JPH0720968B2 - Fluorinated dibenzylidene polyhydric alcohol derivative, non-aqueous gelling agent containing the same, and cosmetics using the same - Google Patents
Fluorinated dibenzylidene polyhydric alcohol derivative, non-aqueous gelling agent containing the same, and cosmetics using the sameInfo
- Publication number
- JPH0720968B2 JPH0720968B2 JP62218311A JP21831187A JPH0720968B2 JP H0720968 B2 JPH0720968 B2 JP H0720968B2 JP 62218311 A JP62218311 A JP 62218311A JP 21831187 A JP21831187 A JP 21831187A JP H0720968 B2 JPH0720968 B2 JP H0720968B2
- Authority
- JP
- Japan
- Prior art keywords
- polyhydric alcohol
- fluorinated
- same
- alcohol derivative
- cosmetics
- 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.)
- Expired - Lifetime
Links
- 150000005846 sugar alcohols Polymers 0.000 title claims description 28
- 239000002537 cosmetic Substances 0.000 title claims description 16
- 239000003349 gelling agent Substances 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- -1 2,5-difluoro, 2 , 6-difluoro-substituted phenyl group Chemical group 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229960002920 sorbitol Drugs 0.000 description 6
- 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 description 5
- 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 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 150000003935 benzaldehydes Chemical class 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 3
- PIKNVEVCWAAOMJ-UHFFFAOYSA-N 3-fluorobenzaldehyde Chemical compound FC1=CC=CC(C=O)=C1 PIKNVEVCWAAOMJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000003020 moisturizing effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JSRAITUAGKVUKD-YVECIDJPSA-N (2R,3R,4S,5R)-7-(3-fluorophenyl)hept-6-ene-1,2,3,4,5,6-hexol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC(F)=C1 JSRAITUAGKVUKD-YVECIDJPSA-N 0.000 description 2
- HAPLZHXMWPQVPH-YVECIDJPSA-N (2r,3r,4s,5r)-7-(4-chlorophenyl)hept-6-ene-1,2,3,4,5,6-hexol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=C(Cl)C=C1 HAPLZHXMWPQVPH-YVECIDJPSA-N 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FBXFSONDSA-N Allitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-FBXFSONDSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KAZBKCHUSA-N D-altritol Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KAZBKCHUSA-N 0.000 description 1
- FBPFZTCFMRRESA-ZXXMMSQZSA-N D-iditol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-ZXXMMSQZSA-N 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- XHRPOTDGOASDJS-UHFFFAOYSA-N cholesterol n-octadecanoate Natural products C12CCC3(C)C(C(C)CCCC(C)C)CCC3C2CC=C2C1(C)CCC(OC(=O)CCCCCCCCCCCCCCCCC)C2 XHRPOTDGOASDJS-UHFFFAOYSA-N 0.000 description 1
- XHRPOTDGOASDJS-XNTGVSEISA-N cholesteryl stearate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)CCCCCCCCCCCCCCCCC)C1 XHRPOTDGOASDJS-XNTGVSEISA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003676 hair preparation Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/042—Gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
- A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Cosmetics (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規なフツ素化ジベンジリデン多価アルコール
誘導体、更に詳細には、有機溶媒に対して強力なゲル化
能を有する次の一般式（Ｉ） （式中、ｍ及びｎは同時に０とはならない０〜５の整数
を示し、ｐは０〜２の整数を示す） で表わされるフツ素化ジベンジリデン多価アルコール誘
導体、及びこれを有効成分として含有する非水系ゲル化
剤、並びにこれを用いた化粧料に関する。TECHNICAL FIELD The present invention relates to a novel fluorinated dibenzylidene polyhydric alcohol derivative, more specifically, the following general formula having a strong gelling ability to an organic solvent. (I) (In the formula, m and n represent an integer of 0 to 5, which are not 0 at the same time, and p represents an integer of 0 to 2), and a fluorinated dibenzylidene polyhydric alcohol derivative represented by The present invention relates to a contained non-aqueous gelling agent and a cosmetic using the same.
従来、有機溶媒を固化させる非水系ゲル化剤としては、
金属セツケン、12−ヒドロキシステアリン酸、Ｎ−アシ
ルアミノ酸アミド、ジベンジリデンソルビトール等が知
られている。Conventionally, as a non-aqueous gelling agent for solidifying an organic solvent,
Metallic soap, 12-hydroxystearic acid, N-acyl amino acid amide, dibenzylidene sorbitol and the like are known.
