JP7175556B2 - Cosmetic gel composition - Google Patents
Cosmetic gel composition Download PDFInfo
- Publication number
- JP7175556B2 JP7175556B2 JP2018111590A JP2018111590A JP7175556B2 JP 7175556 B2 JP7175556 B2 JP 7175556B2 JP 2018111590 A JP2018111590 A JP 2018111590A JP 2018111590 A JP2018111590 A JP 2018111590A JP 7175556 B2 JP7175556 B2 JP 7175556B2
- Authority
- JP
- Japan
- Prior art keywords
- viscosity
- gel composition
- gel
- light irradiation
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 76
- 239000002537 cosmetic Substances 0.000 title claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- 229920002125 Sokalan® Polymers 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 10
- 230000014759 maintenance of location Effects 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- 235000010356 sorbitol Nutrition 0.000 claims description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 239000003349 gelling agent Substances 0.000 claims description 5
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
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- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 claims description 4
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- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 claims description 4
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- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
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- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
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- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229940008099 dimethicone Drugs 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 239000000499 gel Substances 0.000 description 52
- 235000000346 sugar Nutrition 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 150000005846 sugar alcohols Chemical class 0.000 description 16
- 230000007423 decrease Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
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- 238000011156 evaluation Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 7
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- 229910052799 carbon Inorganic materials 0.000 description 4
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- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 3
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- 239000007864 aqueous solution Substances 0.000 description 3
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- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- 239000008406 cosmetic ingredient Substances 0.000 description 2
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- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 2
- 150000002584 ketoses Chemical class 0.000 description 2
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- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
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Images
Landscapes
- Cosmetics (AREA)
Description
本発明はジェル状の化粧料用組成物に関する。 TECHNICAL FIELD The present invention relates to a gel-like cosmetic composition.
ジェル状を呈する化粧料が多数提供されている。ジェル(ゲル)を形成するために様々な技術が存在するが、水性化粧料やO/W型の化粧料には、一般的に多糖類や合成高分子化合物などの水性ゲル化剤を添加して、組成物をゲル化する手法が採用される。なかでもカルボキシビニルポリマーは、高い増粘性と、肌に塗布したときにみずみずしくさっぱりとした使用感を与えられること、さらに取り扱いの容易さなどから、化粧料用のゲル化剤として多用されている。 A large number of gel-like cosmetics are provided. There are various techniques for forming gels (gels), but aqueous gelling agents such as polysaccharides and synthetic polymer compounds are generally added to aqueous cosmetics and O/W type cosmetics. Therefore, a technique of gelling the composition is employed. Carboxyvinyl polymers, among others, are widely used as gelling agents for cosmetics because of their high viscosity-increasing properties, their ability to impart a fresh and refreshing feeling when applied to the skin, and their ease of handling.
カルボキシビニルポリマーは、主としてアクリル酸を重合した合成陰イオン性高分子化合物である。水に溶解してアルカリ剤で中和することで容易にゲル状を呈するので、化粧料組成物の増粘剤として第一に選択される。
しかしながら、カルボキシビニルポリマーにより形成されたゲル状組成物は、光(紫外線)や経時変化により組成物の粘度が低下するという問題が知られている。このため、カルボキシビニルポリマーにより形成されたゲル状組成物の粘度低下を抑制するための技術が多数提案されており、その代表的な技術として、無機酸や有機酸類を添加して粘度低下を抑制する方法や、他のゲル化剤を併用する方法などが提案されている。
Carboxyvinyl polymers are synthetic anionic polymeric compounds that are primarily acrylic acid polymerized. When dissolved in water and neutralized with an alkaline agent, it readily forms a gel, and is therefore the first choice as a thickening agent for cosmetic compositions.
However, gel compositions formed from carboxyvinyl polymer are known to have a problem that the viscosity of the composition decreases due to light (ultraviolet rays) and changes over time. For this reason, a number of techniques have been proposed for suppressing the viscosity reduction of gel compositions formed from carboxyvinyl polymer. A representative technique is to add an inorganic acid or an organic acid to suppress the viscosity reduction. There have been proposed a method of using a gelling agent, a method of using other gelling agents in combination, and the like.
例えば、特許文献1には、カルボキシビニルポリマーおよび/またはアルキル変性カルボキシビニルポリマーとN-アシル化アミノ酸を含む増粘組成物が記載されている。そして、この組成物は紫外線による粘度の低下が抑制されると記載されている。
特許文献2には、カルボキシビニルポリマーとキサンタンガムおよびカラギーナンからなる群から選ばれるガム質と、ヒドロキシプロピルセルロースおよびヒドロキシエチルセルロースから選ばれるセルロース系高分子を含む増粘組成物が記載されている。この組成物は、紫外線や配合成分の影響を受けにくく、安定性の低下を引き起こさないことが記載されている。
For example, US Pat. No. 6,200,000 describes thickening compositions comprising carboxyvinyl polymers and/or alkyl-modified carboxyvinyl polymers and N-acylated amino acids. It is also described that this composition is inhibited from lowering in viscosity due to ultraviolet rays.
Patent Document 2 describes a thickening composition containing a gum substance selected from the group consisting of carboxyvinyl polymer, xanthan gum and carrageenan, and a cellulosic polymer selected from hydroxypropyl cellulose and hydroxyethyl cellulose. It is described that this composition is not easily affected by ultraviolet rays and ingredients, and does not cause a decrease in stability.
