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JP6752607B2 - Deodorant cosmetics - Google Patents

Deodorant cosmetics Download PDF

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Publication number
JP6752607B2
JP6752607B2 JP2016084231A JP2016084231A JP6752607B2 JP 6752607 B2 JP6752607 B2 JP 6752607B2 JP 2016084231 A JP2016084231 A JP 2016084231A JP 2016084231 A JP2016084231 A JP 2016084231A JP 6752607 B2 JP6752607 B2 JP 6752607B2
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histidine
nonenal
solution
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JP2017193504A (en
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克真 鞍本
克真 鞍本
佑介 河内
佑介 河内
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Naris Cosmetics Co Ltd
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Naris Cosmetics Co Ltd
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Description

本発明は、加齢臭の主な原因物質とされる2−ノネナールを消臭する化粧料に関する。さらに詳しくは、本発明は、高い消臭効果を発揮し、また、消臭効果を損なうことなく安定して発揮することのできる化粧料に関する。
The present invention relates to a cosmetic that deodorizes 2-nonenal, which is a main causative substance of aging odor. More specifically, the present invention relates to a cosmetic that exhibits a high deodorizing effect and can be stably exerted without impairing the deodorizing effect.

近年、加齢に伴い身体や頭部から発生する臭いに対してのケアに注目が集まってきており、それらの臭いを炭などの多孔性物質が吸着することにより除去する技術(特許文献1)や原因となる常在菌の繁殖を抑制する技術(特許文献2)、香料成分などでマスキングする技術、ブドウ糖と特定のアミノ酸で消臭化する技術(特許文献3)などが開発されている。このような加齢に伴った不快な臭いは一般的に加齢臭と呼ばれており、夏場の汗臭などとともに不快なものとされ、解消が求められている。 In recent years, attention has been focused on care for odors generated from the body and head with aging, and a technique for removing those odors by adsorbing a porous substance such as charcoal (Patent Document 1). (Patent Document 2), a technique for suppressing the growth of indigenous bacteria that cause the problem, a technique for masking with a fragrance component, and a technique for deodorizing with glucose and a specific amino acid (Patent Document 3) have been developed. Such an unpleasant odor associated with aging is generally called an aging odor, and is considered to be unpleasant along with the sweat odor in summer, and its elimination is required.

その一方で、加齢臭の主な原因物質として2−ノネナールが提唱されており、この成分は加齢とともに増大することが示されている。特に加齢臭が発生する年齢とされる40歳以降で顕著に増大することが確認されている。2−ノネナールはω7不飽和脂肪酸の酸化的分解によって発生し、過酸化脂質がその酸化的分解を促進することが示されている。
発生した2−ノネナールを消臭する物質については、L−ヒスチジンに極めて高い2−ノネナールの消臭効果があることが知られている。しかし、L−ヒスチジンは特定の化合物と併用した場合、著しく消臭効果が低減し、安定性も経時的に減少する事が問題点であった。
On the other hand, 2-nonenal has been proposed as a major causative substance of aging odor, and it has been shown that this component increases with aging. In particular, it has been confirmed that it increases remarkably after the age of 40, which is considered to be the age at which the odor of aging occurs. 2-Nonenal is generated by the oxidative degradation of omega-7 unsaturated fatty acids, and lipid peroxides have been shown to promote their oxidative degradation.
As for the substance that deodorizes the generated 2-nonenal, it is known that L-histidine has an extremely high deodorizing effect of 2-nonenal. However, when L-histidine is used in combination with a specific compound, there is a problem that the deodorizing effect is remarkably reduced and the stability is also reduced with time.

特開2002−145747JP 2002-145747 特開2008−110999Japanese Patent Application Laid-Open No. 2008-110999 特開2010−013418JP 2010-013418

本発明は、L−ヒスチジンの消臭効果および安定性が特定の化合物:成分(C)との共存時に著しく低下する現象に対し、これを改善した化粧料を提供することを目的とする。 An object of the present invention is to provide a cosmetic product in which the deodorant effect and stability of L-histidine are significantly reduced when coexisting with a specific compound: component (C).

