Deodorant

Abstract

To discover a novel component of natural origin that is safe for consumption within the body, and inactivates allyl methyl sulfide produced within the body.SOLUTION: A deodorant is primarily composed of hop cone flower.EFFECT: A small intake of the deodorant allows for the inactivation of allyl methyl sulfide remaining within the body.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a deodorant that inactivates allyl methyl sulfide, which is one of the components of the so-called garlic odor and remains in the body for a long time, to eliminate the odor, and the main component is obtained from hops. In the following, in this application, bad breath originating from the oral cavity will be referred to as "bad breath", and bad breath and sweat odor originating from internal organs such as the intestines will be referred to as "body odor". [Background technology]

[0002] It is said that the garlic odor is generated when cells containing alliin (an odorless substance) are destroyed during cooking or eating, and react with allinase to form allicin. This allicin is an unstable substance that changes into vinylditins, ajoenes, and allyl sulfides, which are the odorous components unique to garlic.

[0003] There are two types of allyl sulfides: those that can be detected several hours after eating, and those that can be detected even after about a day. In the case of those that can be detected several hours after eating, the concentration in the breath reaches a maximum about 1-2 hours after taking garlic, and then decreases to the initial concentration over the next 2-3 hours. Compounds of this type include diallyl sulfide, allyl methyl disulfide, diallyl disulfide, and diallyl trisulfide. 「 mouth "Smell" Although this varies depending on the individual and the amount consumed, it is said to last for about three hours, and can be reduced by carefully brushing your teeth, etc.

[0004] On the other hand, the type that can be detected even after about one day reaches a maximum concentration in the breath about 4 to 5 hours after garlic ingestion, and then gradually decreases over about 30 hours or more. An example of this type of compound is allyl methyl sulfide. This latter allyl methyl sulfide is: Not only does it cause bad breath, but it also has stomach Bad breath and what is called "burp" from the intestines 」、 In addition, recent reports have shown that the "Body odor" from the skin This is released from the body as a stench and is perceived as an unpleasant odor.

[0005] Conventional , Po The main components are lyphenol, catechin, tannin, and furfuryl radical. In compounds There are many kinds of deodorants that inactivate allyl methyl sulfide. For example, the applicant disclosed a deodorant using 1,4-cineole or 1,8-cineole in Japanese Patent No. 6342382 (Patent Document 1) as a technology for inactivating allyl methyl sulfide, a deodorant using hexane from either or both loquat seeds and bayberry seeds in Japanese Patent No. 6455859 (Patent Document 2), and a deodorant using a mixture of two or more terpenes, which are plant-derived biological substances and have a high deodorant effect against sulfide-based, thiol-based, aldehyde-based, nitrogen-based, and fatty acid-based malodorous components, as the main raw material in Japanese Patent Application Laid-Open No. 2018-191694 (Patent Document 3).

[0006] By the way, in recent years, there has been a rise in the use of hop-derived substances, which are the raw material for beer. , many It has been discovered that it has a variety of functions, such as stomach strengthening, analgesic effect, improvement of menopausal symptoms, prolongation of sleep time, improvement of insulin sensitivity in type II diabetes patients, increasing secretion of gastric juices, and obesity prevention, as well as the alleviation of hay fever symptoms, prevention of Alzheimer's disease, activation of aromatase in epidermal cells, and inhibition of aromatase in breast cancer cells.

[0007] For example, Patent Document 4 (JP Patent Publication 10-25232 A) discloses that a polyphenol-like substance contained in hop bracts, which is adsorbed to a gel-type synthetic resin, is used as a deodorizing material. It has been confirmed that the deodorizing material disclosed in Patent Document 4 has a superior deodorizing effect on butyric acid, methyl mercaptan, and skatole compared to sodium copper chlorophyllin.