特許文献3には、アルキル変性カルボキシビニルポリマーと、メタリン酸を含有する乳化組成物が開示されている。この乳化組成物は、光安定性に優れていることが記載されている。
特許文献4には、(a)植物抽出物の1種または2種以上、(b)カルボキシビニルポリマー、(c)有機酸あるいは無機酸の水溶性アルカリ金属塩の1種または2種以上を含有し、且つ500~3000cpsの粘度を有する皮膚化粧料組成物が記載されている。そして有機酸あるいは無機酸の水溶性アルカリ金属塩として、クエン酸3ナトリウム、リン酸1ナトリウム、リン酸2ナトリウム、リン酸カリウム、リン酸2カリウム、コハク酸ナトリウムが例示されている。この組成物は、高温保存による粘度低下が抑制されると記載されている。
Patent Document 3 discloses an emulsion composition containing an alkyl-modified carboxyvinyl polymer and metaphosphoric acid. This emulsion composition is described as having excellent photostability.
Patent Document 4 contains (a) one or more plant extracts, (b) carboxyvinyl polymer, and (c) one or more water-soluble alkali metal salts of organic acids or inorganic acids. and has a viscosity of 500-3000 cps. Examples of water-soluble alkali metal salts of organic acids or inorganic acids include trisodium citrate, monosodium phosphate, disodium phosphate, potassium phosphate, dipotassium phosphate and sodium succinate. This composition is described as being inhibited from lowering in viscosity due to high-temperature storage.
特許文献5には、水溶性カルボキシビニルポリマーと、塩基性物質と、デキストリンと、メチルセルロースと、エデト酸三ナトリウムまたはエチレンジアミンヒドロキシエチル三酢酸三ナトリウムとを含有するメーキャップ化粧料が記載されている。この化粧料は、長期間使用しても粘度安定性が良く、1ヶ月経過した化粧料も安定性に変化がないことが記載されている。 Patent Document 5 describes a makeup cosmetic containing a water-soluble carboxyvinyl polymer, a basic substance, dextrin, methylcellulose, and trisodium edetate or trisodium ethylenediaminehydroxyethyltriacetate. It is described that this cosmetic has good viscosity stability even when used for a long period of time, and that there is no change in the stability of the cosmetic even after one month has passed.
また、本出願人は、クエルセチン又はクエルセチン配糖体が、カリボキシビニルポリマーで形成されたゲルの安定化剤として有用であることを見出し、これを有効成分として含有するゲル安定性の高い、水溶性高分子化合物含有化粧料の発明を特許出願している(特許文献6参照)。 The present applicant also found that quercetin or quercetin glycosides are useful as stabilizers for gels formed from carboxyvinyl polymers. has filed a patent application for an invention of a cosmetic containing a high molecular weight compound (see Patent Document 6).
カルボキシビニルポリマーを含むジェル状組成物は、従来技術に記載されているとおり、紫外線や長期保存により粘度が低下することに課題があり、それを解決するための提案も複数なされているが、いずれも十分に満足いくものではなかった。
本願発明者は、カルボキシビニルポリマーを含有するジェル状組成物にクエン酸及び/又はその塩と、糖及び/又は糖アルコールを含有させると、光照射による組成物の粘度低下が顕著に抑制されるという現象を見出した。
本発明は、この知見に基づきなされたものである。
すなわち本発明は、カルボキシビニルポリマーと、クエン酸及び/又はその塩と、糖及び/又は糖アルコールを組み合わせて得られる、粘度安定性に優れたジェル状組成物、ジェル状化粧料の提供を課題とする。さらにジェル状化粧料の新たな安定化技術を提供することを課題とする。
Gel-like compositions containing carboxyvinyl polymer, as described in the prior art, have a problem in that the viscosity decreases due to ultraviolet rays and long-term storage, and several proposals have been made to solve this problem. was also not entirely satisfactory.
The inventors of the present application have found that when a gel composition containing a carboxyvinyl polymer contains citric acid and/or a salt thereof and a sugar and/or a sugar alcohol, the decrease in the viscosity of the composition due to light irradiation is remarkably suppressed. A phenomenon was discovered.
The present invention is made based on this finding.
That is, an object of the present invention is to provide a gel-like composition and a gel-like cosmetic having excellent viscosity stability obtained by combining a carboxyvinyl polymer, citric acid and/or a salt thereof, and a sugar and/or a sugar alcohol. and Another object of the present invention is to provide a new technique for stabilizing gel cosmetics.
本発明の構成は、次のとおりである。
(1)次の(A)~(C)を含有するジェル状組成物。
(A)カルボキシビニルポリマー
(B)クエン酸及び/又はその塩
(C)糖及び/又は糖アルコールから選択される1以上の物質
(2)(B)クエン酸及び/又はその塩の含有量が、ジェル状組成物あたりクエン酸として0.001~0.03質量%である(1)に記載のジェル状組成物。
(3)糖がグルコース、ラフィノース及びトレハロースから選ばれる1以上を含むものであり、糖アルコールがソルビトール、マンニトール、エリスリトール及びグリセリンから選ばれる1以上を含むものである(1)又は(2)に記載のジェル状組成物。
(4)糖及び/又は糖アルコールの含有量が0.5~10質量%である(1)~(3)のいずれかに記載のジェル状組成物。
(5)化粧料用である(1)~(4)のいずれかに記載のジェル状組成物。
The configuration of the present invention is as follows.