以上の問題を解決するため、本発明者が鋭意検討した結果、L−ヒスチジンの成分(C)による消臭効果および安定性の低下が、ピロ亜硫酸塩、亜硫酸塩、亜硫酸水素塩を用いることで改善することを見出した。さらにこれら3成分を組み合わせることによって、製剤の経時安定化についても相乗的に効果が上昇することが判明した。 As a result of diligent studies by the present inventor in order to solve the above problems, the deodorizing effect and the decrease in stability due to the component (C) of L-histidine can be reduced by using pyrosulfite, sulfite, and hydrogen sulfite. I found it to improve. Furthermore, it was found that the combination of these three components synergistically increases the effect of stabilizing the preparation over time.

すなわち本発明は
次の成分(A)〜(C)、
(A)L−ヒスチジン
(B)ピロ亜硫酸塩、亜硫酸塩、亜硫酸水素塩から選択される1種又は2種以上
(C)サリチル酸、サリチル酸の誘導体及びサリチル酸の塩、塩化ベンザルコニウム、塩化ベンザルコニウムの誘導体及び塩化ベンザルコニウムの塩、トリクロサン、トリクロサンの誘導体及びトリクロサンの塩、イソプロピルメチルフェノールから選択される1種又は2種以上
を含有する化粧料である。
That is, the present invention describes the following components (A) to (C),
(A) L-histidine (B) One or more selected from pyrosulfite, sulfite, hydrogen sulfite (C) Salicylic acid, derivatives of salicylic acid and salts of salicylic acid, benzalkonium chloride, benzalkonium chloride A cosmetic containing one or more selected from nium derivatives and benzalkonium chloride salts, triclosan, triclosan derivatives and triclosan salts, and isopropylmethylphenol.

本発明によれば、L−ヒスチジンを用いた消臭化粧料について、L−ヒスチジンの消臭効果および安定性が特定の成分、成分(C)の配合時に低下するのを、効果的に防ぐことが可能となる。 According to the present invention, with respect to a deodorant cosmetic using L-histidine, it is possible to effectively prevent the deodorant effect and stability of L-histidine from being lowered when a specific component, the component (C), is blended. Is possible.

以下、本発明について更に詳しく説明する。 Hereinafter, the present invention will be described in more detail.

本発明に用いられる成分(A)L−ヒスチジンは、本発明において2−ノネナールを消臭するために配合している。 The component (A) L-histidine used in the present invention is blended in the present invention to deodorize 2-nonenal.

本発明に用いられる成分(A)L−ヒスチジンは望ましくは0.01%〜5%が望ましい。さらに望ましくは0.1%〜3%が望ましい。 The component (A) L-histidine used in the present invention is preferably 0.01% to 5%. More preferably, 0.1% to 3% is desirable.

本発明に用いられる成分(B)ピロ亜硫酸塩、亜硫酸塩、亜硫酸水素塩は、これらに成分(A)と成分(C)とを共に配合することで、偶然にも成分(A)の消臭効果が効果的に保持できた。塩の種類は特に限定されず、成分(B)は還元能を有する成分であることが望ましい。 The component (B) pyrosulfite, sulfite, and hydrogen sulfite used in the present invention accidentally deodorize the component (A) by blending the component (A) and the component (C) together. The effect could be maintained effectively. The type of salt is not particularly limited, and it is desirable that the component (B) is a component having a reducing ability.

本発明に用いられる成分(B)は望ましくは0.001%〜1%が望ましい。さらに望ましくは0.01%〜0.1%が望ましい。 The component (B) used in the present invention is preferably 0.001% to 1%. More preferably, 0.01% to 0.1% is desirable.

本発明に用いられる成分(C)は化粧品添加物として、医薬部外品の有効成分、添加物として一般的に汎用されている成分であり、ニキビ予防や頭皮のふけ・かゆみ予防を目的としスキンケア、トイレタリー製品などに幅広く配合される。洗浄剤やスキンケア化粧品においては製品の抗菌力向上を目的に配合する場合もある。 The ingredient (C) used in the present invention is a cosmetic additive, an active ingredient of quasi-drugs, and a commonly used ingredient as an additive, and is used for skin care for the purpose of preventing dandruff and scalp dandruff and itching. , Widely used in toiletry products. In detergents and skin care cosmetics, it may be added for the purpose of improving the antibacterial activity of the product.

成分(C)は特に医薬部外品の殺菌有効成分としては欠かすことのできない成分である。医薬部外品の中でも腋臭の防止効果や頭皮のふけ・かゆみの予防などを効果効能とする医薬部外品には必須成分として配合する必要がある。 Ingredient (C) is an indispensable ingredient as a bactericidal active ingredient for quasi-drugs. Among quasi-drugs, it is necessary to add it as an essential ingredient to quasi-drugs that have the effect of preventing axillary odor and the prevention of dandruff and itch on the scalp.

