with a septum cupper. After standing for 5 minutes, 50 mL of the gas in the sample bottle is collected using a gas collection pump (AP-20, manufactured by KITAGAWA; NeedlEx, manufactured by Shinwa Kako), and gas chromatography (GC-8A, Shimadzu Corporation) Product analysis) to determine the concentration of linalool in the gas phase.

Comparative Example 4
Comparative Example 4 is the same as Example 4 except that the γ-cyclodextrin fixed chitosan thin film is not attached.

  The results are shown in FIG. In the γ-cyclodextrin-fixed chitosan thin film application group, the linalool concentration increased from 2 hours after standing compared with the group to which the thin film was not attached, and the tendency continued for about 6 hours. This suggests that linalool is once supported by γ-cyclodextrin to suppress volatilization and then released slowly.

Claims (6)

  A thin film on which a carrier capable of supporting an aromatic molecule and capable of slow-releasing the supported aromatic molecule is immobilized.   A thin film in which a carrier capable of sustained release of an aromatic molecule is immobilized and the aromatic molecule is supported on the carrier.   The aromatic molecule is monoterpene hydrocarbons, sesquiterpene hydrocarbons, monoterpene alcohols, sesquiterpene alcohols, diterpene alcohols, terpene aldehydes, aromatic aldehydes, ketones, esters, phenols, The thin film according to claim 1 or 2, which is one or more selected from the group consisting of oxides and lactones.   The thin film according to any one of claims 1 to 3, wherein the carrier is one or more selected from the group consisting of cyclic oligosaccharides, polyacids, mesoporous silica particles, and silver nanoparticles.   The thin film according to claim 4, wherein the cyclic oligosaccharide is γ-cyclodextrin.   A kit for deodorization and aroma, comprising: (A) a thin film on which a carrier capable of supporting an aromatic molecule and capable of slow release of the supported aromatic molecule is immobilized, and (B) the aromatic molecule.