JP7129046B2 - functional film - Google Patents

Description

The present invention relates to a functional film containing microcapsules.

Wearing items such as shoes, helmets, gloves, and highly airtight clothing that are poorly ventilated and used in high-humidity environments (hereinafter also referred to as "high-humidity items") may emit foul-smelling substances while worn. , and malodorous substances remain on the wearer after the wearer takes off the high-humidity article, giving discomfort to the wearer. Powder types and spray types are known as articles having a deodorizing effect on such malodorous substances. However, the powder type has the problem that the powder does not completely dissolve on the surface of the deodorizing object, and the surface becomes powdery, and the surface of the deodorizing object tends to become dirty due to cumulative use. . In addition to contamination of the object to be deodorized due to cumulative use, the spray type may impose a psychological burden on the user because the use of the spray may be known to the surroundings due to the jetting sound during use. Furthermore, there is also a problem that the deodorizing effect is low in durability and needs to be used frequently.

Microcapsules encapsulating the component are known as another method of applying a component having a deodorizing effect such as perfume to an object.
For example, in US Pat. No. 5,200,000, a product comprising a functionalized substrate comprising at least two planar water-soluble films carrying a coating of a functional composition, wherein the coating is between the two films There is disclosed a product wherein said functional composition comprises microcapsules.
Patent Document 2 discloses a scented sheet having a protective layer on top of a layer containing microencapsulated perfume. Patent Document 3 discloses a patch containing a malodour reducing agent. Patent Document 3 describes that the odor reducing agent is encapsulated in microcapsules.

Japanese Patent Publication No. 2009-536117 JP-A-2012-6262 Japanese Patent Publication No. 2008-539867

However, in the technique of Patent Document 1, air permeability is poor, and the film swells in a high-humidity environment (hereinafter also referred to as a "high-humidity environment"), the mechanical strength of the film decreases, and the film deforms or breaks. There is a problem that the surface of the object is contaminated by the
In the technique of Patent Document 2, a thermoplastic resin is used as a binder for forming the fragrance-containing layer, and the protective layer provided on the fragrance-containing layer is made of a water-based resin, thereby improving the water resistance of the sheet. , was insufficient for use in high-humidity environments.
Since the technique of Patent Document 3 is not intended for use in a high-humidity environment, there is a problem that the back sheet is plasticized and deformed due to moisture absorption.
As described above, in the techniques of Patent Documents 1 to 3, since the mechanical strength of the film in a high humidity environment is not sufficient, the object is contaminated by deformation or breakage of the film due to moisture absorption, and the object is encapsulated in the microcapsules. However, it has not been possible to sufficiently exhibit the function of the active ingredient, and it has not been able to sufficiently meet the needs of consumers who want to obtain the function continuously.
In addition, when applying a film containing microcapsules encapsulating an active ingredient to high-humidity wearables, it has high adhesiveness to objects under high-humidity environments, and the function of the active ingredient is fully exhibited. It is desired to provide wearers with comfort.
An object of the present invention is to provide a functional film that has high mechanical strength and excellent adhesiveness even in a high-humidity environment, and that can continuously release an active ingredient encapsulated in microcapsules. Make it an issue.

The present inventors have developed a functional film containing microcapsules encapsulating an active ingredient, a microcapsule-carrying layer containing a crosslinked body of a water-soluble polymer having a hydroxy group, and an adhesive layer, wherein the crosslinked body is the The present inventors have found that the above problems can be solved by cross-linking a water-soluble polymer with a cross-linking agent and setting the content of the cross-linking agent to the water-soluble polymer within a specific range.
That is, the present invention contains microcapsules (A) encapsulating an active ingredient (a), a microcapsule carrier layer containing a crosslinked product (B) of a water-soluble polymer (b) having a hydroxy group, and an adhesive layer. A functional film that
The crosslinked body (B) is obtained by crosslinking the water-soluble polymer (b) with a crosslinking agent (c),
Provided is a functional film in which the content of the cross-linking agent (c) relative to 100 parts by mass of the water-soluble polymer (b) is 1 part by mass or more and 6 parts by mass or less.

ADVANTAGE OF THE INVENTION According to the present invention, there is provided a functional film that has high mechanical strength and excellent adhesion even in a high-humidity environment, and that can continuously release an active ingredient encapsulated in microcapsules. be able to.

It is a schematic diagram of a test sample for measuring adhesive strength. FIG. 3 is a schematic diagram showing a state of attaching a functional film to an insole in use evaluation.

[Functional film]
The functional film of the present invention (hereinafter also simply referred to as "functional film" or "film") is a microcapsule (A) encapsulating an active ingredient (a) (hereinafter simply referred to as "microcapsule (A)" ), and a crosslinked body (B) of a water-soluble polymer (b) having a hydroxy group (hereinafter also simply referred to as "crosslinked body (B)") containing a microcapsule carrying layer (hereinafter simply referred to as "microcapsule carrying layer") and an adhesive layer, wherein the crosslinked body (B) is obtained by crosslinking the water-soluble polymer (b) with a crosslinking agent (c), and the water-soluble polymer (b) The content of the cross-linking agent (c) with respect to 100 parts by mass is 1 part by mass or more and 6 parts by mass or less.
In the present invention, the term "water-soluble polymer" refers to a polymer whose dissolved amount is 1 mg or more when the polymer reaches a constant weight after being dried at 105°C for 2 hours and dissolved in 100 g of water at 50°C. . The dissolved amount of the water-soluble polymer (b) is preferably 1 g or more, more preferably 5 g or more.

The functional film of the present invention has high mechanical strength and excellent adhesiveness even in a high-humidity environment, and can continuously release the active ingredient encapsulated in the microcapsules. Although the reason is not clear, it is considered as follows.
The functional film of the present invention contains microcapsules encapsulating an active ingredient, a microcapsule-carrying layer containing a crosslinked water-soluble polymer having a hydroxy group, and an adhesive layer. The crosslinked product is obtained by cross-linking the water-soluble polymer with a cross-linking agent, and the content of the cross-linking agent relative to the water-soluble polymer is within a specific range. It is possible to efficiently introduce a crosslinked structure by suppressing the presence inside, and it has high mechanical strength and excellent adhesiveness even in a high humidity environment, and the active ingredient encapsulated in the microcapsule Sustained release is believed to be possible.

[Microcapsule carrying layer]
The microcapsule-carrying layer contains microcapsules (A) and crosslinked bodies (B).
Hereinafter, the microcapsules (A) and the crosslinked product (B) will be described in order.