成分(C)の塩の種類、誘導体の種類は特に限定されず、成分の母体構造が共通していれば成分(A)の消臭効果及び安定性を損ない、損なわれた効果や安定性が成分(B)の存在時に改善した。 The type of salt and the type of derivative of the component (C) are not particularly limited, and if the parental structure of the component is common, the deodorant effect and stability of the component (A) are impaired, and the impaired effect and stability are impaired. Improved in the presence of component (B).

本発明の皮膚洗浄用組成物は液状、ペースト状、クリーム状、およびジェル状など剤型には寄らず適用することができる。 The skin cleansing composition of the present invention can be applied regardless of the dosage form such as liquid, paste, cream, and gel.

以下に実施例を挙げて、本発明を更に説明する。なお、これらは本発明を何ら限定するものではない。配合量は組成物全量に対する質量%である。 The present invention will be further described below with reference to examples. It should be noted that these do not limit the present invention in any way. The blending amount is mass% with respect to the total amount of the composition.

本実施例で用いた評価項目について説明する。
1.「消臭効果(分析)」
「評価方法」
2−ノネナール除去能の評価は、HPLCを利用した測定方法(分析化学, 46(1) , 31-36, 1997)を改変して2−ノネナールの量を測定することにより行った。
The evaluation items used in this example will be described.
1. "Deodorant effect (analysis)"
"Evaluation method"
The 2-nonenal removing ability was evaluated by modifying the measurement method using HPLC (Analytical Chemistry, 46 (1), 31-36, 1997) to measure the amount of 2-nonenal.

実施例もしくは比較例の化粧料を、95%エタノール水溶液を溶媒として50%溶液として試料とした。
陽性対象には、2−ノネナールの除去効果が知られているL−リジン(特開2011−156227)と、同じ塩基性アミノ酸のL−ヒスチジンを用いた。L−リジンは50%エタノール水溶液を溶媒として1%溶液とし、L−ヒスチジンは1%水溶液を調整し、試験に用いた。
The cosmetics of Examples or Comparative Examples were used as samples using a 95% ethanol aqueous solution as a solvent and a 50% solution.
For the positive subject, L-lysine (Japanese Patent Laid-Open No. 2011-156227), which is known to have a 2-nonenal removing effect, and L-histidine, which is the same basic amino acid, were used. A 1% solution of L-lysine was prepared using a 50% ethanol aqueous solution as a solvent, and a 1% aqueous solution of L-histidine was prepared and used in the test.

上記試料又は陽性対照であるL−リジン溶液、又はL‐ヒスチジン溶液を500μLと、95%エタノールを溶媒として調製した5μM2‐ノネナール溶液500μLとを混合後、32℃の恒温槽で8時間温めた。Controlには試料の代わりに95%エタノール水溶液を用いた。その後DNPA液500μLを混合後、45℃の恒温槽で30min反応させた(反応液)。DNPA液とは、DNPH(2,4‐Dinitrophenyl hydrazine Hydrochloride) 25mg, 99.5%エタノール45mL, 濃塩酸1mL, 蒸留水 4mLの混合液を指す。反応液は 氷水で約10min冷却し、反応を停止させた。反応を停止させた反応液はろ過後、HPLCにて解析を行った。2-ノネナールの検出はリテンションタイム11.5minに確認された。体臭成分である2‐ノネナールの除去率は、以下の式に従いピーク面積から求めた。 After mixing 500 μL of the above sample or L-lysine solution or L-histidine solution as a positive control with 500 μL of a 5 μM2-nonenal solution prepared using 95% ethanol as a solvent, the mixture was heated in a constant temperature bath at 32 ° C. for 8 hours. A 95% aqueous ethanol solution was used as the control instead of the sample. Then, 500 μL of the DNPA solution was mixed and then reacted in a constant temperature bath at 45 ° C. for 30 minutes (reaction solution). The DNPA solution refers to a mixed solution of DNPH (2,4-Dinitrophenyl hydrazine Hydrochloride) 25 mg, 99.5% ethanol 45 mL, concentrated hydrochloric acid 1 mL, and distilled water 4 mL. The reaction solution was cooled with ice water for about 10 minutes to stop the reaction. The reaction solution in which the reaction was stopped was filtered and then analyzed by HPLC. Detection of 2-nonenal was confirmed with a retention time of 11.5 min. The removal rate of 2-nonenal, which is a body odor component, was calculated from the peak area according to the following formula.

