JP7453036B2 - Skin external preparations - Google Patents

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JP7453036B2
JP7453036B2 JP2020061214A JP2020061214A JP7453036B2 JP 7453036 B2 JP7453036 B2 JP 7453036B2 JP 2020061214 A JP2020061214 A JP 2020061214A JP 2020061214 A JP2020061214 A JP 2020061214A JP 7453036 B2 JP7453036 B2 JP 7453036B2
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JP2021161032A (en
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千尋 中野
佑介 河内
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Naris Cosmetics Co Ltd
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本発明はキチンナノファイバー及び表面キトサン化キチンナノファイバーを含む皮膚外用剤に関する。 The present invention relates to a skin external preparation containing chitin nanofibers and chitin nanofibers whose surface has been chitosanated.

キチンやキトサンは優れた抗菌性、保湿性、生体適合性および安全性などが報告されており、従来、医用材料、医薬、化粧品、食品、繊維、農業、水処理等に利用されている。 Chitin and chitosan have been reported to have excellent antibacterial properties, moisturizing properties, biocompatibility, and safety, and have been used in medical materials, medicines, cosmetics, foods, textiles, agriculture, water treatment, etc.

キチンやキトサンは、一般に水不溶性である上、適正な溶媒が少ないことによりその利用が制限されていたが、近年、キチンやキトサンをナノファイバー化することにより、比較的簡単に水系溶媒に均一に分散でき安定に配合可能となった。 Chitin and chitosan are generally water-insoluble, and their use has been limited due to the lack of suitable solvents. However, in recent years, chitin and chitosan have been made into nanofibers, making it relatively easy to apply them uniformly to aqueous solvents. It can be dispersed and stably blended.

これらの利便性の改善に伴い、キチンナノファイバーやキトナンナノファイバーが保湿効果を目的として化粧料に利用されている。さらに、キチンナノファイバーやキトサンナノファイバーを用いることは、保湿効果以外にもアトピー性皮膚炎や褥瘡、火傷等の角層の損傷に対する治療・予防効果が報告されており、皮膚上皮の厚さを増加させることも示されている。(特許文献1) With these improvements in convenience, chitin nanofibers and chitonan nanofibers are being used in cosmetics for the purpose of moisturizing effects. Furthermore, in addition to moisturizing effects, the use of chitin nanofibers and chitosan nanofibers has been reported to have therapeutic and preventive effects on damage to the stratum corneum such as atopic dermatitis, pressure ulcers, and burns, and to reduce the thickness of the skin epithelium. It has also been shown to increase (Patent Document 1)

しかし、ナノファイバー化したキチンやキトサンは、一時的に水に分散させることは可能だが、経時で沈降・凝集する問題があった。 However, although nanofibers such as chitin and chitosan can be temporarily dispersed in water, they have the problem of settling and agglomerating over time.

このような分散安定性を解決する一般的な手段として高分子を併用することが考えられる。高分子は沈降抑制し、分散安定性を向上する他、しっとり感の付与、肌なじみを良くするために用いられることが知られている。しかし、ナノファイバー化したキチンやキトサンは、高分子を併用すると、凝集が生じやすいことが知られているため、配合することにより安定性が悪くなるといった課題があった。凝集は、ナノファイバー繊維同士のイオン的な結合や、高分子の繊維がキチンおよびキトサンの繊維と絡まるためと考えられる。
A common means for solving such dispersion stability is to use polymers in combination. It is known that polymers are used to suppress sedimentation and improve dispersion stability, as well as to impart a moist feel and improve skin compatibility. However, it is known that nanofiber-formed chitin and chitosan tend to aggregate when used in combination with polymers, so there is a problem in that their stability deteriorates when they are blended. The aggregation is thought to be due to ionic bonds between nanofiber fibers and entanglement of polymeric fibers with chitin and chitosan fibers.