<Microcapsule (A)>
The microcapsules (A) enclose the active ingredient (a).
In the present invention, "active ingredient (a)" refers to an ingredient that can exhibit its function by being released from microcapsules (A). Examples of the active ingredient (a) include perfumes, perfume precursors, oils, antioxidants, preservatives, bactericides, pest repellents, insecticides, cooling agents, dyes, pigments, silicones, solvents, and oil-soluble polymers. etc. Among these, one or more selected from perfumes, perfume precursors, oils, cooling agents, pest repellents, and antioxidants, more preferably one or more selected from perfumes and perfume precursors. . The active ingredient (a) may be used alone or in combination of two or more.

Examples of the perfume precursor include compounds that release perfume components in response to water, compounds that release perfume components in response to light, and the like.
Examples of the compound that reacts with water to release a fragrance component include a silicate ester compound having an alkoxy component derived from a fragrance alcohol, a fatty acid ester compound having an alkoxy component derived from a fragrance alcohol, a carbonyl component derived from a fragrance aldehyde or a fragrance ketone, and an alcohol. Acetal compound or hemiacetal compound obtained by reaction of compound, Schiff base compound obtained by reaction of carbonyl component derived from fragrance aldehyde or fragrance ketone and primary amine compound, carbonyl component derived from fragrance aldehyde or fragrance ketone and hydrazine compound Examples thereof include hemiaminal compounds and hydrazone compounds obtained by the reaction.
Compounds that release fragrance components in response to light include 2-nitrobenzyl ether compounds having alkoxy components derived from fragrance alcohols, α-keto ester compounds having carbonyl components derived from fragrance aldehydes or fragrance ketones, and alkoxy compounds derived from fragrance alcohols. a coumaric acid ester compound having a These perfume precursors may be used as polymers, for example reaction products of some carboxyl groups of polyacrylic acid and perfume alcohols.

Microcapsules (A) preferably have a shell and a core containing active ingredient (a) inside the shell.
The constituent components of the shell of the microcapsules (A) are not particularly limited as long as they can stably enclose the active ingredient (a). Specific examples of the component include melamine resin, melamine-formaldehyde resin, phenol-formaldehyde resin, polyacrylate resin, polymethacrylate resin, polyurea resin, polyamide resin, polyester resin, polyurethane resin, silica, gelatin, gum arabic, gelatin/ gum arabic, agar, cellulose, cellulose derivatives, or combinations thereof. Among these, preferably one selected from melamine-formaldehyde resins, phenol-formaldehyde resins, polyacrylate resins, polymethacrylate resins, polyurea resins, polyamide resins, silica, gelatin, gum arabic, agar, cellulose, and cellulose derivatives above, more preferably one or more selected from polyacrylate resins, polymethacrylate resins, and silica, still more preferably one or more selected from polyacrylate resins and polymethacrylate resins, and even more preferably is a polymethacrylate resin.
Microcapsules (A) can be produced by appropriately selecting a conventionally known method. For example, when the constituent component of the shell contains one or more selected from polyacrylate resins and polymethacrylate resins, an oily solution obtained by mixing the active ingredient (a) to be encapsulated, a monomer and an oil-soluble polymerization initiator, and an emulsifier. and an aqueous solution obtained by mixing water, followed by emulsification to obtain a monomer emulsion, and then polymerizing the monomers of the monomer emulsion.

The calculated value of the common logarithm "logP" of the partition coefficient (n-octanol/water) of the active ingredient (a) (hereinafter also referred to as "ClogP value") improves the encapsulation rate of the active ingredient in the microcapsules, From the viewpoint of improving the sustained release of the active ingredient, it is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 10. It is below.
Here, the logP value is an index representing the hydrophilicity/hydrophobicity of a compound, and the ClogP value is described in A. Leo Comprehensive Medicinal Chemistry, Vol.4 C. Hansch, PGSammens, JB Taylor and CARamsden, Eds., P.295, Pergamon Press, "Calculated logP (ClogP)" calculated by the method described in 1990, ClogP values calculated by the program CLOGP v4.01. For example, when the active ingredient (a) is a perfume composition containing a plurality of perfume ingredients and oils, the ClogP value of the perfume composition is obtained by multiplying the ClogP value of each perfume ingredient and oil by the volume ratio in the perfume composition. , and the sum of them.

The oil-water interfacial tension of the active ingredient (a) at 25° C. is preferably 10 mN/m or more, more It is preferably 15 mN/m or more, more preferably 20 mN/m or more, and preferably 50 mN/m or less, more preferably 40 mN/m or less, still more preferably 30 mN/m or less.
The oil-water interfacial tension can be measured, for example, by a contact angle meter "Drop Master DM-501" (trade name, manufactured by Kyowa Interface Science Co., Ltd.).

The volume average particle diameter of the microcapsules (A) is preferably 0.01 μm or more, more preferably 0.1 μm or more, from the viewpoint of increasing the amount of the active ingredient to be encapsulated and sufficiently exhibiting the function of the active ingredient. , More preferably 0.5 μm or more, and from the viewpoint of suppressing the falling off of the microcapsules from the functional film and improving the handleability of the functional film, preferably 300 μm or less, more preferably 200 μm or less, and further It is preferably 100 μm or less.
In the present invention, the volume average particle diameter of the microcapsules (A) is measured using a laser diffraction/scattering particle size distribution analyzer "LA-950" (trade name, manufactured by Horiba, Ltd.). can be done. In that case, the measurement uses a flow cell, the medium is water, and the refractive index is set to 1.45-0i. A suspension containing microcapsules (A) is added to the flow cell, measurement is performed at a concentration at which the transmittance is around 90%, and the average particle diameter is determined on a volume basis.

The content of the microcapsules (A) in the microcapsule-carrying layer is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 3% by mass or more, from the viewpoint of sufficiently obtaining the effect of the active ingredient. , Still more preferably 5% by mass or more, still more preferably 10% by mass or more, and from the viewpoint of improving the mechanical strength of the functional film, preferably 50% by mass or less, more preferably 40% by mass or less , more preferably 30% by mass or less.