[0008] However, in Patent Document 4, state As described above, there was a problem in that the deodorizing effect against allyl methyl sulfide was low. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Patent No. 6342382 [Patent Document 2] Patent No. 6455859 [Patent Document 3] JP 2018-191694 A [Patent Document 4] Japanese Patent Application Publication No. 10-25232 Summary of the Invention [Problem to be solved by the invention]

[0010] The problem that the present invention aims to solve is that, in the past, deodorizing materials that are polyphenol-like substances derived from hops and adsorbed onto gel-type synthetic resins were not able to effectively inactivate small amounts of allyl methyl sulfide and other substances that remain in the body. [Means for solving the problem]

[0011] In order to solve the above problems, the present invention uses hop cones as a main ingredient. Effect of the Invention

[0012] The present invention has the advantage that it can effectively eliminate odors by inactivating allyl methyl sulfide and the like with a small amount of the compound. In addition, the present invention has the advantage that it is safe to ingest, and when ingested, it can inactivate allyl methyl sulfide and the like in the components of bad breath and body odor by converting them into other compounds, thereby suppressing their emission to the outside of the body as bad breath and body odor. As described above, the present invention inactivates malodorous components by converting them into other compounds, and does not deodorize by masking them with other odors. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention focuses on the multifunctionality of hop-derived ingredients, and is the result of extensive research and development. It has been discovered that hop-derived ingredients have deodorizing effects, in particular, that they remain in the body for a long time when ingested, and gradually We have found a component that can be used as the main component of a deodorant that inactivates allyl methyl sulfide and other compounds that are released outside the body and recognized as a foul odor, thereby eliminating the unpleasant odor. That is, the deodorant of the present invention is made mainly of hop cones.

[0014] In the present invention, "hops" also includes, for example, waste hops after beer production, and there is technical significance in reusing such materials that would otherwise be discarded.

[0015] The present invention has been made based on the following findings. The odorous components derived from garlic are mainly AMS (allyl methyl sulfide), DAS (diallyl sulfide), AMDS (allyl methyl disulfide), DADS (diallyl disulfide), and DATS (diallyl trisulfide).

[0016] Of the above, DAS, AMDS, DADS, and DATS are reported to peak about 0.5 to 1.0 hours after ingestion and then return to pre-ingestion levels about 1.5 to 2.0 hours after ingestion. On the other hand, AMS is reported to peak about 4.5 hours after ingestion and remain in the body for 30.0 hours, although the concentration gradually decreases.

[0017] In addition, AMS and DADS are not only transmitted through breath (bad breath), but also through the skin. Skin It has been reported that DADS was detected in the neck, lower abdomen, buttocks, chest, and forearms, while AMS was detected in the neck, chest, arms, and buttocks.

[0018] The odor components, mainly AMS, that remain in the body for such a long time and are released Against In order to find an effective deodorizing component, the applicant conducted the following experiments, focusing on hop cones, which are the main component in the production of beer.

[0019] (Deodorizing effect of hop cones) First of all, we investigated whether AMS and other substances have a deodorizing effect in hop cones. The naturally dried hop cones are crushed in a mixer and then further pulverized in a mortar (hop powder). Hop powder was weighed out in 30 mL amounts into GC (gas chromatography) vials at 6.25, 12.5, 25.0, 50.0, and 100.0 mg. AMS was injected at 0.01% (2.0 μL) After leaving it at room temperature for 2 hours, 2.0 mL of HS (headspace) gas was collected. The entire amount was injected into GC and the AMS peak value was measured.

[0020] [Table 1]

[0021] As a result of the above, it was found that 100.0 mg of hop powder can reduce the odor concentration of AMS, which is the odor component derived from garlic that has the longest retention time in the body, to 50% or less (deodorization rate of 50% or more), which is the odor concentration at which the odor component is not noticeable because it is blended in with other odor components in the outside air. This shows that hop cones have a deodorizing effect against AMS and other odor components.

[0022] (Deodorizing effect of oxidized hop powder) Next, we investigated the case where the hop powder was oxidized. With The purpose of the present invention is to find a main component that has a deodorizing effect against AMS, etc., so the oxidation method By law There is no technical significance.

[0023] In other words, if the main components having a high deodorizing rate against AMS and the like are oxidized or peroxidized components, then the object of the present invention is to find them, and therefore, hereinafter, in the present invention, the term "oxidation" is defined to include both oxidation and peroxidation in the original sense.