しかしながら、これら非水系ゲル化剤のうち、金属セツ
ケン、12−ヒドロキシステアリン酸、Ｎ−アシルアミノ
酸アミド等は低極性有機溶媒をゲル化することはできる
が、エチレングリコール、グリセリン等の高極性有機溶
媒は全くゲル化できないという欠点があつた。また、ジ
ベンジリデンソルビトールは低極性から高極性まで広い
範囲の有機溶媒をゲル化できる優れた性質を有するが、
これをゲル化剤として化粧品等に応用すると、形成され
たゲルから溶媒がしみ出したり、ゲルの強度が不十分で
あるという問題点があつた。However, among these non-aqueous gelling agents, metal soap, 12-hydroxystearic acid, N-acyl amino acid amide and the like can gel low polar organic solvents, but high polar organic solvents such as ethylene glycol and glycerin. Had a drawback that it could not gel at all. Further, dibenzylidene sorbitol has an excellent property of gelling a wide range of organic solvents from low polarity to high polarity,
When this is applied to cosmetics as a gelling agent, there are problems that the solvent exudes from the formed gel and that the strength of the gel is insufficient.
斯かる問題点を解決すべく、本発明者らは鋭意研究を重
ねた結果、前記一般式（Ｉ）で表わされる新規なフツ素
化ジベンジリデン多価アルコール誘導体が広い範囲の有
機溶媒を強固かつ安定にゲル化する能力を有すること、
及びこれによつて得られたゲルが化粧料として優れた性
質を有することを見出し、本発明を完成した。In order to solve such a problem, the inventors of the present invention have conducted extensive studies, and as a result, the novel fluorinated dibenzylidene polyhydric alcohol derivative represented by the above general formula (I) can be used in a wide range of organic solvents. Having the ability to gel stably
Moreover, they have found that the gel obtained thereby has excellent properties as a cosmetic, and completed the present invention.
すなわち、本発明は、有機溶媒に対して強力なゲル化能
を有する前記一般式（Ｉ）で表わされるフツ素化ジベン
ジリデン多価アルコール誘導体、及びこれを有効成分と
して含有する非水系ゲル化剤、並びに該ゲル化剤と化粧
料油成分とを含有する化粧料を提供するものである。That is, the present invention provides a fluorinated dibenzylidene polyhydric alcohol derivative represented by the general formula (I) having a strong gelling ability to an organic solvent, and a non-aqueous gelling agent containing the derivative. And a cosmetic containing the gelling agent and a cosmetic oil component.
前記式（Ｉ）で表わされるフツ素化ジベンジリデン多価
アルコール誘導体において、フエニル基上のフツ素原子
の置換数及び置換位置は特に制限されず、例えば１置換
体であれば、４−フルオロ、３−フルオロ、２−フルオ
ロ置換フエニル基が、２置換体であれば、3,4−ジフル
オロ、3,5−ジフルオロ、2,3−ジフルオロ、2,4−ジフ
ルオロ、2,5−ジフルオロ、2,6−ジフルオロ置換フエニ
ル基等が挙げられる。また、化合物（Ｉ）の２つのフエ
ニル基はフツ素置換様式の異つたものであつても良い。In the fluorinated dibenzylidene polyhydric alcohol derivative represented by the above formula (I), the number of substitutions and the substitution position of the fluorine atom on the phenyl group are not particularly limited. When the 3-fluoro or 2-fluoro substituted phenyl group is a disubstituted product, 3,4-difluoro, 3,5-difluoro, 2,3-difluoro, 2,4-difluoro, 2,5-difluoro, 2 , 6-difluoro-substituted phenyl group and the like. In addition, the two phenyl groups of the compound (I) may have different fluorine substitution modes.
化合物（Ｉ）の骨格となる多価アルコール（糖アルコー
ル）は、５〜７価の糖アルコールであればいずれでもよ
く、例えば光学活性体若しくはラセミ体のソルビトー
ル、イデイトール、アリトール、アルトリトール、キシ
リトール、リビトール等が挙げられる。The polyhydric alcohol (sugar alcohol) serving as the skeleton of the compound (I) may be any 5- to 7-valent sugar alcohol, for example, optically active or racemic sorbitol, iditol, allitol, altritol, xylitol, Examples include ribitol.