<Crosslinked body (B)>
The crosslinked product (B) is obtained by crosslinking a water-soluble polymer (b) having a hydroxy group with a crosslinking agent (c).
The crosslinked body (B) preferably has a partially reversible crosslinked structure. When the crosslinked body (B) has a reversible crosslinked structure, the water-soluble polymer (b) is water-soluble before crosslinked, but the introduction of the crosslinked structure improves the moisture resistance of the functional film and improves mechanical properties. Strength and adhesion can be improved. Further, since the crosslinked structure is reversible, the crosslinked structure is cut by a stimulus such as water, and when the adhesive layer is water-soluble, the functional film can be removed by washing or the like after use. Moreover, when it is desired that only the microcapsules (A) adhere to clothes or the like during washing, the functional film can be dissolved as necessary.
As used herein, the term "reversible crosslinked structure" refers to physical crosslinks in which polymer chains are crosslinked by non-covalent bonds such as van der Waals bonds, ionic bonds, coordinate bonds, and hydrogen bonds, and hydrolysis-dehydration. It also includes chemical cross-linking in which polymer chains are cross-linked by reversible reactions such as condensation reaction, Diels-Alder reaction, sol-gel reaction, etc. under the environment of daily life such as water, oxygen and light. From the viewpoint of stability and ease of handling, the crosslinked body (B) preferably has a crosslinked structure formed by physical crosslinking.
As used herein, "partially reversible crosslinked structure" means that the reversible crosslinked structure is introduced into a part of the structure of the crosslinked product (B).

(Water-soluble polymer (b))
The water-soluble polymer (b) forming the crosslinked body (B) has a hydroxy group, and examples thereof include polyvinyl alcohols such as polyvinyl alcohol and modified polyvinyl alcohol; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; Cellulose derivatives such as carboxymethyl cellulose are included. The water-soluble polymer (b) may be used singly or in combination of two or more as long as the moisture resistance is not impaired. Among these, from the viewpoint of moisture resistance, polyvinyl alcohols are preferable, at least one selected from polyvinyl alcohol and modified polyvinyl alcohol is more preferable, and polyvinyl alcohol is still more preferable.
Specific examples of commercially available polyvinyl alcohol include "Gosenol" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Mowiol" series manufactured by Kuraray Europe Ltd., and the like.

When polyvinyl alcohol is used as the water-soluble polymer (b), the degree of saponification of polyvinyl alcohol is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 85 mol%, from the viewpoint of improving moisture resistance. and preferably 95 mol % or less, more preferably 92 mol % or less, still more preferably 90 mol % or less. In particular, when the functional film is required to be water-soluble as described above, the content is preferably 95 mol % or less, more preferably 92 mol % or less, and even more preferably 90 mol % or less.
The weight average molecular weight of the water-soluble polymer (b) is not particularly limited, but from the viewpoint of improving the mechanical strength of the film, it is preferably 5,000 or more, more preferably 20,000 or more, and still more preferably 100,000 or more. And, from the viewpoint of suppressing the viscosity increase of the polymer solution when producing the film and improving the ease of production, it is preferably 1,000,000 or less, more preferably 700,000 or less, and still more preferably 500,000 or less.

(Crosslinking agent (c))
The cross-linking agent (c) is not particularly limited as long as it can introduce a cross-linked structure into the polymer (b). Compounds are preferred. From this point of view, the cross-linking agent (c) is preferably one or more selected from polybasic inorganic acids and organic compounds having two or more functional groups in the molecule of at least one selected from hydroxy groups and carboxy groups. .

Examples of the polybasic inorganic acid include, for example, sulfuric acid, polyphosphoric acid, compounds of hydrogen and acid groups containing nonmetallic elements such as boric acid, and salts thereof; metal hydroxides such as aluminum hydroxide; titanium tetraalkoxide, etc. and metal alkoxides exhibiting Lewis acidity.
Examples of the organic compound include unsaturated dicarboxylic acids such as maleic acid and fumaric acid; aromatic dicarboxylic acids such as phthalic acid and terephthalic acid; polyvalent carboxylic acids such as hydroxy acids such as malic acid and citric acid; and salts thereof. are mentioned.
Among these, from the viewpoint of safety for the user of the functional film, more preferably one or more selected from polybasic inorganic acids, polyvalent carboxylic acids, and salts thereof, which are reversible under mild conditions From the viewpoint of being able to introduce a crosslinked structure, polybasic inorganic acids and salts thereof are more preferable, boric acid and salts thereof are more preferable, and boric acid and borax (Na ₂ B ₄ O ₇ · 10H ₂ O), more preferably boric acid.
The boric acid includes not only orthoboric acid (B(OH) ₃ ), but also metaboric acid (HBO ₂ ), tetraboric acid (H ₂ B ₄ O ₇ ), boric anhydride (B ₂ O ₃ ), and the like. included.
Examples of the borate include orthoborate (e.g., InBO ₃ , ScBO ₃ , YBO ₃ , LaBO ₃ , Mg ₃ (BO ₃ ) ₂ , Co ₃ (BO ₃ ) ₂ ), and diborate. ₍ e.g. _Mg2B2O5 , _Co2B2O5 ), metaborate ₍ e.g. _LiBO2 , Ca _{( BO2} ) ₂ , _NaBO2 , _KBO2 ), tetraborate ₍ e.g. _Na2 B ₄ O _{7.10H 2} O), pentaborate (eg, KB ₅ O _{8.4H 2} O, CsB ₅ O ₅ ), and the like.

The content of the cross-linking agent (c) with respect to 100 parts by mass of the water-soluble polymer (b) is 1 part by mass or more, preferably 1 part by mass, from the viewpoint of improving the moisture resistance of the film and improving the mechanical strength and adhesiveness. 5 parts by mass or more, more preferably 2 parts by mass or more, still more preferably 2.5 parts by mass or more, and suppresses the presence of unreacted cross-linking agents that do not contribute to the formation of a cross-linked structure in the film. , From the viewpoint of improving mechanical strength and adhesiveness, it is 6 parts by mass or less, preferably 5.5 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 4.5 parts by mass or less, and even more preferably is 4 parts by mass or less.

The total content of the microcapsules (A) and the crosslinked body (B) in the microcapsule-carrying layer is preferably 80% by mass or more, from the viewpoint of improving the moisture resistance of the film and improving the mechanical strength and adhesiveness. Preferably 90% by mass or more, more preferably 95% by mass or more, and preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.7% by mass or less, and still more Preferably, it may be 99.5% by mass or less.

<Other ingredients>
(Plasticizer)
The microcapsule-carrying layer may further contain a plasticizer from the viewpoint of adjusting mechanical strength such as tensile strength and physical properties of the functional film such as water solubility.
The plasticizer is not particularly limited as long as it has low volatility and little change in physical properties during storage or use of the film. For example, polyhydric alcohols such as glycerin, diglycerin, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, tripropylene Polyhydric alcohol alkyl such as glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol monomethyl ether Ether; ethylene glycol alkyl ether acetate such as ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like.

