JP7320213B2 - Antimicrobial composition and insole comprising same - Google Patents

Description

The present invention relates to antimicrobial compositions. The present invention further relates to an insole that is placed on the inner sole surface of footwear, such as shoes, comprising the antimicrobial composition.

The number of patients with tinea pedis and tinea unguium in Japan is estimated to reach 10% or more of the total population, mainly elderly people. It has been pointed out that the fact that trichophytosis spreads in the environment, survives for a long period of time, and becomes a source of infection is one of the reasons for the increase in the number of patients. Environmental studies are revealing that the insides of shoes, in particular, are often contaminated with ringworm fungi. Contamination with microorganisms such as trichophyton not only causes foul odors, but also causes the development of tinea pedis patients, delay in healing, reinfection, and the like.

The co-inventors of the present application previously invented an antimicrobial composition containing terpenealdehyde as an active ingredient and suitable for application to shoes and the like (Patent Document 1). The antimicrobially active composition can provide antiseptic action through the volatile component, is effective against a wide variety of microorganisms, including ringworm, candida, and bacillus subtilis, and is effective in reducing ringworm infections and malodors. It was something that could work.

In Patent Document 1, "The dosage form of the antimicrobial composition of the present invention is not particularly limited as long as it is a form used for the purpose of the present invention. Specifically, it can be in the form of a liquid, a spray, a gel, a kit for gel generation, or a form impregnated with a polymer or a porous material." No further specific considerations of materials or structures are made.

At present, there are many commercially available products labeled as antibacterial insoles, but these do not actually have sufficient ability to disinfect the inside of shoes.

JP 2017-206466 A

An object of the present invention is to provide means for safely and sustainably using terpene aldehyde, which is an antimicrobial active ingredient, in footwear or the like.

The present invention is based on the discovery that the addition of an acyclic terpene aldehyde to a mixture containing a specific fiber and a specific polymer to form a composition maintains the release of antimicrobial activity for a significantly longer period of time. is. It is also based on the discovery that incorporation of such compositions into insoles results in highly effective disinfection within shoes.

The present invention includes at least the following embodiments.
[1]
a) a carrier that is a mixture of fibrous material, which is leather fiber, cotton fiber, or a combination thereof, and a rubber having double bonds in its main chain; and b) an antimicrobial component that is added to said carrier. An antimicrobial composition, wherein the antimicrobial component comprises an acyclic terpene aldehyde.
[2]
The antimicrobial composition according to [1], wherein the carrier contains 50 to 98% by weight of the fiber and 2 to 50% by weight of the rubber.
[3]
The antimicrobial composition of [1] or [2], wherein the acyclic terpene aldehyde comprises citral, citronellal, hydroxycitronellal, or a combination thereof.
[4]
[1]-[ 3], the antimicrobial composition according to any one of the above.
[5]
an insole underlayer;
an insole upper layer laminated on the insole lower layer;
An insole comprising the antimicrobial composition according to any one of [1] to [4] sandwiched between the lower insole layer and the upper insole layer,
the insole upper layer has a breathable region in the region overlying the antimicrobial composition;
Insole.
[6]
(i) an insole comprising a lower insole layer and an upper insole layer laminated on the lower insole layer; and (ii) enclosed in an airtight container according to any one of [1] to [4]. An antimicrobial insole kit comprising an antimicrobial composition of
The lamination of the lower insole layer and the upper insole layer includes a non-adhesive region where the lower insole layer and the upper insole layer are not adhered to each other. It is configured so that the antimicrobial composition can be sandwiched between the bedding layers,
The insole upper layer has an air-permeable region in a portion constituting the non-adhesive region,
Antimicrobial insole kit.
[7]
(i) an insole comprising a carrier that is a mixture of fibers that are leather fibers, cotton fibers, or combinations thereof, and rubber having double bonds in its main chain; and (ii) for impregnating said carrier. An antimicrobial insole kit comprising an airtight container containing a liquid antimicrobial component of
the liquid antimicrobial component comprises an acyclic terpene aldehyde;
Antimicrobial insole kit.

The active ingredient, terpene aldehyde, usually volatilizes quickly and loses its antimicrobial activity in a relatively short time. However, according to embodiments of the present invention, the sustained release of the active ingredient is achieved, and the antimicrobial activity can be maintained for a long period of time, such as one week or more, and the antimicrobial effect can be maintained for a long period of time. You can provide insoles that do.

Although it is possible to synthesize terpene aldehyde, it is originally derived from natural materials such as lemongrass, and is a volatile substance that not only has antimicrobial properties but also emits a pleasant fragrance (refreshing aroma). Accordingly, embodiments of the present invention can provide antimicrobial activity and sustained release of refreshing fragrance in a manner that is completely safe for users of footwear and the like.

FIG. 1 is a side view of a user wearing a shoe having an insole laid on the inner bottom surface according to an embodiment of the present invention (that is, a left foot viewed from the right). (A) is a top view of an insole according to one embodiment of the present invention. FIG. 2B is a view showing a state in which the upper insole layer of the insole of FIG. 2A is partially separated from the lower insole layer and folded back; In (B) the antimicrobial composition 40 is exposed. FIG. 3 is a diagram showing an overview of an insole kit according to one embodiment of the present invention. FIG. 4 is a diagram showing experimental results of Example 1 comparing the sustained release properties of antimicrobial components from different carrier materials. FIG. 5 shows the experimental results of Example 2 comparing the sustained release properties of antimicrobial components from different carrier materials. Figure 6 shows further experimental results of Example 2 comparing the sustained release properties of antimicrobial components from different carrier materials. Figure 7 shows further experimental results of Example 2 comparing the sustained release properties of antimicrobial components from different carrier materials. FIG. 8 is a diagram showing the positions on the surface of the insole to which the trichophyton-containing filter paper pieces were attached in Examples 3(a) and 4 to 5(b). FIG. 9 shows the results of comparing the growth of trichophyton from the trichophyton-containing filter paper pieces attached to positions 1 to 4 of the insole in Example 4. FIG. FIG. 10 shows the results of comparing the growth of trichophyton from the trichophyton-containing filter paper pieces attached to positions 1 to 4 of the insole in Example 5. FIG.

