JP2006225403A - Oily gel cleansing cream - Google Patents
Oily gel cleansing cream Download PDFInfo
- Publication number
- JP2006225403A JP2006225403A JP2006139961A JP2006139961A JP2006225403A JP 2006225403 A JP2006225403 A JP 2006225403A JP 2006139961 A JP2006139961 A JP 2006139961A JP 2006139961 A JP2006139961 A JP 2006139961A JP 2006225403 A JP2006225403 A JP 2006225403A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- group
- chain
- oil
- cleansing
- 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.)
- Granted
Links
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 26
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 17
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- 125000003277 amino group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
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- 238000004140 cleaning Methods 0.000 description 6
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- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
- 229930007845 β-thujaplicin Natural products 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、多量の油性成分を安定に配合した、皮膚等に塗布して水洗した時に残油感がなく、かさつきのない、使用感に優れたクレンジング化粧料に関し、特に香粧品として有用な油性ゲル状クレンジングに関する。 The present invention relates to a cleansing cosmetic composition that is stably blended with a large amount of an oily component, has no residual oil feeling when applied to the skin or the like, and has no bulkiness, and is excellent in use feeling, and is particularly useful as a cosmetic product. It relates to oily gel cleansing.
従来より提案されているゲル状のクレンジング剤には、水溶性高分子で形成したタイプや油をゲル化剤でゲル化させたタイプ、水中油型もしくは油中水型の乳化タイプのものが挙げられる。そしてこれらのクレンジング剤のほとんどが、ゲル化させるためにノニオン性界面活性剤(特許文献1〜2参照)を使用している。しかしながら、この方法ではゲル化させるために界面活性剤を多量に配合する必要がある。そのために、皮膚のかさつき等による使用感の悪さや油性成分含量の低下によるクレンジング性の低下、安定性の問題があった。 The gel-type cleansing agents that have been proposed in the past include those formed with water-soluble polymers, those obtained by gelling oil with a gelling agent, and those emulsified in oil-in-water or water-in-oil type. It is done. And most of these cleansing agents use nonionic surfactant (refer patent documents 1-2) in order to make it gelatinize. However, in this method, it is necessary to add a large amount of a surfactant in order to cause gelation. For this reason, there are problems such as poor usability due to skin roughness and the like, a decrease in cleansing property due to a decrease in oily component content, and stability.
本発明は、該油性ゲル状クレンジングを皮膚等に塗布、水洗した時に多量の油性成分を含有しながら残油感がなく、皮膚のかさつきのない、使用感に優れた透明〜半透明の油性ゲル状クレンジングを提供することを目的とするものである。 The present invention is a transparent to translucent oily gel that contains a large amount of oily components and does not feel residual oil when it is applied to the skin or the like and washed with water. The purpose is to provide state cleansing.
本発明者らは、前記課題を解決すべく鋭意検討を重ねた結果、長鎖疎水基と親水基とを分子内に2個以上ずつ有する多鎖多親水基型化合物を1種以上、分子内に水酸基を2個以上有するポリヒドロキシル化合物の1種以上、油性成分の1種以上、及びHLBが2〜14であるノニオン性界面活性剤の1種以上を含有することを特徴とする油性ゲル状クレンジングとすることで、多量の油性成分を安定に配合しながら、皮膚等に塗布して水洗した時に残油感がなく、かさつきのない、使用感に優れていること、またこの組成物は水への分散性が極めてよいことから、この油性ゲル状クレンジングが、使用感の優れた香粧品として有用なものであることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that one or more multi-chain polyhydrophilic group type compounds each having two or more long-chain hydrophobic groups and hydrophilic groups in the molecule Containing at least one polyhydroxyl compound having two or more hydroxyl groups, at least one oily component, and at least one nonionic surfactant having an HLB of 2 to 14 By cleansing, while stably blending a large amount of oily components, when applied to the skin and washed with water, there is no residual oil feeling, no bulkiness, excellent use feeling, and this composition is Since the dispersibility in water is very good, it was found that this oily gel cleansing is useful as a cosmetic product with excellent usability, and the present invention has been completed.
即ち本発明は、下記の通りである。
1.1)長鎖疎水基と親水基とを分子内に2個以上ずつ有する多鎖多親水基型化合物の1種以上、2)分子内に水酸基を2個以上有するポリヒドロキシル化合物の1種以上、3)油性成分の1種以上、及び4)HLBが2〜14であるノニオン性界面活性剤を含有することを特徴とする油性ゲル状クレンジング。
2.油性ゲル状クレンジング中の水分含量が50質量%以下であり、かつ該油性ゲル状クレンジング中の組成が、1)多鎖多親水基型化合物の総量が0.1〜40質量%、2)ポリヒドロキシル化合物の総量が1〜60質量%、3)油性成分の総量が1〜95質量%、4)HLBが2〜14であるノニオン性界面活性剤の総量が0.1〜20%(但し、水分含量と1)〜4)の合計は100質量%)である組成物を含有することを特徴とする1.に記載の油性ゲル状クレンジング。
That is, the present invention is as follows.
1.1) One or more types of multi-chain polyhydrophilic group type compounds having two or more long-chain hydrophobic groups and hydrophilic groups in the molecule 2) One type of polyhydroxyl compound having two or more hydroxyl groups in the molecule 3) One or more kinds of oily components, and 4) a nonionic surfactant having an HLB of 2 to 14, containing an oily gel cleansing.
2. The water content in the oily gel cleansing is 50% by mass or less, and the composition in the oily gel cleansing is 1) the total amount of the multi-chain polyhydrophilic group type compound is 0.1 to 40% by mass, 2) poly The total amount of hydroxyl compounds is 1 to 60% by mass, 3) The total amount of oily components is 1 to 95% by mass, 4) The total amount of nonionic surfactants having HLB of 2 to 14 is 0.1 to 20% (provided that 1. A composition containing a water content and a total of 1) to 4) of 100% by mass). Oil-based gel cleansing as described in 1.
3.該油性ゲル状クレンジング中の1)多鎖多親水基型化合物の少なくとも1種が、分子内にアミノ酸残基を有するものであることを特徴とする1.または2.に記載の油性ゲル
状クレンジング。
4.該油性ゲル状クレンジング中の1)多鎖多親水基型化合物の少なくとも1種が下記一般式(1)に示す化合物であることを特徴とする1.〜3.のいずれかに記載の油性ゲル状クレンジング。
3. In the oily gel cleansing, 1) at least one of the multi-chain polyhydrophilic group type compounds has an amino acid residue in the molecule. Or 2. Oil-based gel cleansing as described in 1.
4). 1. In the oily gel cleansing, 1) at least one of the multi-chain polyhydrophilic group type compounds is a compound represented by the following general formula (1): ~ 3. Oil-based gel cleansing according to any of the above.
(上記一般式(1)において、Xはヒドロキシル基、アミノ基、チオール基から選ばれる1種または2種以上からなるm個の官能基を有する分子量100万以下の直鎖または分枝鎖または環状鎖または芳香族炭化水素鎖であるスペーサーであり、Xは、前記ヒドロキシル基、アミノ基、チオール基以外の置換基を有していてもよく、QはZを介してXに付くn個の下記一般式(2)で表される置換基であり、それぞれ独立で、すなわち、同一でも異なっていてもよく、
R1COは炭素原子数8〜20の飽和または不飽和の脂肪酸から誘導される長鎖アシル基を示し、R2は水素であるか、またはヒドロキシル基またはカルボキシル基が置換していてもよい炭素原子数1〜3の低級アルキル基を示し、Yはカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基および/またはそれらの塩を示し、j、kはそれぞれ独立に0,1,2のいずれかであり、かつj、kは同時に0ではなく、nは2〜20の整数を示す)
(In the above general formula (1), X is a linear, branched or cyclic group having a molecular weight of 1 million or less having m functional groups consisting of one or more selected from hydroxyl group, amino group and thiol group. Is a spacer that is a chain or an aromatic hydrocarbon chain, and X may have a substituent other than the hydroxyl group, amino group, and thiol group, and Q is the following n attached to X through Z Each of the substituents represented by the general formula (2) is independent, that is, may be the same or different;
R 1 CO represents a long-chain acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms, R 2 is hydrogen, or a carbon which may be substituted by a hydroxyl group or a carboxyl group A lower alkyl group having 1 to 3 atoms; Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group and / or a salt thereof; j and k are each independently 0, 1, 2; And j and k are not 0 at the same time, and n is an integer of 2 to 20)
5.該油性ゲル状クレンジング中の1)多鎖多親水基型化合物の少なくとも1種が上記一般式(1)に示す化合物であって、上記一般式(1)において、Xは前記m個の官能基以外の置換基を有していてもよい炭素数1〜40の直鎖または分枝鎖または環状鎖または芳香族炭化水素鎖であるスペーサーであることを特徴とする1.〜4.のいずれかに記載の油性ゲル状クレンジング。
6.該油性ゲル状クレンジングを皮膚等に塗布、水洗した時に残油感がなく、かさつきのない、使用感に優れたクレンジング化粧料として用いることを特徴とする1.〜5.のいずれかに記載の油性ゲル状クレンジング。
5. In the oily gel cleansing, 1) at least one of the multi-chain polyhydrophilic group type compounds is a compound represented by the general formula (1), and in the general formula (1), X is the m functional groups. 1. A spacer which is a linear, branched, cyclic, or aromatic hydrocarbon chain having 1 to 40 carbon atoms that may have a substituent other than 1. ~ 4. Oil-based gel cleansing according to any of the above.
6). The oily gel cleansing composition is used as a cleansing cosmetic composition that does not feel residual oil when it is applied to the skin or the like and washed with water, and does not become bulky and has an excellent feeling of use. ~ 5. Oil-based gel cleansing according to any of the above.
本発明の油性ゲル状クレンジングは、長鎖疎水基と親水基とを分子内に2個以上ずつ有する多鎖多親水基型化合物を1種または2種以上、分子内に水酸基を2個以上有するポリヒドロキシル化合物の1種または2種以上、及び油性成分の1種または2種以上、HLBが2−14であるノニオン性界面活性剤の1種または2種以上を含有することを特徴とする油性ゲル状クレンジングであって、この範囲外の油性ゲル状クレンジングに比し、皮膚等に塗布し、水洗した時に残油感がなく、かさつきがない、使用感に優れて、安定性の高いものであることが明らかである。 The oily gel-like cleansing of the present invention has one or more multi-chain polyhydrophilic group-type compounds each having two or more long-chain hydrophobic groups and hydrophilic groups in the molecule, and two or more hydroxyl groups in the molecule. One or more kinds of polyhydroxyl compounds, one or more kinds of oily components, and one or more kinds of nonionic surfactants having an HLB of 2-14 Gel cleansing, compared to oily gel cleansing outside this range, no oil residue, no bulkiness when applied to skin, etc., washed with water, excellent use feeling and high stability It is clear that
以下、本発明を、特にその実施態様を中心に、詳細に説明する。
本発明の油性ゲル状クレンジングにおいて、1)多鎖多親水基型化合物としては、長鎖疎水基としてはそれぞれ独立に、炭素数8〜20個の飽和または不飽和の直鎖、分枝鎖、環状鎖からなる疎水基を有し、親水基としてはそれぞれ独立に、カルボキシル基、スルホン酸基、硫酸残基、リン酸残基またはそれらの塩等、あるいはオキシアルキレン基、ポリエチレングリコール基等、またはアミノ基、4級アンモニウム基、ピリジニウム基、スルホニウム基またはそれらの塩等を有するものである。
Hereinafter, the present invention will be described in detail, particularly focusing on its embodiments.
In the oily gel cleansing of the present invention, 1) as a multi-chain polyhydrophilic group type compound, each of the long-chain hydrophobic groups is independently a saturated or unsaturated straight chain or branched chain having 8 to 20 carbon atoms, It has a hydrophobic group consisting of a cyclic chain, and each hydrophilic group is independently a carboxyl group, a sulfonic acid group, a sulfuric acid residue, a phosphoric acid residue or a salt thereof, an oxyalkylene group, a polyethylene glycol group, or the like, or It has an amino group, a quaternary ammonium group, a pyridinium group, a sulfonium group, or a salt thereof.
例えば、多鎖多親水基型化合物の長鎖疎水基としては、例えば、n−オクチル、n−ノニル、n−デシル、n−ウンデシル、n−ドデシル、n−トリデシル、n−テトラデシル、n−ペンタデシル、n−ヘキサデシル、n−ヘプタデシル、n−オクタデシル、n−ノナデシル、n−エイコシル等の各残基とこれらの分枝鎖異性体、ならびにこれらに対応した、1カ所、2カ所または3カ所に不飽和部分を有する不飽和残基等が挙げられる。
また、多鎖多親水基型化合物の長鎖疎水基としては、炭素原子数8〜20の飽和または不飽和の脂肪酸から誘導される長鎖アシル基であり、
For example, the long-chain hydrophobic group of the multi-chain poly-hydrophilic group type compound includes, for example, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl. , N-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, etc. and their branched isomers, and corresponding one, two or three non-residues Examples include unsaturated residues having a saturated portion.