<式1>

Figure 0006752607
<Formula 1>
Figure 0006752607

<HPLC 条件>
カラム; CHEMCOBOND 5−ODS−W size6.0×150 (6A)
流速 ; 1.5 mL/min
カラム温度 ; 50 ℃
移動相 ; CH3CN:H2O = 80:20( V/V)
検出器/測定波長 ;紫外可視検出器/365 nm
<HPLC conditions>
Column; CHEMCOBOND 5-ODS-W size 6.0 × 150 (6A)
Flow velocity; 1.5 mL / min
Column temperature; 50 ° C
Mobile phase; CH3CN: H2O = 80:20 (V / V)
Detector / measurement wavelength; UV-visible detector / 365 nm

「評価基準」
上記方法でL−ヒスチジンの2−ノネナールの除去率によって以下のように評価した。
○:除去率80%以上
△:除去率40%以上、80%未満
×:除去率1%以上、40%未満
××:除去率1%未満
"Evaluation criteria"
It was evaluated as follows according to the removal rate of 2-nonenal of L-histidine by the above method.
◯: Removal rate 80% or more Δ: Removal rate 40% or more, less than 80% ×: Removal rate 1% or more, less than 40% × ×: Removal rate less than 1%

2.「消臭効果(官能)」
「評価方法」
実施例もしくは比較例の化粧料を、水を溶媒として50%溶液として試料とした。陰性対照として水を用いた。10μM2−ノネナール溶液と試料を1:1の割合で混合し、10分後のにおいを評価することによって確認した。なお、評価は熟練の評価者5名で行った。
「評価基準」
上記試験結果から、各試料と混合した溶液のにおいに以下のようにスコアをつけた。
5点:においなし
4点:ほとんどにおいなし
3点:においは低減しているが残っている
2点:わずかににおいが減っている
1点:変化なし
続いて評価者5名の平均スコアを算出し、以下のように評価を行った。
○:4点以上
△:2点以上4点未満
×:2点未満
2. "Deodorant effect (sensuality)"
"Evaluation method"
The cosmetics of Examples or Comparative Examples were used as samples using water as a solvent and a 50% solution. Water was used as a negative control. It was confirmed by mixing a 10 μM2-nonenal solution and a sample at a ratio of 1: 1 and evaluating the odor after 10 minutes. The evaluation was carried out by five skilled evaluators.
"Evaluation criteria"
From the above test results, the odor of the solution mixed with each sample was scored as follows.
5 points: No odor 4 points: Almost no odor 3 points: Smell is reduced but remains 2 points: Smell is slightly reduced 1 point: No change Next, the average score of 5 evaluators is calculated. Then, the evaluation was performed as follows.
◯: 4 points or more △: 2 points or more and less than 4 points ×: Less than 2 points

3.「安定性」
「評価方法」
実施例および比較例の化粧料を60℃下に1週間静置し、熟練の評価者が外観の経時変化を目視により確認することで評価を行った。
「評価基準」
上記方法により経時変化を確認し、経時変化の度合いにより以下のように評価を行った。
○:変化なし
×:黄色に変色している。
3. "Stability"
"Evaluation method"
The cosmetics of Examples and Comparative Examples were allowed to stand at 60 ° C. for 1 week, and the evaluation was performed by a skilled evaluator visually confirming the change over time in appearance.
"Evaluation criteria"
The change with time was confirmed by the above method, and the evaluation was performed as follows according to the degree of change with time.
◯: No change ×: The color has changed to yellow.

Figure 0006752607
Figure 0006752607

Figure 0006752607
Figure 0006752607

比較例2、3、および7〜9を参照すると、成分(A)と成分(C)が共存することにより、消臭効果、安定性共に非常に悪いことが伺える。これに対し、実施例を参照すると、成分(B)が配合された場合、消臭効果、安定性共に非常に良好である。 With reference to Comparative Examples 2, 3 and 7 to 9, it can be seen that the coexistence of the component (A) and the component (C) causes very poor deodorant effect and stability. On the other hand, referring to the examples, when the component (B) is blended, both the deodorant effect and the stability are very good.