[0024] In the following, we investigated how the deodorizing rate for AMS and the like changes when the compounds are "oxidized" as defined above, regardless of whether an oxidation reaction or a peroxidation reaction occurs in each compound when oxidized by heating.

[0025] The naturally dried hop cones are crushed in a mixer and then further pulverized in a mortar (hop powder). The hop powder was placed flat in a petri dish and heated (oxidized) at 80℃ for 15 hours (oxidized hop powder). Oxidized hop powder was weighed out in 30 mL amounts into GC (gas chromatography) vials at 6.25, 12.5, 25.0, 50.0, and 100.0 mg. AMS was injected at 0.01% (2.0 μL) After leaving it at room temperature for 2 hours, 2.0 mL of HS (headspace) gas was collected. The entire amount was injected into GC and the AMS peak value was measured.

[0026] [Table 2]

[0027] As a result of the above, oxidized hop powder was able to achieve a deodorizing rate of over 70% at 12.5 mg, which is 1 / 8 the amount of hop powder. This shows that by oxidizing hop powder, a high deodorizing rate can be obtained with a smaller amount of hop powder.

[0028] (Deodorizing ingredient extraction) Next, in order to obtain a component with a greater deodorizing effect in even smaller amounts, the components of hop powder were extracted and examined. (1) Extract A was obtained from hop powder using an organic solvent, for example toluene in this example, and the deodorizing rate for AMS per 1.0 mg was examined. The deodorizing rate was 12.1%.

[0029] (2) Extract B was obtained from Extract A using an organic solvent, for example, methanol in this example, and the deodorizing rate against AMS per 1.0 mg of Extract B was examined. The deodorizing rate was 49.3%.

[0030] In addition to the above-mentioned toluene and methanol, the organic solvent for extraction used in the process of obtaining Extract A and Extract B may be, for example, cyclohexane, ethyl acetate, chloroform, acetone, isopropanol, acetonitrile, or hexane. Also, a mixture of these organic solvents with water may be used.

[0031] Furthermore, in the process of obtaining Extract A and Extract B, supercritical carbon dioxide extraction may be used instead of the organic solvent or the mixture of the organic solvent and water. Since the deodorant of the present application is intended to be ingested by the human body, if supercritical carbon dioxide extraction is used, there is no need to consider the effects of the organic solvent on the human body, and the extract can be made safer.

[0032] (3) Extract B from silica Using the gel chromatography technique After purification, "Strong Activity Category 1" was obtained, and the deodorizing rate against AMS at 1.0 mg was examined. The deodorizing rate was 46.5%.

[0033] (5) Strongly active category 1 from moreover the above silica Using the gel chromatography technique purification Repeat the operation As a result, "Strong Activity Category 2" was obtained, and the deodorizing rate against AMS at 1.0 mg of each was examined. The deodorizing rate was 87.1%.

[0034] (6) For each of the "highly active category 2" Mass spectrometer (LC-MS / MS) When analyzed using the above, it was found that each contained the following components: Strong activity category 2: Xanthohumol C (xanthohumol C ) molecular weight 352 : Humulones Molecular weight 348 or 362 : Humulinones Molecular weight 364 or 378 : Lupulones, molecular weight 400 or 414 : Hulupones: molecular weight 318 or 332 *The fact that each component has an -s in its English name and that there are two types of molecular weight will be explained later.

[0035] It is known that hops contain the following components: hop resin 15-30%, essential oil 0.5-3%, tannins and polyphenols 3-6%, water 8-12%, protein 15%, amino acids 0.1%, lipids 1-5%, inorganic substances 1-5%, monosaccharides 2%, pectin 2%, cellulose and lignin 40-50%. Here, in the present invention, attention is focused on hop resin, which is the component with the largest amount.

[0036] ( Estimation ) (1) Among hop resins, The fraction soluble in n-hexane, etc. soft resin, The fraction that is insoluble in n-hexane, etc., but soluble in ether and cold methanol is Hard resin and Call. Extracted from hop ingredients 「 Strongly active category 2 」 The above components are It is extracted from hop powder with toluene (which is more polar than ether or cold methanol, closer to n-hexane). Contains a lot of soft resin components Included This suggests that the soft resin components in hops can inactivate AMS in small amounts. Estimation did.