The long-chain hydrophobic group of the multi-chain polyhydrophilic group-type compound is a long-chain acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms,
例えばカプリル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、マルガリン酸、ステアリン酸、ノナデカン酸、アラキン酸のような直鎖脂肪酸;
2−ブチル−5−メチルペンタン酸、2−イソブチル−5−メチルペンタン酸、ジメチルオクタン酸、ジメチルノナン酸、2−ブチル−5−メチルヘキサン酸、メチルウンデカン酸、ジメチルデカン酸、2−エチル−3−メチルノナン酸、2,2−ジメチル−4−エチルオクタン酸、メチルドコサン酸、2−プロピル−3−メチルノナン酸、メチルトリデカン酸、ジメチルドデカン酸、2−ブチル−3−メチルノナン酸、メチルテトラデカン酸、エチルトリデカン酸、プロピルドデカン酸、ブチルウンデカン酸、ペンチルデカン酸、ヘキシルノナン酸、2−(3−メチルブチル)−3−メチルノナン酸、2−(2−メチルブチル)−3−メチルノナン酸、ブチルエチルノナン酸、
Linear fatty acids such as caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid;
2-butyl-5-methylpentanoic acid, 2-isobutyl-5-methylpentanoic acid, dimethyloctanoic acid, dimethylnonanoic acid, 2-butyl-5-methylhexanoic acid, methylundecanoic acid, dimethyldecanoic acid, 2-ethyl- 3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic acid, methyldocosanoic acid, 2-propyl-3-methylnonanoic acid, methyltridecanoic acid, dimethyldodecanoic acid, 2-butyl-3-methylnonanoic acid, methyltetradecanoic acid , Ethyltridecanoic acid, propyldodecanoic acid, butylundecanoic acid, pentyldecanoic acid, hexylnonanoic acid, 2- (3-methylbutyl) -3-methylnonanoic acid, 2- (2-methylbutyl) -3-methylnonanoic acid, butylethylnonane acid,
メチルペンタデカン酸、エチルテトラデカン酸、プロピルトリデカン酸、ブチルドデカン酸、ペンチルウンデカン酸、ヘキシルデカン酸、ヘプチルノナン酸、ジメチルテトラデカン酸、ブチルペンチルヘプタン酸、トリメチルトリデカン酸、メチルヘキサデカン酸、エチルペンタデカン酸、プロピルテトラデカン酸、ブチルトリデカン酸、ペンチルドデカン酸、ヘキシルウンデカン酸、ヘプチルデカン酸、メチルヘプチルノナン酸、
ジペンチルヘプタン酸、メチルヘプタデカン酸、エチルヘキサデカン酸、エチルヘキサデカン酸、プロピルペンタデカン酸、ブチルテトラデカン酸、ペンチルトリデカン酸、ヘキシルドデカン酸、ヘプチルウンデカン酸、オクチルデカン酸、ジメチルヘキサデカン酸、
Methylpentadecanoic acid, ethyltetradecanoic acid, propyltridecanoic acid, butyldodecanoic acid, pentylundecanoic acid, hexyldecanoic acid, heptylnonanoic acid, dimethyltetradecanoic acid, butylpentylheptanoic acid, trimethyltridecanoic acid, methylhexadecanoic acid, ethylpentadecanoic acid, propyl Tetradecanoic acid, butyltridecanoic acid, pentyldodecanoic acid, hexylundecanoic acid, heptyldecanoic acid, methylheptylnonanoic acid,
Dipentylheptanoic acid, methylheptadecanoic acid, ethylhexadecanoic acid, ethylhexadecanoic acid, propylpentadecanoic acid, butyltetradecanoic acid, pentyltridecanoic acid, hexyldecanoic acid, heptylundecanoic acid, octyldecanoic acid, dimethylhexadecanoic acid,
メチルオクチルノナン酸、メチルオクタデカン酸、エチルヘプタデカン酸、ジメチルヘプタデカン酸、メチルオクチルデカン酸、メチルノナデカン酸、メチルノナデカン酸、ジメチルオクタデカン酸、ブチルヘプチルノナン酸のような分岐脂肪酸;
オクテン酸、ノネン酸、デセン酸、カプロレイン酸、ウンデシレン酸、リンデル酸、トウハク酸、ラウロレイン酸、トリデセン酸、ツズ酸、ミリストレイン酸、ペンタデセン酸、ヘキセデセン酸、パルミトレイン酸、ヘプタデセン酸、オクタデセン酸、オレイン酸、ノナデセン酸、ゴンドイン酸のような直鎖モノエン酸;
メチルヘプテン酸、メチルノネン酸、メチルウンデセン酸、ジメチルデセン酸、メチルドデセン酸、メチルトリデセン酸、ジメチルドデセン酸、ジメチルトリデセン酸、メチルオクタデセン酸、ジメチルヘプタデセン酸、エチルオクタデセン酸のような分岐モノエン酸;
Branched fatty acids such as methyloctylnonanoic acid, methyloctadecanoic acid, ethylheptadecanoic acid, dimethylheptadecanoic acid, methyloctyldecanoic acid, methylnonadecanoic acid, methylnonadecanoic acid, dimethyloctadecanoic acid, butylheptylnonanoic acid;
Octenoic acid, nonenoic acid, decenoic acid, caproleic acid, undecylenic acid, Lindellic acid, touric acid, lauroleic acid, tridecenoic acid, tuzuic acid, myristoleic acid, pentadecenoic acid, hexedenoic acid, palmitoleic acid, heptadecenoic acid, octadecenoic acid, Linear monoenoic acids such as oleic acid, nonadecenoic acid, gondoic acid;
Such as methylheptenoic acid, methylnonenoic acid, methylundecenoic acid, dimethyldecenoic acid, methyldodecenoic acid, methyltridecenoic acid, dimethyldodecenoic acid, dimethyltridecenoic acid, methyloctadecenoic acid, dimethylheptadecenoic acid, ethyloctadecenoic acid Branched monoenoic acid;
リノール酸、リノエライジン酸、エレオステアリン酸、リノレン酸、リノレンエライジン酸、プソイドエレオステアリン酸、パリナリン酸、アラキドン酸のようなジまたはトリエン酸;
オクチン酸、ノニン酸、デシン酸、ウンデシン酸、ドデシン酸、トリデシン酸、テトラデシン酸、ペンタデシン酸、ヘプタデシン酸、オクタデシン酸、ノナデシン酸、ジメチルオクタデシン酸のようなアセチレン酸;
メチレンオクタデセン酸、メチレンオクタデカン酸、アレプロール酸、アレプレスチン酸、アレプリル酸、アレプリン酸、ヒドノカルプン酸、ショールムーグリン酸、ゴルリン酸、α−シクロペンチル酸、α−シクロヘキシル酸、α−シクロペンチルエチル酸のような環状酸から誘導されるアシル基等があげられる。
Di- or trienoic acids such as linoleic acid, linoleic acid, eleostearic acid, linolenic acid, linolenic elaidic acid, pseudoeleostearic acid, parinaric acid, arachidonic acid;
Acetylene acids such as octinoic acid, nonic acid, decinic acid, undecinic acid, dodecinic acid, tridecinic acid, tetradecinic acid, pentadecinic acid, heptadesinic acid, octadecinic acid, nonadesinic acid, dimethyloctadesinic acid;
Of methyleneoctadecenoic acid, methyleneoctadecanoic acid, aleprolic acid, alepresinic acid, allepuric acid, alepuric acid, hydnocarpic acid, shoulmuric acid, gorulic acid, α-cyclopentylic acid, α-cyclohexylic acid, α-cyclopentylethylic acid And acyl groups derived from such cyclic acids.
また天然油脂から得られる脂肪酸由来のアシル基でも良く、上記の炭素原子数8〜20の飽和または不飽和脂肪酸を80%以上含む混合脂肪酸由来のアシル基であれば良い。例えば、ヤシ油脂肪酸、パーム油脂肪酸、アマニ油脂肪酸、ヒマワリ油脂肪酸、大豆油脂肪酸、ゴマ油脂肪酸、ヒマシ油脂肪酸、オリーブ油脂肪酸、ツバキ油脂肪酸、菜種油脂肪酸、パーム核油脂肪酸等から誘導されるアシル基等が挙げられる。長鎖疎水基は、長鎖アシル基で、分子中の長鎖疎水基は同一であるのが好ましい。これら多鎖多親水基型化合物は2種以上組み合わせて用いても良い。 Moreover, the acyl group derived from the fatty acid obtained from natural fats and oils may be sufficient, and what is necessary is just the acyl group derived from the mixed fatty acid containing 80% or more of said saturated or unsaturated fatty acid having 8-20 carbon atoms. For example, acyl groups derived from palm oil fatty acid, palm oil fatty acid, linseed oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, castor oil fatty acid, olive oil fatty acid, camellia oil fatty acid, rapeseed oil fatty acid, palm kernel oil fatty acid, etc. Etc. The long-chain hydrophobic group is a long-chain acyl group, and the long-chain hydrophobic group in the molecule is preferably the same. Two or more of these polychain polyhydrophilic group type compounds may be used in combination.
本発明の油性ゲル状クレンジングにおいて、1)多鎖多親水基型化合物の例を挙げると、構造的には、分子内に長鎖疎水基と親水基をそれぞれ少なくとも1個以上有する界面活性剤を適当なスペーサーで連結した構造のものであり、この構造であればよく、これまで公知になっている化合物でよい。スペーサーとしては、置換基を有していてもよい分子量100万以下の直鎖または分枝鎖または環状鎖または芳香族炭化水素鎖がよい。より好ましくは、炭素数1〜40の直鎖または分枝鎖または環状鎖または芳香族炭化水素鎖であるスペーサーがよい。 In the oily gel-like cleansing of the present invention, 1) As an example of a multi-chain polyhydrophilic group type compound, structurally, a surfactant having at least one long-chain hydrophobic group and one hydrophilic group in the molecule is provided. It has a structure connected with an appropriate spacer, and this structure may be used, and any known compound may be used. The spacer is preferably a linear, branched, cyclic, or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have a substituent. More preferably, a spacer which is a straight chain, branched chain, cyclic chain or aromatic hydrocarbon chain having 1 to 40 carbon atoms is preferred.
本発明の油性ゲル状クレンジングにおいて、1)多鎖多親水基型化合物の親水基はそれぞれ独立に、カルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基および/またはそれらの塩であることが好ましい。ここで塩としては、例えばアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、有機アミン塩、塩基性アミノ酸塩等が挙げられ、具体的には、ナトリウム、カリウム、リチウム等のアルカリ金属、カルシウム、マグネシウム等のアルカリ土類金属、アルミニウム、亜鉛等の金属、アンモニア、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミン等の有機アミン、アルギニン、リジン等の塩基性アミノ酸等から任意に選ばれる1種または2種以上との塩である。これらの中でも、ナトリウム塩、カリウム塩、有機アミン塩、塩基性アミノ酸塩が特に好ましい。 In the oily gel cleansing of the present invention, 1) the hydrophilic groups of the multi-chain polyhydrophilic group type compound are each independently a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group and / or a salt thereof. Is preferred. Here, examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, basic amino acid salts, and the like, specifically, alkali metals such as sodium, potassium, lithium, calcium, 1 selected arbitrarily from alkaline earth metals such as magnesium, metals such as aluminum and zinc, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, basic amino acids such as arginine and lysine A salt with a seed or two or more. Among these, sodium salts, potassium salts, organic amine salts, and basic amino acid salts are particularly preferable.
本発明の油性ゲル状クレンジングにおいて、1)多鎖多親水基型化合物の少なくとも1種が、分子内にアミノ酸残基を有する界面活性剤であることが、生分解性の点、皮膚のような外用剤などへ用いたときの低刺激性の点から好ましい。さらには、多鎖多親水基型化合物の少なくとも1種が上記一般式(1)および(2)で示されるアシル化合物であることが、さらに好ましい。ここでいうアシル化合物とは構造的には上記一般式(1)および(2)に示すように分子内に少なくとも1個以上のアシル基と親水基とを有する化合物を適当なスペーサーで連結した構造のものである。 In the oily gel cleansing of the present invention, it is 1) that at least one of the multi-chain polyhydrophilic group type compound is a surfactant having an amino acid residue in the molecule. It is preferable from the viewpoint of hypoallergenicity when used for external preparations. Furthermore, it is more preferable that at least one of the multi-chain polyhydrophilic group type compounds is an acyl compound represented by the above general formulas (1) and (2). The acyl compound here is structurally a structure in which a compound having at least one acyl group and a hydrophilic group in the molecule is connected by an appropriate spacer as shown in the general formulas (1) and (2). belongs to.
上記一般式(2)中、R1COで示される長鎖アシル基は独立して、すなわち、それぞれ異なっても同一でもよく、上記したように炭素原子数8〜20の飽和または不飽和の脂肪酸から誘導されるものであれば何でも良く、直鎖、分岐、環状を問わない。また、分子中のR1COは、同一であるのが反応条件等からみても好ましい。
上記一般式(2)中、R2は水素であるか、またはヒドロキシル基またはカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基またはそれらの塩等が置換していてもよい炭素原子数1〜3の低級アルキル基を示し、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシ(イソ)プロピル基、ジヒドロキシ(イソ)プロピル基、カルボキシメチル基、カルボキシエチル基、カルボキシプロピル基、スルホエチル基等が挙げられる。
上記一般式(1)中、Xに結合したn個の置換基Q(上記一般式(2))は、それぞれ互いに、異なっても同一でもよい。また、上記一般式(2)は、いわゆる酸性アミノ酸がN−アシル化されたものを示すものであり、それらは光学異性体例えばD−体、L−体、ラセミ体であるかは問わない。
In the general formula (2), the long-chain acyl group represented by R 1 CO may be independent, that is, each may be different or the same, and as described above, a saturated or unsaturated fatty acid having 8 to 20 carbon atoms. Any material can be used as long as it is derived from the straight chain, branched or cyclic. Further, R 1 CO in the molecule are the same is preferably be viewed such as the reaction conditions.
In the general formula (2), R 2 is hydrogen, or the number of carbon atoms that may be substituted by a hydroxyl group or a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof. 1 to 3 lower alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, hydroxymethyl group, hydroxyethyl group, hydroxy (iso) propyl group, dihydroxy (iso) propyl group, carboxymethyl group, A carboxyethyl group, a carboxypropyl group, a sulfoethyl group, etc. are mentioned.
In the general formula (1), n substituents Q bonded to X (the above general formula (2)) may be different from each other or the same. Moreover, the said General formula (2) shows what the so-called acidic amino acid was N-acylated, and it does not ask | require whether they are optical isomers, for example, D-form, L-form, and a racemate.
酸性アミノ酸は、分子中に存在するカルボキシル基とアミノ基の数がそれぞれ2個と1個のモノアミノジカルボン酸であり、アミノ基はN−メチル基またはN−エチル基でもかまわない。また光学異性体例えばD−体、L−体、ラセミ体であるかは問わない。酸性アミノ酸としては、例えばグルタミン酸、アスパラギン酸、ランチオニン、β−メチルランチオニン、シスタチオニン、ジエンコール酸、フェリニン、アミノマロン酸、β−オキシアスパラギン酸、α−アミノ−α−メチルコハク酸、β−オキシグルタミン酸、γ−オキシグルタミン酸、γ−メチルグルタミン酸、γ−メチレングルタミン酸、γ−メチル−γ−オキシグルタミン酸、α−アミノアジピン酸、α−アミノ−γ−オキシアジピン酸、α−アミノピメリン酸、α−アミノ−γ−オキシピメリン酸、β−アミノピメリン酸、α−アミノスベリン酸、α−アミノセバシン酸、パントテン酸等が挙げられる。
Xに付くn個の置換基(上記一般式(2))は、酸性アミノ酸がL−酸性アミノ酸分子である場合が、生分解性に優れることから好ましい。それらの中でも、置換基は同一である方が好ましい。
The acidic amino acid is a monoaminodicarboxylic acid having 2 and 1 carboxyl groups and 1 amino group, respectively, in the molecule, and the amino group may be an N-methyl group or an N-ethyl group. It does not matter whether it is an optical isomer, for example, a D-form, an L-form, or a racemate. Examples of acidic amino acids include glutamic acid, aspartic acid, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid, β-oxyglutamic acid. , Γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid, α-amino- Examples thereof include γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-aminosebacic acid, pantothenic acid and the like.
The n substituents (the above general formula (2)) attached to X are preferable because the acidic amino acid is an L-acidic amino acid molecule because it is excellent in biodegradability. Among these, it is preferable that the substituents are the same.
上記一般式(2)中、Zは、Xに置換したm個(m≧n、かつ、2〜20の整数)の官能基(ヒドロキシル基、アミノ基、チオール基)に由来する結合部(−O−、−NR3−、−S−)である。ここで、R3は水素、または炭素原子数1〜10のアルキル基またはアルケニル基またはアリール基またはアルキルアリール基である。
上記一般式(1)中、Xはヒドロキシル基、アミノ基、チオール基から選ばれる1種または2種以上からなるm個の官能基を有する分子量100万以下の直鎖または分枝鎖または環状鎖または芳香族炭化水素鎖であるスペーサーであり、Xは、前記ヒドロキシル基、アミノ基、チオール基以外の置換基を有していてもよい。
上記一般式(1)中、Xは好ましくはヒドロキシル基、アミノ基、チオール基から選ばれる1種または2種以上の官能基をm個有する分子量100万以下のm価の化合物の残基であって、ヒドロキシル基、アミノ基、チオール基以外の置換基を有していてもよい化合物残基である。ここで、m価の上記化合物は、m個の官能基に由来する結合を作りうることを意味する。それらは光学異性体例えばD−体、L−体、ラセミ体であるかは問わない。
In the above general formula (2), Z represents a bonding portion (-) derived from m functional groups (hydroxyl group, amino group, thiol group) substituted with X (m ≧ n and an integer of 2 to 20). O -, - NR 3 -, - it is S-). Here, R 3 is hydrogen, or an alkyl group, alkenyl group, aryl group or alkylaryl group having 1 to 10 carbon atoms.