The microcapsule-carrying layer may further contain functional ingredients in addition to the microcapsules (A). Functional ingredients include fragrances, fragrance precursors, deodorants, oils, antioxidants, UV absorbers, deposition aids, adsorbents, bactericides, pest repellents, insecticides, cooling agents, dyes, and pigments. , silicones, lubricants, antistatic agents, preservatives, and the like.

(Deodorants)
As the deodorant, both a deodorant using a chemical reaction and a deodorant using physical adsorption can be suitably used.
Examples of deodorants using chemical reactions include (1) inorganic acids, organic acids, basic inorganic compounds, and basic organic compounds using neutralization reaction, and (2) Schiff base formation reaction accompanying dehydration condensation. (3) unsaturated carbonyl compounds and thiol compounds using Michael addition reaction, (4) olefin compounds using cycloaddition reaction, and the like.
As the deodorant utilizing physical adsorption, porous particles having a BET specific surface area of 1 m ² /g or more can be suitably used, and inorganic particles or organic particles may be used.

Examples of porous inorganic particles include activated carbon, charcoal, silica gel, zeolite, alumina oxide, and titanium oxide.
Porous organic particles include porous polymer particles such as porous polystyrene particles, porous polyacrylic (or methacrylic) particles, porous polyester particles, and the like. The porous polymer particles may be homopolymers, copolymers of two or more monomers, and may be further modified particles.
The volume average particle diameter of the porous particles is preferably 0.01 μm or more, more preferably 0.5 μm or more, from the viewpoint of preventing burial in the microcapsule-carrying layer and allowing the functional ingredient to act efficiently. And, from the viewpoint of preventing falling off from the film and improving ease of handling, the thickness is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less.
The BET specific surface area of the porous particles is preferably 10 m ² /g or more, more preferably 50 m ² /g or more, still more preferably 100 m ² /g or more, from the viewpoint of promoting the deodorizing effect. It is preferably 300 m ² /g or less, more preferably 200 m ² /g or less, from the viewpoint of the strength of the particles.

(Deposition aid)
The deposition aid is not particularly limited as long as it enhances the adsorptivity to the object. Examples of the deposition aid include cationized guar gum, cationized tara gum, cationized fenugreek gum, cationized locust bin gum, cationized starch, and the like.

(Thickness of microcapsule-carrying layer)
The thickness of the microcapsule-carrying layer in the functional film is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, from the viewpoint of imparting sufficient mechanical strength to the functional film. From the viewpoint of reducing discomfort such as appearance when the film is attached to an object, the thickness is preferably 800 μm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The microcapsule-carrying layer does not necessarily have to have a constant thickness, and may have voids as long as it can exhibit a sufficient effect when the functional film is used.

(Physical properties of microcapsule-carrying layer)
In the functional film, the microcapsule-carrying layer preferably does not lose its mechanical strength even under high humidity conditions. For example, when the thickness of the microcapsule-carrying layer is 50 μm and the content of the microcapsules (A) is 20% by mass, the maximum tensile stress of the microcapsule-carrying layer is under low humidity conditions (temperature 25±2° C., humidity 25 ± 2%), from the viewpoint of improving the mechanical strength and adhesive strength of the functional film, it is preferably 17 MPa or more, more preferably 20 MPa or more, still more preferably 23 MPa or more, and preferably 40 MPa or less, It is more preferably 35 MPa or less, still more preferably 30 MPa or less.
Further, when the thickness of the microcapsule-carrying layer is 50 μm and the content of the microcapsules (A) is 20% by mass, the maximum tensile stress of the microcapsule-carrying layer is under high humidity conditions (temperature 25±2° C., humidity 84±2%), it is preferably 16 MPa or more, more preferably 18 MPa or more, still more preferably 20 MPa or more, and preferably 40 MPa or less, more preferably 35 MPa or less, still more preferably 30 MPa or less.
The maximum tensile stress can be specifically measured by the method described in Examples.

The functional film may have a structure containing at least one microcapsule-carrying layer, and may have a structure in which two or more microcapsule-carrying layers are laminated via other layers. When two or more microcapsule-carrying layers are contained, by combining microcapsule-carrying layers with different thicknesses and strengths, the active ingredient (a) of the microcapsules (A) is released in multiple stages to the functional film. can be given the function to Microcapsules (A) containing different active ingredients (a) can also be used for each microcapsule-carrying layer.

[Adhesive layer]
The functional film contains at least one adhesive layer.
The adhesive layer preferably contains an adhesive that is adhesive at room temperature, and the adhesive layer may be water-soluble. Further, the adhesive layer does not necessarily have to have a constant thickness, and may have voids as long as a sufficient adhesive effect can be exhibited when the functional film is used.
Although the adhesive is not particularly limited, examples thereof include acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives, and the like. Among them, acrylic pressure-sensitive adhesives or rubber-based pressure-sensitive adhesives are preferable, and acrylic pressure-sensitive adhesives are more preferable, from the viewpoint of adhesiveness.
Starch etc. are mentioned as an adhesive agent which forms the adhesive layer which has water solubility.
Although the thickness of the adhesive layer is not particularly limited, it is preferably 1 μm or more, more preferably 5 μm or more, and preferably 100 μm or less, more preferably 50 μm or less.

[Release layer]
Further, as one aspect of the functional film, a release layer may be provided on the outer surface of the microcapsule-carrying layer from the viewpoint of preventing adhesion to unintended surfaces.
The release layer can be formed by applying a release agent to the microcapsule-carrying layer.
The release agent is not particularly limited as long as it has little effect on the adhesive layer after release and is low in toxicity. Examples include silicone, nitrocellulose, starch, modified starch, zein, casein, and polyvinyl chloride. , polyvinyl butyral, polyvinyl acetate or its copolymer, polyvinyl alcohol, polyethylene, polypropylene, polyfluorocarbon, acrylic resin and the like. The release agent can be used singly or as a mixture of two or more. Moreover, from the viewpoint of controlling the releasability, a wax containing polyamide or a hydrocarbon may be used as an additive.
The thickness of the release layer is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more, and preferably 100 µm or less, more preferably 50 µm or less.

[Release liner]
The functional film of the present invention may be provided with a release liner on the outer surface of the adhesive layer from the viewpoint of preventing adhesion to unintended surfaces during storage or use.
The release liner is not particularly limited as long as it prevents the functional film from adhering to unintended surfaces during storage or use and can be easily peeled off from the adhesive layer of the functional film by human power. . Examples of the release liner include paper or film coated with a release agent, creped or embossed film, and the like.
As the release agent, the same ones as mentioned for the release layer can be used.