本発明のフツ素化ジベンジリデン多価アルコール誘導体
（Ｉ）の製造法は特に限定されず、例えば特公昭47−74
60号に記載の方法に準じて、多価アルコールとフツ素化
ベンズアルデヒドを酸触媒の存在下に反応させ、生成す
る水を溶媒と共沸留去することにより製造することがで
きる。The method for producing the fluorinated dibenzylidene polyhydric alcohol derivative (I) of the present invention is not particularly limited. For example, JP-B-47-74.
According to the method described in No. 60, it can be produced by reacting a polyhydric alcohol with a fluorinated benzaldehyde in the presence of an acid catalyst, and azeotropically distilling off the produced water with a solvent.
この反応に用いる原料の多価アルコールとフツ素化ベン
ズアルデヒドの比率は、多価アルコール１モルに対して
フツ素化ベンズアルデヒド1.6〜2.2モルが好ましい。フ
ツ素化ベンズアルデヒドが1.6モル未満ではフツ素化モ
ノベンジリデン多価アルコール誘導体が、また2.2モル
を超えるとフツ素化トリベンジリデン多価アルコール誘
導体がそれぞれ副生し、目的とするフツ素化ジベンジリ
デン多価アルコール誘導体の収率が低下する。酸触媒と
しては、硫酸、リン酸、ｐ−トリエンスルホン酸等、一
般に用いられる公知の酸触媒を用いることができ、これ
らは多価アルコールに対して、通常0.1〜10モル％用い
るのが好ましい。溶媒としては、反応に不活性でかつ水
と共沸する性質を有する有機溶媒であれば、いずれでも
使用できるが、ベンゼン、トルエン、シクロヘキサンが
好ましい。The ratio of polyhydric alcohol as a raw material used in this reaction and fluorinated benzaldehyde is preferably 1.6 to 2.2 mol of fluorinated benzaldehyde to 1 mol of polyhydric alcohol. When the amount of fluorinated benzaldehyde is less than 1.6 mol, the fluorinated monobenzylidene polyhydric alcohol derivative is produced as a by-product, and when it exceeds 2.2 mol, the fluorinated tribenzylidene polyhydric alcohol derivative is produced as a by-product. The yield of the polyhydric alcohol derivative decreases. As the acid catalyst, known acid catalysts generally used such as sulfuric acid, phosphoric acid and p-trienesulfonic acid can be used, and these are usually preferably used in an amount of 0.1 to 10 mol% based on the polyhydric alcohol. As the solvent, any organic solvent which is inert to the reaction and has an azeotropic property with water can be used, but benzene, toluene and cyclohexane are preferable.
かくして得られたフツ素化ジベンジリデン多価アルコー
ル誘導体（Ｉ）は従来公知のジベンジリデンソルビトー
ル及びその誘導体に比べて強力なゲル化能を有する。例
えば、1,3;2,4−ビス（３−フルオロベンジリデン）−
Ｄ−ソルビトール（以下、３−Ｆ−DBSと略称する）及
び1,3;2,4−ビス（４−フルオロベンジリデン）−Ｄ−
ソルビトール（以下、４−Ｆ−DBSと略称する）と公知
の1,3;2,4−ジベンジリデン−Ｄ−ソルビトール（以
下、DBSと略称する）のゲル化能を比較すると、３−Ｆ
−DBSのｐ−キシレン、エタノール、エチレングリコー
ルに対するゲル強度（g/cm2）は、それぞれ75、180、26
8であり、４−Ｆ−DBSのそれは120、30、310である。こ
れに対して、DBSのゲル強度は45、31、155であり、全般
的に本発明のフツ素化誘導体の方がDBSよりも高いゲル
強度を示している。また、形成したゲルからの溶媒のし
み出しも、本発明のフツ素化誘導体を用いることによつ
て著しく抑えることができる。このような高いゲル化能
及びゲルからの溶媒しみ出し抑制の効果は、本発明のフ
ツ素化されたジベンジリデン多価アルコール誘導体
（Ｉ）にのみ特有のものであり、塩素等の他のハロゲン
で置換されたジベンジリデン多価アルコール誘導体で
は、このような優れた効果をあげることはできない。た
とえば、公知の1,3;2,4−ビス（４−クロロベンジリデ
ン）−Ｄ−ソルビトールでは、ｐ−キシレン、エタノー
ル、エチレングリコールに対するゲル強度（g/cm2）
は、それぞれ０、０、180にすぎず、本発明のフツ素化
誘導体のような優れた効果はない。なお、上記において
ゲル化能は、ゲル化剤100mgを溶媒9.9gに加熱溶解し、
室温で１週間放置した後のゲル強度をレオメーターによ
り測定して求めた。The fluorinated dibenzylidene polyhydric alcohol derivative (I) thus obtained has a stronger gelling ability than conventionally known dibenzylidene sorbitol and its derivatives. For example, 1,3; 2,4-bis (3-fluorobenzylidene)-
D-sorbitol (hereinafter abbreviated as 3-F-DBS) and 1,3; 2,4-bis (4-fluorobenzylidene) -D-
Comparing the gelling abilities of sorbitol (hereinafter abbreviated as 4-F-DBS) and known 1,3; 2,4-dibenzylidene-D-sorbitol (hereinafter abbreviated as DBS), 3-F
-The gel strength (g / cm 2 ) of p-xylene, ethanol and ethylene glycol of DBS is 75, 180 and 26, respectively.