In the general formula (1), X is a linear, branched or cyclic chain having a molecular weight of 1 million or less and having m functional groups consisting of one or more selected from a hydroxyl group, an amino group and a thiol group. Or it is a spacer which is an aromatic hydrocarbon chain | strand, and X may have substituents other than the said hydroxyl group, an amino group, and a thiol group.
In the general formula (1), X is preferably a residue of an m-valent compound having a molecular weight of 1 million or less and having m functional groups of one kind or two or more kinds selected from a hydroxyl group, an amino group and a thiol group. And a compound residue that may have a substituent other than a hydroxyl group, an amino group, and a thiol group. Here, the m-valent compound means that a bond derived from m functional groups can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.
このようなm価の化合物としては、例えば、セリン、トレオニン、システイン、シスチン、シスチンジスルホキシド、シスタチオニン、メチオニン、アルギニン、リジン、チロシン、ヒスチジン、トリプトファン、オキシプロリン等のアミノ酸類;
アミノエタノール、アミノプロパノール、アミノブタノール、アミノペンタノール、アミノヘキサノール、アミノプロパンジオール、アミノエチルエタノールアミン、アミノエチルアミノエタノール、アミノクレゾール、アミノナフトール、アミノナフトールスルホン酸、アミノヒドロキシ安息香酸、アミノヒドロキシブタン酸、アミノフェノール、アミノフェネチルアルコール、グルコサミン等の分子内にアミノ基とヒドロキシル基を有する化合物類;
Examples of such m-valent compounds include amino acids such as serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, and oxyproline;
Aminoethanol, aminopropanol, aminobutanol, aminopentanol, aminohexanol, aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, aminonaphtholsulfonic acid, aminohydroxybenzoic acid, aminohydroxybutanoic acid Compounds having an amino group and a hydroxyl group in the molecule such as aminophenol, aminophenethyl alcohol, glucosamine;
メルカプトエタノール、メルカプトフェノール、メルカプトプロパンジオール、グルコチオース等の分子内にチオール基とヒドロキシル基を有する化合物類;
アミノチオフェノール、アミノトリアゾールチオール等の分子内にチオール基とアミノ基を有する化合物類;
が挙げられる。また、タンパク質やペプチド等、またはそれらを加水分解したもの等でも良い。
Compounds having a thiol group and a hydroxyl group in the molecule such as mercaptoethanol, mercaptophenol, mercaptopropanediol, glucothiose;
Compounds having a thiol group and an amino group in the molecule such as aminothiophenol and aminotriazole thiol;
Is mentioned. Further, proteins, peptides, etc., or those obtained by hydrolyzing them may be used.
また、上記一般式(1)中、Xは好ましくはヒドロキシル基以外の置換基を有していてもよい分子量100万以下のm価(m≧n)のポリヒドロキシル化合物残基である。ここで、m価のポリヒドロキシル化合物は、m個のエステル結合を作りうることを意味する。それらは光学異性体例えばD−体、L−体、ラセミ体であるかは問わない。
このようなm価のポリヒドロキシル化合物としては、例えばエチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、ペンタンジオール、1,6−ヘキサンジオール、シクロヘキサンジオール、ジメチロールシクロヘキサン、ネオペンチルグリコール、1,8−オクタンジオール、
2,2,4−トリメチル−1,3−ペンタンジオール、イソプレングリコール、3−メチル−1,5−ペンタンジオール、ソルバイト、カテコール、レゾルシン、ヒドロキノン、ビスフェノールA、ビスフェノールF、水添ビスフェノールA、水添ビスフェノールF、
In the general formula (1), X is preferably an m-valent (m ≧ n) polyhydroxyl compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a hydroxyl group. Here, the m-valent polyhydroxyl compound means that m ester bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.
Examples of such m-valent polyhydroxyl compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , Pentanediol, 1,6-hexanediol, cyclohexanediol, dimethylolcyclohexane, neopentyl glycol, 1,8-octanediol,
2,2,4-trimethyl-1,3-pentanediol, isoprene glycol, 3-methyl-1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated Bisphenol F,
ダイマージオール、ジメチロールプロピオン酸、ジメチロールブタン酸、酒石酸、ジヒドロキシ酒石酸、メバロン酸、3,4−ジヒドロキシけい皮酸、3,4−ジヒドロキシヒドロけい皮酸、ヒドロキシ安息香酸、ジヒドロキシステアリン酸、ジヒドロキシフェニルアラニン等およびこれらの各異性体等の2価ヒドロキシル化合物;
グリセリン、トリオキシイソブタン、1,2,3−ブタントリオール、1,2,3−ペンタントリオール、2−メチル−1,2,3−プロパントリオール、2−メチル−2,3,4−ブタントリオール、2−エチル−1,2,3−ブタントリオール、2,3,4−ペンタントリオール、
Dimerdiol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, dihydroxytartaric acid, mevalonic acid, 3,4-dihydroxycinnamic acid, 3,4-dihydroxyhydrocinnamic acid, hydroxybenzoic acid, dihydroxystearic acid, dihydroxyphenylalanine And divalent hydroxyl compounds such as each of these isomers;
Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol,
2,3,4−ヘキサントリオール、4−プロピル−3,4,5−ヘプタントリオール、2,4−ジメチル−2,3,4−ペンタントリオール、1,2,4−ブタントリオール、1,2,4−ペンタントリオール、トリメチロールエタン、トリメチロールプロパン、ジエタノールアミン、トリエタノールアミン、トリヒドロキシステアリン酸等の3価ポリヒドロキシル化合物;
ペンタエリスリトール、エリスリトール、1,2,3,4−ペンタンテトロール、2,3,4,5−ヘキサンテトロール、1,2,4,5−ペンタンテトロール、1,3,4,5−ヘキサンテトロール、ジグリセリン、ソルビタン等の4価ポリヒドロキシル化合物;
アドニトール、アラビトール、キシリトール、トリグリセリン等の5価ポリヒドロキシル化合物;
ジペンタエリスリトール、ソルビトール、マンニトール、イジトール、イノシトール、ダルシトール、タロース、アロース等の6価ポリヒドロキシル化合物;
またはこれらの脱水縮合物、ポリグリセリン等が挙げられる。
2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2, Trivalent polyhydroxyl compounds such as 4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine, trihydroxystearic acid;
Pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexane Tetravalent polyhydroxyl compounds such as tetrol, diglycerin and sorbitan;
Pentavalent polyhydroxyl compounds such as adonitol, arabitol, xylitol, triglycerin;
Hexavalent polyhydroxyl compounds such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose;
Or these dehydration condensates, polyglycerol, etc. are mentioned.
また、糖類、例えばエリスロース、スレオース、エリスルロース等のテトロース;
リボース、アラビノース、キシロース、リクソース、キシルロース、リブロース等のペントース;アロース、アルトロース、グルコース、マンノース、ギューロース、イドース、ガラクトース、タロース、フラクトース、ソルボース、プシコース、タガトース等のヘキソース等の単糖類;
マルトース、イソマルトース、セロビオース、ゲンチオビオース、メリビオース、ラク
トース、ツラノース、トレハロース、サッカロース、マンニトリオース、セロトリオース、ゲンチアノース、ラフィノース、メレチトース、セロテトロース、スタキオース等のオリゴ糖類が挙げられる。
Sugars such as tetroses such as erythrose, sreose, erythrulose;
Pentose such as ribose, arabinose, xylose, lyxose, xylulose, ribulose; monosaccharides such as hexose such as allose, altrose, glucose, mannose, guylose, idose, galactose, talose, fructose, sorbose, psicose, tagatose;
Examples thereof include oligosaccharides such as maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, tulanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meletitose, cellotetorose, stachyose and the like.
また、その他の糖類、例えばヘプトース、デオキシ糖、アミノ糖、チオ糖、セレノ糖、アルドン糖、ウロン酸、糖酸、ケトアルドン酸、アンヒドロ糖、不飽和糖、糖エステル、糖エーテル、グリコシド等の残基でもよく、デンプン、グリコーゲン、セルロース、キチン、キトサン等の多糖類またはそれらを加水分解したものでもよい。
また、上記一般式(1)中、Xは好ましくはアミノ基以外の置換基を有していてもよい分子量100万以下のm価のポリアミノ化合物残基である。ここで、m価のポリアミノ化合物は、m個の酸アミド結合を作りうることを意味する。それらは光学異性体例えばD−体、L−体、ラセミ体であるかは問わない。
In addition, other saccharides such as heptose, deoxy sugar, amino sugar, thio sugar, seleno sugar, aldone sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether, glycoside, etc. It may be a group, and may be a polysaccharide such as starch, glycogen, cellulose, chitin, chitosan or the like, or a hydrolyzed product thereof.
In the general formula (1), X is preferably an m-valent polyamino compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than an amino group. Here, the m-valent polyamino compound means that m acid amide bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.
このようなm価のポリアミノ化合物としては、例えばN,N’−ジメチルヒドラジン、エチレンジアミン、N,N’−ジメチルエチレンジアミン、ジアミノプロパン、ジアミノブタン、ジアミノペンタン、ジアミノヘキサン、ジアミノヘプタン、ジアミノオクタン、ジアミノノナン、ジアミノデカン、ジアミノドデカン、ジアミノアジピン酸、ジアミノプロパン酸、ジアミノブタン酸およびこれらの各異性体等の脂肪族ジアミン類;
ジエチレントリアミン、トリアミノヘキサン、トリアミノドデカン、1,8−ジアミノ−4−アミノメチル−オクタン、2,6−ジアミノカプリン酸−2−アミノエチルエステル、1,3,6−トリアミノヘキサン、1,6,11−トリアミノウンデカン、ジ(アミノエチル)アミンおよびこれらの各異性体等の脂肪族トリアミン類;
Examples of such m-valent polyamino compounds include N, N′-dimethylhydrazine, ethylenediamine, N, N′-dimethylethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, Aliphatic diamines such as diaminodecane, diaminododecane, diaminoadipic acid, diaminopropanoic acid, diaminobutanoic acid and their isomers;
Diethylenetriamine, triaminohexane, triaminododecane, 1,8-diamino-4-aminomethyl-octane, 2,6-diaminocapric acid-2-aminoethyl ester, 1,3,6-triaminohexane, 1,6 , 11-triaminoundecane, aliphatic triamines such as di (aminoethyl) amine and isomers thereof;
ジアミノシクロブタン、ジアミノシクロヘキサン、3−アミノメチル−3,5,5−トリメチルシクロヘキシルアミン、トリアミノシクロヘキサン等の脂環族ポリアミン類;
ジアミノベンゼン、ジアミノトルエン、ジアミノ安息香酸、ジアミノアントラキノン、ジアミノベンゼンスルホン酸、ジアミノ安息香酸、およびこれらの各異性体等の芳香族ポリアミン類;
ジアミノキシレン、ジ(アミノメチル)ベンゼン、ジ(アミノメチル)ピリジン、ジ(アミノメチル)ナフタレン、およびこれらの各異性体等の芳香脂肪族ポリアミン類;
ジアミノヒドロキシプロパンおよびこれらの各異性体等のヒドロキシル基が置換したポリアミン類等が挙げられる。
Alicyclic polyamines such as diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, triaminocyclohexane;
Aromatic polyamines such as diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, diaminobenzenesulfonic acid, diaminobenzoic acid, and their respective isomers;
Araliphatic polyamines such as diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, di (aminomethyl) naphthalene, and their isomers;
And polyamines substituted with hydroxyl groups such as diaminohydroxypropane and isomers thereof.
また、上記一般式(1)中、Xは好ましくはチオール基以外の置換基を有していてもよい分子量100万以下のm価のポリチオール化合物残基である。ここで、m価のポリチオール化合物は、m個のチオエステル結合を作りうることを意味する。それらは光学異性体例えばD−体、L−体、ラセミ体であるかは問わない。
このようなm価のポリチオール化合物としては、例えば、ジチオエチレングリコール、ジチオエリトリトール、ジチオトレイトール等のジチオール化合物類等が挙げられる。
Xは上に挙げた化合物の残基の中でも、炭素数1〜40の場合が好ましい、さらに好ましくはXは炭素数1〜20である。また、Xは天然に存在する型である場合の方が、生分解性に優れるという点で好ましい。
In the general formula (1), X is preferably an m-valent polythiol compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a thiol group. Here, the m-valent polythiol compound means that m thioester bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.
Examples of such m-valent polythiol compounds include dithiol compounds such as dithioethylene glycol, dithioerythritol, and dithiothreitol.
X is preferably a group having 1 to 40 carbon atoms among the residues of the compounds listed above, and more preferably X has 1 to 20 carbon atoms. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.
上記一般式(2)中、Yで示されるカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基およびX中に含まれうるカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基等は、種々の塩基性物質との間に塩を形成し得る。
かかる塩としては、例えばアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、有機アミン塩、塩基性アミノ酸塩、多価金属塩等が挙げられ、具体的には、ナトリウム、カリウム、リチウム等のアルカリ金属、カルシウム、マグネシウム等のアルカリ土類金属、アルミニウム、亜鉛、鉄、コバルト、チタン、ジルコニウム等の金属、アンモニア、モノ
エタノールアミン、ジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミン等の有機アミン、アルギニン、リジン等の塩基性アミノ酸等から任意に選ばれる1種または2種以上との塩である。
In the general formula (2), a carboxyl group represented by Y, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group, and a carboxyl group, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group, etc. that can be contained in X Can form salts with various basic substances.
Examples of such salts include alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, basic amino acid salts, polyvalent metal salts, and the like, specifically, alkalis such as sodium, potassium, and lithium. Metals, alkaline earth metals such as calcium and magnesium, metals such as aluminum, zinc, iron, cobalt, titanium and zirconium, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, arginine and lysine Or a salt with one or more kinds selected arbitrarily from basic amino acids and the like.
このような上記一般式(1)および(2)で示されるアシル化合物の製造方法としては、下記一般式(3)で示されるN−アシル酸性アミノ酸無水物と分子内にヒドロキシル基、アミノ基、チオール基から選ばれる1種または2種以上のm個の官能基を有する化合物とを、水および/または水と有機溶媒との混合溶媒中で反応させることによって、またはテトラヒドロフラン、ベンゼン、トルエン、キシレン、四塩化炭素、クロロホルム、アセトン等の不活性溶媒を使用して、あるいは無溶媒で−5℃〜200℃でいずれかの融点以上の温度で混合して反応することで得ることができる。 As a method for producing the acyl compounds represented by the above general formulas (1) and (2), an N-acyl acidic amino acid anhydride represented by the following general formula (3) and a hydroxyl group, an amino group, By reacting a compound having one or more kinds of m functional groups selected from thiol groups in water and / or a mixed solvent of water and an organic solvent, or tetrahydrofuran, benzene, toluene, xylene It can be obtained by using an inert solvent such as carbon tetrachloride, chloroform or acetone, or by mixing and reacting at −5 ° C. to 200 ° C. at a temperature equal to or higher than any melting point without solvent.