(Production of functional film)
There are no particular restrictions on the method for producing the functional film.
For example, a method (I) of forming a microcapsule-carrying layer on a substrate and then forming an adhesive layer on the microcapsule-carrying layer, forming a microcapsule-carrying layer on the substrate, and removing the microcapsules from the substrate A method (II) of peeling off as a carrier layer film and attaching it to an adhesive layer separately formed on a substrate, a method of forming an adhesive layer on a substrate and then forming a microcapsule carrier layer on the adhesive layer ( III) and the like.
In addition, it is preferable that the base material is finally peeled off or removed.

Formation of the microcapsule-carrying layer is carried out by forming a coating layer containing the microcapsules (A), the polymer (b) and the cross-linking agent (c), and then cross-linking the polymer (b) and the cross-linking agent (c). It is preferred to form body (B).
As a method for forming the coating layer, a method (i ), a composition for forming a microcapsule carrying layer (2-1) containing the microcapsules (A) and the polymer (b) is applied onto a substrate to form a layer containing the microcapsules (A) and the polymer (b) Method (ii), in which the microcapsule carrying layer-forming composition (2-2) containing the cross-linking agent (c) is applied onto the layer after forming in advance. Among them, the method (i) is preferable from the viewpoint of the cross-linking reaction between the polymer (b) and the cross-linking agent (c).

Substrates used for forming the microcapsule-carrying layer include, for example, polyesters such as polyethylene terephthalate, polylactic acid and polycaprolactone; polyolefins such as polypropylene and polyethylene; films such as polyvinyl chloride, polyamide and cellulose; condenser paper and paraffin paper. and other papers.
The thickness of the substrate is not particularly limited, and is preferably 10 µm or more, preferably 800 µm or less, more preferably 500 µm or less, and even more preferably 200 µm or less.

From the viewpoint of coating properties and obtaining a smooth functional film, the composition for forming a microcapsule-carrying layer is preferably in the form of a solution by adding an aqueous solvent.
In the case of the method (i), the solid content concentration of the microcapsule-carrying layer-forming composition is preferably 3% by mass or more, more preferably 5% by mass, from the viewpoint of promoting drying during film formation and from the viewpoint of work efficiency. As described above, it is more preferably 7% by mass or more, and from the viewpoint of obtaining a smooth functional film, it is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. The composition may further contain an organic solvent from the viewpoint of adjusting viscosity and the like.

The coating method of each layer in the production of the functional film is not particularly limited, and for example, bar coating method, roll coater method, screen method, flexographic method, spin coating method, dip method, spray method, slide coating method, etc. can be used as appropriate. can be selected.
When the composition for forming a microcapsule carrying layer contains a solvent, it is preferable to have a drying step of drying the solvent after coating the composition. Drying can be performed, for example, at a temperature of 50° C. or higher and 150° C. or lower and within a range of 0.5 hours or more and 5 hours or less.

The conditions for the cross-linking reaction between the polymer (b) and the cross-linking agent (c) can be appropriately selected according to the type of the cross-linking agent (c). For example, when boric acid is used as the cross-linking agent (c), cross-linking is preferably carried out by the drying step described above.

The functional film of the invention can be used for various purposes.
For example, as an embodiment of a functional film, it imparts a fragrance effect, deodorant effect, or deodorant effect to an object in an environment exposed to high humidity and low breathability such as shoes and helmets. morphology. For example, the functional film may be cut into a seal-like or tape-like shape and attached to the insole (insole) of the shoe. At this time, the shoe wearer's foot and the insole are rubbed by walking, and the microcapsules (A) contained in the microcapsule-carrying layer of the functional film collapse and are included in the wearer's foot and shoe. active ingredient (a) can be applied. The functional film can be peeled off from the insole at any timing, and the insole with the functional film attached may be washed in a washing machine or the like. At this time, when the functional film is water-soluble, the functional film can be dissolved and removed during washing.

Another embodiment of the functional film includes a form in which it is attached to the surface of clothing such as underwear. The functional film may be cut into seals or tapes and attached to collars, sleeves, or the like of clothing. At this time, the action of the wearer causes the tape attached to the clothing to be rubbed, and the microcapsules (A) contained in the microcapsule-carrying layer of the functional film are disintegrated and the activity contained in the wearer's clothing is disintegrated. Component (a) can be applied. The functional film can be peeled off from clothing at any time, and can be removed by washing with a washing machine or the like. At this time, when the functional film is water-soluble, the functional film can be dissolved and removed during washing.

Another embodiment of applying the functional film to clothing includes a form in which it is attached to clothing before washing. When the functional film is water-soluble, the functional film dissolves during the washing process, so that the microcapsules (A) supported by the microcapsule-carrying layer remain on the part of the clothing to which they are attached, and are washed. The garment can be endowed with the function of releasing the active ingredient (a) even later. In particular, by attaching two or more types of functional films using microcapsules (A) containing different active ingredients (a) to individual clothes, different functions of the active ingredient (a) are imparted to each piece of clothing. be able to.

Furthermore, as another embodiment of applying the functional film to clothes, there is a form in which the active ingredient (a) is applied in a process different from that of conventional detergents, finishing agents, etc. in the washing work of clothes. For example, the functional film may be cut into a tape of any size, and the tape may be put into a washing tub in the washing or rinsing process. In this case, the functional film is dissolved by washing water or rinsing water, the microcapsules (A) contained in the microcapsule-carrying layer are released, and the microcapsules (A) are applied to the entire clothes in the washing tub. be able to.

As described above, a preferred embodiment of the functional film is a microcapsule-carrying layer containing microcapsules (A) encapsulating an active ingredient (a) and a crosslinked product (B) of a water-soluble polymer (b) having a hydroxy group. and an adhesive layer, wherein the crosslinked product (B) is obtained by cross-linking the water-soluble polymer (b) with a cross-linking agent (c), and the water-soluble polymer (b) is 100 mass The content of the cross-linking agent (c) per part is 1 part by mass or more and 6 parts by mass or less.
Examples of objects to be scented, deodorized or deodorized include undershirts, T-shirts, Y-shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, tights, gloves, shoe insoles (insoles ) and other textile products; and articles that come into direct or indirect contact with the human body, such as leather products such as leather gloves and leather shoes. Among them, from the viewpoint of mechanical strength and adhesiveness in a high-humidity environment, and from the viewpoint of sustained release of the active ingredient encapsulated in the microcapsules, it is preferably a high-humidity wearable article, and more preferably shoes or a helmet. is.