8 and those of 4-F-DBS are 120, 30, 310. On the other hand, the gel strength of DBS is 45, 31, and 155, and the fluorinated derivatives of the present invention generally show higher gel strength than DBS. Further, the exudation of the solvent from the formed gel can be remarkably suppressed by using the fluorinated derivative of the present invention. Such a high gelling ability and the effect of suppressing the solvent exudation from the gel are unique to the fluorinated dibenzylidene polyhydric alcohol derivative (I) of the present invention, and other halogen such as chlorine. Such an excellent effect cannot be obtained by the dibenzylidene polyhydric alcohol derivative substituted with. For example, in the known 1,3; 2,4-bis (4-chlorobenzylidene) -D-sorbitol, gel strength (g / cm 2 ) against p-xylene, ethanol and ethylene glycol
Are only 0, 0 and 180, respectively, and do not have the excellent effects of the fluorinated derivative of the present invention. In the above, the gelling ability is obtained by heating and dissolving 100 mg of a gelling agent in 9.9 g of a solvent,
The gel strength after standing for 1 week at room temperature was measured by a rheometer and determined.
本発明のフツ素化ジベンジリデン多価アルコール誘導体
（Ｉ）は種々の溶媒をゲル化することができるのでゲル
化粧品、特に保湿効果等を目的とするゲル化粧品として
有利に利用することができる。Since the fluorinated dibenzylidene polyhydric alcohol derivative (I) of the present invention can gelate various solvents, it can be advantageously used as gel cosmetics, particularly gel cosmetics for the purpose of moisturizing effect and the like.
フツ素化ジベンジリデン多価アルコール誘導体（Ｉ）を
用いた場合の配合例を示せばそれぞれ次の通りである。The formulation examples when the fluorinated dibenzylidene polyhydric alcohol derivative (I) is used are as follows.
上記の化粧料は、例えばリツプステイツク、リツプクリ
ーム、アイステイツク、スキンケアジエル、薬用化粧
料、ボデイトリートメント、毛髪化粧料（整髪用ジエ
ル、ステツク）等の化粧料とすることができ、これに応
じて任意成分、例えばグリセリン、ポリエチレングリコ
ール等の水性保湿剤；リンゴ酸ジエステル、コレステロ
ール−ステアレート等の高極性液状の油性保湿剤；エタ
ノール、イソプロピルアルコール等のアルコール類を好
ましくは１〜30％、その他に、美白剤、紫外線吸収剤、
薬効剤、着色剤、顔料、防腐剤等を好ましくは0.1〜10
％程度、それぞれ本発明の効果を損なわない限度内で添
加、配合することができる。 The above-mentioned cosmetics can be cosmetics such as lipstick, lipcream, eyestay, skin care gel, medicated cosmetics, body treatment, hair cosmetics (hairdressing gel, sticks), etc. For example, aqueous humectants such as glycerin and polyethylene glycol; oily moisturizers of highly polar liquids such as malic acid diester and cholesterol-stearate; alcohols such as ethanol and isopropyl alcohol, preferably 1 to 30%; , UV absorber,
A medicinal agent, a coloring agent, a pigment, an antiseptic agent, etc., preferably 0.1 to 10
%, Each of which can be added and compounded within a limit not impairing the effects of the present invention.
本発明のフツ素化ジベンジリデン多価アルコール誘導体
（Ｉ）を用いることによつて、種々の有機溶媒を強固か
つ安定にゲル化することが可能となつた。したがつて、
本発明のフツ素化ジベンジリデン多価アルコール誘導体
（Ｉ）は、ゲル形態の化粧料の配合成分として有利に利
用することができる。By using the fluorinated dibenzylidene polyhydric alcohol derivative (I) of the present invention, various organic solvents can be strongly and stably gelled. Therefore,
INDUSTRIAL APPLICABILITY The fluorinated dibenzylidene polyhydric alcohol derivative (I) of the present invention can be advantageously used as a blending component of gel-type cosmetics.