または上記一般式(1)および(2)で示されるアシル化合物は、N−アシル酸性アミノ酸モノ低級エステル(例えば、メチルエステル、エチルエステル)とポリヒドロキシル化合物またはポリアミノ化合物またはポリチオール化合物、または分子内にヒドロキシル基、アミノ基、チオール基のうちいずれか2種または3種を有する化合物とをジメチルホルムアミド等の適当な溶媒中に溶解し、炭酸カリウム等の触媒を加え、減圧下に−5℃〜250℃で加熱反応させた後反応溶媒を除去することで得ることができる。あるいは、無溶媒で加熱溶融し、水酸化ナトリウム等の触媒を加えて室温〜250℃でエステル交換反応させてアシル化合物を得ることができる。
本発明の油性ゲル状クレンジングにおいて、この中に含まれる4)ノニオン性界面活性剤のHLBは2〜14であって、好ましくは、HLBが5〜12である。さらに好ましくは、HLBが7〜11である。ここで、HLBがこの範囲外であってもゲル状の剤型になることはあるが、油性成分が分離して安定性に乏しかったり、残油感があったりし、使用感が好ましくなくなることがある。
Alternatively, the acyl compounds represented by the above general formulas (1) and (2) are an N-acyl acidic amino acid mono-lower ester (for example, methyl ester, ethyl ester) and a polyhydroxyl compound, a polyamino compound, a polythiol compound, or a molecule. A compound having any two or three of hydroxyl group, amino group, and thiol group is dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and -5 ° C to 250 ° C under reduced pressure. It can be obtained by carrying out a heating reaction at 0 ° C. and then removing the reaction solvent. Alternatively, the acyl compound can be obtained by melting with heating without a solvent, adding a catalyst such as sodium hydroxide, and performing a transesterification reaction at room temperature to 250 ° C.
In the oily gel cleansing of the present invention, the HLB of 4) nonionic surfactant contained therein is 2 to 14, and preferably 5 to 12. More preferably, HLB is 7-11. Here, even if the HLB is out of this range, it may become a gel-like dosage form, but the oily component is separated and the stability is poor, there is a feeling of residual oil, and the feeling of use becomes unfavorable. There is.
ノニオン性界面活性剤としては、例えば、ソルビタン脂肪酸エステル類;
ソルビタンモノラウレート、ソルビタンモノミリステート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノイソステアレート、ソルビタンモノオレエート、ソルビタンセキスオレエート、ソルビタントリオレエート、ペンタ−2−エチルヘキシル酸ジグリセロールソルビタン、テトラ−2−エチルヘキシル酸ジグリセロールソルビタン等、
グリセリンまたはポリグリセリン脂肪酸エステル類;
モノラウリン酸グリセリル、モノミリスチン酸グリセリル、モノパルミチン酸グリセリル、モノイソステアリン酸グリセリル、モノステアリン酸グリセリル、モノ綿実油脂肪酸グリセリル、モノエルカ酸グリセリル、セスキオレイン酸グリセリル、α,α‘−オレイン酸ピログルタミン酸グリセリル、セスキカプリル酸ポリグリセリル、ジオレイン酸ポリグリセリル等、
Examples of nonionic surfactants include sorbitan fatty acid esters;
Sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, Tetra-2-ethylhexyl diglycerol sorbitan, etc.
Glycerin or polyglycerin fatty acid esters;
Glyceryl monolaurate, glyceryl monomyristate, glyceryl monopalmitate, glyceryl monoisostearate, glyceryl monostearate, mono-seed oil fatty acid glyceryl, glyceryl monoerucate, glyceryl sesquioleate, glyceryl α, α'-pyroglutamate oleate, sesqui Polyglyceryl caprylate, polyglyceryl dioleate, etc.
プロピレングリコール脂肪酸エステル類;
モノラウリン酸プロピレングリコール、モノミリスチン酸プロピレングリコール、モノパルミチン酸プロピレングリコール、モノイソステアリン酸プロピレングリコール、モノステアリン酸プロピレングリコール等
硬化ヒマシ油誘導体類、グリセリンアルキルエーテル類、
POE−ソルビタン脂肪酸エステル類;
POE−ソルビタンモノステアレート、POE−ソルビタンモノイソステアレート、POE−ソルビタンモノオレエート、POE−ソルビタンテトラオレエート等、
POEソルビット脂肪酸エステル類;
POE−ソルビットモノラウレート、POE−ソルビットモノミリステート、POE−ソルビットモノパルミテート、POE−ソルビットモノステアレート、POE−ソルビットモノイソステアレート、POE−モノオレエート、POE−ソルビットペンタオレエート等、
Propylene glycol fatty acid esters;
Hardened castor oil derivatives such as propylene glycol monolaurate, propylene glycol monomyristate, propylene glycol monopalmitate, propylene glycol monoisostearate, propylene glycol monostearate, glycerin alkyl ethers,
POE-sorbitan fatty acid esters;
POE-sorbitan monostearate, POE-sorbitan monoisostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.
POE sorbite fatty acid esters;
POE-sorbite monolaurate, POE-sorbite monomyristate, POE-sorbite monopalmitate, POE-sorbite monostearate, POE-sorbite monoisostearate, POE-monooleate, POE-sorbite pentaoleate, etc.
POE−グリセリン脂肪酸エステル類;
POE−グリセリンモノステアレート、POE−グリセリンモノイソステアレート、POE−グリセリントリイソステアレート、POE−グリセリンモノオレエート等、
POE−脂肪酸エステル類;
POE−ジステアレート、POE−ジイソステアレート、POE−ジオレエート、ジステアリン酸エチレングリコール等、
POE−アルキルエーテル類;
POE−ラウリルエーテル、POE−ミリストイルエーテル、POE−パルミトイルエーテル、POE−ステアリルエーテル、POE−イソステアリルエーテル、POE−オレイルエーテル、POE−ベヘニルエーテル、POE−2−オクチルドデシルエーテル、POE−コレスタノールエーテル等、
POE-glycerin fatty acid esters;
POE-glycerol monostearate, POE-glycerol monoisostearate, POE-glycerol triisostearate, POE-glycerol monooleate, etc.
POE-fatty acid esters;
POE-distearate, POE-diisostearate, POE-diolate, ethylene glycol distearate, etc.
POE-alkyl ethers;
POE-lauryl ether, POE-myristoyl ether, POE-palmitoyl ether, POE-stearyl ether, POE-isostearyl ether, POE-oleyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc. ,
POE・POP−アルキルエーテル類;
POE・POP−セチルエーテル、POE・POP−2−デシルテトラデシルエーテル、POE・POP−モノブチルエーテル、POE・POP−水添ラノリン、POE・POP−グリセリンエーテル等、
POE−ヒマシ油または硬化ヒマシ油誘導体類;
POE−ヒマシ油、POE−硬化ヒマシ油、POE−硬化ヒマシ油モノイソステアレート、POE−硬化ヒマシ油トリイソステアレート、POE−硬化ヒマシ油モノピログルタミン酸モノイソステアリン酸ジエステル、POE−硬化ヒマシ油マレイン酸等、
POE−ミツロウ・ラノリン誘導体類;
POE−ソルビットミツロウ等、
POE / POP-alkyl ethers;
POE · POP-cetyl ether, POE · POP-2-decyltetradecyl ether, POE · POP-monobutyl ether, POE · POP-hydrogenated lanolin, POE · POP-glycerin ether, etc.
POE-castor oil or hydrogenated castor oil derivatives;
POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor oil malee Acids, etc.
POE-beeswax lanolin derivatives;
POE-Sorbit beeswax, etc.
アルカノールアミド類;
ヤシ油脂肪酸ジエタノールアミド、ラウリン酸モノエタノールアミド、脂肪酸イソプロパノールアミド等、
POE−プロピレングリコール脂肪酸エステル類、POE−アルキルアミン類、POE−脂肪酸アミド類、ショ糖脂肪酸エステル類、アルキルエトキシジメチルアミンオキシド類、トリオレイルリン酸類、ポリオキシエチレン・メチルポリシロキサン共重合体類、ポリ(オキシエチレン・オキシプロピレン)メチルポリシロキサン共重合体類、ポリオキシアルキレン・アルコキシ変性メチルポリシロキサン共重合体類、ジメチルポリシロキサンポリエチレングリコール共重合体類、ポリ(オキシエチレン・オキシプロピレン)ジメチルポリシロキサン共重合体類等が挙げられる。
Alkanolamides;
Coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.
POE-propylene glycol fatty acid esters, POE-alkylamines, POE-fatty acid amides, sucrose fatty acid esters, alkylethoxydimethylamine oxides, trioleyl phosphates, polyoxyethylene / methylpolysiloxane copolymers, Poly (oxyethylene / oxypropylene) methylpolysiloxane copolymers, polyoxyalkylene / alkoxy-modified methylpolysiloxane copolymers, dimethylpolysiloxane polyethylene glycol copolymers, poly (oxyethylene / oxypropylene) dimethylpoly Examples thereof include siloxane copolymers.
中でも、ポリグリセリン脂肪酸エステルを用いた場合にジェルの水溶性を調整することが可能であり有効である。
特に、該ノニオン性界面活性剤の脂肪酸部分は、炭素数が10以下の中鎖脂肪酸を疎水
基とする場合には、手が濡れている場合や浴室内のような多湿な環境においてもゲル状が直ちに破れることなく使用できる耐水性の油性ゲル状クレンジングを得ることができるので好ましく、さらにその効果は、該ノニオン性界面活性剤の疎水基がカプリル酸である場合に高く、わけても該ノニオン性界面活性剤の疎水基がカプリル酸であるものを該ノニオン性界面活性剤の疎水基がオレイン酸であるものと併用した時に最適の使用感が得られる。
該ノニオン性界面活性剤のポリグリセリン部分の内、グリセリン残基は2以上30以下の数を取りうるが、2以上15以下の時により好適であり、2以上7以下である時に最適の使用感が得られる。
Among these, when a polyglycerol fatty acid ester is used, it is possible and effective to adjust the water solubility of the gel.
In particular, the fatty acid portion of the nonionic surfactant has a gel-like state even when the hand is wet or in a humid environment such as in a bathroom when a medium chain fatty acid having 10 or less carbon atoms is used as a hydrophobic group. It is preferable because a water-resistant oily gel cleansing that can be used without being immediately broken can be obtained, and the effect is high when the hydrophobic group of the nonionic surfactant is caprylic acid, especially the nonionic interface. When the hydrophobic group of the activator is caprylic acid and the hydrophobic group of the nonionic surfactant is combined with oleic acid, an optimal feeling of use can be obtained.
Of the polyglycerin moiety of the nonionic surfactant, the number of glycerin residues can be 2 or more and 30 or less, but it is more suitable when it is 2 or more and 15 or less, and optimal feeling when it is 2 or more and 7 or less. Is obtained.
また、該ノニオン性界面活性剤のエステル化度は本願発明のHLB範囲を満たす範囲で任意の値を取る事が可能であるが、5%以上90%以下の範囲で特に明瞭な効果が認められ、7%以上75%以下の範囲で顕著な効果が認められる。中でも10%以上50%以下の範囲である時にその効果は最大となる。このような条件を満たす物としては、たとえば、ジカプリル酸ポリグリセリル−6(HLB=13)、トリカプリル酸ポリグリセリル−6(HLB=11)、テトラカプリル酸ポリグリセリル−6(HLB=9)などを挙げる事が出来る。
該ノニオン性界面活性剤の配合量は1質量%以上90質量%以下の値を取りうるが、該ノニオン性界面活性剤の配合量が多いと、併用する油性成分の量に制約が生じるため、これを確保するためには60質量%以下であることが好ましく、他の成分をも配合するためには30質量%以下とする事が望ましい。また、組成物に実用上十分な耐水性を付与するためには5質量%以上配合する事が望ましく、10質量%以上配合することにより最適の耐水性が得られる。
The degree of esterification of the nonionic surfactant can take any value within the range satisfying the HLB range of the present invention, but a particularly clear effect is recognized within the range of 5% to 90%. In the range of 7% to 75%, a remarkable effect is recognized. In particular, the effect is maximized when it is in the range of 10% to 50%. Examples of those satisfying such conditions include polyglyceryl-6 dicaprylate (HLB = 13), polyglyceryl-6 tricaprylate (HLB = 11), polyglyceryl-6 tetracaprylate (HLB = 9), and the like. I can do it.
The blending amount of the nonionic surfactant can take a value of 1% by mass or more and 90% by mass or less, but if the blending amount of the nonionic surfactant is large, the amount of the oily component used in combination is limited. In order to ensure this, the amount is preferably 60% by mass or less, and in order to mix other components, it is preferably 30% by mass or less. Further, in order to impart practically sufficient water resistance to the composition, it is desirable to blend 5% by mass or more, and by blending 10% by mass or more, optimum water resistance can be obtained.
本発明の油性ゲル状クレンジングにおいて、その他の界面活性剤として、1)多鎖多親水基型化合物以外にも、本発明の目的が損なわれない限り、その他の界面活性剤を含むことができる。こうした界面活性剤としては、例えば、分子内に長鎖疎水基および/または親水基が1個である構造のアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤等である。中でも該水溶液中にアニオン性界面活性剤としてN−長鎖アシルアミノ酸型界面活性剤またはアシルペプチド型界面活性剤を含有したものが好ましい。 In the oil-based gel cleansing of the present invention, other surfactants can be included as other surfactants in addition to 1) a multi-chain polyhydrophilic group type compound as long as the object of the present invention is not impaired. Examples of such surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants having a structure having one long-chain hydrophobic group and / or one hydrophilic group in the molecule. Etc. Among them, those containing an N-long chain acylamino acid type surfactant or an acyl peptide type surfactant as an anionic surfactant in the aqueous solution are preferable.
ここでいうN−長鎖アシルアミノ酸とは、アミノ酸のアミノ基に、炭素数8〜20の飽和または不飽和の脂肪酸から誘導されるアシル基を導入したものである。N−長鎖アシルアミノ酸中のアミノ酸残基はα−アミノ酸、β−アミノ酸、γ−アミノ酸やω−アミノ酸等各種アミノ酸であり、アミノ基はN−メチル体、N−エチル体であってもかまわない。また光学異性体すなわちD−体、L−体、ラセミ体であるかは問わない。
例えば、グルタミン酸、アスパラギン酸、グリシン、アラニン、バリイン、ロイシン、イソロイシン、セリン、トレオニン、システイン、シスチン、メチオニン、リジン、アルギニン、フェニルアラニン、チロシン、ヒスチジン、トリプトファン、プロリン、オキシプロリン、ランチオニン、β−メチルランチオニン、シスタチオニン、ジエンコール酸、フェリニン、アミノマロン酸、β−オキシアスパラギン酸、α−アミノ−α−メチルコハク酸、β−オキシグルタミン酸、γ−オキシグルタミン酸、γ−メチルグルタミン酸、γ−メチレングルタミン酸、γ−メチル−γ−オキシグルタミン酸、α−アミノアジピン酸、α,α’−ジアミノアジピン酸、β,β’−ジアミノアジピン酸、α−アミノ−γ−オキシアジピン酸、α−アミノピメリン酸、α−アミノ−γ−オキシピメリン酸、β−アミノピメリン酸、α−アミノスベリン酸、α−アミノセバシン酸、パントテン酸、サルコシン、タウリン、メチルタウリン等である。
The N-long chain acylamino acid herein is one in which an acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms is introduced into the amino group of the amino acid. The amino acid residues in N-long chain acylamino acids are various amino acids such as α-amino acid, β-amino acid, γ-amino acid and ω-amino acid, and the amino group may be N-methyl or N-ethyl. Absent. It does not matter whether it is an optical isomer, that is, a D-form, an L-form, or a racemate.