In one aspect, the present disclosure provides a) a carrier that is a mixture comprising a fibrous material that is leather fiber, cotton fiber, or a combination thereof, and a rubber having a double bond in its main chain; and b) the carrier. An antimicrobial composition is provided that includes an added antimicrobial component. Leather fibers, as known to those skilled in the art, are fibrous materials obtained from mammalian hides, particularly cow hides, and are typically prepared by crushing the hides of cows. Cotton fiber, as known to those skilled in the art, is a fibrous material that is harvested from around the seeds of the cotton plant. The cotton fibers may be unprocessed or may be processed such as spinning. More preferably, the carrier in this embodiment contains leather fibers.

As is commonly understood by those skilled in the art, rubbers are polymers having repeating units. In the present disclosure, "rubber having a double bond in its main chain" means a rubber that is a polymer containing double bonds in the main chain portion of repeating units. Examples of rubbers having double bonds in the backbone include isoprene rubber, styrene-butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber (CR), and nitrile-butadiene rubber (NBR). is not limited to The carrier in the present embodiment may contain two or more types of rubber having a double bond in the main chain.

In the present disclosure, isoprene rubber means rubber composed mainly of polyisoprene (preferably cis-polyisoprene), examples of which include natural rubber (NR) and synthetic isoprene rubber (IR). The rubber having a double bond in the main chain in this embodiment is preferably natural rubber, synthetic isoprene rubber, or a combination thereof, and more preferably contains or consists of natural rubber.

The carrier in the present embodiment is a mixture containing rubber having a double bond in its main chain and the above fibrous matter, and the rubber can also serve as a binder that binds the fibrous matter together. That is, the carrier is not a layered structure in which a fiber layer and a rubber layer exist separately, but a mixture of fibers and rubber. The presence of fibrous material may provide porosity for the penetration, accumulation, passage, etc. of the antimicrobial component, but in addition the rubber itself may be foamed.

More than half of the total weight of the carrier may be made up of said fibrous material. The carrier preferably contains 50 to 98% by weight of the fiber and 2 to 50% by weight of the rubber. More preferably, the fiber content of the carrier is 60-80% by weight. Further, the rubber content of the carrier is more preferably 5 to 30% by weight.

The carrier may contain one or more additional components other than the rubber having double bonds in its backbone and the fibrous material described above. The total content of such additional ingredients is usually less than 50% of the total weight of the carrier. Examples of such additional ingredients include rubbers without double bonds in the main chain, non-rubber polymers or binders, fibrous materials other than leather fibers and cotton fibers, natural oils and fats, colorants and flavoring agents. include, but are not limited to.

The size and shape of the carrier can be changed as appropriate depending on the application. For example, for applications to be placed within a footwear insole, as described below, the carrier has dimensions that do not extend beyond the plane of the insole and the surface area of the insole (i.e., the side facing the sole of the wearer's foot). surface area), for example 8 cm wide and 25 cm long or less, or 8 cm wide and 10 cm long or less. The thickness of the carrier in that case may be 1 mm or less, preferably 0.7 mm or less. The shape of the flake when viewed from above can be appropriately determined by those skilled in the art, and may be, for example, circular, elliptical, square, rectangular, etc., but is not limited to these.

In the antimicrobial composition of this embodiment, an antimicrobial component is added to the carrier. An antimicrobial component is a component capable of providing antimicrobial activity, ie, activity that partially or completely inhibits the survival and/or growth of microorganisms, and comprises at least an acyclic terpene aldehyde. A terpene aldehyde, as understood by those skilled in the art, is an aldehyde compound having an isoprene structure as a constituent unit. The acyclic terpene aldehyde in this embodiment is a terpene aldehyde that does not contain a cyclic structure, and examples thereof include linear or branched acyclic C8-12 terpene aldehydes. More specific examples include, but are not limited to, citral (geranial, neral), citronellal, hydroxycitronellal, etc., and mixtures thereof. The acyclic terpene aldehyde in this embodiment is preferably derived from plants. Citral is a particularly preferred acyclic terpene aldehyde in this embodiment. Acyclic terpene aldehydes are normally volatile liquids at room temperature (25°C).

In the present disclosure, "adding the antimicrobial component to the carrier" means impregnating, absorbing, and/or adsorbing the antimicrobial component onto the carrier. However, it is understood that the impregnation, absorption and/or adsorption is not permanent and the volatilizing antimicrobial component may be released from the carrier. One of the features of this embodiment is that the release is more sustained over time, that is, it becomes a sustained release. Although not bound by any particular theory, it is believed that the affinity between the double bond structure and/or branched structure contained in the structural unit of terpene aldehyde and the double bond structure and/or branched structure in the main chain of the rubber gradually increases. It is thought that it contributes to release.

Addition of the antimicrobial component to the carrier is accomplished, for example, by an impregnation process involving dripping, spraying, or injecting the liquid form of the antimicrobial component onto the carrier, or immersing the carrier in the liquid form of the antimicrobial component. obtain. During these impregnation treatments, the antimicrobial component may be mixed or diluted with other liquid components (for example, alcohol such as ethanol).

The amount of the antimicrobial component added to the carrier should be appropriately determined by the user according to various conditions such as cost constraints and the desired antimicrobial activity level, and is not particularly limited. It is understood that As an example, the amount of antimicrobial component applied to the carrier during impregnation can be 0.3 μL or more, preferably 0.5 μL or more, more preferably 1 μL or more, and even more preferably 1 μL or more per cm ² of surface area of the carrier. It can be 10 μL or more. The antimicrobial component is not necessarily applied to the entire surface of the carrier, and it is possible that the antimicrobial component is applied only to a part of the surface.

In addition to the acyclic terpene aldehyde (first aldehyde) described above, the antimicrobial component may further contain a second aldehyde different from the acyclic terpene aldehyde. Such second aldehydes can be acyclic aliphatic aldehydes, terpene aldehydes (especially cyclic terpene aldehydes), or aromatic aldehydes. A plurality of different "second aldehydes" may be contained in the antimicrobial component. The second aldehyde is normally liquid at room temperature (25°C). Either or both of the first aldehyde and the second aldehyde are preferably plant essential oil-derived components. Although the acyclic terpene aldehyde alone provides antimicrobial activity, as described in US Pat. can get. Preferably, the antimicrobial component contains a greater amount, ie, a greater volume, of the acyclic terpene aldehyde than the second aldehyde.