WO2012/036283号公報WO2012/036283 publication

本発明は上記の従来技術に鑑みてなされたものであり、特定の成分(A)を含みながらも、使用感および安定性に優れた皮膚外用剤を提供することを課題とする。
The present invention has been made in view of the above-mentioned prior art, and an object of the present invention is to provide an external preparation for skin that has excellent usability and stability even though it contains a specific component (A).

上記課題を達成するため、本発明者は鋭意研究を行った結果、成分(A)キチンナノファイバー及び表面キトサン化キチンナノファイバーと成分(B)で示される特定の高分子を組み合わせる事によって、凝集がなく保存安定性に優れ、使用感に優れる皮膚外用剤を見出すことができた。
成分(B)について、具体的には、グルコース、ガラクトース、マンノースおよびキシロースからなる群から選ばれる1種以上の単糖で構成される水溶性増粘多糖類及び疎水変性ポリエーテルウレタンから選ばれる1種又は2種以上を配合した皮膚外用剤が、使用感および保存安定性に優れることを見出した。
In order to achieve the above object, the present inventor conducted intensive research and found that by combining component (A) chitin nanofibers and chitin nanofibers with surface chitosanization, and a specific polymer represented by component (B), aggregation We were able to find a topical skin preparation that is free of oxidation, has excellent storage stability, and is comfortable to use.
Regarding component (B), specifically, one selected from water-soluble thickening polysaccharide composed of one or more monosaccharides selected from the group consisting of glucose, galactose, mannose and xylose, and hydrophobically modified polyether urethane. It has been found that a skin preparation containing one or more of these seeds has excellent usability and storage stability.

本発明は、キチンナノファイバーや表面キトサン化キチンナノファイバーを含みながらも使用感および保存安定性に優れた皮膚外用剤を提供することができる。
INDUSTRIAL APPLICABILITY The present invention can provide an external preparation for skin that has excellent usability and storage stability even though it contains chitin nanofibers or chitin nanofibers whose surface has been chitosanated.

図1はキチンナノファイバー又は表面キトサン化キチンナノファイバーの繊維幅および繊維長を模式的に示した図である。FIG. 1 is a diagram schematically showing the fiber width and fiber length of chitin nanofibers or surface-chitosanated chitin nanofibers.

本発明でいうナノファイバーとは、平均繊維幅をナノレベル(nm)まで高度に解繊維した微細繊維であり、平均繊維幅が2nmから 200nm、繊維長が100nm以上の繊維状物質である。 Nanofibers as used in the present invention are fine fibers whose average fiber width has been highly defibrillated to the nano level (nm), and are fibrous substances with an average fiber width of 2 nm to 200 nm and a fiber length of 100 nm or more.

本発明に用いられる成分(A)キチンナノファイバーは、特に限定されていないが、カニ殻などの甲殻から得られたキチンを超極細繊維の状態で取り出したキチンナノファイバー等が挙げられる。例えば、キチンナノファイバーを乾燥したものは、定量するとき、窒素(N:14.01)として6.5~8.5%を含むこと等が挙げられる。サイズとしては、例えば、平均繊維幅が2nmから 200nm、繊維長が1μm以上の繊維状物質であるもの等が挙げられる。市販品の例としては、製品名:マリンナノファイバーキチンNF(表示名:キチン/株式会社マリンナノファイバー社製)等が挙げられる。 Component (A) chitin nanofibers used in the present invention are not particularly limited, but include chitin nanofibers obtained by extracting chitin obtained from shells such as crab shells in the form of ultrafine fibers. For example, dried chitin nanofibers contain 6.5 to 8.5% nitrogen (N: 14.01) when quantitatively determined. Examples of the size include fibrous substances with an average fiber width of 2 nm to 200 nm and a fiber length of 1 μm or more. Examples of commercially available products include product name: Marine Nanofiber Chitin NF (display name: Chitin/manufactured by Marine Nanofiber Co., Ltd.).