[0037] Soft resin of hops The main component of is α acid and β acid and , Each contains five structurally similar homologues. The structures of the α-acids and β-acids are the below described of 1 ( Structural formula 1 ), as shown in Chemical Formula 2 (Structural Formula 2), both groups have different co- "Ko", n- "Normal", ad- "Add", post- "post", pre- "Pre" There are homologues of It is known that It is known that isomerized alpha acids have isomerized homologues. It is also known that the oxidation of humulones produces oxidized compounds called humulinones, and the oxidation of lupulones produces oxidized compounds called hulupones, and they are known to have many homologues as well. For these reasons, in (6) above, -s is added to the English notation to indicate that it includes homologues of each component in "Strong Activity Category 2," and also because there are two types of molecular weight, depending on the basic structure and the homologues, this is stated.

[0038] [ka] (Structural formula 1)

[0039] [ka] (Structural formula 2)

[0040] (2) We hypothesized that soft resin components containing alpha acids and beta acids obtained in strong activity category 2 would achieve a higher deodorizing rate with even smaller amounts than hop powder or oxidized hop powder.

[0041] (Check proof) (1) First, to support the hypothesis that the soft resin component has a deodorizing effect against AMS, etc., ,tree Santohumor C The amount of xanthohumol isolated was 0.1 mg and 1.0 mg. C The deodorizing rates for AMS were investigated, and the results showed that the deodorizing rates were approximately 0.5% and 4.0%, respectively.

[0042] Xanthohumol C teeth , Po Lifenoh Transformation It is not expected that the deodorizing rate would change significantly even if the amount was increased to 30.0 mg or if the product was oxidized. is hard Since it belongs to the soft resin category, by elimination from the strong activity category 2, it is believed that the soft resin component contains a deodorizing component against AMS, etc. Estimation It was verified that the above was correct. In addition, the "polyphenol-like substance contained in hop bracts" in Patent Document 4 is this xanthohumol. C I suspect this is the case.

[0043] Therefore, xanthohumol C Except for 「 Strongly active category 2 」 Lupron, Humulinone, Humulone, centre Since both Lupon and Lupon are soft resin components, it is believed that soft resin components are effective in deodorizing AMS. Estimation This has increased the credibility that this is correct.

[0044] (2) The following experiments were conducted. - Strong activity category 2 to the above xanthohumolC The "soft resin component" was extracted. Dissolved in acetone 0.1, 0.3, 1.0, 3.0, 10.0, and 30.0 mg were weighed into 30 mL GC (gas chromatography) vials. Allow to stand and acetone to evaporate Inject 5μL of odorous component (solution) Ta After leaving it at room temperature for 2 hours, 2.0 mL of HS (headspace) gas was collected. The entire amount was injected into GC and measured.

[0045] The odorous components include AMS, as well as the aforementioned AMS, DAS, AMDS, DADS, and DAT, as well as DMS (dimethyl sulfide), DMDS (dimethyl disulfide), AMTS (allyl methyl trisulfide), and DMTS (dimethyl Bird The deodorizing rate of DMS and DMDS was investigated. Although DMS and DMDS are not derived from garlic, they are considered to be sulfide (sulfur-based) odor-causing substances.

[0046] [Table 3]

[0047] From the above, it was found that for soft resin components, 3.0 mg of AMS and DADS will achieve a deodorizing rate of over 50%. Of particular note is that for AMS, a deodorizing rate of over 50% will be achieved with about 1 / 4 the amount of oxidized hop powder, and a deodorizing rate of over 80% will be achieved with about 1 / 2 the amount. It was also found that for other malodorous components except DMS, a deodorizing rate of at least 80% will be achieved with about 30.0 mg, and for DMS, a deodorizing rate of over 50% will be achieved with about 30.0 mg.