The acyclic aliphatic aldehyde as the second aldehyde is a compound in which a linear or branched alkyl group having no cyclic structure is substituted with a formyl group (CHO). Acyclic aliphatic aldehydes can be, for example, but not limited to, linear or branched C1-20 alkanals, C6-12 alkanals, or C8-10 alkanals. More specific examples include methanal, ethanal, propanal, isopropanal, butanal, isobutanal, tert-butanal, pentanal, 2-methylbutanal, 3-methylbutanal, 2,2-dimethylpropanal, hexanal, 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, 2,2-dimethylbutanal, 2,3-dimethylbutanal, 3,3-dimethylbutanal, 2-ethylbutanal, 3- ethylbutanal, heptanal, 2-methylhexanal, 3-methylhexanal, 4-methylhexanal, 5-methylhexanal, 2,2-dimethylpentanal, 2,3-dimethylpentanal, 2,4-dimethylpentanal, 3,3-dimethylpentanal, 3,4-dimethylpentanal, 4,4-dimethylpentanal, 2-ethylpentanal, 3-ethylpentanal, 2-propylpentanal, 2,2,3-trimethylbuta nal, 2,3,3-trimethylbutanal, 2-methyl 2-ethylbutanal, 2-ethyl 3-methylbutanal, octanal, 2-methylheptanal, 3-methylheptanal, 4-methylheptanal, 5-methylheptanal, 6-methylheptanal, 2,2-dimethylhexanal, 2,3-dimethylhexanal, 2,4-dimethylhexanal, 2,5-dimethylhexanal, 3,3-dimethylhexanal, 3,4 -dimethylhexanal, 3,5-dimethylhexanal, 4,4-dimethylhexanal, 4,5-dimethylhexanal, 5,5-dimethylhexanal, 2-ethylhexanal, 3-ethylhexanal, 4-ethylhexanal, 2,2 ,3-trimethylpentanal, 2,2,4-trimethylpentanal, 2,3,3-trimethylpentanal, 2,3,4-trimethylpentanal, 2,4,4-trimethylpentanal, 3,3 ,4-trimethylpentanal, 3,4,4-trimethylpentanal, 2-methyl 2-ethylpentanal, 2-methyl 3-ethylpentanal, 2-ethyl 3-methylpentanal, 3-ethyl 3-methyl Pentanal, 2-ethyl 4-methylpentanal, 3-ethyl 4-methylpentanal, 2-propylpentanal, 2,2,3,3-tetramethylbutanal, 2,2,3,4-tetramethyl butanal, 2,2,4,4-tetramethylbutanal, 2,3,3,4-tetramethylbutanal, 2,3,4,4-tetramethylbutanal, 3,3,4,4- Tetramethylbutanal, 2,2-diethylbutanal, nonanal, 2-methyloctanal, 3-methyloctanal, 4-methyloctanal, 5-methyloctanal, 6-methyloctanal, 7-methyloctanal , 2,2-dimethylheptanal, 2,3-dimethylheptanal, 2,4-dimethylheptanal, 2,5-dimethylheptanal, 2,6-dimethylheptanal, 3,3-dimethylheptanal, 3 ,4-dimethylheptanal, 3,5-dimethylheptanal, 3,6-dimethylheptanal, 4,4-dimethylheptanal, 4,5-dimethylheptanal, 4,6-dimethylheptanal, 5,5 -dimethylheptanal, 5,6-dimethylheptanal, 6,6-dimethylheptanal, 2-ethylheptanal, 3-ethylheptanal, 4-ethylheptanal, 5-ethylheptanal, 2,2,3 -trimethylhexanal, 2,2,4-trimethylhexanal, 2,2,5-trimethylhexanal, 2,3,3-trimethylhexanal, 2,3,4-trimethylhexanal, 2,3,5-trimethylhexanal, 2 ,4,4-trimethylhexanal, 2,4,5-trimethylhexanal, 2,5,5-trimethylhexanal, 3,3,4-trimethylhexanal, 3,3,5-trimethylhexanal, 3,4,4- trimethylhexanal, 3,4,5-trimethylhexanal, 3,5,5-trimethylhexanal, 2-methyl 2-ethylhexanal, 2-methyl 3-ethylhexanal, 2-methyl 4-ethylhexanal, 2-ethyl 3-methyl Hexanal, 3-methyl 3-ethylhexanal, 3-methyl 4-ethylhexanal, 2-ethyl 4-methylhexanal, 3-ethyl 4-methylhexanal, 4-ethyl 4-methylhexanal, 2-propylhexanal, 3-propyl Hexanal, 2,2,3,3-tetramethylpentanal, 2,2,3,4-tetramethylpentanal, 2,2,3,5-tetramethylpentanal, 2,2,4,4-tetra methyl pentanal, 2,2,4,5-tetramethylpentanal, 2,3,3,4-tetramethylpentanal, 2,3,3,5-tetramethylpentanal, 2,3,4,4 -tetramethylpentanal, 2,3,4,5 tetramethylpentanal, 2,3,5,5-tetramethylpentanal, 3,3,4,4-tetramethylpentanal, 3,3,4, 5-tetramethylpentanal, 3,3,5,5-tetramethylpentanal, 3,4,4,5-tetramethylpentanal, 3,4,5,5-tetramethylpentanal, 4,4, 5,5-tetramethylpentanal, 2,2-diethylpentanal, 2,3-diethylpentanal, 3,3-diethylpentanal, 2-methyl 2-propylpentanal, 3-methyl 2-propylpentanal , 4-methyl 2-propylpentanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal, pentadecanal, hexadecanal, heptadecanal, octadecanal, nonadecanal, and icosanal. Octanal, nonanal, decanal, and trimethylhexanal are examples of particularly suitable acyclic aliphatic aldehydes.

The second aldehyde can be a cyclic terpene aldehyde. Cyclic terpene aldehydes are terpene aldehydes containing a cyclic structure, and particularly preferred examples include cyclic terpene aldehydes having 8 to 12 carbon atoms, more specifically perillaldehyde, but are limited to these. not.