次に実施例を挙げて本発明を更に詳しく説明する。 Next, the present invention will be described in more detail with reference to examples.
実施例１ 1,3;2,4−ビス（３−フルオロベンジリデン）−Ｄ−ソ
ルビトール（３−Ｆ−DBS）の合成： 攪拌装置及び上部に還流冷却器を備えた液−液分離器を
付した500ml容のフラスコに、Ｄ−ソルビトール15.30g
（84mmol）、３−フルオロベンズアルデヒド19.86g（16
0mmol）、ベンゼン320ml及びｐ−トルエンスルホン酸一
水和物0.61g（3.2mmol）を仕込み、強く攪拌しながら加
熱還流し、４時間かけて生成した水を除去した。次い
で、反応混合物を室温まで冷却後、析出したゲル状物質
をろ別し、得られた固体を５％水酸化ナトリウム水溶液
及び水で洗浄した。この生成物をジオキサンから再結晶
し、白色固体の目的化合物（３−Ｆ−DBS）を24.50g
（収率77％）得た。Example 1 Synthesis of 1,3; 2,4-bis (3-fluorobenzylidene) -D-sorbitol (3-F-DBS): A liquid-liquid separator equipped with a stirrer and a reflux condenser at the top was attached. 15.30 g of D-sorbitol was added to the prepared 500 ml flask.
(84 mmol), 19.86 g of 3-fluorobenzaldehyde (16
0 mmol), 320 ml of benzene and 0.61 g (3.2 mmol) of p-toluenesulfonic acid monohydrate were charged, and the mixture was heated under reflux with vigorous stirring to remove water produced over 4 hours. Then, the reaction mixture was cooled to room temperature, the precipitated gel-like substance was filtered off, and the obtained solid was washed with a 5% aqueous sodium hydroxide solution and water. This product was recrystallized from dioxane to obtain 24.50 g of the target compound (3-F-DBS) as a white solid.
(Yield 77%).
融点（℃）:215.0−216.8 元素分析：C20H20F2O6として 計算値（％）;C60.91,H5.11 実測値（％）;C60.67,H5.11 IR（KBr,cm-1）:3220,2870,1593,1455,1344,1257,1095,
1023,873,7621 HNMR（DMSO−d6，δppm）:3.35−4.45（m,9H）、4.87
（bs,1H）、5.64（s,2H）、7.05−7.50（m,8H） MS:394（M+） 実施例２ 1,3;2,4−ビス（４−フルオロベンジリデン）−Ｄ−ソ
ルビトール（４−Ｆ−DBS）の合成： 実施例１の３−フルオロベンズアルデヒドの代わりに４
−フルオロベンズアルデヒド19.86g（160mmol）を用い
る以外は実施例１と同様にして、1,3;2,4−ビス（４−
フルオロベンジリデン）−Ｄ−ソルビトール21.67g（収
率68.7％）を得た。Melting point (° C): 215.0-216.8 Elemental analysis: Calculated as C 20 H 20 F 2 O 6 (%); C60.91, H5.11 Measured value (%); C60.67, H5.11 IR (KBr, cm -1 ): 3220,2870,1593,1455,1344,1257,1095,
1023,873,762 1 H NMR (DMSO-d 6 , δppm): 3.35-4.45 (m, 9H), 4.87
(Bs, 1H), 5.64 (s, 2H), 7.05-7.50 (m, 8H) MS: 394 (M + ) Example 2 1,3; 2,4-bis (4-fluorobenzylidene) -D-sorbitol Synthesis of (4-F-DBS): 4 instead of 3-fluorobenzaldehyde of Example 1
In the same manner as in Example 1 except that 19.86 g (160 mmol) of -fluorobenzaldehyde was used, 1,3; 2,4-bis (4-
Fluorobenzylidene) -D-sorbitol (21.67 g, yield 68.7%) was obtained.