本発明に用いられる成分(A)表面キトサン化キチンナノファイバーは、特に限定されていないが、上記のキチンナノファイバーを加水分解して部分的に表面を脱アセチル化して得られるもの等が挙げられる。特に脱アセチル化度は限定されるものではないが、20%以上が好ましい。サイズとしては、例えば、平均繊維幅が2nmから 200nm、繊維長が1μm以上の繊維状物質であるもの等が挙げられる。市販品の例としては、製品名:マリンナノファイバー部分加水分解キチンNF(表示名:加水分解キチン/株式会社マリンナノファイバー社製)等が挙げられる。 Component (A) surface-chitosanated chitin nanofibers used in the present invention are not particularly limited, but include those obtained by hydrolyzing the above chitin nanofibers and partially deacetylating the surface. . Although the degree of deacetylation is not particularly limited, it is preferably 20% or more. Examples of the size include fibrous materials with an average fiber width of 2 nm to 200 nm and a fiber length of 1 μm or more. Examples of commercially available products include product name: Marine Nanofiber Partially Hydrolyzed Chitin NF (display name: Hydrolyzed Chitin/manufactured by Marine Nanofiber Co., Ltd.).

本発明の皮膚外用剤において、成分(A)は1種を選んで配合してもよく、2種以上を組み合わせて配合しても良い。 In the skin external preparation of the present invention, one type of component (A) may be selected and blended, or two or more types may be blended in combination.

本発明の皮膚外用剤においては、ナノファイバーの配合量は特に限定されるものではないが、効果、使用感などの観点から0.001~0.8質量%とすることが好ましい。 In the external skin preparation of the present invention, the amount of nanofibers to be blended is not particularly limited, but is preferably 0.001 to 0.8% by mass from the viewpoint of effectiveness and feeling of use.

本発明に用いられる成分(A)は、より分散性を高めるために、高圧処理等で機械的に解繊してもよい。 Component (A) used in the present invention may be mechanically defibrated by high pressure treatment or the like in order to further improve dispersibility.

本発明に用いられる成分(B)は、グルコース、ガラクトース、マンノースおよびキシロースからなる群から選ばれる1種以上の単糖で構成される水溶性増粘多糖類、または疎水変性ポリエーテルウレタンである。 Component (B) used in the present invention is a water-soluble polysaccharide thickener composed of one or more monosaccharides selected from the group consisting of glucose, galactose, mannose, and xylose, or a hydrophobically modified polyether urethane.

成分(B)は、基本的にはこれら4種以外の単糖を全く含まない多糖類の事を指すが、多糖類は天然由来の物もあるため、一部不純物程度にこれら以外の単糖も含むことができる。具体的には、多糖類中のこれら4種の単糖の構成率は95%以上、好ましくは98%以上を含むものとする。 Component (B) basically refers to a polysaccharide that does not contain any monosaccharides other than these four types, but since some polysaccharides are naturally derived, some monosaccharides other than these may be present as impurities. can also be included. Specifically, the composition ratio of these four types of monosaccharides in the polysaccharide is 95% or more, preferably 98% or more.

成分(B)を構成する単糖は一部置換基で置換されていても、されていなくても特に制限はないが、好ましくは置換基がない、もしくは水溶性を維持し、増粘性を有する範囲であれば、非イオン性の置換基で置換されていることが望ましい。 There is no particular restriction whether the monosaccharide constituting component (B) is partially substituted with a substituent or not, but it is preferably free of substituents or maintains water solubility and has thickening properties. Within this range, it is desirable that the substituent be substituted with a nonionic substituent.

成分(B)の水溶性増粘多糖類は、特に制限はされないが、水溶性の性質があり、水を増粘させることを特徴とする。さらに詳細には、単糖同士がグリコシド結合により結合した構造を有し、分岐の有無や重合度などは特に制限はない。 The water-soluble thickening polysaccharide of component (B) is not particularly limited, but is characterized by being water-soluble and thickening water. More specifically, it has a structure in which monosaccharides are bonded to each other through glycosidic bonds, and there are no particular restrictions on the presence or absence of branching or the degree of polymerization.