(1) A gel composition containing the following (A) to (C).
(A) carboxyvinyl polymer (B) citric acid and/or salts thereof (C) one or more substances selected from sugars and/or sugar alcohols (2) (B) content of citric acid and/or salts thereof , The gel composition according to (1), which is 0.001 to 0.03% by mass as citric acid per gel composition.
(3) The gel according to (1) or (2), wherein the sugar contains one or more selected from glucose, raffinose and trehalose, and the sugar alcohol contains one or more selected from sorbitol, mannitol, erythritol and glycerin. composition.
(4) The gel composition according to any one of (1) to (3), wherein the sugar and/or sugar alcohol content is 0.5 to 10% by mass.
(5) The gel composition according to any one of (1) to (4), which is used for cosmetics.
本発明のジェル状組成物は、高い粘性と、塗布した時にみずみずしくさっぱりとした使用感が得られる。また光照射しても粘度が低下しにくいので、必ずしも遮光容器に充填しなくてもジェル状態が維持され、長期安定性に優れた状態で提供できる。本発明のジェル状組成物は使用感が良好であり、長期間保存しても光による粘度変化(粘度低下)が発生しにくく充填する容器を選ばない。加えて、本発明の構成成分であるクエン酸及び/又はその塩と糖及び/又は糖アルコールは、安全性の高い成分であり、かつ組成物自体に色や匂いを付加しない成分のため、これらで構成された本発明のジェル状組成物も透明~半透明でありほぼ無臭である。このため、化粧料用途として応用範囲が広く、さらに着色や賦香することもできる。本発明のジェル状組成物は化粧料とすることが最適である。 The gel composition of the present invention provides a high viscosity and a fresh and refreshing feel when applied. In addition, since the viscosity does not easily decrease even when irradiated with light, the gel state is maintained without necessarily filling the light-shielding container, and the product can be provided in a state with excellent long-term stability. The gel-like composition of the present invention has a good feel when used, and even when stored for a long period of time, the viscosity change (viscosity reduction) due to light is unlikely to occur, and the container to be filled is not limited. In addition, citric acid and/or its salts and sugars and/or sugar alcohols, which are the components of the present invention, are highly safe ingredients and do not add color or odor to the composition itself. The gel composition of the present invention composed of is also transparent to translucent and almost odorless. Therefore, it has a wide range of application as a cosmetic, and can be used for coloring and fragrance. The gel composition of the present invention is optimally used as a cosmetic.
本願は、(A)カルボキシビニルポリマー、(B)クエン酸及び/又はその塩、(C)糖及び/又は糖アルコールを含有するジェル状組成物及びジェル状化粧料に係る発明である。
なお、本願明細書においては、「ジェル」及び「ゲル」の用語が混在するがいずれも同義である。本発明のジェル状組成物は光を照射しても粘度が低下しにくいことが特徴である。したがって粘度の高い液体(ゼリー状液体)だけでなく、流動性のある中粘度であっても光照射前後での粘度維持率が55%を超えていれば本発明に含まれる。本発明のジェル状組成物は、光照射前の粘度が5000mPa・s以上であって、光照射後の粘度維持率が55%を超えるものである。より好ましくは、B型粘度計(25℃、4号ローターまたは3号ローター、12回転、30秒)で測定したときの粘度が10000~100000mPa・sであって、光照射後の粘度維持率が55%を超えるものである。
The present application relates to gel compositions and gel cosmetics containing (A) carboxyvinyl polymer, (B) citric acid and/or salts thereof, and (C) sugar and/or sugar alcohol.
In the specification of the present application, the terms "gel" and "gel" are used interchangeably, but both have the same meaning. The gel-like composition of the present invention is characterized in that its viscosity does not easily decrease even when exposed to light. Therefore, not only high-viscosity liquids (jelly-like liquids) but also liquid medium-viscosity liquids are included in the present invention as long as the viscosity retention rate before and after light irradiation exceeds 55%. The gel composition of the present invention has a viscosity of 5000 mPa·s or more before light irradiation and a viscosity retention rate of more than 55% after light irradiation. More preferably, the viscosity is 10000 to 100000 mPa s when measured with a Brookfield viscometer (25 ° C., No. 4 rotor or No. 3 rotor, 12 revolutions, 30 seconds), and the viscosity maintenance rate after light irradiation is more than 55%.