For example, glutamic acid, aspartic acid, glycine, alanine, valin, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, proline, oxyproline, lanthionine, β-methyllunch Onine, cystathionine, dienecholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid, β-oxyglutamic acid, γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ -Methyl-γ-oxyglutamic acid, α-aminoadipic acid, α, α'-diaminoadipic acid, β, β'-diaminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid, α-amino Mino-γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-aminosebacic acid, pantothenic acid, sarcosine, taurine, methyltaurine and the like.
アシル基としては、炭素原子数8〜20の飽和または不飽和の脂肪酸から誘導されるも
のであれば何でも良く、直鎖、分岐、環状を問わない。N−長鎖アシルアミノ酸がN−長鎖アシル−L−アミノ酸であることが生分解性の点から好ましい。
また、ここでいうアシルペプチドとは、タンパク質を加水分解した後、アシル化して得られるものである。
特にアシルアミノ酸型界面活性剤を混合した場合には、ゲル形成に必要な1)多鎖多親水基型化合物の添加量を少なくすることができ、また生成ゲルの延びを良くすることができ、この点において好ましい。
Any acyl group may be used as long as it is derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms, and may be linear, branched or cyclic. From the viewpoint of biodegradability, the N-long chain acylamino acid is preferably an N-long chain acyl-L-amino acid.
The acyl peptide referred to here is obtained by hydrolyzing a protein and then acylating.
In particular, when an acylamino acid type surfactant is mixed, the amount of addition of 1) multi-chain polyhydrophilic group type compound necessary for gel formation can be reduced, and the extension of the generated gel can be improved. This is preferable.
本発明の油性ゲル状クレンジングにおいて、2)分子内に水酸基を2個以上有するポリヒドロキシル化合物としては、例えばエチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、ペンタンジオール、1,6−ヘキサンジオール、シクロヘキサンジオール、ジメチロールシクロヘキサン、ネオペンチルグリコール、1,8−オクタンジオール、
2,2,4−トリメチル−1,3−ペンタンジオール、イソプレングリコール、3−メチル−1,5−ペンタンジオール、ソルバイト、カテコール、レゾルシン、ヒドロキノン、ビスフェノールA、ビスフェノールF、水添ビスフェノールA、水添ビスフェノールF、
In the oily gel cleansing of the present invention, 2) Examples of polyhydroxyl compounds having two or more hydroxyl groups in the molecule include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, cyclohexanediol, dimethylolcyclohexane, neopentylglycol, 1,8-octanediol,
2,2,4-trimethyl-1,3-pentanediol, isoprene glycol, 3-methyl-1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated Bisphenol F,
ダイマージオール、ジメチロールプロピオン酸、ジメチロールブタン酸、酒石酸、ジヒドロキシ酒石酸、メバロン酸、3,4−ジヒドロキシけい皮酸、3,4−ジヒドロキシヒドロけい皮酸、ヒドロキシ安息香酸、ジヒドロキシステアリン酸、ジヒドロキシフェニルアラニン等およびこれらの各異性体等の2価ヒドロキシル化合物;
グリセリン、トリオキシイソブタン、1,2,3−ブタントリオール、1,2,3−ペンタントリオール、2−メチル−1,2,3−プロパントリオール、2−メチル−2,3,4−ブタントリオール、2−エチル−1,2,3−ブタントリオール、2,3,4−ペンタントリオール、
Dimerdiol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, dihydroxytartaric acid, mevalonic acid, 3,4-dihydroxycinnamic acid, 3,4-dihydroxyhydrocinnamic acid, hydroxybenzoic acid, dihydroxystearic acid, dihydroxyphenylalanine And divalent hydroxyl compounds such as each of these isomers;
Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol,
2,3,4−ヘキサントリオール、4−プロピル−3,4,5−ヘプタントリオール、2,4−ジメチル−2,3,4−ペンタントリオール、1,2,4−ブタントリオール、1,2,4−ペンタントリオール、トリメチロールエタン、トリメチロールプロパン、ジエタノールアミン、トリエタノールアミン、トリヒドロキシステアリン酸等の3価ポリヒドロキシル化合物;
ペンタエリスリトール、エリスリトール、1,2,3,4−ペンタンテトロール、2,3,4,5−ヘキサンテトロール、1,2,4,5−ペンタンテトロール、1,3,4,5−ヘキサンテトロール、ジグリセリン、ソルビタン等の4価ポリヒドロキシル化合物;
アドニトール、アラビトール、キシリトール、トリグリセリン等の5価ポリヒドロキシル化合物;
ジペンタエリスリトール、ソルビトール、マンニトール、イジトール、イノシトール、ダルシトール、タロース、アロース等の6価ポリヒドロキシル化合物;
またはこれらの脱水縮合物、ポリグリセリン等が挙げられる。
2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2, Trivalent polyhydroxyl compounds such as 4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine, trihydroxystearic acid;
Pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexane Tetravalent polyhydroxyl compounds such as tetrol, diglycerin and sorbitan;
Pentavalent polyhydroxyl compounds such as adonitol, arabitol, xylitol, triglycerin;
Hexavalent polyhydroxyl compounds such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose;
Or these dehydration condensates, polyglycerol, etc. are mentioned.
また、糖類、例えばエリスロース、スレオース、エリスルロース等のテトロース;
リボース、アラビノース、キシロース、リクソース、キシルロース、リブロース等のペントース;アロース、アルトロース、グルコース、マンノース、ギューロース、イドース、ガラクトース、タロース、フラクトース、ソルボース、プシコース、タガトース等のヘキソース等の単糖類;
マルトース、イソマルトース、セロビオース、ゲンチオビオース、メリビオース、ラクトース、ツラノース、トレハロース、サッカロース、マンニトリオース、セロトリオース、ゲンチアノース、ラフィノース、メレチトース、セロテトロース、スタキオース等のオ
リゴ糖類が挙げられる。
Sugars such as tetroses such as erythrose, sreose, erythrulose;
Pentose such as ribose, arabinose, xylose, lyxose, xylulose, ribulose; monosaccharides such as hexose such as allose, altrose, glucose, mannose, guylose, idose, galactose, talose, fructose, sorbose, psicose, tagatose;
Examples thereof include oligosaccharides such as maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, tulanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meletitose, cellotetorose, stachyose and the like.
また、その他の糖類、例えばヘプトース、デオキシ糖、アミノ糖、チオ糖、セレノ糖、アルドン糖、ウロン酸、糖酸、ケトアルドン酸、アンヒドロ糖、不飽和糖、糖エステル、糖エーテル、グリコシド等の残基でもよく、デンプン、グリコーゲン、セルロース、キチン、キトサン等の多糖類またはそれらを加水分解したものでもよい。これらポリヒドロキシル化合物は2種以上組み合わせて用いても良い。ポリヒドロキシル化合物として好ましくは、3価以上のポリヒドロキシル化合物がよい。 In addition, other saccharides such as heptose, deoxy sugar, amino sugar, thio sugar, seleno sugar, aldone sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether, glycoside, etc. It may be a group, and may be a polysaccharide such as starch, glycogen, cellulose, chitin, chitosan or the like, or a hydrolyzed product thereof. Two or more of these polyhydroxyl compounds may be used in combination. The polyhydroxyl compound is preferably a trihydroxy or higher polyhydroxyl compound.
本発明の油性ゲル状クレンジングにおいて、3)油性成分としては、液状油または固体脂のいずれをも使用することができ、化粧料や外用の医薬品などの成分として慣用されている油性成分でもよい。
アボガド油、タートル油、トウモロコシ油、アーモンド油、オリーブ油、カカオ油、ゴマ油、サフラワー油、大豆油、ツバキ油、パーシック油、ひまし油、ぶどう種子油、マカデミアナッツ油、ミンク油、綿実油、モクロウ、ヤシ油、卵黄油、パーム油、パーム核油、トリイソオクタン酸グリセリン、トリ2−エチルヘキサン酸グリセリルコレステロール脂肪酸エステル、小麦胚芽油、サザンカ油、アマニ油、月見草油、エノ油、落花生油、茶実油、カヤ油、コメヌカ油、シナギル油、日本キリ油、ホホバ油、胚芽油、トリオクタン酸グリセリン、トリイソパルミチン酸グリセリン、馬油、硬化やし油、牛脂、牛脚脂、羊脂、硬化牛脂、豚脂、牛骨脂、モクロウ核油、硬化油、モクロウ、硬化ひまし油等の油脂、;
In the oily gel cleansing of the present invention, 3) As the oily component, either liquid oil or solid fat can be used, and an oily component commonly used as a component of cosmetics, external medicines and the like may be used.
Avocado oil, turtle oil, corn oil, almond oil, olive oil, cacao oil, sesame oil, safflower oil, soybean oil, camellia oil, persic oil, castor oil, vine seed oil, macadamia nut oil, mink oil, cottonseed oil, molasses, palm oil , Egg yolk oil, palm oil, palm kernel oil, glyceryl triisooctanoate, glyceryl tri-2-ethylhexanoate, wheat germ oil, sasanqua oil, flaxseed oil, evening primrose oil, eno oil, peanut oil, tea seed oil, Kaya oil, rice bran oil, cinnagyl oil, Japanese kiri oil, jojoba oil, germ oil, trioctanoic acid glycerin, triisopalmitic acid glycerin, horse oil, hardened palm oil, beef tallow, bovine leg fat, sheep fat, hardened beef tallow, pork Fats and oils such as beef fat, beef bone oil, owl kernel oil, hydrogenated oil, owl, hydrogenated castor oil
流動パラフィン、ワセリン、セレシン、マイクロクリスタリンワックス、イソパラフィン、オゾケライト、スクワレン、プリスタン、スクワラン等の炭化水素;
ミツロウ、鯨ロウ、ラノリン、カルナバロウ、キャンデリラロウ、綿ロウ、ベイベリーロウ、イボタロウ、モンタンロウ、ヌカロウ、ラノリン、カボックロウ、酢酸ラノリン、液状ラノリン、サトウキビロウ、ラノリン脂肪酸イソプロピル、ラウリン酸ヘキシル、還元ラノリン、ジョジョバロウ、硬質ラノリン、セラックロウ、ポリオキシエチレンラノリンアルコールエーテル、ポリオキシエチレンラノリンアルコールアセテート、ラノリン脂肪酸ポリエチレングルコール、ポリオキシエチレン水素添加ラノリンアルコールエーテルおよびその誘導体等のロウ;
Hydrocarbons such as liquid paraffin, petrolatum, ceresin, microcrystalline wax, isoparaffin, ozokerite, squalene, pristane, squalane;
Beeswax, whale wax, lanolin, carnauba wax, candelilla wax, cotton wax, bayberry wax, ibotarou, montan wax, nukarou, lanolin, cabbage wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, jojoba wax Waxes such as hard lanolin, shellac wax, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, polyoxyethylene hydrogenated lanolin alcohol ether and derivatives thereof;
ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、オレイン酸、ベヘニン酸、ウンデシレン酸、ラノリン脂肪酸、硬質ラノリン脂肪酸、軟質ラノリン脂肪酸、リノール酸、リノレン酸、エイコサペンタエン酸、12−ヒドロキシステアリン酸等の高級脂肪酸;
ラウリルアルコール、セタノール、セトステアリルアルコール、ステアリルアルコール、オレイルアルコール、ベヘニルアルコール、ラノリンアルコール、水添ラノリンアルコール、へキシルデカノール、オクチルドデカノール等の高級アルコール;
コレステロール、フィトステロール等のステロール類;
Lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, behenic acid, undecylenic acid, lanolin fatty acid, hard lanolin fatty acid, soft lanolin fatty acid, linoleic acid, linolenic acid, eicosapentaenoic acid, 12-hydroxystearic acid Higher fatty acids such as;
Higher alcohols such as lauryl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldodecanol;
Sterols such as cholesterol and phytosterol;
ミリスチン酸イソプロピル、ステアリン酸ブチル、オクタン酸セチル、ミリスチン酸オクチルドデシル、パルミチン酸イソプロピル、ラウリン酸ヘキシル、ミリスチン酸ミリスチル、オレイン酸デシル、ジメチルオクタン酸ヘキシルデシル、乳酸セチル、乳酸ミリスチル、酢酸ラノリン、ステアリン酸イソセチル、イソステアレン酸イソセチル、12−ヒドロキシステアリル酸コレステリル、ジ−2−エチルヘキシル酸エチレングリコール、ジペンタエリスリトール脂肪酸エステル、モノイソステアリン酸N−アルキルグリコール、ジカプリン酸ネオペンチルグリコール、リンゴ酸ジイソステアリル、ジ−2−ヘプチルウンデカン酸グリセリン、トリ−2−エチルヘキシル酸トリメチロールプロパン、トリイソステアリン酸トリメチロールプロパン、テトラ−2−エチルヘキシル酸ペンタエリスリト
ール、トリ−2−エチルヘキシル酸グリセリン、トリイソステアリン酸トリメチロールプロパン、セチル−2−エチルヘキサノエート、2−エチルヘキシルパルミテート、トリミリスチン酸グリセリン、トリ−2−ヘプチルウンデカン酸グリセライド、ヒマシ油脂肪酸メチルエステル、オレイン酸オイル、セトステアリルアルコール、アセトグリセライド、パルミチン酸−2−ヘプチルウンデシル、アジピン酸ジイソプロピル、N−ラウロイル−L−グルタミン酸−2−オクチルドデシルエステル、アジピン酸ジ−2−ヘプチルウンデシル、エチルラウレート、セパチン酸ジ−2−エチルヘキシル、ミリスチン酸−2−ヘキシルデシル、パルミチン酸−2−ヘキシルデシル、アジピン酸−2−ヘキシルデシル、セバチル酸ジイソプロピル、コハク酸−2−エチルヘキシル、酢酸エチル、酢酸ブチル、酢酸アミル、クエン酸トリエチル等のエステル油;
金属石鹸、ジメチルポリシロキサン、ポリエーテル変性シリコーン、アルコール変性シリコーン、メチルフェニルポリシロキサン、エポキシ変性シリコーン、フッ素変性シリコーン、アルキル変性シリコーン、アルコキシ変性シリコーン、アミノ変性シリコーン、揮発性シリコーン、環状シリコーン等のシリコーン類等の揮発性および不揮発性の油性成分;等が挙げられる。これら油性成分は2種以上組み合わせて用いても良い。
Isopropyl myristate, butyl stearate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, stearic acid Isocetyl, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, monoisostearate N-alkyl glycol, neopentyl glycol dicaprate, diisostearyl malate, di- 2-glyceryl 2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate Bread, pentaerythritol tetra-2-ethylhexylate, glycerol tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl-2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2- Heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic oil, cetostearyl alcohol, acetoglyceride, palmitic acid-2-heptylundecyl, adipic acid diisopropyl, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, adipine Di-2-heptyl undecyl acid, ethyl laurate, di-2-ethylhexyl sepatate, 2-hexyl decyl myristate, 2-hexyl decyl palmitate, adipine 2-hexyl decyl, Sebachiru acid diisopropyl succinate 2-ethylhexyl, ethyl acetate, butyl acetate, amyl acetate, ester oils such as triethyl citrate;
Silicone such as metal soap, dimethylpolysiloxane, polyether-modified silicone, alcohol-modified silicone, methylphenylpolysiloxane, epoxy-modified silicone, fluorine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, amino-modified silicone, volatile silicone, and cyclic silicone And other volatile and non-volatile oily components; Two or more of these oil components may be used in combination.