An aromatic aldehyde as the second aldehyde is an aromatic compound having a formyl group (CHO). Examples of aromatic hydrocarbon rings of aromatic compounds include benzene, naphthalene, azulene, anthracene, chrysene, pyrene, coronene, and kekulene, with benzene being particularly preferred. In the aromatic aldehyde, the aromatic hydrocarbon ring may have a formyl group, a C1-6 alkanal group, a C2-6 alkenal group, or a C2-6 alkynal group as a substituent, preferably a formyl group, It may have a C1-4 alkanal group, a C2-4 alkenal group, or a C2-4 alkynal group, more preferably a formyl group or a propenal group. The aromatic hydrocarbon ring may be substituted with 1 to 2 substituents other than an aldehyde group, examples of such substituents include a hydroxyl group, a linear or branched C1-6 alkyl group, A linear or branched C1-6 alkoxy group can be mentioned, preferably a hydroxyl group, an isopropyl group or a methoxy group. The aromatic aldehyde as the second aldehyde is preferably a naturally occurring compound. Further specific examples of aromatic aldehydes include benzaldehyde optionally substituted with 1 to 2 substituents and cinnamaldehyde optionally substituted with 1 to 2 substituents. Benzaldehyde, cinnamaldehyde, cuminaldehyde, and vanillin are particularly preferred examples.

Generally, either or both of the first aldehyde and the second aldehyde may be substituted with substituents, eg, 1-2 substituents. Examples of substituents include, but are not limited to, hydroxyl groups, C1-4 alkyl groups, and C1-4 alkoxy groups.

Applications in which the present antimicrobial composition can be utilized include, as will be described later, installation in insoles of footwear, installation in other small spaces such as socks, shoeboxes, cupboards, door mats, bath mats, etc. Applications include, but are not limited to:

The discussion of carrier composition and antimicrobial component composition provided above also applies to the insole and insole kit embodiments described below.

In another aspect, the disclosure provides an insole comprising the antimicrobial composition described above. An insole, as commonly understood by those skilled in the art, is a member that is laid on the inner bottom surface of footwear. Insoles are commonly used to provide footwear with functions such as, for example, cushioning, deodorization, and size adjustment. Footwear is most typically shoes, but insoles can be attached to a wide variety of footwear such as boots, slippers, and sandals. Insoles may be provided (sold) as part of the footwear, originally installed within the footwear, or may be provided (sold) as a separate component and installed by individual users in their own footwear. There is also

In this disclosure, expressions such as "over," "upper," "upward," and the like, used in the context of insoles, refer to the direction toward the head of the person wearing the footwear with the insole while standing. represents the position, side, or direction of the . Conversely, expressions such as "under," "below," "downward," etc. refer to a position, side, or direction away from the head of a person wearing footwear with an insole while standing. show. As used in the context of insoles, the term "front" refers to the position, side, or direction toward the toe along the toe-heel axis of the wearer's foot, and the term "back" refers to the wearer's foot. Represents the position, side, or direction of heel-to-heel along the toe-to-heel axis. The term "outer" used in the context of insoles refers to the right side in right footwear insoles and the left side in left footwear insoles. The expression "inside" used in the context of insoles refers to the left side in right footwear insoles and the right side in left footwear insoles.

FIG. 1 shows a side view of one embodiment of an insole. The insole 10 of the present embodiment has a laminated structure including at least a lower insole layer 20 and an upper insole layer 30 laminated on the lower insole layer 20 . In FIG. 1, the place where the insole 10 is laid on the inner bottom surface of the shoe for the left foot is depicted together with the wearer's left foot. In FIG. 1, t indicates the upward direction (top), b indicates the downward direction (bottom), f indicates the front direction (front), and r indicates the rear direction (rear).

The insole of the present embodiment is characterized as having antimicrobial functionality, but otherwise may function similarly to conventional insoles. Therefore, the shape, size, thickness, etc. of the insole 10 including the insole lower layer 20 and the insole upper layer 30 can be appropriately selected by those skilled in the art based on their common knowledge. In the embodiment shown in FIG. 1, the undersole layer 20 is partially thickened in accordance with the shape of the sole and has a curved shape on the outer side, the inner side, and the rear side. Laminated thereon is a flexible insole upper layer 30 having a uniform thickness.

Materials for the lower insole layer 20 and the upper insole layer 30 can also be appropriately selected from materials known to those skilled in the art, such as polyurethane, polyester, ethylene vinyl acetate copolymer (EVA), silicone, and rubber ( Polymers (which may be foams) such as the rubbers mentioned above, which may be of the same type with double bonds in the backbone, or natural materials such as leather, cork, cotton, wool, and paper It can be material derived from raw materials, or any combination thereof. The lower insole layer 20 and the upper insole layer 30 may be made of the same material or may be made of different materials. Either one or both of the lower insole layer 20 and the upper insole layer 30 may each consist of multiple layers. The multiple layers may be made of the same material as each other, or may be made of different materials.

In the insole 10 of the present embodiment, the antimicrobial composition described above, that is, a carrier having a specific composition to which a terpene aldehyde antimicrobial component is added, is sandwiched between the lower insole layer 20 and the upper insole layer 30. It is characterized by The antimicrobial composition 40 may be fixed to the lower insole layer 20 and/or the upper insole layer 30, or may be removable without being fixed.

FIG. 2 shows a plan view of one embodiment of an insole for the left foot. As shown in FIG. 2A, the insole includes a heel corresponding region 10a corresponding to the heel of the foot, an arch corresponding region 10b corresponding to the arch of the foot, and a toe corresponding region corresponding to the toe of the foot. 10c. The heel corresponding region 10a, the arch corresponding region 10b, and the toe corresponding region 10c are located in the rear third, the middle third, and the front third, respectively, along the longitudinal length of the insole. can be one of In FIG. 2, f indicates the front direction, r indicates the rear direction, o indicates the outward direction (out), and i indicates the inward direction (in).

In the particular embodiment shown in FIG. 2, substantially the entire toe-corresponding region 10c is a non-adhesive region in which the lower insole layer 20 and the upper insole layer 30 are not adhered to each other. As shown in FIG. 2A, the lower insole layer 20 and the upper insole layer 30 are overlapped over the entire surface, but when not worn, a portion of the upper insole layer 30 is separated from the lower insole layer 20 as shown in FIG. 2B. It can be lifted upwards or folded backwards. Then, the antimicrobial composition 40 sandwiched between the lower insole layer 20 and the upper insole layer 30 is exposed on the upper surface of the lower insole layer 20 . Such an embodiment is preferred because it facilitates replacement of the antimicrobial composition 40 or replenishment of the antimicrobial component.