(A)成分:カルボキシビニルポリマー
カルボキシビニルポリマーは、カルボキシル基を有する水溶性ポリマーであり、主にアクリル酸の重合体である。
カルボキシビニルポリマーは、白色の酸性粉末であり、その1%水溶液のpHは約3である。カルボキシビニルポリマーは、塩基性化合物を用いて中和することにより、粘性の異なる様々な粘液(ジェル)を調製することができる。中和に用いる塩基性化合物としては、トリエタノールアミン、モノエタノールアミン、ジイソプロパノールアミン、トリエチルアミン、水酸化ナトリウム、水酸化カリウム、アルギニンなどを例示することができる。塩基性化合物の配合量は特に限定されず、ジェル状組成物や化粧料の粘度が好適な範囲内となるように適宜調整すればよい。
本発明で用いるカルボキシビニルポリマーは、増粘剤として汎用されている市販品を使用すれば良く、例えばNTC-CARBOMER380/381(日光ケミカルズ)、ハイビスワコー103/104/105(富士フイルム和光純薬)やカーボポール980/981(日本ルーブリゾール)などを例示できる。
カルボキシビニルポリマーの配合量は、組成物あたり、0.05~1質量%、より好ましくは0.1~0.7質量%とすることが好ましい。0.05質量%に満たないと、十分な粘度が得られない恐れがある。1質量%を超えて配合するとぬるつくなど使用感が悪くなる恐れがある。
(A) Component: Carboxyvinyl Polymer Carboxyvinyl polymer is a water-soluble polymer having a carboxyl group, and is mainly a polymer of acrylic acid.
Carboxyvinyl polymer is a white, acidic powder with a pH of about 3 in a 1% aqueous solution. Carboxyvinyl polymer can be neutralized with a basic compound to prepare various mucilages (gels) with different viscosities. Basic compounds used for neutralization include triethanolamine, monoethanolamine, diisopropanolamine, triethylamine, sodium hydroxide, potassium hydroxide, arginine, and the like. The amount of the basic compound to be blended is not particularly limited, and may be appropriately adjusted so that the viscosity of the gel composition or cosmetic is within a suitable range.
The carboxyvinyl polymer used in the present invention may be a commercially available product commonly used as a thickening agent, such as NTC-CARBOMER 380/381 (Nikko Chemicals), Hibis Wako 103/104/105 (Fuji Film Wako Pure Chemical). and Carbopol 980/981 (Nippon Lubrizol).
The content of the carboxyvinyl polymer is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.7% by mass, based on the composition. If the amount is less than 0.05% by mass, there is a possibility that sufficient viscosity cannot be obtained. If the content exceeds 1% by mass, there is a possibility that the feeling of use may be deteriorated, such as feeling slimy.
(B)成分:クエン酸及び/又はその塩
本発明のジェル状組成物にはクエン酸及び/又はクエン酸の塩を必須成分として含有する。クエン酸の塩は、ナトリウム塩又はカリウム塩が好ましい。本発明のジェル状組成物において、組成物あたりクエン酸またはクエン酸の塩は、クエン酸として0.001~0.03質量%含有することが好ましい。含有量が0.001質量%に満たないとジェル状組成物の粘度低下を防止する効果が低くなる恐れがある。また、0.03質量%を超えるとべたつきが生じる恐れがある。
クエン酸及び/又はその塩は(C)成分の糖及び/又は糖アルコールと共存することでカルボキシビニルポリマーによって形成されるジェル状組成物の安定性を維持し、粘度低下を防止する。
(B) Component: Citric acid and/or its salt The gel composition of the present invention contains citric acid and/or a salt of citric acid as an essential component. The salt of citric acid is preferably sodium salt or potassium salt. The gel composition of the present invention preferably contains 0.001 to 0.03% by mass of citric acid or a salt of citric acid as citric acid per composition. If the content is less than 0.001% by mass, the effect of preventing the decrease in viscosity of the gel composition may be reduced. Moreover, if it exceeds 0.03% by mass, stickiness may occur.
Citric acid and/or its salt maintains the stability of the gel-like composition formed by the carboxyvinyl polymer and prevents viscosity reduction by coexisting with the sugar and/or sugar alcohol of component (C).
(C)成分:糖及び/又は糖アルコール
本発明でいう糖とは、単糖またはオリゴ糖である。単糖とはアルデヒド基を有するアルドース、またはケトン基を有するケトースであって、三炭糖(トリオース)、四炭糖(テトロース)、五炭糖(ペントース)、六炭糖(ヘキソース)、七炭糖(ヘプトース)のいずれであっても良い。三炭糖としてはグリセルアルデヒド・ジヒドロキシアセトン、四炭糖としてはエリトロース・トレオース・エリトルロース、五炭糖としてはリボース・アラビノース・リキソース・キシロース・アピオース・リブロース・キシルロース、六炭糖としてはアロース・アルトロース・グルコース・マンノース・グロース・イドース・ガラクトース・タロース・プシコース・フルクトース・ソルボース・タガトース、七単糖としては、セドヘプツロース、コリオースを例示できる。
単糖の場合は、入手のしやすさなどからグルコース、マンノース、ガラクトースが好ましく、グルコースが特に好ましい。
オリゴ糖とは2個以上の単糖がグルコシド結合でつながったものである。二糖としては、グルコース二分子が結合したマルトース、トレハロース、イソマルトースなどが例示できる。また構成する単糖が異なったヘテロの二糖であるラクトースやスクロースも使用可能である。二糖としては、グルコースがα1-1結合したトレハロースが特に好ましい。また三糖としては、ラフィノース、マルトトリオースなどが例示でき、ラフィノースが特に好ましい。
(C) Component: Sugar and/or Sugar Alcohol The sugar referred to in the present invention is monosaccharide or oligosaccharide. A monosaccharide is an aldose having an aldehyde group or a ketose having a ketone group, such as triose, tetrose, pentose, hexose, and hexose. Any sugar (heptose) may be used. Glyceraldehyde and dihydroxyacetone as three-carbon sugars, erythrose, threose and erythrulose as four-carbon sugars, ribose, arabinose, lyxose, xylose, apiose, ribulose and xylulose as five-carbon sugars, allose and alto as hexoses Lose, glucose, mannose, gulose, idose, galactose, talose, psicose, fructose, sorbose, tagatose, and the heptasaccharide include sedoheptulose and colyose.