本発明の油性ゲル状クレンジングは、1)多鎖多親水基型化合物の1種以上、2)分子内に水酸基を2個以上有するポリヒドロキシル化合物の1種以上、3)油性成分の1種以上、および4)HLBが2〜14であるノニオン性界面活性剤の1種以上を含有することを特徴とする油性ゲル状クレンジングであって、該組成物中の水分含量が50質量%以下であり、かつ該組成物中の組成が、1)多鎖多親水基型化合物の総量が0.1〜40質量%、2)ポリヒドロキシル化合物の総量が1〜60質量%、3)油性成分の総量が1〜95質量%、4)HLBが2〜14であるノニオン性界面活性剤の総量が0.1〜20%(但し、水分含量と1)〜4)の合計は100質量%)である組成物を含有することが好ましい。ここで、1)多鎖多親水基型化合物、2)ポリヒドロキシル化合物、3)油性成分、4)HLBが2〜14であるノニオン性界面活性剤のそれぞれの総量は、それぞれに該当する成分の総和である。各成分の組成がこの範囲外であってもゲル状の剤型になることはあるが皮膚等に塗布した場合に残油感があったり、油性成分が分離して安定性に乏しかったり、ゲル形成力が不十分であったり、目的によっては汚れの洗浄力が低下したり、伸びが悪くなる等使用感が好ましくなくなることがある。 The oily gel-like cleansing of the present invention is 1) one or more types of multi-chain polyhydrophilic group type compounds, 2) one or more types of polyhydroxyl compounds having two or more hydroxyl groups in the molecule, and 3) one or more types of oily components. And 4) an oily gel cleansing characterized by containing one or more nonionic surfactants having an HLB of 2 to 14, wherein the water content in the composition is 50% by mass or less In addition, the composition in the composition is 1) the total amount of the multi-chain polyhydrophilic group type compound is 0.1 to 40% by mass, 2) the total amount of the polyhydroxyl compound is 1 to 60% by mass, and 3) the total amount of the oil component Is 1 to 95% by mass, 4) The total amount of nonionic surfactants having HLB of 2 to 14 is 0.1 to 20% (however, the total of water content and 1) to 4) is 100% by mass) It is preferable to contain a composition. Here, 1) the multi-chain polyhydrophilic group type compound, 2) the polyhydroxyl compound, 3) the oil component, 4) the total amount of the nonionic surfactant having HLB of 2 to 14, It is the sum. Even if the composition of each component is outside this range, it may become a gel-like dosage form, but when applied to the skin etc., there is a feeling of residual oil, the oily component is separated and the stability is poor, The feeling of use may be unfavorable, for example, the forming power may be insufficient, the cleaning power of dirt may be reduced depending on the purpose, and the elongation may deteriorate.
本発明の油性ゲル状クレンジングにおいては、1)多鎖多親水基型化合物、2)ポリヒドロキシル化合物、3)油性成分、4)HLBが2〜14であるノニオン性界面活性剤の各成分組成は、好ましくは、1)多鎖多親水基型化合物の総量が0.1〜25質量%、2)ポリヒドロキシル化合物の総量が1〜40質量%、3)油性成分の総量が20〜80質量%、4)ノニオン性界面活性剤の総量が0.1〜15質量%とする。さらに好ましくは、1)多鎖多親水基型化合物の総量が0.1〜15質量%、2)ポリヒドロキシル化合物の総量が1〜30質量%、3)油性成分の総量が30〜70質量%、4)ノニオン性界面活性剤の総量が0.5〜10質量%とする。 In the oily gel cleansing of the present invention, each component composition of 1) a multi-chain polyhydrophilic group type compound, 2) a polyhydroxyl compound, 3) an oily component, and 4) a nonionic surfactant having an HLB of 2 to 14 Preferably, 1) the total amount of the multi-chain polyhydrophilic group type compound is 0.1 to 25% by mass, 2) the total amount of the polyhydroxyl compound is 1 to 40% by mass, and 3) the total amount of the oily component is 20 to 80% by mass. 4) The total amount of nonionic surfactant shall be 0.1-15 mass%. More preferably, 1) the total amount of the multi-chain polyhydrophilic group type compound is 0.1 to 15% by mass, 2) the total amount of the polyhydroxyl compound is 1 to 30% by mass, and 3) the total amount of the oil component is 30 to 70% by mass. 4) The total amount of nonionic surfactant shall be 0.5-10 mass%.
本発明の油性ゲル状クレンジングにおいて、水分含量は50質量%以下が好ましい。この範囲外ではゲル状を安定に保持しにくい場合がある。水分含量はより好ましくは、30質量%以下0.1質量%以上である。さらに好ましくは、20質量%以下1.0質量%以上とする。
本発明の油性ゲル状クレンジングにおいて、外観が透明な油性ゲル状クレンジングを得るためには該組成物中の1)多鎖多親水基型化合物、2)ポリヒドロキシル化合物、4)HLBが2〜14であるノニオン性界面活性剤および水等の油性成分以外から成る水相と、3)油性成分からなる油相との屈折率の差を±0.05以下とすることが好ましい。両相の屈折率の差がこの範囲を外れると、外観の透明な組成物を得にくく、両相の屈折率差は0に近づける方がよい。より好ましくは、両相の屈折率の差を±0.03以下とする。
さらに好ましくは、両相の屈折率差を±0.01以下とする。
In the oily gel cleansing of the present invention, the water content is preferably 50% by mass or less. Outside this range, it may be difficult to stably maintain the gel state. The water content is more preferably 30% by mass or less and 0.1% by mass or more. More preferably, it is 20 mass% or less and 1.0 mass% or more.
In the oily gel cleansing of the present invention, in order to obtain an oily gel cleansing having a transparent appearance, 1) a multi-chain polyhydrophilic group compound, 2) a polyhydroxyl compound, and 4) HLB in the composition are 2 to 14 It is preferable that the difference in refractive index between an aqueous phase composed of a nonionic surfactant other than the above and an oily component such as water and an oily phase composed of 3) an oily component be ± 0.05 or less. If the difference in refractive index between the two phases is outside this range, it is difficult to obtain a transparent composition having an appearance, and the difference in refractive index between the two phases is preferably close to zero. More preferably, the difference in refractive index between both phases is set to ± 0.03 or less.
More preferably, the refractive index difference between both phases is set to ± 0.01 or less.
本発明の油性ゲル状クレンジングを製造するには、1)多鎖多親水基型化合物、2)ポリヒドロキシル化合物、3)油性成分、4)HLBが2〜14であるノニオン性界面活性剤および場合によっては水を高せん断力の下で攪拌・混合することにより製造される。好ましい製造方法としては、油性成分以外の成分を十分に攪拌・混合し、これに油性成分を添加していく方法がよい。
本発明の毛髪化粧料を製造する方法の一つとしては、油性成分をゲル化することのできる公知のゲル化剤を用いることができる。例えば、具体的には、デキストリン脂肪酸エステル、グリセリン脂肪酸エステル、 ヒドロキシステアリン酸、ラウロイルグルタミン酸ジブチルアミド等の長鎖アシルアミノ酸のアミドまたはエステル誘導体、等を挙げることができる。前記デキストリン脂肪酸エステルとしては、例えば(パルミチン酸/オクタン酸)デキストリン、ミリスチン酸デキストリン、パルミチン酸デキストリン、ステアリン酸イヌリン等が挙げられる。
また、グリセリン脂肪酸エステルとしては、例えば(ベヘン酸/エイコサン二酸)グリセリル等が挙げられる。
In order to produce the oily gel cleansing of the present invention, 1) a multi-chain polyhydrophilic group type compound, 2) a polyhydroxyl compound, 3) an oily component, 4) a nonionic surfactant having an HLB of 2 to 14 and the case Some are produced by stirring and mixing water under high shear force. As a preferable production method, a method in which components other than the oil component are sufficiently stirred and mixed and the oil component is added thereto is preferable.
As one of the methods for producing the hair cosmetic composition of the present invention, a known gelling agent capable of gelling an oily component can be used. Specific examples include dextrin fatty acid esters, glycerin fatty acid esters, amides or ester derivatives of long-chain acylamino acids such as hydroxystearic acid and lauroylglutamic acid dibutylamide. Examples of the dextrin fatty acid ester include (palmitic acid / octanoic acid) dextrin, dextrin myristate, dextrin palmitate, inulin stearate and the like.
Examples of the glycerin fatty acid ester include (behenic acid / eicosanedioic acid) glyceryl.
かくして得られる、本発明の油性ゲル状クレンジングの特徴は、
1)皮膚等に塗布し水洗したときの残油感がなく、また塗布後水を添加すると極めて容易にエマルジョン状態に微分散する、2)使用した後のかさつきがほとんどなく使用感がよい、3)ゲル形成力が高く、経時的にも非常に安定なゲルを保つ、という特徴があり、これまでの課題を解決するものである。
The characteristics of the oily gel cleansing of the present invention thus obtained are as follows:
1) There is no residual oil feeling when applied to the skin etc. and washed with water, and it is very easily finely dispersed in the emulsion state when water is added after application. 2) There is almost no bulkiness after use and the feeling of use is good. ) It has a feature that it has a high gel-forming ability and maintains a very stable gel over time, and solves the problems so far.
本発明の油性ゲル状クレンジングは、クレンジング剤以外にも例えば家庭用(衣料、台所、住居、食器、コンタクトレンズ等)洗浄剤、香粧品、食品、医薬品等の人に接触する組成物から工業用洗浄剤等に幅広く適用することができる。
本発明の油性ゲル状クレンジングは、その形態が液体状、固体状、ゲル状、ペースト、スラリー、ミスト状、液晶、粉体、エアゾール等の目的に応じて種々の形態で用いることができる。但し、この形態に限定されることはない。
本発明に於ける香粧品とは、薬事法に言う医薬部外品および化粧品の総称であり、具体的には、医薬部外品としては口中清涼剤、腋臭防止剤、てんか粉類、養毛剤、除毛剤、染毛剤、パーマネントウェーブ用剤、浴用剤、薬用化粧品、薬用歯磨き類などを列挙することができ、
In addition to the cleansing agent, the oily gel cleansing of the present invention is for industrial use from compositions that come into contact with humans such as household cleaners (clothing, kitchen, dwelling, tableware, contact lenses, etc.), cosmetics, foods, pharmaceuticals, etc. It can be widely applied to cleaning agents.
The oily gel cleansing of the present invention can be used in various forms depending on the purpose such as liquid, solid, gel, paste, slurry, mist, liquid crystal, powder, aerosol and the like. However, it is not limited to this form.
The cosmetic product in the present invention is a generic name for quasi-drugs and cosmetics referred to in the Pharmaceutical Affairs Law. Specifically, quasi-drugs include mouth fresheners, odor control agents, tempered powders, hair nourishing agents, List hair removal agents, hair dyes, permanent wave agents, bath agents, medicated cosmetics, medicated toothpastes, etc.
化粧品としては、化粧石鹸、洗顔料(クリーム・ペースト状、液・ジェル状、顆粒・粉末状、エアゾール使用など)、シャンプー、リンスなどの清浄用化粧品;
染毛料、ヘアトリートメント剤(クリーム状、ミスト状、オイル状、ジェル状その他の形態の物および枝毛コート剤を含む)、ヘアセット剤(髪油、セットローション、カーラーローション、ポマード、チック、びんつけ油、ヘアスプレー、ヘアミスト、ヘアリキッド、ヘアフォーム、ヘアジェル、ウォーターグリース)などの頭髪用化粧品;
一般クリーム、乳液(クレンジングクリーム、コールドクリーム、バニシングクリーム、ハンドクリームなど)、ひげ剃り用クリーム(アフターシェービングクリーム、シェービングクリームなど)、化粧水(ハンドローション、一般化粧水など)、オーデコロン、ひげ剃り用ローション(アフターシェービングローション、シェービングローションなど)、化粧油、パックなどの基礎化粧品;
Cosmetics include cosmetic soap, face wash (cream / paste, liquid / gel, granule / powder, aerosol, etc.), shampoo, rinse, etc.
Hair dyes, hair treatments (including cream, mist, oil, gel and other forms and split hair coats), hair set (hair oil, set lotion, curler lotion, pomade, tics, bottles Cosmetics for hair, such as oiling, hair spray, hair mist, hair liquid, hair foam, hair gel, water grease);
General cream, milky lotion (cleansing cream, cold cream, burnishing cream, hand cream, etc.), shaving cream (after shaving cream, shaving cream, etc.), lotion (hand lotion, general lotion, etc.), cologne, shaving Basic cosmetics such as lotions (after shaving lotions, shaving lotions, etc.), cosmetic oils, packs;
おしろい(クリームおしろい、固形おしろい、粉おしろい、タルカムパウダー、練りおしろい、ベビーパウダー、ボディパウダー、水おしろいなど)、パウダー、ファンデーション(クリーム状、液状、固形など)、ほお紅、まゆずみ、アイクリーム、アイシャドウマスカラなどのメークアップ化粧品;
一般香水、練り香水、粉末香水などの香水類; ゲルタイプ、液体タイプ、陶器タイプ等の芳香剤、消臭剤、脱臭剤;
日焼け・日焼け止めクリーム、日焼け・日焼け止めローション、日焼け・日焼け止めオイルなどの日焼け・日焼け止め化粧品;
Oshiroi (Cream Occasion, Solid Oroze, Powder Ooiro, Talcum Powder, Kneading Oro, Baby Powder, Body Powder, Water Osoiro, etc.), Powder, Foundation (Cream, Liquid, Solid etc.), Blusher, Eyebrows, Eye Cream, Eye Makeup cosmetics such as shadow mascara;
Perfumes such as general perfume, kneaded perfume, powdered perfume; fragrance, deodorant, deodorant such as gel type, liquid type, ceramic type;
Sunscreen / sunscreen cosmetics such as sunscreen / sunscreen cream, sunscreen / sunscreen lotion, sunscreen / sunscreen oil;
爪クリーム、エナメル、エナメル除去液などの爪化粧品;
アイライナー化粧品;
口紅、リップクリームなどの口唇化粧品;
歯磨きなどの口腔化粧品;
バスソルト、バスオイル、バブルバスなどの浴用化粧品などを列挙することができる。
Nail cosmetics such as nail cream, enamel, enamel remover;
Eyeliner cosmetics;
Lip cosmetics such as lipstick and lip balm;
Oral cosmetics such as toothpaste;
Listed are bath cosmetics such as bath salt, bath oil, and bubble bath.
また本発明の油性ゲル状クレンジングにおいては、本発明の目的が損なわれない限り、用途、目的に応じ各種の基材と併用することができる。
具体的には、アラビアゴム、トラガントゴム等の天然ゴム類、サポニン等のグルコシド類、メチルセルロース、カルボキシセルロース、ヒドロキシメチルセルロース等のセルロース誘導体、リグニンスルホン酸塩、セラック等の天然高分子、ポリアクリル酸塩、スチレン−アクリル酸共重合物の塩、ビニルナフタレン−マレイン酸共重合物の塩、β−ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩、リン酸塩などの陰イオン性高分子やポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール等のノニオン性高分子等の分散剤;
Moreover, in the oil-based gel cleansing of this invention, unless the objective of this invention is impaired, it can use together with various base materials according to a use and the objective.