That is, in embodiments in which replacement of the antimicrobial composition 40 or replenishment of the antimicrobial component is planned, during the lamination of the lower insole layer 20 and the upper insole layer 30, the lower insole layer 20 and the upper insole layer 30 are combined. By providing a non-adhesive region where the two are not adhered to each other, the antimicrobial composition 40 can be sandwiched between the lower insole layer 20 and the upper insole layer 30 in the non-adhesive region. preferable. It will be appreciated that such a configuration allows for the removal of the antimicrobial composition 40 as well as the insertion of the antimicrobial composition 40 or antimicrobial component.

A connecting member 50 may be installed in the non-bonded area. The connecting member is a member that allows the layers to be reversibly connected to each other, that is, to be attached and detached. can be In the particular embodiment shown in FIG. 2B, the upper surface of the lower insole layer 20 and the lower surface of the upper insole layer 30 in the non-bonded areas are provided with corresponding connecting members 50a and 50b, respectively. When the laminated structure of the lower insole layer 20 and the upper insole layer 30 is restored as shown in FIG. 2A, the connecting member connects the two layers to each other. It also allows the upper insole layer 30 to be separated from the lower insole layer 20 as shown in FIG. 2B.

Although FIG. 2 illustrates an embodiment in which the antimicrobial composition 40 or carrier is replaceable, the antimicrobial composition 40 or carrier is permanently (ie, non-removably) attached to the insole 10. Other embodiments are also contemplated. That is, embodiments are also contemplated that do not have non-bonded areas that may separate the upper insole layer 30 from the lower insole layer 20 . For example, the insole 10 itself may be a single use disposable. Alternatively, an implementation in which the carrier is permanently attached to the insole 10 and only the antimicrobial component is replenished externally to the laminated structure of the lower insole layer 20 and the upper insole layer 30 (e.g., through the upper surface of the upper insole layer 30). There can be forms.

The antimicrobial composition 40 may be placed in any of the heel corresponding region 10a, the arch corresponding region 10b, and the toe corresponding region 10c, or may extend over a plurality of them. As shown in FIG. 2, it is particularly preferred that the antimicrobial composition 40 is disposed within the toe-corresponding region 10c. When providing the above-described non-adhesive regions and connecting members, their providing positions can be appropriately changed by those skilled in the art according to the intended position of the antimicrobial composition 40 .

The insole upper layer 30 has breathable areas in the areas overlying the antimicrobial composition 40 . The antimicrobial components that volatilize from the antimicrobial composition 40 are delivered upward through this breathable region and diffused into the space within the footwear. Any breathable material known to those skilled in the art can be selected to form this breathable region. Alternatively, breathability of the breathable region may be provided by the presence of one or more vents. Although the insole upper layer 30 may have only one vent with a pore size large enough to allow the volatilizing antimicrobial component to pass through, it is more preferable to have a plurality of vents, in which case each It is understood that the size of the vent can be relatively small. Preferably, the breathable regions are formed by a material having a mesh structure, with the natural interstices of the mesh providing breathability. The entire insole upper layer 30 may be breathable, not just the area covered by the antimicrobial composition 40 . An embodiment in which the entire insole upper layer 30 has a mesh structure, as shown in FIG. 2, is particularly preferred.

In another aspect, the present disclosure provides an antimicrobial insole kit comprising an insole and a carrier of specific composition to which is added the antimicrobial composition described above, ie, a terpene aldehyde antimicrobial component. The insole in the kit of this embodiment can be essentially the same as the insole in the embodiments described above, for example, a similar insole as shown in FIG. The microbial composition is made replaceable. Both embodiments in which the antimicrobial composition to be used first is provided attached to the insole from the beginning and aspects in which the antimicrobial composition is initially provided without being attached to the insole are contemplated. be. In the latter case, a procedure is required for the user to apply the antimicrobial composition to the insole at the time of first use.

The insole included in the kit of the present embodiment includes at least a lower insole layer and an upper insole layer laminated on the lower insole layer. The lamination of the lower insole layer and the upper insole layer includes a non-adhered region where the lower insole layer and the upper insole layer are not adhered to each other, and the non-adhered region provides resistance between the lower insole layer and the upper insole layer. It is configured so that it can sandwich a microbial composition. The insole upper layer has an air-permeable region in the portion constituting the non-bonded region. The breathable region is as described above, preferably a mesh structure. Further, as described above, a connecting member may be provided that reversibly connects the lower insole layer and the upper insole layer in the non-bonded area.

The kit of this embodiment further comprises an antimicrobial composition enclosed in an airtight container. Various embodiments of antimicrobial compositions are described above. In the present disclosure, an airtight container means a container that can at least partially prevent the antimicrobial component that volatilizes from the antimicrobial composition from leaking to the outside. Airtight containers are typically bags, but may be other forms of containers such as boxes, bottles, and cans. Although it is preferred that one container contains one antimicrobial composition, embodiments in which one container contains multiple antimicrobial compositions are also contemplated. The insole of the kit may also be enclosed in an airtight container.

The airtight container is preferably composed of a synthetic polymer, examples of which include polyester, particularly polyethylene terephthalate, polyacrylonitrile, ethylene-vinyl alcohol copolymer, polypropylene, polyethylene, nylon, cyclic polyolefin, and the like. are not limited to these. The wall of the airtight container preferably has a laminated structure containing one or more synthetic polymer layers, and it is more preferred that the laminated structure further contains a metal layer such as aluminum from the viewpoint of improving the airtightness.

FIG. 3 shows an example of a kit according to this embodiment. In this example, the kit includes an insole 10 and multiple antimicrobial compositions 40 individually packaged in multiple airtight containers 45 . The insole 10 includes at least a lower insole layer and an upper insole layer, and in this particular example, the entire upper insole layer is mesh to provide breathable areas in the portions that constitute the non-bonded areas. It is In this particular example, the non-adhesive area is located in the area corresponding to the toe and sandwiches the antimicrobial composition to be used first (the position and shape of which is indicated by the dashed line). The airtight container 45 is an airtight bag formed by two sheets facing each other at their peripheries, each of which consists of a synthetic polymer laminate structure, in which the airtightness is enhanced. The antimicrobial composition 40 enclosed in the airtight container 45 is not visible unless the airtight container 45 is opened because of the included aluminum layer for the airtight container 45 . In this example, a notch 46 is made at one place of the joint portion of the peripheral edge so that the user can easily open the airtight container 45 by hand.