実施例1、2、3では成分Bの配合量を変化させているが、0.001%でも十分な効果が得られていることが分かる。また、実施例4に示したとおり成分Aの配合量が0.01%でも十分な消臭効果が得られていることが分かる。 In Examples 1, 2 and 3, the blending amount of the component B is changed, but it can be seen that a sufficient effect is obtained even at 0.001%. Further, as shown in Example 4, it can be seen that a sufficient deodorizing effect is obtained even when the blending amount of the component A is 0.01%.

なお、安定性の評価において色調の変化が起こっているものは、使用感にも変動が起きている傾向があり、成分(A)、成分(B)及び成分(C)が共存することにより、使用感の変化を抑える利点も確認された。 It should be noted that, in the evaluation of stability, those having a change in color tone tend to have a change in usability, and the coexistence of the component (A), the component (B) and the component (C) causes the change. The advantage of suppressing changes in usability was also confirmed.

以上の結果から、処方に成分(C)を配合する際に、成分(A)を用いて消臭効果を付与したい場合は、成分(B)を組み合わせて配合することで、より高い消臭効果と安定性を付与することができる。
From the above results, when the ingredient (C) is added to the prescription, if the ingredient (A) is used to give a deodorizing effect, the ingredient (B) can be combined and added to achieve a higher deodorizing effect. And stability can be imparted.

常法にて、各処方の組成物を作製した。いずれの処方においても本発明の効果を奏することが確認された。
(1)シャンプー
配合成分 配合量(%)
水 残量
L−ヒスチジン 0.3
亜硫酸Na 0.05
サリチル酸 0.20
塩化Na 適量
pH調整剤 適量
防腐剤 適量
グリセリン 8.00
エデト酸塩 0.05
ラウレス硫酸Na 12.00
PPG−2コカミド 2.00
ラウリルヒドロキシスルタイン 3.00
ポリクオタニウム−10 0.05
合計(%) 100.00

The compositions of each formulation were prepared by a conventional method. It was confirmed that the effects of the present invention were exhibited in all the formulations.
(1) Shampoo compounding ingredient compounding amount (%)
Remaining water L-histidine 0.3
Sodium sulfite 0.05
Salicylic acid 0.20
Na Chloride Appropriate amount pH adjuster Appropriate amount Preservative Appropriate amount Glycerin 8.00
Edetate 0.05
Sodium Laureth Sulfate 12.00
PPG-2 Cocamide 2.00
Lauryl hydroxysultaine 3.00
Polyquaternium-10 0.05
Total (%) 100.00

(2)化粧水
配合成分 配合量(%)
水 残量
L−ヒスチジン 0.15
亜硫酸Na 0.05
サリチル酸 0.20
エタノール 40.00
pH調整剤 適量
防腐剤 適量
1,3−BG 8.00
エデト酸塩 0.01
L−メントール 0.20
合計(%) 100.00
(2) Toner compounding amount (%)
Remaining water L-histidine 0.15
Sodium sulfite 0.05
Salicylic acid 0.20
Ethanol 40.00
Acidity regulator Appropriate amount Preservative Appropriate amount 1,3-BG 8.00
Edetate 0.01
L-menthol 0.20
Total (%) 100.00

Claims (2)

次の成分(A)〜(C)、
(A)L−ヒスチジン
(B)ピロ亜硫酸塩、亜硫酸塩、亜硫酸水素塩から選択される1種又は2種以上
(C)サリチル酸、塩化ベンザルコニウム、トリクロサン、イソプロピルメチルフェノールから選択される1種又は2種以上
を含有する洗浄用化粧料。
The following components (A) to (C),
(A) L-histidine (B) pyrosulfite, sulfite, one or more (C) salicylic acid is selected from bisulfite, chloride Benzarukoniu arm, Torikurosa down, 1 selected from isopropyl methylphenol A cleaning cosmetic containing seeds or two or more.
成分(A)L−ヒスチジンの配合量が0.01%〜5%
成分(B)の配合量が0.001%〜1%
である請求項1記載の洗浄用化粧料。
Ingredient (A) L-histidine blended amount is 0.01% to 5%
The amount of component (B) is 0.001% to 1%
The cleaning cosmetic according to claim 1.
JP2016084231A 2016-04-20 2016-04-20 Deodorant cosmetics Active JP6752607B2 (en)

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