In the case of monosaccharides, glucose, mannose, and galactose are preferred, and glucose is particularly preferred, because of their availability.
Oligosaccharides are two or more monosaccharides linked by glucosidic bonds. Examples of disaccharides include maltose, trehalose, and isomaltose, which are bound to two molecules of glucose. In addition, lactose and sucrose, which are heterodisaccharides having different constituent monosaccharides, can also be used. As the disaccharide, trehalose in which glucose is α1-1 linked is particularly preferred. Examples of trisaccharides include raffinose and maltotriose, with raffinose being particularly preferred.
本発明でいう糖アルコールとは、アルドースやケトースのカルボニル基が還元されて生成した化合物である。本発明にあっては、通常食品や医薬品又は化粧料に用いられる化合物であればどのような物質であっても使用可能である。好ましい物質として、グリセリン、エリスリトール、ソルビトール、マンニトール、マルチトールを例示することができる。特に好ましくはソルビトールである。
また、糖と糖アルコールの反応生成物であるガラクトシルグリセロールやグルコシルグリセロールなどの誘導体も本発明に用いることができる。
本発明のジェル状組成物において、糖及び/又は糖アルコールを組成物あたり0.5~10質量%、好ましくは1~5質量%含有すると好ましい。糖及び/又は糖アルコールは、(B)成分のクエン酸及び/又はその塩と共存することでカルボキシビニルポリマーによって形成されるジェルの安定性を維持し、粘度低下を防止する。
The sugar alcohol referred to in the present invention is a compound produced by reduction of the carbonyl group of aldose or ketose. In the present invention, any substance can be used as long as it is a compound that is commonly used in foods, pharmaceuticals, or cosmetics. Preferred substances include glycerin, erythritol, sorbitol, mannitol and maltitol. Sorbitol is particularly preferred.
Derivatives such as galactosylglycerol and glucosylglycerol, which are reaction products of sugar and sugar alcohol, can also be used in the present invention.
The gel composition of the present invention preferably contains sugar and/or sugar alcohol in an amount of 0.5 to 10% by mass, preferably 1 to 5% by mass. The sugar and/or sugar alcohol maintain the stability of the gel formed by the carboxyvinyl polymer and prevent viscosity reduction by coexisting with the citric acid and/or its salt of component (B).
本発明のジェル状組成物は水を含むことが好ましい。水は、精製水が好ましい。本発明のジェル状組成物全量に対する水の含有量は特に限定されないが、使用感の観点から20~98質量%、より好ましくは40~98質量%含有すると好ましい。なお、水を含まなくてもカルボキシビニルポリマーで増粘した系、例えばカルボキシビニルポリマーとエタノールと塩基性物質による増粘組成物やカルボキシビニルポリマーとグリセリンと塩基性物質による増粘組成物に本発明を適用することも可能である。ただしこれらの非水系の系であっても、クエン酸及び/又はその塩を溶解させて組成物に配合するための水は必要である。 The gel composition of the present invention preferably contains water. Water is preferably purified water. The content of water relative to the total amount of the gel composition of the present invention is not particularly limited, but it is preferably 20 to 98% by mass, more preferably 40 to 98% by mass, from the viewpoint of feeling during use. In addition, the present invention can be applied to a system thickened with a carboxyvinyl polymer even if it does not contain water, for example, a thickened composition of a carboxyvinyl polymer, ethanol and a basic substance, or a thickened composition of a carboxyvinyl polymer, glycerin and a basic substance. can also be applied. However, even these non-aqueous systems require water for dissolving citric acid and/or its salts and blending them into the composition.
本発明のジェル状組成物には、本発明の効果を阻害しない範囲で、界面活性剤、油剤、美容成分、色素、香料などを任意で配合することができる。 The gel composition of the present invention may optionally contain surfactants, oils, cosmetic ingredients, pigments, fragrances, etc., as long as they do not impair the effects of the present invention.
界面活性剤としては、例えば、ポリオキシエチレン硬化ヒマシ油、ポリグリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリエーテル変性シリコーンなどが挙げられる。 Examples of surfactants include polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyether-modified silicone and the like.
油剤としては、例えば、オリーブ油、ツバキ油、マカデミアナッツ油、アボカド油、カルナバロウ、キャンデリラロウ、ホホバ油、ミツロウ、ラノリン、流動パラフィン、パラフィン、ワセリン、セレシン、マイクロクリスタリンワックス、スクワレン、スクワラン、ミリスチン酸イソプロピル、ミリスチン酸2-オクチルドデシル、2-エチルヘキサン酸セチル、メチルポリシロキサン、メチルフェニルポリシロキサンなどが挙げられる。 Examples of oils include olive oil, camellia oil, macadamia nut oil, avocado oil, carnauba wax, candelilla wax, jojoba oil, beeswax, lanolin, liquid paraffin, paraffin, petrolatum, ceresin, microcrystalline wax, squalene, squalane, and isopropyl myristate. , 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, methylpolysiloxane, methylphenylpolysiloxane, and the like.