For example, when the antimicrobial composition 40 initially applied to the insole has lost its antimicrobial efficacy, the user of the kit can remove the antimicrobial composition 40 from the non-adhesive area of the insole and remove the antimicrobial composition 40 from the airtight container 45 . The use of the antimicrobial insole can be continued for an even longer period of time by instead inserting a fresh antimicrobial composition 40 removed from the package into the non-adhesive area of the insole.

In yet another aspect, the present disclosure provides an antimicrobial insole kit including an insole comprising a carrier of the specific composition described above and an airtight container containing a liquid antimicrobial component for impregnating the carrier. do. The composition of the carrier and the liquid antimicrobial component are as described above. That is, the carrier is a mixture comprising fibrous materials such as leather fibers, cotton fibers, or combinations thereof, and rubber having double bonds in the main chain, and the liquid antimicrobial component comprises at least an acyclic terpene aldehyde. . The airtight container in this embodiment is typically a plastic or glass bottle, but may be other forms of container such as bags, boxes, cans, and the like. Preferably, the airtight container includes a dropper (pipette) structure or a spray structure so that the liquid antimicrobial component can be dripped or sprayed onto the carrier. In that case, the airtight container preferably further includes a cap that covers the dropper (pipette) structure or the spray structure to ensure airtightness when not in use.

The user of the kit of the present embodiment can replenish and sustain the antimicrobial activity of the insole by appropriately impregnating the carrier of the insole with the liquid antimicrobial component supplied from the airtight container.

The carrier in the kit of this embodiment may constitute part or all of the insole in various forms. For example, similar to the embodiments described above, the insole comprises a lower insole layer and an upper insole layer, with a carrier sandwiched between the lower insole layer and the upper insole layer (underneath the breathable region of the upper insole layer). It may be In this case the carrier need not be removable. As in the above-described embodiments, it is preferred that the lower insole layer and the upper insole layer are configured to be manually separable, as this facilitates replenishment of the carrier with the liquid antimicrobial component. Alternatively, the carrier may be replenished with the liquid antimicrobial component from above the upper insole layer, permeating the upper insole layer or through pores present in the upper insole layer. In this case, the lower insole layer and the upper insole layer need not be manually separable. Alternatively, part or all of the insole upper layer itself or the insole itself may consist of the carrier.

[Example 1]
Magtube L (manufactured by Nittetsuko Co., Ltd.) is a commercially available sustained-release carrier material based on porous basic magnesium carbonate, and is known to have the property of taking in and slowly releasing liquids. The present inventors have found that a mixture of cotton fiber and styrene-butadiene rubber exhibits much better sustained release than Magtube-L for the antimicrobial component based on the acyclic terpene aldehyde. An experiment illustrating this is described below.

(Method)
A 10% concentration antimicrobial component was prepared by adding 20 μL of perillaldehyde to 40 μL of citral, which is an acyclic terpene aldehyde, and diluting it with 540 μL of ethanol. References to the amount of antimicrobial component hereinafter refer to the volume of this ethanol dilution. The test material in this example is a mixture of cotton fiber (70% by weight) and styrene-butadiene rubber (30% by weight) (hereinafter referred to as test material D), and has a planar shape of 2 cm square. Magtube L is a powder, which was put on a piece of paper for medicine packaging and made into a flat shape of 2 cm square for use in the test. Experimental details are shown in the table below.

20 μL or 40 μL of the above antimicrobial component was dropped into the center of test material D or magtube L (both 2 cm square) and impregnated. For two-ply samples, the antimicrobial component was dripped between the two plies. No. 17 to 20 are experiments in which an ethanol solution of terbinafine was used as an antimicrobial component instead of the acyclic terpene aldehyde mixture. These samples were then left in a windless fume hood for 7 days. After that, while attaching each sample to the lower surface of the lid of a 3.5 cm diameter petri dish with double-sided tape, prepare a Sabouraud agar medium in the petri dish inoculated with Candida albicans (100 cells/dish), The petri dishes were covered with the lids, sealed with parafilm, and allowed to stand at 25° C. for 24 hours. If the antimicrobial component still remains in the sample that has been left for 7 days, it is believed that it will descend from the lid and act on Candida (fungus) on the agar medium during this standing time. After the standing, the lid was removed and the petri dish was cultured at 37°C for 5 hours.

(result)
FIG. 4 shows the results of fungal colony formation after the above culture. Fungal colonies that reflect the growth state of the fungal colonies are observed as white spots in the Petri dish. The observation of many and/or large white colonies covering the agar medium indicates that less antimicrobial activity remained in test material D or magtube L, which had been left for 7 days beforehand. On the contrary, when the agar medium is almost transparent, it indicates that the antibacterial activity remained strong. A particularly strong antibacterial activity was detected when test material D was used as the main impregnated carrier, as indicated by the arrow in FIG. When terbinafine was used as an active ingredient instead of terpenealdehyde, no residual strong antibacterial activity was observed (Experiment Nos. 17 to 20). The control shown on the right of FIG. 4 represents an experiment in which the addition of the antimicrobial component was omitted.

This result indicates that test material D retained the volatile terpene aldehyde antimicrobial component for a long period of time and was able to sustainably release the antifungal activity of the antimicrobial component for at least one week. . This sustained release effect was much stronger than Magtube L, a commercially available sustained release material. In addition, this sustained release was a specific effect of the terpenealdehyde-based antimicrobial component.

[Example 2]
In the experiments of Example 1 above, it was found that the sustained release properties of terpenealdehyde-based antimicrobial components can vary significantly depending on the composition of the carrier. Therefore, using essentially the same experimental procedure as in Example 1, a variety of different carrier materials were tested. The carrier materials tested and their compositions (in % by weight) are exemplified in Table 2 below.

As in Example 1, citral and perillaldehyde diluted in ethanol were used as the antimicrobial component and were dripped onto each test strip to impregnate it. The standing time in the draft chamber (7 days), standing time at 25° C. (24 hours), and culture time at 37° C. (5 hours) are also the same as in Example 1. Test Material D in Table 2 is the same as Test Material D in Example 1.