成分(B)の具体例としてはローカストビーンガム、グアーガム、タラガム、プルラン、タマリンドガム等が挙げられ、これらの水溶性増粘多糖類であれば、使用感および保存安定性に優れた皮膚外用剤を提供することができる。 Specific examples of component (B) include locust bean gum, guar gum, tara gum, pullulan, tamarind gum, etc. These water-soluble thickening polysaccharides can be used as external skin preparations with excellent usability and storage stability. can be provided.

成分(B)の疎水変性ポリエーテルウレタンは会合性増粘剤である。会合性増粘剤は、親水基部を骨格とし、末端に疎水性部分を持つコポリマーであり、水中でコポリマーの疎水性部分同士が会合し増粘作用を示すものをいう。このような会合性増粘剤は、水中でコポリマーの疎水性部分同士が会合し、親水部がループ状、ブリッジ状をなし、増粘作用を示す。 Component (B), hydrophobically modified polyether urethane, is an associative thickener. An associative thickener is a copolymer with a hydrophilic group as a skeleton and a hydrophobic portion at the end, and the hydrophobic portions of the copolymer associate with each other in water to exhibit a thickening effect. In such an associative thickener, the hydrophobic parts of the copolymer associate with each other in water, and the hydrophilic part forms a loop or bridge shape, thereby exhibiting a thickening effect.

疎水変性ポリエーテルウレタンは、特に限定されないが、例えば、(PEG-240/デシルテトラデセス-20/HDI)コポリマー、ビスステアリルPEG/PPG-8/6(SMDI/PEG-400)コポリマー等が挙げられる。 The hydrophobically modified polyether urethane is not particularly limited, but examples include (PEG-240/decyltetradeceth-20/HDI) copolymer, bisstearyl PEG/PPG-8/6 (SMDI/PEG-400) copolymer, etc. It will be done.

本発明の皮膚外用剤において、成分(B)は1種を選んで配合してもよく、2種以上を組み合わせて配合しても良い。 In the skin external preparation of the present invention, one type of component (B) may be selected and blended, or two or more types may be blended in combination.

本発明の皮膚外用剤において、成分(B)の配合量は特に限定されるものではないが、安定性や使用性などの観点から0.0005質量%~4質量%とすることが好ましい。特に好ましく0.001質量%~3質量%である。 In the skin external preparation of the present invention, the amount of component (B) blended is not particularly limited, but from the viewpoint of stability and usability, it is preferably 0.0005% by mass to 4% by mass. Particularly preferred is 0.001% by mass to 3% by mass.

本発明に用いられるキチンナノファイバー又は表面キトサン化キチンナノファイバーの安定性や皮膚に対する安全性面を勘案すると、調製する皮膚外用剤は中性から弱酸性が好ましい。具体的には、pH3~8が好ましい。 Considering the stability of the chitin nanofibers or chitin nanofibers whose surface has been chitosanated used in the present invention and the safety to the skin, the prepared external skin preparation is preferably neutral to weakly acidic. Specifically, pH 3 to 8 is preferred.

本発明の皮膚外用剤には、必要に応じて本発明の効果を阻害しない質的、量的範囲内で、水、多価アルコール、低級アルコール、pH調整剤、界面活性剤、防腐剤、キレート剤、薬効成分、油剤、シリコーン、酸化防止剤、紫外線吸収剤、香料、色素等、通常化粧品や医薬部外品に用いられている成分も配合することができる。
The skin external preparation of the present invention may contain water, polyhydric alcohol, lower alcohol, pH adjuster, surfactant, preservative, chelate, as necessary, within a qualitative and quantitative range that does not impede the effects of the present invention. Ingredients commonly used in cosmetics and quasi-drugs, such as agents, medicinal ingredients, oils, silicones, antioxidants, ultraviolet absorbers, fragrances, and pigments, can also be blended.