融点（℃）:205.5−207.5 元素分析：C20H20F2O6として 計算値（％）;C60.91,H5.11 実測値（％）;C60.55,H5.12 IR（KBr,cm-1）:3286,2872,1611,1518,1404,1227,1092,
1020,834,7951 HNMR（DMSO−d6，δppm）:3.35−4.55（m,9H）、4.89
（ｄ、Ｊ＝5.5Hz,1H）、5.67（s,2H）、7.15−7.35（m,
4H）、7.45−7.65（m,4H） MS:394（M+） 実施例３ 1,3;2,4−ビス（3,4−ジフルオロベンジリデン）−Ｄ−
ソルビトール（3,4−Ｆ−DBS）の合成： 実施例１の３−フルオロベンズアルデヒドの代わりに3,
4−ジフルオロベンズアルデヒド22.74g（160mmol）を用
いる以外は実施例１と同様にして、1,3;2,4−ビス（3,4
−ジフルオロベンジリデン）−Ｄ−ソルビトール26.38g
（収率73.0％）を得た。Melting point (° C): 205.5-207.5 Elemental analysis: Calculated as C 20 H 20 F 2 O 6 (%); C60.91, H5.11 Measured value (%); C60.55, H5.12 IR (KBr, cm -1 ): 3286,2872,1611,1518,1404,1227,1092,
1020,834,795 1 H NMR (DMSO-d 6 , δppm): 3.35-4.55 (m, 9H), 4.89
(D, J = 5.5Hz, 1H), 5.67 (s, 2H), 7.15-7.35 (m,
4H), 7.45-7.65 (m, 4H) MS: 394 (M + ) Example 3 1,3; 2,4-bis (3,4-difluorobenzylidene) -D-
Synthesis of sorbitol (3,4-F-DBS): Instead of 3-fluorobenzaldehyde of Example 1, 3,
1,3; 2,4-bis (3,4) was prepared in the same manner as in Example 1 except that 22.74 g (160 mmol) of 4-difluorobenzaldehyde was used.
-Difluorobenzylidene) -D-sorbitol 26.38 g
(Yield 73.0%) was obtained.
融点（℃）:216.6−217.1 元素分析：C20H18F4O6として 計算値（％）;C55.82,H4.22 実測値（％）;C55.82,H4.22 IR（KBr,cm-1）:3220,2884,1617,1524,1437,1287,1089,
1023,8011 HNMR（DMSO−d6，δppm）:3.35−4.55（m,9H）、4.97
（ｄ、Ｊ＝5.5Hz,1H）、5.67（s,2H）、7.27−7.58（m,
6H） MS:430（M+） 実施例４〜12 実施例１〜３で得たフツ素化ジベンジリデン多価アルコ
ール誘導体100mgを第１表に示した溶媒9.9gにそれぞれ
加熱・溶解し、室温で１週間放置した後、レオーメータ
ーによりゲル強度を測定し、また目視による溶媒のしみ
出しの有無を調べた。結果を第１表に示す。Melting point (° C): 216.6-217.1 Elemental analysis: Calculated as C 20 H 18 F 4 O 6 (%); C55.82, H4.22 Measured value (%); C55.82, H4.22 IR (KBr, cm -1 ): 3220,2884,1617,1524,1437,1287,1089,
1023,801 1 HNMR (DMSO-d 6 , δppm): 3.35-4.55 (m, 9H), 4.97
(D, J = 5.5Hz, 1H), 5.67 (s, 2H), 7.27-7.58 (m,
6H) MS: 430 (M + ) Examples 4 to 12 100 mg of the fluorinated dibenzylidene polyhydric alcohol derivative obtained in Examples 1 to 3 was dissolved in 9.9 g of the solvent shown in Table 1 at room temperature. After being left for 1 week at room temperature, the gel strength was measured with a rheometer, and the presence or absence of solvent bleeding was visually checked. The results are shown in Table 1.
比較例１〜６ 実施例４〜12と同様にして1,3:2,4−ジベンジリデン−
Ｄ−ソルビトール及び1,3;2,4−ビス（４−クロロベン
ジリデン）−Ｄ−ソルビトールのゲル強度及び溶媒のし
み出しの有無を調べた。結果を第２表に示す。Comparative Examples 1 to 6 1,3: 2,4-dibenzylidene-as in Examples 4 to 12
The gel strength of D-sorbitol and 1,3; 2,4-bis (4-chlorobenzylidene) -D-sorbitol and the presence or absence of solvent exudation were examined. The results are shown in Table 2.