FIG. 5 shows a photograph of the petri dish after culturing at 37° C. for 5 hours. In FIG. 5, the designations 20 μL and 40 μL respectively represent the amounts of the antimicrobial component dropped onto the test material, and the alphabetical symbols represent the types of test material shown in Table 2 above. Antibacterial activity, determined by visual observation of white fungal colonies, was highest for test materials G and H, followed by I and D, which were nearly equally strong. Antimicrobial activity was weaker in test material E, even weaker in F, and the weakest antimicrobial activity in A, B, and C. That is, the results of G, H≧I≈D>E>F≧A, B, and C were obtained with respect to the strength of the antibacterial activity remaining after being left for 7 days.

In order to confirm the reproducibility of the above results, the same experimental procedure was repeated while including a replicate experiment with two petri dishes each. The results are shown in FIGS. Almost the same result as the above experiment was obtained. That is, the order of strength of the observed antibacterial activity was G, H, I≧D>E>F>A, B, C.

As described above, test materials G, H, I and D exhibited strong and sustained antimicrobial activity, but the test materials (carrier materials) themselves provided antimicrobial activity independently of the added antimicrobial component. The possibility was also considered. To rule out that possibility, a comparative experiment was performed following the same experimental procedure as above but without the addition of the antimicrobial component. As a result, no antimicrobial activity was observed from the test material itself to which no antimicrobial component was added (results not shown). Therefore, it was confirmed that the sustained and strong antibacterial activity was due to the sustained release of the added terpene aldehyde antimicrobial component.

From the results exemplified above, the carrier, which is a mixture containing leather fiber and/or cotton fiber and rubber having a double bond in the main chain, is remarkably excellent in sustained release of the terpene aldehyde antimicrobial component. It was found that A mixture containing leather fibers and isoprene rubber was found to be particularly favorable.

[Example 3]
The carrier to which the terpene aldehyde antimicrobial component was added was incorporated into an insole, and this antimicrobial insole was attached to leather shoes (business shoes). Using this experimental system, the sterilization effect against trichophyton sprayed in shoes was examined.

(Method)
The test material G in Example 2 was processed into a shape indicated by reference numeral 40 in FIG. 2 and a thickness of 0.6 mm to prepare a carrier. To this carrier, 100 μL of an ethanol solution containing citral and perillaldehyde at a volume ratio of 5:1 (antimicrobial component concentration of 1%, 3%, or 5%) was added dropwise to obtain an antimicrobial composition. . This antimicrobial composition was incorporated into an insole having a bottom layer and a mesh top layer as shown in FIG.

On the other hand, 500 CFU of T. mentagrophytes TIMM2789 was dropped on a piece of thick filter paper, and as shown in FIG. The antimicrobial composition is sandwiched directly under position (2) of positions (1) to (4) of the filter strip shown in FIG. 8a (see FIG. 2). This insole was laid on the inner bottom surface of men's leather shoes. This leather shoe was covered with aluminum foil and allowed to stand at 30° C. for 3 days in order to reproduce the airtightness inside the shoe when worn by a person.

After that, the above filter paper piece was taken out from the shoe, adhered to an agar medium in a petri dish, and the petri dish was cultured at 30° C. for 4 days. All experiments were performed on three insoles attached to three leather shoes on one leg.

(result)
After 4 days of culture, it was observed that the filter paper strips transferred from the shoe environment to the agar medium had white hyphae of Trichophyton fungi extending outside the contours of the filter paper strips. A photograph of the petri dish was taken, and the area of growth of trichophyton fungi around the piece of filter paper was analyzed using image analysis software. Table 3 summarizes a comparison of trichophytosis growth areas measured by image analysis. A control is a control experiment in which the dripping of the antimicrobial component onto the carrier was omitted. The numbers 1-4 in the first row of Table 3 indicate the position of the filter paper strip when applied to the insole surface, as shown in Figure 8a.

From the results shown in Table 3, it is clear that the presence of the antimicrobial component tends to suppress the growth of trichophytosis. A significant reduction in the area of trichophyton growth was observed at any concentration of the antimicrobial component. At 5% concentration of the antimicrobial component, a significant difference from the control was also obtained in the growth inhibitory effect of ringworm fungus even in the heel area (4) far from the antimicrobial composition. From the above, it was shown that trichophytosis in shoes can be eliminated by adding a terpene aldehyde antimicrobial component to a sustained-release carrier and placing it in shoes.

[Example 4]
In Example 3, since the number of Trichophyton fungi adhered to the filter paper pieces was large, it was considered that the suppression of mycelial growth was difficult to identify, that is, the sensitivity of the experiment was low. Therefore, the sustained-release sterilization effect of test material G was verified again by reducing the number of Trichophyton fungi. Specifically, 8 CFU/5 μL of Trichophyton to be adhered to each piece of filter paper, and 200 μL of the antimicrobial component added to the carrier. In addition, the positions where the filter paper pieces were attached to the insole were as shown in FIG. The leather shoes were covered with aluminum foil and allowed to stand at 30° C. for 4 days, and the petri dish to which the filter paper pieces were transplanted was cultured for 5 days. Other than that, the experiment was conducted in the same manner as in Example 3. It should be noted that the antimicrobial composition is sandwiched immediately below position "2" among positions 1 to 4 of the filter paper piece shown in Fig. 8b (see Fig. 2).

(result)
As shown in Figure 9a, in the control experiment in which the addition of the antimicrobial component was omitted, trichophytosis grew from the filter paper strips at all positions 1-4 within the shoe (Figure 9a left), whereas the concentration of 5 % of the antimicrobial component added, the growth of trichophyton was completely inhibited from the filter paper pieces at any of positions 1 to 4 (Fig. 9a, right). ). All replicate experiments similarly inhibited the growth of Trichophyton.

In addition, as shown in FIG. 9b, for the position of "2" closest to the antimicrobial composition in the shoe (see FIGS. 8b and 2), inhibition of the growth of Trichophyton according to the concentration of the antimicrobial component was observed. (results of triplicate experiments for each concentration are shown side by side).

From the above results, it was proved that when the insole provided with the antimicrobial composition was installed in the shoe, the effect of sterilizing the trichophyton in the shoe was obtained. It was found that the degree of this effect depends on the concentration of the antimicrobial component, and that when a 5% concentration of the antimicrobial component is added to the carrier, a remarkable sterilization effect can be obtained throughout the shoe.