以下に実施例を挙げて本発明をより詳細に説明するが、本発明はこれらにより限定されるものではない。 The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

実施例1~8および比較例1~11について、下記表1および2に示す処方の化粧水を用いて、保存安定性(凝集)、肌なじみの良さについて以下の評価方法により評価した。
[化粧水の製法]
表1および2に示す成分Cに成分Bを投入し、よく撹拌した後成分Aを追加投入して化粧水を得た。
For Examples 1 to 8 and Comparative Examples 1 to 11, the storage stability (aggregation) and skin compatibility were evaluated using the following evaluation methods using lotions with the formulations shown in Tables 1 and 2 below.
[Manufacturing method of lotion]
Component B was added to component C shown in Tables 1 and 2, and after stirring well, component A was added to obtain a lotion.

Figure 0007453036000001

*1 マリンナノファイバー(登録商標)部分加水分解キチンNF
Figure 0007453036000001

*1 Marine nanofiber (registered trademark) partially hydrolyzed chitin NF

Figure 0007453036000002

*1 マリンナノファイバー(登録商標)部分加水分解キチンNF
Figure 0007453036000002

*1 Marine nanofiber (registered trademark) partially hydrolyzed chitin NF

調製した化粧水の安定性について評価した。
[凝集の評価基準]
表1に示す実施例処方および表2に示す比較例処方で作製した化粧水を用い、室温で1日静置したときの外観について、以下の基準により評価した。
◎:凝集が全く見られない。
〇:わずかに凝集が見られるが、化粧料としての品質上問題ないレベルである。
△:凝集が見られ、化粧料としての品質上問題となるレベルである。
×:凝集が著しく、化粧料としての品質上問題となるレベルである。
[肌なじみの評価]
評価項目について、15名の専門パネルが評価し、以下の基準にて示した。
◎:11名以上が良いと評価した。
〇:7~10名が良いと評価した。
△:4~6名が良いと評価した。
×:良いと評価した人が3名以下。
The stability of the prepared lotion was evaluated.
[Agglutination evaluation criteria]
Using lotions prepared with the example formulations shown in Table 1 and the comparative example formulations shown in Table 2, the appearance when left at room temperature for one day was evaluated according to the following criteria.
◎: No aggregation is observed.
○: Slight aggregation is observed, but it is at a level that poses no problem in terms of quality as a cosmetic.
Δ: Aggregation was observed, which was at a level that would pose a quality problem as a cosmetic.
×: Significant aggregation, which is at a level that poses a quality problem as a cosmetic.
[Evaluation of skin familiarity]
The evaluation items were evaluated by a panel of 15 experts and indicated based on the following criteria.
◎: 11 or more people evaluated it as good.
○: 7 to 10 people rated it as good.
△: 4 to 6 people evaluated it as good.
×: 3 or less people rated it as good.

表2に示される比較例1の化粧水では、混合後に凝集および沈降が観察され、肌なじみも悪かった。 In the lotion of Comparative Example 1 shown in Table 2, aggregation and sedimentation were observed after mixing, and it did not blend well with the skin.

表1の結果から、実施例1~8は、肌なじみが良く、安定性に優れていた。 From the results shown in Table 1, Examples 1 to 8 had good skin compatibility and excellent stability.