A preferred method of using the functional film includes a microcapsule-carrying layer containing microcapsules (A) encapsulating an active ingredient (a) and a crosslinked product (B) of a water-soluble polymer (b) having a hydroxy group, and an adhesive A functional film containing a layer, wherein the crosslinked body (B) is obtained by crosslinking the water-soluble polymer (b) with a crosslinking agent (c), and the water-soluble polymer (b) is 100 parts by mass of the The content of the cross-linking agent (c) is 1 part by mass or more and 6 parts by mass or less, and the functional film is attached to the adherend via the adhesive layer, and the adherend is scented, deodorized, or deodorized. is a method of doing
Examples of the adherend include the above-mentioned perfume, deodorant, or deodorant objects. From the viewpoint of effective release, high-humidity wearables are preferable, and shoes or helmets are more preferable. When attached to a shoe or helmet, it is preferably attached to the inner surface of the shoe or helmet that comes into direct or indirect contact with the human body.

In the following Synthesis Examples, Production Examples, Examples and Comparative Examples, "parts" and "%" are "mass parts" and "mass%" unless otherwise specified.
The volume average particle diameter in the following was measured by the following method.
(Volume average particle size)
The average particle size of the emulsified droplets and microcapsules (A) in the emulsion was measured using a laser diffraction/scattering particle size distribution analyzer “LA-950” (trade name, manufactured by Horiba, Ltd.). A flow cell was used for the measurement, the medium was water, and the refractive index was set to 1.45-0i. An emulsified liquid or a suspension containing microcapsules (A) was added to the flow cell, measurement was carried out at a concentration at which the transmittance was around 90%, and the average particle size was determined on a volume basis.

(Synthesis of fragrance-encapsulating polymethacrylate microcapsules)
Synthesis example 1
To 1575.0 g of ion-exchanged water, polyvinyl alcohol (trade name: Gosenol GH-20, manufactured by Nippon Synthetic Chemical Co., Ltd., saponification degree 86.5 to 89.0 mol%, 4% aqueous solution viscosity at 20 ° C. 40 to 46 MPa · s) 32.5 g was added and dissolved at 90°C, then cooled to room temperature to form an aqueous phase. In addition, 40.0 g of methacrylic acid (Wako Pure Chemical Industries, Ltd.), 29.0 g of ethylene glycol dimethacrylate (trade name: NK Ester 1G, Shin-Nakamura Chemical Co., Ltd.), and active ingredient (a) in Table 1 below 805.0 g of the fragrance composition (CLogP: 4.2), polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) (trade name: V-65, Wako Pure Chemical Industries, Ltd.) 1.0 g was mixed and dissolved to form an oil phase. The water phase and the oil phase were emulsified by a homomixer to obtain an emulsified liquid having a volume average particle size of 27 μm. After the emulsified liquid was transferred to a 500 mL four-necked flask, the pressure reduction to 22 kPa and the introduction of nitrogen were repeated three times to perform nitrogen replacement. Thereafter, the polymerization reaction is performed by heating at 65° C. for 5 hours and at 75° C. for 3 hours to form a suspension (microcapsule effective min: 35.2%).

(Production of microcapsule-carrying layer film)
Production example 1
10% concentration polyvinyl alcohol (trade name: Gosenol GH-20, manufactured by Nippon Synthetic Chemical Co., Ltd., saponification degree 86.5 to 89.0 mol%, 4% aqueous solution viscosity at 20 ° C. 40 to 46 MPa s) ( 29.0 g of the aqueous solution (hereinafter also referred to as “PVA-1”), 2.14 g of the suspension containing the perfume-encapsulating polymethacrylate microcapsules obtained in Synthesis Example 1, 1.80 g of an aqueous solution of 5% boric acid, edible After 0.03 g of a blue dye was added and mixed, the mixture was allowed to stand still for one day to defoam, thereby obtaining a composition 1 for forming a microcapsule carrying layer.
The resulting composition 1 was cast on a polyester film (trade name: Lumirror, film thickness: 50 μm, manufactured by Toray Industries, Inc.) using a bar coater, dried in a constant temperature bath at 80° C. for 3 hours, and supported with microcapsules. formed a layer. After drying, the microcapsule-carrying layer was peeled off from the polyester film to obtain a film 1 composed of the microcapsule-carrying layer having a thickness of 50 μm (hereinafter also referred to as “microcapsule-carrying layer film” or “carrying layer film”), and various evaluations were performed. used for

Production example 2
29.0 g of 10% concentration PVA-1 aqueous solution, 2.14 g of suspension containing fragrance-encapsulating polymethacrylate microcapsules obtained in Synthesis Example 1, 2.90 g of 5% concentration boric acid aqueous solution, 0 edible blue pigment After adding and mixing 0.03 g of the mixture, the mixture was allowed to stand still for one day to defoam, and a composition 2 for forming a microcapsule carrying layer was obtained.
The resulting composition 2 was cast on a polyester film (trade name: Lumirror, film thickness: 50 μm, manufactured by Toray Industries, Inc.) using a bar coater, dried in a constant temperature bath at 80° C. for 3 hours, and supported with microcapsules. formed a layer. After drying, the microcapsule-carrying layer was peeled off from the polyester film to obtain a microcapsule-carrying layer film 2 having a thickness of 50 μm, which was used for various evaluations.

Production example 3
30.0 g of a 10% concentration PVA-1 aqueous solution, 1.67 g of the suspension containing the perfume-encapsulating polymethacrylate microcapsules obtained in Synthesis Example 1, and the method described in Example 1 of JP-A-2010-138344. 0.20 g of porous polymer particles (2-vinylpyridine/divinylbenzene copolymer, volume average particle diameter of 19.3 μm, BET specific surface area of 169 m ² /g), 1.80 g of a 5% concentration boric acid aqueous solution, After adding and mixing 0.03 g of an edible blue colorant, the mixture was allowed to stand still for one day to defoam, thereby obtaining a composition 3 for forming a microcapsule carrying layer.
The obtained composition 3 was cast on a polyester film (trade name: Lumirror, film thickness: 50 μm, manufactured by Toray Industries, Inc.) using a bar coater, then dried in a constant temperature bath at 80° C. for 3 hours to support microcapsules. formed a layer. After drying, the microcapsule-carrying layer was peeled off from the polyester film to obtain a microcapsule-carrying layer film 3 having a thickness of 50 μm, which was used for various evaluations.