[Example 5]
Based on Example 4, the experimental conditions were adjusted in order to further improve the detection sensitivity, and the number of cases was increased to conduct verification experiments. Specifically, 5 CFU/5 μL of T. mentagrophytes TIMM2789 was dropped on a piece of thick filter paper. As shown in FIG. 8b, two pieces of the above filter paper were attached to four positions (1 to 4) on the surface of the insole, arranging them side by side. Other experimental procedures and experimental conditions were the same as in Example 4. FIG. 10 shows a photograph of the petri dish after each piece of filter paper was transplanted from the environment inside the leather shoe with the antimicrobial composition at position "2" of the insole to the petri dish and cultured. In FIG. 10, the leftmost column shows the culture results from the control shoe without the addition of antimicrobial ingredients, and the three right columns show antimicrobial ingredients added to the carrier at concentrations of 1%, 3%, and 5%, respectively. Figure 10 shows culture results from a pair of shoes made from The numbers 1-4 in the petri dish correspond to the positions on the insole surface shown in FIG. 8b.

The sizes of trichophyton colonies observed in the dish shown in FIG. 10 were scored as follows. 0 point: no growth of trichophyton, 1 point: slight growth of trichophyton, 2 points: moderate growth of trichophyton, 3 points: strong growth of trichophyton. The scores were tabulated as shown in Table 4 below.

The above results show that an antimicrobial composition obtained by adding an antimicrobial component to a sustained-release carrier, which is a mixture containing leather fiber and a rubber having a double bond in the main chain (isoprene rubber), was used as an insole for shoes. demonstrated that use at concentrations as low as 1% of the antimicrobial component provided the ability to effectively disinfect trichophyton in shoes. Furthermore, when the same experiment as in this example was performed with the antimicrobial component concentration (% by volume in the ethanol solution) lowered to 0.3% and 0.1%, at least the position of "2" (Fig. 8b) , the average area of tinea fungal growth from the filter paper pieces was significantly reduced compared to the control with 0% antimicrobial component (both concentrations of 0.3% and 0.1% were obtained in the control). reduced to about 60-70% of the total area; data not shown). In other words, it was found that the sterilization effect was maintained even when the concentration of the antimicrobial component was as low as 0.1%.

Although exemplary embodiments of the invention have been described in further detail through examples, the invention is not limited to these specific embodiments. In particular, since it is known that antimicrobial components mainly composed of acyclic terpene aldehydes are effective against not only Trichophyton but also various microorganisms including other fungi and bacteria (Patent Document 1), It will be appreciated that the antimicrobial compositions of the present disclosure may be applied in a variety of applications other than those illustrated in the above examples.

In the present disclosure, "-" indicating a numerical range means that the numerical values described before and after it are included as a lower limit and an upper limit, respectively. When multiple possible numerical ranges are listed separately, such as "A to B" and "C to D," the lower or upper limit of one is combined with the upper or lower limit of the other numerical range (e.g., "A to D ""C to B") should also be taken as disclosed herein. Also, when a combination of a first element and a second element is described, and multiple possible options for each of the first element and the second element are described, each option for the first element and each alternative of the second element should be construed as disclosed herein. In the present disclosure, the phrase "comprising" (eg, "comprising E and F") means including at least the elements specified therein, and elements other than those specified (e.g., E elements and G elements other than F elements), and embodiments consisting only of the elements specified therein (E elements and F elements).

Claims (9)

an insole underlayer;
an insole upper layer laminated on the insole lower layer;
an antimicrobial composition sandwiched between the lower insole layer and the upper insole layer,
The antimicrobial composition comprises
a) a carrier that is a mixture of fibrous materials, which are leather fibers, cotton fibers, or combinations thereof, and rubber having double bonds in the main chain, and
b) an antimicrobial component added to the carrier
wherein the antimicrobial component comprises an acyclic terpene aldehyde;
the insole upper layer has a breathable region in the region overlying the antimicrobial composition;
Insole. The insole according to claim 1, wherein the carrier contains 50 to 98% by weight of the fiber and 2 to 50% by weight of the rubber.. 3. The insole of claim 1 or 2, wherein the acyclic terpene aldehyde comprises citral, citronellal, hydroxycitronellal, or combinations thereof. Claims 1-3, wherein the antimicrobial component further comprises a second aldehyde different from the acyclic terpene aldehyde and selected from acyclic aliphatic aldehydes, terpene aldehydes, and aromatic aldehydes. An insole according to any one of the preceding paragraphs . An antimicrobial insole kit comprising: (i) an insole comprising an undersole layer and an insole top layer laminated onto said undersole layer; and (ii) an antimicrobial composition enclosed in an airtight container. and
The antimicrobial composition comprises
a) a carrier that is a mixture of fibrous materials, which are leather fibers, cotton fibers, or combinations thereof, and rubber having double bonds in the main chain, and
b) an antimicrobial component added to the carrier
wherein the antimicrobial component comprises an acyclic terpene aldehyde;
The lamination of the lower insole layer and the upper insole layer includes a non-adhesive region where the lower insole layer and the upper insole layer are not adhered to each other. It is configured so that the antimicrobial composition can be sandwiched between the bedding layers,
The insole upper layer has an air-permeable region in a portion constituting the non-adhesive region,
Antimicrobial insole kit. 6. The antimicrobial insole kit according to claim 5, wherein said carrier comprises 50-98% by weight of said fibrous material and 2-50% by weight of said rubber. 7. The antimicrobial insole kit of claim 5 or 6, wherein the acyclic terpene aldehyde comprises citral, citronellal, hydroxycitronellal, or combinations thereof. Claims 5-7, wherein the antimicrobial component further comprises a second aldehyde different from the acyclic terpene aldehyde and selected from acyclic aliphatic aldehydes, terpene aldehydes, and aromatic aldehydes. The antimicrobial insole kit according to any one of Claims 1 to 3 . (i) an insole comprising a carrier that is a mixture of fibers that are leather fibers, cotton fibers, or combinations thereof, and rubber having double bonds in its main chain; and (ii) for impregnating said carrier. An antimicrobial insole kit comprising an airtight container containing a liquid antimicrobial component of
the liquid antimicrobial component comprises an acyclic terpene aldehyde;
Antimicrobial insole kit.