Specifically, natural rubbers such as gum arabic and tragacanth, glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxycellulose, and hydroxymethylcellulose, natural polymers such as lignin sulfonate and shellac, polyacrylates, Styrene-acrylic acid copolymer salt, vinyl naphthalene-maleic acid copolymer salt, β-naphthalene sulfonic acid formalin condensate sodium salt, anionic polymer such as phosphate, polyvinyl alcohol, polyvinyl pyrrolidone, Dispersants such as nonionic polymers such as polyethylene glycol;
高級脂肪酸塩(石鹸);疎水基部の炭素数8〜20の高級脂肪酸の塩、
N−アシルアミノ酸型アニオン界面活性剤;アシル基としては、炭素数8〜20のもので前記したようなものが挙げられ、構成アミノ酸としては、グルタミン酸やアスパラギン酸等の前記した酸性アミノ酸類、またはグリシン、アラニン、バリン、ロイシン、イソロイシン、プロリン、メチオニン、システイン、トリプトファン、チロシン、フェニルアラニン、アスパラギン、グルタミン、セリン、トレオニン、オキシプロリン、β−アミノプロピオン酸、γ−アミノ酪酸、アントラニル酸、m−アミノ安息香酸、p−アミノ安息香酸、等のアミノ酸等;アルキルエーテルカルボン酸塩、アミドエーテルカルボン酸塩等、アルキル硫酸エステル塩(AS)、ポリオキシエチレンアルキルエーテル硫酸エステル塩(AES)、アルキルエーテル硫酸塩、高級脂肪酸エステルの硫酸塩、高級脂肪酸アルキロールアミドの硫酸塩、硫酸化油脂、ポリオキシエチレンスチレン化フェニルエーテル硫酸塩、アルファ−オレフィンスルホン酸塩(AOS)、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキルスルホン酸塩(SAS)、ジアルキルスルホコハク酸塩、アルファースルホン化脂肪酸塩、アルカンスルホン酸塩、高級脂肪酸エステルのスルホン酸塩、アルファースルホン化脂肪酸塩、高級脂肪酸アミドのスルホン酸塩、N−アシル−N−アルキルタウリン塩、N−アシル−N−メチルタウリン塩、アルキルリン酸塩、アルキルエーテルリン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩、ポリオキシエチレンアルキルフェニルエーテルリン酸塩、ナフタリンスルフォン酸塩ホルマリン縮合物などのアニオン性界面活性剤;
Higher fatty acid salt (soap); salt of higher fatty acid having 8 to 20 carbon atoms in the hydrophobic base,
N-acyl amino acid type anionic surfactant; examples of the acyl group include those having 8 to 20 carbon atoms as described above, and examples of the constituent amino acids include the above-mentioned acidic amino acids such as glutamic acid and aspartic acid, or Glycine, alanine, valine, leucine, isoleucine, proline, methionine, cysteine, tryptophan, tyrosine, phenylalanine, asparagine, glutamine, serine, threonine, oxyproline, β-aminopropionic acid, γ-aminobutyric acid, anthranilic acid, m-amino Amino acids such as benzoic acid, p-aminobenzoic acid, etc .; alkyl ether carboxylates, amide ether carboxylates, etc., alkyl sulfate esters (AS), polyoxyethylene alkyl ether sulfates (AES), alkyl ether sulfates Acid salt, sulfate of higher fatty acid ester, sulfate of higher fatty acid alkylolamide, sulfated oil, polyoxyethylene styrenated phenyl ether sulfate, alpha-olefin sulfonate (AOS), alkylbenzene sulfonate, alkylnaphthalene Sulfonates, alkyl sulfonates (SAS), dialkyl sulfosuccinates, alpha-sulfonated fatty acid salts, alkane sulfonates, sulfonates of higher fatty acid esters, alpha-sulfonated fatty acid salts, sulfonates of higher fatty acid amides, N-acyl-N-alkyl taurate, N-acyl-N-methyl taurate, alkyl phosphate, alkyl ether phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, Naphtha Anionic surfactants such as Nsurufon formalin condensate;
アルキルベタイン類、アルキルアミドベタイン類、アルキルスルホベタイン類、イミダゾリニウムベタイン類、レシチン類などの両性界面活性剤;
ポリオキシエチレンアルキルエーテル(AE)、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンポリスチリルフェニルエーテル、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシアルキレン脂肪酸エステル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレン脂肪酸アルカノールアミド、ポリオキシアルキレンアルキルグルコシド、ポリオキシアルキレン硬化ひまし油、ポリオキシアルキレンアルキルアミン、ポリオキシアルキレンアルキルフェニルエーテル、等の酸化エチレン縮合型、
Amphoteric surfactants such as alkylbetaines, alkylamidobetaines, alkylsulfobetaines, imidazolinium betaines, lecithins;
Polyoxyethylene alkyl ether (AE), polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene Sorbitan fatty acid ester, polyoxyalkylene fatty acid alkanolamide, polyoxyalkylene alkyl glucoside, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene alkyl amine, polyoxyalkylene alkyl phenyl ether, and other ethylene oxide condensation types,
多価アルコール脂肪酸部分エステル、ポリオキシエチレン多価アルコール脂肪酸部分エステル、ポリオキシエチレン脂肪酸エステル、(ポリ)グリセリン脂肪酸エステル、ポリオキシエチレン硬化ひまし油、ポリオキシエチレンアルキルアミン、トリエタノールアミン脂肪酸部分エステル、アルキルポリグルコシド、プロピレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、ショ等脂肪酸エステル等の多価アルコールエステル、脂肪酸アルカノールアミド、糖アミンアシル化物、トリエタノールアミン脂肪酸部分エステル、脂肪酸アルキロールアミド、アルキルアミンオキサイド、などのノニオン性界面活性剤;
第1〜第3級脂肪アミン塩、塩化アルキルアンモニウム塩、テトラアルキルアンモニウム塩、トリアルキルベンジルアンモニウム塩、アルキルピリジニウム塩、アルキルヒドロキシエチルイミダゾリニウム塩、ジアルキルモルフォリニウム塩、アルキルイソキノリウム塩、ベンゼトニウム塩、ベンザルコニウム塩などのカチオン性界面活性剤;
Polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, (poly) glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, triethanolamine fatty acid partial ester, alkyl Nonion such as polyglucoside, propylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid ester such as sho, fatty acid alkanolamide, sugar amine acylated product, triethanolamine fatty acid partial ester, fatty acid alkylolamide, alkylamine oxide, etc. Surfactants;
Primary to tertiary fatty amine salts, alkylammonium chloride salts, tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridinium salts, alkylhydroxyethylimidazolinium salts, dialkylmorpholinium salts, alkylisoquinolium salts, Cationic surfactants such as benzethonium salts and benzalkonium salts;
アルギン酸ナトリウム、デンプン誘導体、トラガントゴムなどの高分子界面活性剤;
リン脂質、レシチン、ラノリン、コレステロール、サポニンなどの天然界面活性剤;
N−メチルグリシン、N,N−ジメチルグリシン、N,N,N−トリメチルグリシン、N−エチルグリシン、グリシルベタイン等のアルキルグリシン類、ソルビトール、ラフィノース、ピロリドンカルボン酸塩類、乳酸塩類、ヒアルロン酸塩類、セラミド類、トレハロース、キシロビオース、マルトース、ショ糖、ブドウ糖、植物性粘質多糖等の(多)糖類およびその誘導体、水溶性キチン、キトサン、ペクチン、コンドロイチン硫酸およびその塩等のグリコサミノグリカンおよびその塩、グリシン、セリン、スレオニン、アラニン、アスパラギン酸、チロシン、バリン、ロイシン、アルギニン、グルタミン、プロリン酸等のアミノ酸およびその塩等、アミノカルボニル反応物等の糖アミノ酸化合物、アロエ、マロニエ等の植物抽出液、尿素、尿酸、アンモニア、グルコサミン、クレアチニン、DNA、RNA等の核酸関連物質などの保湿剤;
Polymeric surfactants such as sodium alginate, starch derivatives, tragacanth gum;
Natural surfactants such as phospholipids, lecithin, lanolin, cholesterol, saponins;
Alkylglycines such as N-methylglycine, N, N-dimethylglycine, N, N, N-trimethylglycine, N-ethylglycine, glycylbetaine, sorbitol, raffinose, pyrrolidonecarboxylates, lactates, hyaluronates , Ceramides, trehalose, xylobiose, maltose, sucrose, glucose, (poly) saccharides and derivatives thereof such as plant mucous polysaccharides, glycosaminoglycans such as water-soluble chitin, chitosan, pectin, chondroitin sulfate and salts thereof, and Its salts, amino acids such as glycine, serine, threonine, alanine, aspartic acid, tyrosine, valine, leucine, arginine, glutamine, prophosphoric acid, etc., sugar amino acid compounds such as aminocarbonyl reaction products, plants such as aloe, maronier Extract, urea Uric acid, ammonia, glucosamine, creatinine, DNA, humectants, such as nucleic acid-related substance such as RNA;
ヒドロキシエチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロースヒドロキシプロピルトリメチルアンモニウムクロリドエーテル、メチルセルロース、エチルセルロース、ヒドロキシプロピルセルロース、メチルヒドロキシプロピルセルロース、可溶性デンプン、カルボキシメチルデンプン、メチルデンプン、
アルギン酸プロピレングリコールエステル、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルメチルエーテル、カルボキシビニルポリマー、ポリアクリル酸塩、グアーガム、ローカストビンガム、クインスシード、カラギーナン、ガラクタン、アラビアガム、ペクチン、マンナン、デンプン、キサンタンガム、デキストラン、サクシノグルカン、カードラン、ヒアルロン酸、ゼラチン、カゼイン、アルブミン、コラーゲン、メトキシエチレン無水マレイン酸共重合体、両性メタクリル酸エステル共重合体、ポリ塩化ジメチルメチレンピペリジニウム、ポリアクリル酸エステル共重合体、ポリ酢酸ビニル、ニトロセルロース、シリコーンレジン等の水溶性および油溶性高分子;
Hydroxyethylcellulose, carboxymethylcellulose, hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether, methylcellulose, ethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, soluble starch, carboxymethylstarch, methylstarch,
Propylene glycol alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, polyacrylate, guar gum, locust bin gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, dextran, sac Sinoglucan, curdlan, hyaluronic acid, gelatin, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer, polydimethylmethylenepiperidinium chloride, polyacrylate copolymer, Water-soluble and oil-soluble polymers such as polyvinyl acetate, nitrocellulose, silicone resin;
カチオン化セルロース誘導体、カチオン性澱粉、カチオン化グアーガム誘導体、ジアリル第4級アンモニウム塩/アクリルアミド共重合体、4級化ポリビニルピロリドン誘導体、4級化ビニルピロリドン/ビニルイミダゾールポリマー、ポリグリコール/アミン縮合物、4級化コラーゲンポリペプチド、ポリエチレンイミン、カチオン性シリコーンポリマー、アジピン酸/ジメチルアミノヒドロキシプロピルジエチレントリアミンコポリマー、ポリアミノポリアミド、カチオン性キチン誘導体、4級化ポリマー等のカチオン性高分子;
ポリエチレングリコール脂肪酸エステル、ポリオキシエチレン脂肪酸エステルメチルグリコシド、テトラデセンスルホン酸塩等の増粘、増泡成分;
Cationized cellulose derivative, cationic starch, cationized guar gum derivative, diallyl quaternary ammonium salt / acrylamide copolymer, quaternized polyvinylpyrrolidone derivative, quaternized vinylpyrrolidone / vinylimidazole polymer, polyglycol / amine condensate, Cationic polymers such as quaternized collagen polypeptide, polyethyleneimine, cationic silicone polymer, adipic acid / dimethylaminohydroxypropyldiethylenetriamine copolymer, polyaminopolyamide, cationic chitin derivative, quaternized polymer;
Thickening and foam increasing components such as polyethylene glycol fatty acid ester, polyoxyethylene fatty acid ester methyl glycoside, tetradecene sulfonate;
(パルミチン酸/オクタン酸)デキストリン、ミリスチン酸デキストリン、パルミチン酸デキストリン、ステアリン酸イヌリン等のデキストリン脂肪酸エステル、グリセリン脂肪酸エステル、ヒドロキシステアリン酸、ラウロイルグルタミン酸ジブチルアミド等の長鎖アシルアミノ酸のアミドまたはエステル誘導体、(ベヘン酸エイコサン二酸)グリセリル等のグリセリン脂肪酸エステル等の油ゲル化剤;
エチレンジアミン四酢酸およびその塩類、ヒドロキシエチレンジアミン3酢酸およびその塩類、リン酸、アスコルビン酸、コハク酸、グルコン酸、ポリリン酸塩類、メタリン酸塩、ヒノキチール類などの金属イオン封鎖剤;
(Palmitic acid / octanoic acid) dextrin fatty acid ester such as dextrin, myristic acid dextrin, dextrin palmitic acid, inulin stearate, glycerin fatty acid ester, hydroxystearic acid, amide or ester derivative of acylamino acid such as lauroylglutamic acid dibutylamide, (Ecosandioic acid behenate) oil gelling agents such as glyceryl fatty acid esters such as glyceryl;
Sequestering agents such as ethylenediaminetetraacetic acid and its salts, hydroxyethylenediaminetriacetic acid and its salts, phosphoric acid, ascorbic acid, succinic acid, gluconic acid, polyphosphates, metaphosphates, hinokitiles;
パラオキシ安息香酸エステル類、安息香酸およびその塩類、フェノキシエタノール、ヒノキチール、サリチル酸およびその塩類、ソルビン酸およびその塩、デヒドロ酢酸およびその塩、パラクロルメタクレゾール、ヘキサクロロフェン、ホウ酸、レゾルシン、トリブロムサラン、オルトフェニルフェノール、チラム、感光素201号、ハロカルバン、トリクロロカルバニド、酢酸トコフェロール、ジンクピリチオン、フェノール、イソプロピルメチルフェノール、2,4,4−トリクロロ−2−ヒドロキシフェノール、ヘキサクロロフェン、クロルヘキシジン、塩化ベンゼトニウム、塩化ベンザルコニウム、塩化セチルピリジニウム、塩化デカリニウム、塩化ステアリルジメチルアンモニウム、塩化ステアリルトリメチルアンモニウム、塩化セチルトリメチルアンモニウム、塩化メチルベンゼトニウム、塩化ラウリルトリメチルアンモニウム、塩化ラウロイルコラミノホルミルメチルピリジニウム、トリクロサン、ビオゾール等の防腐・抗菌剤;
クエン酸、リンゴ酸、アジピン酸、グルタミン酸、アスパラギン酸等のpH調整剤;
その他トリクロロルカルバニリド、サリチル酸、ジンクピリチオン、イソプロピルメチルフェノールなどのふけ・かゆみ防止剤;
P-hydroxybenzoates, benzoic acid and its salts, phenoxyethanol, hinokitile, salicylic acid and its salts, sorbic acid and its salts, dehydroacetic acid and its salts, parachlormetacresol, hexachlorophene, boric acid, resorcin, tribromosaran, Orthophenylphenol, thiram, photosensitizer 201, halocarban, trichlorocarbanide, tocopherol acetate, zinc pyrithione, phenol, isopropylmethylphenol, 2,4,4-trichloro-2-hydroxyphenol, hexachlorophene, chlorhexidine, benzethonium chloride, Benzalkonium chloride, cetylpyridinium chloride, decalinium chloride, stearyldimethylammonium chloride, stearyltrimethylammonium chloride, chloride Tilt trimethyl ammonium, chloride methyl benzethonium, lauryl trimethyl ammonium chloride, lauroyl Kola amino formyl methyl pyridinium, triclosan, preservative and antibacterial agents such as Biozoru;