美容成分としては、ヒアルロン酸ナトリウム、PCA-Na、ソウハクヒエキスなどが挙げられる。 Examples of cosmetic ingredients include sodium hyaluronate, PCA-Na, and sour extract.
本発明のジェル状組成物は、ジェル状(ゲル状)の剤型である。特に好ましくは、水性ジェルの剤型である。本発明のジェル状組成物の粘度は、B型粘度計(25℃、4号ローターまたは3号ローター、12回転、30秒)で測定したときの粘度が5000mPa・s以上であると好ましく、10000~100000mPa・sであると好ましく、10000~70000mPa・sであるとより一層好ましい。
本発明のジェル状組成物は光を照射しても粘度が低下しにくいことが特徴である。本発明のジェル状組成物は、光照射前の粘度が5000mPa・s以上であって、光照射後の粘度維持率が55%を超えるものである。
The gel-like composition of the present invention is a gel-like (gel-like) dosage form. Particularly preferred is an aqueous gel dosage form. The viscosity of the gel-like composition of the present invention is preferably 5000 mPa s or more, and preferably 10000 mPa s when measured with a Brookfield viscometer (25°C, No. 4 rotor or No. 3 rotor, 12 revolutions, 30 seconds). It is preferably up to 100,000 mPa·s, and more preferably 10,000 to 70,000 mPa·s.
The gel-like composition of the present invention is characterized in that its viscosity does not easily decrease even when exposed to light. The gel composition of the present invention has a viscosity of 5000 mPa·s or more before light irradiation and a viscosity retention rate of more than 55% after light irradiation.
本発明のジェル状組成物及びジェル状化粧料は、常法により製造することができる。カルボキシビニルポリマー水溶液を中和してからB成分(クエン酸及び/又はその塩)とC成分(糖及び/又は糖アルコール)を加えても良いし、すべての成分を容器に投入後、混合撹拌しても良い。 The gel composition and gel cosmetic of the present invention can be produced by a conventional method. After neutralizing the carboxyvinyl polymer aqueous solution, component B (citric acid and/or its salt) and component C (sugar and/or sugar alcohol) may be added, or after all the components are put into a container, they are mixed and stirred. You can
以下に予備試験例、実施例及び比較例のジェル状化粧料を調製し、これを用いた評価試験を示し、本発明を具体的に説明する。
<予備試験例>
0.3%カルボキシビニルポリマー水溶液を水酸化カリウムで中和してpH5.7に調整し、ゲルを形成させた。次にQ-Lab Corporation製Q-SUN Xe-1 Xenon Test Chamberを用いて放射照度40W/m2(照度測定波長域300~400nm)、ブラックパネル温度40℃の条件で光照射を行った。光照射時間0h、4h、8h、24hの試料をサンプリングして試料温度を25℃に調整した後、B型粘度計(25℃、3号ローター、12回転、30秒、レンジ5)を用いて粘度を測定した。測定結果を図1に示す。
EXAMPLES The present invention will be specifically described below by preparing gel-like cosmetics of preliminary test examples, examples and comparative examples, and showing evaluation tests using them.
<Preliminary test example>
A 0.3% carboxyvinyl polymer aqueous solution was neutralized with potassium hydroxide and adjusted to pH 5.7 to form a gel. Next, using a Q-SUN Xe-1 Xenon Test Chamber manufactured by Q-Lab Corporation, light irradiation was performed under the conditions of an irradiance of 40 W/m 2 (illuminance measurement wavelength range of 300 to 400 nm) and a black panel temperature of 40°C. After sampling the samples with light irradiation times of 0 h, 4 h, 8 h, and 24 h and adjusting the sample temperature to 25 ° C., using a B-type viscometer (25 ° C., No. 3 rotor, 12 rotations, 30 seconds, range 5) Viscosity was measured. The measurement results are shown in FIG.
図1に示すとおり、キセノンランプによる光照射で、カルボキシビニルポリマーによる増粘組成物(ジェル状組成物)の粘度が減少することを確認できた。光照射時間依存的に粘度が低下しており、24hの照射後には著しく粘度が低下していることを確認した。 As shown in FIG. 1, it was confirmed that the viscosity of the thickened composition (gel-like composition) of the carboxyvinyl polymer decreased by light irradiation from the xenon lamp. It was confirmed that the viscosity decreased depending on the light irradiation time, and that the viscosity significantly decreased after 24 hours of irradiation.
<実施例・比較例>
実施例、比較例のジェル状組成物を調製し、本発明のジェル状組成物の光照射によるゲルの粘度低下抑制効果を評価した。
1.試験方法
(1)ジェル状組成物の調製
表1及び表2(実施例)、表3(比較例)のジェル状組成物を調製した。
各成分を秤量して総重量で200gとした後、卓上ホモミキサーで5000rpm、3分間の撹拌を行った。その後、脱泡したジェル状化粧料をガラス瓶に100g充填した。これを以下に示す試験の試料とした。
<Example/Comparative example>
EXAMPLES Gel compositions of Examples and Comparative Examples were prepared, and the effect of the gel composition of the present invention on suppressing a reduction in the viscosity of the gel due to light irradiation was evaluated.