実施例13 ゲル状化粧料（リツプクリーム）： （処方） 重量％ （１）３−Ｆ−DBS １ （２）グリセリン 65 （３）ポリエチレングリコール ５ （４）エタノール 28.5 （５）香料 0.5 （製法） （２）〜（４）を混合した後、（１）を加え、加熱溶解
する。（５）を加えて付香した後放冷し、ゲル化させ目
的物を得た。このものは保湿効果に優れ、乾燥後もべと
つきのない優れた使用感を有していた。 Example 13 Gel cosmetic (lip cream): (Formulation) wt% (1) 3-F-DBS 1 (2) Glycerin 65 (3) Polyethylene glycol 5 (4) Ethanol 28.5 (5) Perfume 0.5 (Production method) ( After mixing 2) to 4), 1) is added and dissolved by heating. After adding (5) and perfuming, the mixture was allowed to cool and gelled to obtain the desired product. This product had an excellent moisturizing effect and had an excellent feeling of use without stickiness even after drying.
実施例14 ゲル状化粧料（アイステイツク）： （処方） 重量％ （１）４−Ｆ−DBS １ （２）ステアリルアルコール 20 （３）ラウリルアルコール 48.5 （４）グリセリン 30 （５）香料 0.5 （製法） （２）〜（４）を混合した後、（１）を加え、加熱溶解
する。（５）を加えた後、放冷、ゲル化せしめ、目的物
を得る。このものは保湿効果に優れ、乾燥後もべとつき
のない優れた使用感を有していた。Example 14 Gel cosmetic (eye-stick): (Formulation) wt% (1) 4-F-DBS 1 (2) Stearyl alcohol 20 (3) Lauryl alcohol 48.5 (4) Glycerin 30 (5) Perfume 0.5 (Production method) After mixing (2) to (4), (1) is added and dissolved by heating. After adding (5), the mixture is allowed to cool and gelled to obtain the desired product. This product had an excellent moisturizing effect and had an excellent feeling of use without stickiness even after drying.
実施例15 口紅： （処方） 重量％ （１）3,4−Ｆ−DBS 2.0 （２）グリセリン 55 （３）ポリエチレングリコール 16.5 （４）流動パラフイン 15 （５）カルナバワツクス ３ （６）顔料 ８ （７）香料 0.5 （製法） （２）〜（６）を加熱混合した後（１）を加え、加熱溶
解する。（７）を加えた後、容器に注入し、冷却して成
型する。Example 15 Lipstick: (Formulation) wt% (1) 3,4-F-DBS 2.0 (2) Glycerin 55 (3) Polyethylene glycol 16.5 (4) Liquid paraffin 15 (5) Carnauba wax 3 (6) Pigment 8 (7) Fragrance 0.5 (Production method) After mixing (2) to (6) with heating, (1) is added and dissolved by heating. After adding (7), it is poured into a container, cooled, and molded.
Claims (3)
を示し、ｐは０〜２の整数を示す） で表わされるフツ素化ジベンジリデン多価アルコール誘
導体。1. The following general formula (I): (In the formula, m and n each represent an integer of 0 to 5 which does not become 0 at the same time, and p represents an integer of 0 to 2.) A fluorinated dibenzylidene polyhydric alcohol derivative.
を示し、ｐは０〜２の整数を示す） で表わされるフツ素化ジベンジリデン多価アルコール誘
導体を有効成分として含有する非水系ゲル化剤。2. The following general formula (I): (In the formula, m and n each represent an integer of 0 to 5, which does not become 0 at the same time, and p represents an integer of 0 to 2), which is a non-functional compound containing a fluorinated dibenzylidene polyhydric alcohol derivative Aqueous gelling agent.