一方、表2に示される比較例2~5、11の化粧水では、肌なじみは良好であったが、凝集が観察された。成分(A)配合後、配合前に比べて濁りが生じた。比較例6~10では塗布時になじみが悪く、凝集も見られた。比較例3~6、9、10にあるような一般的な水溶性増粘多糖類ではキチン繊維との凝集が生じ、安定性が悪化する傾向がみられる。しかし、実施例1、2、5~8にあるグルコース、ガラクトース、マンノースおよびキシロースからなる群から選ばれる1種以上の単糖から構成される水溶性増粘多糖類を用いた場合は、成分(A)の保存安定性や使用性は劇的に向上することがわかった。
比較例2、7、8にあるような水溶性高分子であるコポリマーやクロスポリマーに関しても同様に、凝集が起こってしまう。しかし、実施例3、4の疎水変性ポリエーテルウレタンと併用することで成分(A)の保存安定性や使用性は劇的に向上することがわかった。
On the other hand, in the lotions of Comparative Examples 2 to 5 and 11 shown in Table 2, the skin blendability was good, but aggregation was observed. After blending component (A), turbidity occurred compared to before blending. Comparative Examples 6 to 10 showed poor adhesion and agglomeration during application. General water-soluble thickening polysaccharides such as those in Comparative Examples 3 to 6, 9, and 10 tend to aggregate with chitin fibers and deteriorate stability. However, when using the water-soluble polysaccharide thickener composed of one or more monosaccharides selected from the group consisting of glucose, galactose, mannose and xylose in Examples 1, 2, 5 to 8, the component ( It was found that the storage stability and usability of A) were dramatically improved.
Similarly, copolymers and crosspolymers that are water-soluble polymers such as those in Comparative Examples 2, 7, and 8 also cause aggregation. However, it was found that when used in combination with the hydrophobically modified polyether urethanes of Examples 3 and 4, the storage stability and usability of component (A) were dramatically improved.

このように多くの高分子は、より安定性が悪化するといった課題があったが本願請求の高分子であれば凝集が発生することなく、使用性を高める事が出来ている。 As described above, many polymers have had the problem of worsening stability, but the polymer claimed in this application does not cause aggregation and can improve usability.

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。 Compositions of each formulation were prepared in a conventional manner. It was confirmed that the effects of the present invention can be achieved in any formulation.

Figure 0007453036000003
Figure 0007453036000003

Figure 0007453036000004
Figure 0007453036000004

Figure 0007453036000005
Figure 0007453036000005

Figure 0007453036000006
Figure 0007453036000006

本発明は、キチンナノファイバー及び表面キトサン化キチンナノファイバーを含む安定性および使用感に優れた皮膚外用剤として利用できるものである。



INDUSTRIAL APPLICABILITY The present invention can be used as an external skin preparation containing chitin nanofibers and chitin nanofibers whose surface has been chitosanated and has excellent stability and usability.



Claims (3)

次の成分(A)、(B)を含む皮膚外用剤。
成分(A)キチンナノファイバー及び表面キトサン化キチンナノファイバーから選ばれる1種又は2種
成分(B)ローカストビーンガム、タマリンドガム、及び疎水変性ポリエーテルウレタンから選ばれる1種または2種以上
A skin external preparation containing the following ingredients (A) and (B).
Component (A) One or two selected from chitin nanofibers and surface chitosanated chitin nanofibers Component (B) One or more selected from locust bean gum, tamarind gum, and hydrophobically modified polyether urethane.
20℃条件下でpH3~8である請求項1に記載の皮膚外用剤。 The skin external preparation according to claim 1, which has a pH of 3 to 8 at 20°C. 化粧料であることを特徴とする請求項1又は2のいずれかに記載の皮膚外用剤。
The skin external preparation according to claim 1 or 2, which is a cosmetic.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012036283A1 (en) 2010-09-16 2012-03-22 国立大学法人鳥取大学 Cosmetic material, bathwater additive and pharmaceutical composition containing chitin nanofibers or chitosan nanofibers
JP2017533186A (en) 2014-10-29 2017-11-09 ラボラトワール・メディドム・エスアーLaboratoire Medidom S.A. Heat-sterilized preparation containing chitosan and method for preparing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012036283A1 (en) 2010-09-16 2012-03-22 国立大学法人鳥取大学 Cosmetic material, bathwater additive and pharmaceutical composition containing chitin nanofibers or chitosan nanofibers
JP2017533186A (en) 2014-10-29 2017-11-09 ラボラトワール・メディドム・エスアーLaboratoire Medidom S.A. Heat-sterilized preparation containing chitosan and method for preparing the same

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