1. Test method (1) Preparation of gel compositions Gel compositions shown in Tables 1 and 2 (Examples) and Table 3 (Comparative Examples) were prepared.
After each component was weighed to a total weight of 200 g, the mixture was stirred at 5000 rpm for 3 minutes with a desktop homomixer. After that, 100 g of the defoamed gel cosmetic was filled in a glass bottle. This was used as a sample for the tests described below.
(2)光照射試験
Q-Lab Corporation製Q-SUN Xe-1 Xenon Test Chamberを用いて放射照度40W/m2(照度測定波長域300~400nm)、ブラックパネル温度40℃、照射時間24hの条件で光照射試験を行った。
(2) Light irradiation test Using a Q-SUN Xe-1 Xenon Test Chamber manufactured by Q-Lab Corporation, the conditions were an irradiance of 40 W/m 2 (illuminance measurement wavelength range of 300 to 400 nm), a black panel temperature of 40°C, and an irradiation time of 24 hours. A light irradiation test was performed at
(3)粘度測定試験
光照射試験前後の粘度を試料温度25℃にてB型粘度計(3号ローター、12回転、30秒、レンジ5)で測定した。粘度測定は各試料2回ずつ行い平均値を評価に用いた。
粘度維持率(%)={(光照射後の粘度)/(光照射前の粘度)}×100として粘度低下(減粘)の抑制効果を評価した。なお、表には計算値をそのまま載せたが、粘度維持率(%)を評価するときは、小数点以下は切り捨てた数値を下記基準により評価した。
粘度低下抑制効果(減粘抑制効果)の評価として、粘度維持率を評価する基準は下記の通りである。
◎:81%以上
○:71~80%
△:55~70%
×:55%未満
(3) Viscosity measurement test Viscosity before and after the light irradiation test was measured at a sample temperature of 25°C with a Brookfield viscometer (No. 3 rotor, 12 revolutions, 30 seconds, range 5). The viscosity measurement was performed twice for each sample, and the average value was used for evaluation.
Viscosity retention rate (%)={(viscosity after light irradiation)/(viscosity before light irradiation)}×100 was used to evaluate the effect of suppressing viscosity reduction (thinning). The calculated values are listed in the table as they are, but when evaluating the viscosity retention rate (%), the values after the decimal point are rounded down and evaluated according to the following criteria.
As the evaluation of the viscosity reduction suppressing effect (viscosity reduction suppressing effect), the criteria for evaluating the viscosity retention rate are as follows.
◎: 81% or more ○: 71 to 80%
△: 55-70%
×: less than 55%
(4)官能評価試験
光照射前後の試料を、ブラインドでそれぞれ手の甲に0.05gずつ取って塗り広げ、専門の官能評価員1名が、試料の粘度の差異を識別できるかどうかを評価した。この官能評価試験により、試料の粘度の違いがはっきりと識別できたものは、粘度の低下抑制効果(減粘抑制効果)が得られていないと判断した。
○:粘度の差異が全くわからない
△:粘度に違いがあることがややわかる
×:粘度の違いがはっきりとわかる
(4) Sensory Evaluation Test 0.05 g of each sample was spread on the back of the hand with a blind before and after light irradiation, and one expert sensory evaluator evaluated whether differences in viscosity of the samples could be identified. By this sensory evaluation test, it was judged that the effect of suppressing a decrease in viscosity (the effect of suppressing a decrease in viscosity) was not obtained when the difference in the viscosity of the sample could be clearly identified.
○: No difference in viscosity △: Somewhat noticeable difference in viscosity ×: Clear difference in viscosity
2.試験結果
結果を表1~3の下段に示した。
2. Test Results The results are shown in the lower part of Tables 1-3.
実施例1~28のジェル状組成物の粘度は光照射前で10000~70000mPa・sの範囲にあったが、光照射後の減粘抑制効果は粘度維持率の数値から、実施例1~7、9~11、13~15、17、19~21、23~25及び27が◎評価(粘度維持率が81%以上)、実施例8が○評価(粘度維持率が71~80%)、実施例12、16、18、22、26及び28が△評価(粘度維持率が55~70%)であった。また、実施例1~28のジェル状組成物は、光照射後の官能評価試験において、いずれも光照射による粘度低下が官能試験によりほとんど識別できないレベルであった。これらの試験結果から、本発明の構成をとるカルボキシビニルポリマーを含有した増粘組成物(ゲル)の粘度低下抑制効果(減粘抑制効果)は極めて高いと判断した。さらにまた、実施例1~28のいずれのジェル状組成物も、べたついたり、きしんだりせず、カルボキシビニルポリマーを用いたジェル状組成物特有のみずみずしくさっぱりとした使用感は全く損なわれず、優れた使用感であった。
一方、比較例1~17のジェル状組成物は、光照射による粘度低下が著しく、光照射後の粘度維持率は55%を下回り、粘度低下抑制効果(減粘抑制効果)は×と評価した。官能評価試験においても本発明の構成をとらない比較例1~15のジェル状組成物は、いずれも光照射による粘度低下が官能試験によりはっきりとわかるレベルで識別された。
比較例3~9に示したように、クエン酸単独(比較例3、4)ではその他の有機酸(比較例5~9)と比較して減粘抑制効果が高いわけではない。また、比較例10~13に示したようにソルビトールやマンニトール単独でも減粘抑制効果は低かった。また、比較例14~17に示したようにフィチン酸、乳酸、グルコン酸ナトリウム、アデノシン三リン酸とソルビトールを組み合わせた場合にも減粘抑制効果は低かった。これらの結果からクエン酸及び/又はその塩と、糖及び/又は糖アルコールを組み合わせて配合した場合にのみ、特異的に顕著な減粘抑制効果を示すことを見出した。
以上、実施例、比較例の評価結果から本発明のジェル状組成物は、光照射による粘度低下を抑制できることが確認できた。特に使用感は、カルボキシビニルポリマーによる肌に塗布したときのみずみずしいさっぱりした使用感を与えるものであり、化粧料に最適であることがわかった。