[0048] Therefore, the hop resin , soft It is said that the use of resin components such as hop powder and oxidized hop powder can achieve a high deodorizing rate against odorous components such as AMS with even smaller amounts. Uko It was verified that:

[0049] (Oxidized soft resin component) If this is the case, then an oxidized soft resin component (oxidized soft resin component) should be able to provide a higher deodorizing rate with a smaller amount than the above soft resin component, so this was also verified. Deodorization test conditions for oxidized soft resin components is a soft resin component For deodorization measurement and The conditions are The results are shown in Table 4.

[0050] - Strong activity category 2 to the above xanthohumol C The "soft resin component" was extracted. The soft resin component was placed flat in a petri dish and heated (oxidized) at 80℃ for 15 hours (oxidized soft resin component). Dissolved in acetone 0.1, 0.3, 1.0, 3.0, 10.0, and 30.0 mg were weighed into 30 mL GC (gas chromatography) vials. Allow to stand and acetone to evaporate Inject 5μL of odorous component (solution) Ta After leaving it at room temperature for 2 hours, 2.0 mL of HS (headspace) gas was collected. The entire amount was injected into GC and measured.

[0051] [Table 4]

[0052] As a result of the above, it was found that the oxidized soft resin component had a deodorizing rate of about 60% for AMS at 1.0 mg, which is about 1 / 3 the amount of the soft resin component, and a deodorizing rate of nearly 100% at 10.0 mg or more. For DMS, the deodorizing rate was 11.3% at 3.0 mg of the soft resin component, but the deodorizing rate was 74.4% for the oxidized soft resin component.

[0053] In addition, for DAS, the deodorizing rate was 8.6% at 1.0 mg of soft resin components, but with oxidized soft resin components, the deodorizing rate was 65.7%, which was over 50%. The other components generally had the same or higher deodorizing rate as the soft resin components. This shows that the deodorizing rate for AMS and other substances can be improved by oxidizing the soft resin components.

[0054] Here, AMS deodorizer Mechanism About teeth, AMS is oxidized And odorless AMSO To Converted R This has been demonstrated in experiments using a gas chromatograph mass spectrometer.

[0055] Although further research is needed, the experimental results that AMS was converted to AMSO by oxidation suggest that Hop cone extract, soft resin components, alpha acids, beta acids A MS to AMSO acid This oxidation-promoting effect deodorizes AMS. A small amount of the product will provide a reliable and high deodorizing effect. Is It is thought that.

[0056] The soft resin components are comprised of alpha acids and beta acids, and the question of which individual alpha acids, beta acids, and which combinations have a higher deodorizing rate is covered by the present invention, that is, the hop cones and the soft resin components, and it has already been verified that sufficient effects can be obtained, so further verification results will not be described.

[0057] As mentioned above, α-acids and β-acids Cognate There are many types of α-acids, and humulone is an acid. To More Humulinone ( h umulinone), and the beta acid lupulone To More full-bodied ( h It is also known that hop cones are converted into humulinone (α acid), β acid (β acid) and humulinone (α acid) which are not obtained from hop cones, e.g., synthetic humulinone (α acid). Oxidized compounds of ), Hulopon (β acid Oxidized compounds of ) as the main component, the same effect as above can be obtained.

[0058] Incidentally, it has also been verified that the deodorizing rate of AMS and the like described above is not significantly affected by hop cones, whether they are used before or after they are used as a beer ingredient. For this reason, if hop cones, which would normally be discarded after use as a beer ingredient, are reused as the main ingredient of a completely different product, a deodorizer that can deodorize AMS and the like, it can contribute to reducing industrial waste from the perspective of the recent SDGs. In addition, since the deodorizer of the present invention is originally the main ingredient of beer, it is safe to ingest, and furthermore, it can inactivate AMS that is produced in the body and released to the outside.

Claims

1. A deodorant whose main ingredient is hop cones.

2. A deodorant made primarily from soft resin extracted from hop cones.

3. This deodorant mainly contains oxide of hop cones or soft resin component extracted from hop cones.

4. A method for producing a main component of a deodorant, comprising obtaining a soft resin component from hop cones by any one of the following means: extraction with supercritical carbon dioxide, extraction with an organic solvent, or extraction with a mixture of an organic solvent and water.

Images