Production example 4
10% concentration polyvinyl alcohol (trade name: Mowiol 56-98, manufactured by Kuraray Europe Ltd., saponification degree 98.0 to 98.8 mol%, 4% aqueous solution viscosity at 20 ° C. 52 to 60 mPa s) (hereinafter referred to as "PVA -2”) 30.0 g of the aqueous solution, 2.14 g of the suspension containing the fragrance-encapsulating polymethacrylate microcapsules obtained in Synthesis Example 1, 1.80 g of a 5% concentration boric acid aqueous solution, and 0.0 g of an edible blue colorant. After adding and mixing 03 g of the mixture, the mixture was allowed to stand still for defoaming to obtain a composition 4 for forming a microcapsule carrying layer.
The resulting composition 4 was cast on a polyester film (trade name: Lumirror, film thickness: 50 μm, manufactured by Toray Industries, Inc.) using a bar coater, dried in a constant temperature bath at 80° C. for 3 hours, A capsule carrier layer was formed. After drying, the microcapsule-carrying layer was peeled off from the Lumirror film to obtain a microcapsule-carrying layer film 4 having a thickness of 50 μm, which was used for various evaluations.

Comparative production example 1
30.0 g of a 10% concentration PVA-1 aqueous solution, 2.14 g of the suspension containing the fragrance-encapsulating polymethacrylate microcapsules obtained in Synthesis Example 1, and 0.03 g of an edible blue pigment were added and mixed, and then the mixture was allowed to stand still. Degassing was performed by placing the microcapsule-carrying layer-forming composition C1.
The resulting composition C1 is cast on a polyester film (trade name: Lumirror, film thickness: 50 μm, manufactured by Toray Industries, Inc.) using a bar coater, dried in a constant temperature bath at 80° C. for 3 hours, and microcapsules are obtained. A carrier layer was formed. After drying, the microcapsule-carrying layer was peeled off from the Lumirror film to obtain a 50 μm-thick microcapsule-carrying layer film C1, which was used for various evaluations.

Comparative production example 2
29.0 g of a 10% concentration PVA-1 aqueous solution, 2.14 g of the suspension containing the perfume-encapsulating polymethacrylate microcapsules obtained in Synthesis Example 1, 4.06 g of a 5% concentration aqueous boric acid solution, and an edible blue dye After 0.03 g of the mixture was added and mixed, the mixture was allowed to stand still for defoaming to obtain a composition C2 for forming a microcapsule carrying layer.
The resulting composition C2 was cast on a polyester film (trade name: Lumirror, film thickness: 50 μm, manufactured by Toray Industries, Inc.) using a bar coater, dried in a constant temperature bath at 80° C. for 3 hours, and supported with microcapsules. formed a layer. After drying, the microcapsule-carrying layer was peeled off from the polyester film to obtain a 50 μm-thick microcapsule-carrying layer film C2, which was used for various evaluations.

Comparative production example 3
30.0 g of a 10% concentration PVA-2 aqueous solution, 2.14 g of the suspension containing the fragrance-encapsulating polymethacrylate microcapsules obtained in Synthesis Example 1, and 0.03 g of an edible blue pigment were added and mixed, and then allowed to stand. Then, defoaming was performed to obtain a microcapsule-carrying layer-forming composition C3.
The resulting composition C3 was cast on a polyester film (trade name: Lumirror, film thickness: 50 μm, manufactured by Toray Industries, Inc.) using a bar coater, dried in a constant temperature bath at 80° C. for 3 hours, and supported with microcapsules. formed a layer. After drying, the microcapsule-carrying layer was peeled off from the polyester film to obtain a 50 μm-thick microcapsule-carrying layer film C3, which was used for various evaluations.

(Measurement of maximum tensile stress)
Each microcapsule-supporting layer film having a thickness of 50 μm obtained in Production Examples and Comparative Production Examples was cut into a JIS No. 7 dumbbell test piece. The test piece was allowed to stand still for 12 hours or more in a desiccator in which the temperature and humidity were controlled to acclimate to the environment. Then, under low humidity conditions (temperature 25 ± 2 ° C., humidity 25 ± 2%), the speed is 5 mm / min, and under high humidity conditions (temperature 25 ± 2 ° C., humidity 84 ± 2%), the speed is 20 mm / min. Tensile stress was measured (n=5) and the average value was calculated. The results are shown in Tables 2 and 3 below.

(Measurement of water dissolution rate)
Each microcapsule carrying layer film having a thickness of 50 μm obtained in Production Examples 1 to 3 and Comparative Production Examples 1 and 2 was set in a polyethylene terephthalate slide holder having an opening of 3.5 cm×2.5 cm. Add 800 g of tap water at 23 ± 2 ° C. to a 1,000 ml beaker (product number: 1000BK1000, size: outer diameter 110 mm, height 150 mm, AGC Techno Glass Co., Ltd.), and add a rod-shaped stirrer tip (product number: 1-4206-27, Size: length 40 mm, diameter 8 mm, manufactured by AS ONE Co., Ltd.) and a magnetic stirrer (trade name: Fine Stirrer F-202, manufactured by Tokyo Glass Instruments Co., Ltd.) were used for stirring. The rotation speed of the magnetic stirrer was adjusted so that the bottom of the swirl generated by stirring was the same height as the 600 mL scale marked on the wall of the beaker when the stirring state in the beaker was observed from the side of the beaker. Each slide holder was immersed in the beaker, and the time from the start of immersion to the time when undissolved film pieces could not be visually confirmed in the beaker was measured as the time until the film pieces were dissolved (n = 2), The average value was calculated as the water dissolution rate. The results are shown in Table 2 below.
The water dissolution rate of the microcapsule carrier layer film 1 obtained in Production Example 1 was 87 seconds, the water dissolution rate of the microcapsule carrier layer film 2 obtained in Production Example 2 was 143 seconds, and the microcapsules obtained in Production Example 3. The water dissolution rate of the carrier layer film 3 was 119 seconds, and all dissolved quickly.

Example 1
A commercially available polyethylene terephthalate sheet having a thickness of 0.7 mm was cut into a size of 3 cm wide by 1 cm long, and this was used as a base material. Using an acrylic adhesive (trade name: spray glue No. 55, manufactured by 3M Japan Co., Ltd., adhesive component: acrylic acid/isooctyl acrylate copolymer), as shown in FIG. A pressure-sensitive adhesive layer was formed on one side from to 2 cm.
On the other hand, the microcapsule-carrying layer film 1 obtained in Production Example 1 was cut into a size of 6 cm wide by 1 cm long, and one end of the short side of the film 1 was attached to the short side end of the substrate on which the adhesive layer was formed. A functional film 1-1 was obtained in which the material/adhesive layer/microcapsule-carrying layer were laminated in this order.