The viscosities of the gel-like compositions of Examples 1 to 28 were in the range of 10000 to 70000 mPa s before light irradiation. , 9 to 11, 13 to 15, 17, 19 to 21, 23 to 25 and 27 are ◎ evaluation (viscosity maintenance rate is 81% or more), Example 8 is ○ evaluation (viscosity maintenance rate is 71 to 80%), Examples 12, 16, 18, 22, 26 and 28 were evaluated as Δ (viscosity retention rate of 55 to 70%). Further, in the sensory evaluation test after light irradiation, the gel compositions of Examples 1 to 28 all exhibited a level of viscosity reduction due to light irradiation that could hardly be discerned by the sensory test. From these test results, it was determined that the thickening composition (gel) containing the carboxyvinyl polymer according to the present invention has an extremely high viscosity reduction suppressing effect (viscosity suppressing effect). Furthermore, none of the gel compositions of Examples 1 to 28 was sticky or creaky, and did not impair the fresh and refreshing feeling of use peculiar to gel compositions using a carboxyvinyl polymer. It was a feeling of use.
On the other hand, in the gel compositions of Comparative Examples 1 to 17, the viscosity decrease due to light irradiation was remarkable, the viscosity retention rate after light irradiation was less than 55%, and the viscosity decrease suppression effect (viscosity reduction suppression effect) was evaluated as ×. . Also in the sensory evaluation test, the gel compositions of Comparative Examples 1 to 15, which did not adopt the constitution of the present invention, were all identified by the sensory test at a level where the decrease in viscosity due to light irradiation was clearly recognized.
As shown in Comparative Examples 3 to 9, citric acid alone (Comparative Examples 3 and 4) is not as effective in suppressing viscosity reduction as compared to other organic acids (Comparative Examples 5 to 9). In addition, as shown in Comparative Examples 10 to 13, even sorbitol and mannitol alone had a low effect of suppressing viscosity reduction. In addition, as shown in Comparative Examples 14 to 17, when phytic acid, lactic acid, sodium gluconate, adenosine triphosphate and sorbitol were combined, the effect of suppressing viscosity reduction was low. From these results, it was found that only a combination of citric acid and/or its salt and sugar and/or sugar alcohol exhibits a specific and remarkable effect of suppressing viscosity reduction.
As described above, it was confirmed from the evaluation results of Examples and Comparative Examples that the gel composition of the present invention can suppress a decrease in viscosity due to light irradiation. In particular, it was found that the carboxyvinyl polymer gives a fresh and refreshing feeling when applied to the skin, and is most suitable for cosmetics.
Claims (3)
(A)カルボキシビニルポリマーを、ジェル状組成物あたり0.1~0.7質量%
(B)クエン酸及び/又はその塩を、ジェル状組成物あたりクエン酸として0.005~0.03質量%
(C)グルコース、ラフィノース、トレハロース、ソルビトール、マンニトール、エリスリトール及びグリセリンから選択される1以上の物質を、ジェル状組成物あたり1~10質量%
(ただし、1.(a)水溶性保温剤0.5~20重量%;(b)親水性ゲル化剤0.1~20重量%;及び(c)i)ジメチコノール、フルオロシリコーン及びジメチコン又はそれらの混合物からなる群より選択される200,000~540,000の分子量を有するシリコーンゴム;及びii)0.65~100cpsの粘度を有するシリコーンベースキャリアから本質的になるシリコーン成分1.0~10重量%(i)対ii)の比率は10:90~20:80である;上記成分は500~10,000cpsの最終粘度を有する);を含む実質上オイルフリーで水性ゲル形のスキンケア組成物、を除く) A gel composition containing the following (A) to (C) and further containing 40 to 98% by mass of water based on the gel composition.
(A) 0.1 to 0.7% by mass of carboxyvinyl polymer per gel composition
(B) 0.005 to 0.03% by mass of citric acid and/or a salt thereof as citric acid per gel composition
(C) one or more substances selected from glucose, raffinose, trehalose, sorbitol, mannitol, erythritol and glycerin, 1 to 10% by mass per gel composition
(However, 1. (a) 0.5 to 20% by weight of a water-soluble heat retaining agent; (b) 0.1 to 20% by weight of a hydrophilic gelling agent; and (c) i) dimethiconol, fluorosilicone and dimethicone or and ii) 1.0 to 10 weight silicone component consisting essentially of a silicone base carrier having a viscosity of 0.65 to 100 cps. %(i) to ii) ratio is 10:90 to 20:80; said ingredients have a final viscosity of 500 to 10,000 cps); except for)
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