を示し、ｐは０〜２の整数を示す） で表わされるフツ素化ジベンジリデン多価アルコール誘
導体を有効成分として含有する非水系ゲル化剤及び化粧
油成分を含む化粧料。3. The following general formula (I): (In the formula, m and n each represent an integer of 0 to 5, which does not become 0 at the same time, and p represents an integer of 0 to 2), which is a non-functional compound containing a fluorinated dibenzylidene polyhydric alcohol derivative A cosmetic containing an aqueous gelling agent and a cosmetic oil component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62218311A JPH0720968B2 (en) | 1987-09-01 | 1987-09-01 | Fluorinated dibenzylidene polyhydric alcohol derivative, non-aqueous gelling agent containing the same, and cosmetics using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62218311A JPH0720968B2 (en) | 1987-09-01 | 1987-09-01 | Fluorinated dibenzylidene polyhydric alcohol derivative, non-aqueous gelling agent containing the same, and cosmetics using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6462377A JPS6462377A (en) | 1989-03-08 |
| JPH0720968B2 true JPH0720968B2 (en) | 1995-03-08 |
Family
ID=16717856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62218311A Expired - Lifetime JPH0720968B2 (en) | 1987-09-01 | 1987-09-01 | Fluorinated dibenzylidene polyhydric alcohol derivative, non-aqueous gelling agent containing the same, and cosmetics using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0720968B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5609855A (en) * | 1990-04-06 | 1997-03-11 | The Procter & Gamble Company | Gel stick antiperspirant compositions |
| US5106999A (en) * | 1990-06-26 | 1992-04-21 | The Procter & Gamble Company | Process for preparing dibenzylidene-d-sorbitol compounds |
| WO1992019221A2 (en) * | 1991-05-06 | 1992-11-12 | The Procter & Gamble Company | Acid stable gel stick antiperspirant compositions and process for making them |
| JP3188463B2 (en) * | 1992-05-12 | 2001-07-16 | ザ、プロクター、エンド、ギャンブル、カンパニー | Antiperspirant gel stick composition |
| US6190673B1 (en) | 1996-12-20 | 2001-02-20 | The Procter & Gamble Company | Gel compositions containing gellants in the form of alkyl amides of tri-carboxylic acids |
| US6171601B1 (en) | 1996-12-20 | 2001-01-09 | The Procter & Gamble Company | Low residue antiperspirant gel-solid stick compositions |
| US5840286A (en) * | 1996-12-20 | 1998-11-24 | Procter & Gamble Company | Methods of making low residue antiperspirant gel-solid stick compositions |
| WO2002020528A2 (en) * | 2000-09-01 | 2002-03-14 | Milliken & Company | Fluorinated and alkylated alditol derivatives and polyolefin articles containing same |
-
1987
- 1987-09-01 JP JP62218311A patent/JPH0720968B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6462377A (en) | 1989-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4588839A (en) | Sulphonamides derived from 3-benzylidene-camphor and their application as UV filters | |
| JP3939798B2 (en) | Stabilized lactate menthyl ester | |
| JPS609008B2 (en) | cosmetic composition | |
| JPS6391313A (en) | Medicine and antiacne cosmetic composition | |
| EP0031954A2 (en) | Sulphonamides, process for their preparation and medicines containing these compounds | |
| JPH01165524A (en) | Medicine and or comsmetics composition for local adaptation | |
| JPS5923320B2 (en) | Branched fatty acid cholesteryl ester | |
| JP3725564B2 (en) | Benzylidenequinuclidinones | |
| JPH0720968B2 (en) | Fluorinated dibenzylidene polyhydric alcohol derivative, non-aqueous gelling agent containing the same, and cosmetics using the same | |
| TWI860993B (en) | Oxazole compound crystal | |
| US2784233A (en) | Tertiary n- | |
| JPH04134041A (en) | P-xylidene ketone derivative, ultraviolet absorber containing said derivative and cosmetic containing said absorber | |
| FR2593499A1 (en) | AMINOALCOHOLS, PROCESS FOR THEIR PREPARATION AND THEIR USE, IN PARTICULAR THERAPEUTICS | |
| HU189745B (en) | Process for producing benzamido-derivatives | |
| FR2467203A1 (en) | 1,2,4-OXADIAZOLIN-5-ONE DERIVATIVES, PROCESS FOR THEIR PREPARATION AND PHARMACEUTICAL COMPOSITIONS CONTAINING SAME | |
| JP2008512421A (en) | Method for producing enantiomeric imidazole compound | |
| JPS6027647B2 (en) | Cosmetics containing branched fatty acid cholesteryl ester | |
| JPS6328070B2 (en) | ||
| JP3589785B2 (en) | Antifungal agent | |
| JP2691608B2 (en) | Pack cosmetics | |
| JP3492947B2 (en) | Oily solid cosmetic for lips | |
| SU1456012A3 (en) | Method of producing n-(1-cyclohexenylmethyl-2-pyrrolidinylmethyl)-8-ethylsulfonyl-1,5-benzodioxypan-6-carboxamide or hydrochloride thereof | |
| JP2736945B2 (en) | 4- (2,3-dihydroxypropoxy) -4'-substituted dibenzoylmethane derivative, method for producing the same, ultraviolet absorber containing the derivative, intermediate for producing the derivative, and method for producing the intermediate | |
| JPH02270813A (en) | Solid powder cosmetic | |
| JPS6039644B2 (en) | Base material for cosmetics or ointments |