Examples 2-4 and Comparative Examples 1-3
Substrate/adhesive layer/microcapsule-carrying layer in the same manner as in Example 1, except that microcapsule-carrying layer films 2 to 4 and C1 to C3 were used instead of microcapsule-carrying layer film 1 in Example 1. Functional films 1-2 to 1-4 and 1-C1 to 1-C3 laminated in this order were obtained.

(Measurement of adhesive strength)
The functional films obtained in Examples and Comparative Examples, in which substrate/adhesive layer/microcapsule-carrying layer were laminated in this order, were used as test samples. The test sample was allowed to stand still for 12 hours or longer in a desiccator in which the temperature and humidity were controlled to acclimate to the environment. The low humidity condition was a temperature of 25±2° C. and a humidity of 25±2%, and the high humidity condition was a temperature of 25±2° C. and a humidity of 84±2%.
The adhesive strength of the acclimated test sample was measured using a Tensilon universal tester (model: RTC-1210A, manufactured by Orientec Co., Ltd.). Each functional film was tested three times at a tensile speed of 20 mm/sec, and the average value was taken as the adhesive strength of each functional film. Tables 4 and 5 below show the measurement results of the maximum tensile stress of the microcapsule-carrying layer films as well as the measurement results of the adhesive strength.

Since the functional films of Examples 1 to 4 contain a crosslinked product of polyvinyl alcohol crosslinked with a predetermined amount of boric acid, the mechanical strength of the microcapsule-carrying layer under high humidity conditions is lower than that under low humidity conditions. Although it is lowered, the adhesive strength shows a sufficiently excellent value, indicating that the adhesiveness is excellent. On the other hand, in the functional films of Comparative Examples 1 and 2, the mechanical strength of the microcapsule-carrying layer was low under high humidity conditions, the adhesive strength was lowered, and the adhesiveness was poor. Comparative Example 3 has extremely low adhesion strength under low and high humidity conditions, and the adhesion is not sufficient.

Example 5 and Comparative Example 4
The microcapsule-carrying layer films 2 and C1 of Production Example 2 and Comparative Production Example 1 were cut into 4 cm × 2 cm pieces, and an adhesive layer was formed on the film using the acrylic adhesive to form a microcapsule-carrying layer/adhesive layer. Functional films 2-2 and 2-C1 laminated in order were obtained.

(Usage evaluation)
The functional films 2-2 and 2-C1 obtained in Example 5 and Comparative Example 4 were attached to an insole (WORKPLUS (R), manufactured by Midori Anzen Co., Ltd.) at the positions shown in FIG. At this time, the functional film 2-2 of Example 5 was attached to the left leg side, and the functional film 2-C2 of Comparative Example 4 was attached to the right leg side.
Men's leather shoes were fitted with the insoles to which the functional film was attached, and after wearing the socks for one day, the experimenter's socks were evaluated for fragrance and adhesiveness of the functional film to the insole based on the following evaluation criteria. The results are shown in Table 6 below.

[Evaluation criteria for fragrance]
A: A scent was clearly felt.
B: A faint scent was sensed.
C: No scent was felt at all.
[Evaluation Criteria for Adhesiveness]
A: Maintained a perfect adhesion state as it was at the time of application.
B: Slight peeling was observed at the peripheral edge of the film.
C: Most of the film was peeled off, but the adhesion to the insole was maintained.
D: Completely peeled off from the insole.

In both Example 5 and Comparative Example 4, the microcapsules contained in the microcapsule-carrying layer collapsed due to the friction between the sock and the insole when worn, the encapsulated perfume was released, adhered to the sock, and was worn for one day. It was possible to maintain the fragrant property even afterward. However, in Comparative Example 4, the functional film was partially peeled from the insole due to moisture and friction inside the shoe. On the other hand, in Example 5, the adhesion to the insole was maintained, and it was found that the moisture resistance was improved and excellent adhesion could be maintained.

10: Microcapsule carrying layer film 11: Adhesive layer 12: Substrate 13: Adhesive surface 20: Insole 21: Functional film

Claims (11)

A functional film containing microcapsules (A) encapsulating an active ingredient (a), a microcapsule-carrying layer containing a crosslinked product (B) of a water-soluble polymer (b) having a hydroxy group, and an adhesive layer. hand,
The crosslinked body (B) is obtained by crosslinking the water-soluble polymer (b) with a crosslinking agent (c),
A functional film, wherein the content of the cross-linking agent (c) relative to 100 parts by mass of the water-soluble polymer (b) is 1 part by mass or more and 6 parts by mass or less. The functional film according to claim 1, wherein the water-soluble polymer (b) is polyvinyl alcohol. The functional film according to claim 2, wherein the polyvinyl alcohol has a saponification degree of 70 mol% or more and 95 mol% or less. The functional film according to any one of claims 1 to 3, wherein the cross-linking agent (c) is boric acid. 5. The functional film according to any one of claims 1 to 4, wherein the content of said cross-linking agent (c) relative to 100 parts by mass of said water-soluble polymer (b) is 2 parts by mass or more and 6 parts by mass or less. The microcapsules (A) have a shell and a core containing the active ingredient (a) inside the shell,
The shell comprises one or more selected from melamine-formaldehyde resins, phenol-formaldehyde resins, polyacrylate resins, polymethacrylate resins, polyurea resins, polyamide resins, silica, gelatin, gum arabic, agar, cellulose, and cellulose derivatives. 6. The functional film according to any one of claims 1 to 5, containing it as a component. The functionality according to any one of claims 1 to 6, wherein the active ingredient (a) is one or more selected from fragrances, fragrance precursors, oils, cooling agents, pest repellents, and antioxidants. the film. The functional film according to any one of claims 1 to 7, wherein the microcapsules (A) have a volume average particle size of 0.01 µm or more and 300 µm or less. The functional film according to any one of claims 1 to 8, wherein the content of the microcapsules (A) in the microcapsule-carrying layer is 0.5 mass% or more and 50 mass% or less. The functional film according to any one of claims 1 to 9, wherein the total content of the microcapsules (A) and the crosslinked body (B) in the microcapsule-carrying layer is 80% by mass or more and 100% by mass or less. The functional film according to any one of claims 1 to 10 , wherein the microcapsule-carrying layer has a thickness of 10 µm or more and 800 µm or less.

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