PH adjusters such as citric acid, malic acid, adipic acid, glutamic acid, aspartic acid;
Other anti-dandruff and itching agents such as trichlorocarbanilide, salicylic acid, zinc pyrithione, isopropylmethylphenol;
ベンゾフェノン誘導体、パラアミノ安息香酸誘導体、パラメトキシ桂皮酸誘導体、サリチル酸誘導体その他の紫外線吸収剤;
アスコルビン酸およびその塩(ナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩のようなアルカリ金属塩またはアルカリ土類金属塩の他、アンモニウム塩、アミノ酸塩等)、アスコルビン酸誘導体(L−アスコルビン酸アルキルエステル、L−アスコルビン酸リン酸エステル及びその塩、L−アスコルビン酸−2−硫酸エステル及びその塩、L−アスコルビン酸グルコシド等)、アルコキシサリチル酸及びその塩(アルコキシ基としては、例えばメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基等)、ハイドロキノン配糖体及びその誘導体(アルブチン等)、コウジ酸及びその誘導体、エラグ酸、カミツレエキス、アルテアエキス、カンゾウエキス、ソウハクヒエキス、ラズベリーエキス、リンゴフラボノイド、フスマエキス、ビタミンEおよびその誘導体、ヒノキチオール、プラセンタエキス、ルシノール、カモミラET、グルタチオン、チョウジエキス、茶抽出物、アスタキサンチン、牛胎盤エキス、トラネキサム酸およびその誘導体、レゾルシンの誘導体、アズレン、γ―ヒドロキシ酪酸などの美白剤;
Benzophenone derivatives, paraaminobenzoic acid derivatives, paramethoxycinnamic acid derivatives, salicylic acid derivatives and other UV absorbers;
Ascorbic acid and its salts (sodium salt, potassium salt, magnesium salt, alkali metal salt such as calcium salt, alkaline earth metal salt, ammonium salt, amino acid salt, etc.), ascorbic acid derivative (L-ascorbic acid alkyl ester) L-ascorbic acid phosphate and salts thereof, L-ascorbic acid-2-sulfate and salts thereof, L-ascorbic acid glucoside and the like, alkoxysalicylic acid and salts thereof (alkoxy groups include, for example, methoxy group and ethoxy group) , Propoxy group, isopropoxy group, butoxy group, isobutoxy group, etc.), hydroquinone glycosides and derivatives thereof (arbutin, etc.), kojic acid and its derivatives, ellagic acid, chamomile extract, altea extract, licorice extract, sucha akuhi extract, raspberry extract Apple flavonoid, bran extract, vitamin E and its derivatives, hinokitiol, placenta extract, lucinol, chamomile ET, glutathione, clove extract, tea extract, astaxanthin, cow placenta extract, tranexamic acid and its derivatives, derivatives of resorcin, azulene, γ- Whitening agents such as hydroxybutyric acid;
センブリエキス、セファランチン、ビタミンEおよびその誘導体、ガンマーオリザノールなどの血行促進剤;
トウガラシチンキ、ショオウキョウチンキ、カンタリスチンキ、ニコチン酸ベンジルエステルなどの局所刺激剤;
各種ビタミンやアミノ酸などの栄養剤;
女性ホルモン剤;
毛根賦活剤;
グリチルレチン酸、グリチルリチン酸誘導体、アラントイン、アズレン、アミノカプロン酸、ヒドロコルチゾンなどの抗炎症剤;
Blood circulation promoters such as assembly extract, cephalanthin, vitamin E and its derivatives, gamma oryzanol;
Local stimulants such as pepper tincture, ginger tincture, cantharis tincture, nicotinic acid benzyl ester;
Nutrients such as various vitamins and amino acids;
Female hormone agent;
Hair root activator;
Anti-inflammatory agents such as glycyrrhetinic acid, glycyrrhizic acid derivatives, allantoin, azulene, aminocaproic acid, hydrocortisone;
酸化亜鉛、硫酸亜鉛、アラントインヒドロキシアルミニウム、塩化アルミニウム、硫酸
アルミニウム、スルホ石炭酸亜鉛、タンニン酸、クエン酸、乳酸などの収斂剤;
メントール、カンフルなどの清涼剤;
塩酸ジフェンヒドラミン、マレイン酸クロルフェニラミン、グリチルリチン酸誘導体などの抗ヒスタミン剤;
高分子シリコーン、環状シリコーン等のシリコーン系物質;
トコフェロール類、BHA、BHT、没食子酸、NDGAなどの酸化防止剤;
エストラジオール、エストロン、エチニルエストラジオールなどの皮脂抑制剤;
イオウ、サリチル酸、レゾルシンなどの角質剥離・溶解剤;
グリコール酸、乳酸、リンゴ酸、酒石酸、クエン酸等のα‐ヒドロキシ酸;
Astringents such as zinc oxide, zinc sulfate, allantoin hydroxyaluminum, aluminum chloride, aluminum sulfate, zinc sulfocolate, tannic acid, citric acid, lactic acid;
Refreshing agents such as menthol and camphor;
Antihistamines such as diphenhydramine hydrochloride, chlorpheniramine maleate, glycyrrhizic acid derivatives;
Silicone materials such as high molecular silicones and cyclic silicones;
Antioxidants such as tocopherols, BHA, BHT, gallic acid, NDGA;
Sebum inhibitors such as estradiol, estrone, ethinyl estradiol;
Exfoliating / dissolving agents such as sulfur, salicylic acid, resorcin;
Α-hydroxy acids such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid;
タルク、カオリン、セリサイト、炭酸カルシウム、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、炭酸マグネシウム、炭酸カルシウム、硫酸バリウム、酸化クロム、水酸化クロム、タール系色素等、マイカ、(合成)セリサイト、炭化ケイ素、窒化硼素、二酸化チタン、黒酸化チタン、コンジョウ、赤酸化鉄、黒酸化鉄、黄酸化鉄、群青、チタンコーテッドマイカ、オキシ塩化ビスマス、ベンガラ、粘結顔料、グンジョウピンク、グンジョウバイオレット、水酸化クロム、雲母チタン、酸化クロム、酸化アルミニウムコバルト、カーボンブラック、無水ケイ酸、ケイ酸マグネシウム、ベントナイト、(合成)マイカ、酸化ジルコニウム、(メタ)ケイ酸アルミン酸マグネシウム、ケイ酸アルミン酸カルシウム、ポリエチレン粉末、ナイロン粉末、ポリメチルメタクリレート、ポリエチレンテレフタレート−ポリメチルメタクリレート積層末、アクリロニトリル−メタクリル酸共重合粉末、塩化ビニリデン−メタクリル酸共重合粉末、ウールパウダー、シルクパウダー、結晶セルロース、N−アシルリジン、ポリメチルシルセスキオキサン粉末、植物の実や皮を粉末状にしたもの、オキシ塩化ビスマス、雲母チタン、酸化鉄コーティング雲母、酸化鉄雲母チタン、有機顔料処理雲母チタン、アルミニウムパウダー、微粒子酸化チタン、微粒子酸化亜鉛、微粒子酸化チタン被覆雲母チタン、微粒子酸化亜鉛被覆雲母チタン、硫酸バリウム被覆雲母チタン、カルミン、β−カロチン、クロロフィル、サンセットエローFCF、ポンソーSX、エオシンYS、テトラブロモフルオレセイン、ローダミンB、キノリンエローSS、キノリンエローWS、アリザニンシアニングリーン、キニザリングリーン、リソールビンB、リソールビンBCA、パーマトンレッド、ヘリンドンピンクCN、フタロシアニンブルー、β−アポ−8−カロチナール、カプサンチン、リロピン、ビキシン、クロシン、カンタキサンチン、シソニン、ラファニン、ニノシアニン、カルサミン、サフロールイエロー、ルチン、クエルセチン、カカオ色素、リポフラビン、ラッカイン酸、カルミン酸、ケルメス酸、アリザニン、シコニン、アルカニン、ニキノクローム、血色素、クルクミン、ベタニン、等の化粧品用色材: Talc, kaolin, sericite, calcium carbonate, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, barium sulfate, chromium oxide, chromium hydroxide, tar dyes, mica, (synthetic) sericite , Silicon carbide, boron nitride, titanium dioxide, black titanium oxide, conger, red iron oxide, black iron oxide, yellow iron oxide, ultramarine, titanium coated mica, bismuth oxychloride, bengara, caking pigment, gunjo pink, gunjo Violet, chromium hydroxide, mica titanium, chromium oxide, aluminum cobalt oxide, carbon black, silicic anhydride, magnesium silicate, bentonite, (synthetic) mica, zirconium oxide, magnesium (meth) silicate aluminate, aluminate silicate Calcium, polye Len powder, nylon powder, polymethyl methacrylate, polyethylene terephthalate-polymethyl methacrylate laminated powder, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, wool powder, silk powder, crystalline cellulose, N-acyl lysine, poly Methyl silsesquioxane powder, plant fruit or skin powder, bismuth oxychloride, mica titanium, iron oxide coated mica, iron oxide mica titanium, organic pigment treated mica titanium, aluminum powder, fine titanium oxide, fine particles Zinc oxide, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, carmine, β-carotene, chlorophyll, sunset yellow FCF, Ponceau SX, eosin YS, tetrab Lomofluorescein, rhodamine B, quinoline yellow SS, quinoline yellow WS, alizanin cyanine green, quinizarin green, resolbin BCA, resolbin BCA, permaton red, herringdon pink CN, phthalocyanine blue, β-apo-8-carotenal, Capsanthin, lilopine, bixin, crocin, canthaxanthin, shisonin, raphanin, ninocyanin, calsamine, safrole yellow, rutin, quercetin, cacao pigment, lipoflavin, lacainate, carminic acid, kermesic acid, alizanine, shikonin, alkanine, niquinochrome, hemoglobin, Cosmetic colorants such as curcumin and betanin:
精製水、その他、カキョクエキス、N−メチル−L−セリン、ホエイ、ニコチン酸アミド、ジイソプロピルアミンジクロロ酢酸、メバロン酸、γ−アミノ酪酸(γ−アミノ−β−ヒドロキシ酪酸を含む)、アルテアエキス、アロエエキス、アンズ核エキス、ウコンエキス、ウーロン茶エキス、海水乾燥物、加水分解コムギ末、加水分解シルク、カロットエキス、キューカンバエキス、ゲンチアナエキス、酵母エキス、米胚芽油、コンフリーエキス、サボンソウエキス、ジオウエキス、シコンエキス、シラカバエキス、セイヨウハッカエキス、センブリエキス、ビサボロ−ル、プロポリス、ヘチマエキス、ボダイジュエキス、ホップエキス、マロニエエキス、ムクロジエキス、メリッサエキス、ユーカリエキス、ユキノシタエキス、ローズマリーエキス、ローマカミツレエキス、ローヤルゼリーエキス、海草、米ヌカ、カンゾウ、チンピ、トウキ、モモノハの粉砕物、スフィンゴ脂質、グアイアズレン、ビタミンC等を含むことができる。 Purified water, others, oyster extract, N-methyl-L-serine, whey, nicotinamide, diisopropylamine dichloroacetic acid, mevalonic acid, γ-aminobutyric acid (including γ-amino-β-hydroxybutyric acid), altea extract, Aloe extract, apricot kernel extract, turmeric extract, oolong tea extract, dried sea water, hydrolyzed wheat powder, hydrolyzed silk, carrot extract, cucumber extract, gentian extract, yeast extract, rice germ oil, comfrey extract, savonso extract, Giant extract, lion extract, birch extract, Atlantic mint extract, assembly extract, bisabolol, propolis, loofah extract, bodaiju extract, hop extract, marronnier extract, muroji extract, melissa extract, eucalyptus extract, yukinoshita extract, rosemary Can kiss, Roman chamomile extract, royal jelly extract, seaweed, rice bran, licorice, citrus unshiu peel, angelica, pulverized Momonoha, sphingolipids, guaiazulene, may contain vitamin C, and the like.
特に、脂肪酸ジエタノールアミド、ポリオキシエチレンジオレイン酸メチルグルコシド、ジステアリン酸ポリエチレングリコール、テトラデセンスルホン酸塩、ミリスチン酸塩類、ミリスチルジメチルアミンとの併用は粘度、起泡力を増加させる点で有用であり、ま
た、各両イオン性界面活性剤との併用は刺激性を一層低減させるという点に於いてきわめて有用である。
以下で、本発明を実施例等を用いてさらに具体的に説明するが、本発明はこれら実施例等により何ら限定させるものではない。
In particular, combined use with fatty acid diethanolamide, polyoxyethylene dioleic acid methyl glucoside, polyethylene glycol distearate, tetradecene sulfonate, myristic acid salts, myristyl dimethylamine is useful in terms of increasing viscosity and foaming power. In addition, the combined use with each zwitterionic surfactant is extremely useful in that the irritation is further reduced.
Hereinafter, the present invention will be described more specifically using examples and the like, but the present invention is not limited to these examples and the like.
本発明の実施例等で用いる評価手段などは以下の通りである。
[油性ゲル状クレンジングの口紅洗浄時における残油感の評価]
表面を水/エタノール溶液で拭き、十分乾燥させた人工皮革に口紅を塗り(3.14cm2に対し0.001g)、調製した油性ゲル状クレンジング0.06gで摩擦洗浄し、水洗した。これをドライヤーで乾燥し、洗浄部に水滴を落として、水の接触角を接触角計(CA−D型 協和界面科学社製)を用いてN=5で測定した。水の接触角の大きさから、下記基準に従い評価した。
○:水の接触角の平均値が、75°未満
△:水の接触角の平均値が、75°以上〜80°未満
×:水の接触角の平均値が、80°以上
The evaluation means used in the examples of the present invention are as follows.
[Evaluation of residual oil feeling during lipstick cleaning of oily gel cleansing]
The surface was wiped with a water / ethanol solution, lipstick was applied to a sufficiently dried artificial leather (0.001 g with respect to 3.14 cm 2), friction washed with 0.06 g of the prepared oily gel cleansing, and washed with water. This was dried with a drier, water drops were dropped on the washing section, and the contact angle of water was measured at N = 5 using a contact angle meter (CA-D type Kyowa Interface Science Co., Ltd.). Evaluation was performed according to the following criteria from the size of the water contact angle.
○: The average value of the contact angle of water is less than 75 ° △: The average value of the contact angle of water is not less than 75 ° and less than 80 ° ×: The average value of the contact angle of water is not less than 80 °
[油性ゲル状クレンジングの口紅洗浄時における残油感官能評価]
パネラー5人によって、手の甲に口紅を塗り(28.3cm2に対し0.009g)、調製した油性ゲル状クレンジング0.54gで摩擦洗浄し、水洗した後の残油感を下記基準に従い、官能評価を実施した。
○:油性ゲル状クレンジングの洗浄で残油感をほとんど感じない人が、3人以上
△:油性ゲル状クレンジングの洗浄で残油感をほとんど感じない人が、1または2人
×:油性ゲル状クレンジングの洗浄で残油感をほとんど感じない人が、0人
[Sensory evaluation of residual oil feeling during lipstick cleaning of oily gel cleansing]
Panelists put lipstick on the back of the hand (0.009g for 28.3cm2) by five panelists, washed with 0.54g of oily gel cleansing prepared and washed with water. Carried out.
○: 3 or more people who hardly feel the residual oil by washing the oily gel cleansing △: 1 or 2 people who hardly feel the residual oil by washing the oily gel cleansing ×: Oily gel There are no people who feel almost no residual oil after cleansing.
[油性ゲル状クレンジングの口紅洗浄時におけるによるかさつき官能評価]
パネラー5人によって、手の甲に口紅を塗り(0.009g、28.3cm2)、調製した油性ゲル状クレンジング0.54gで摩擦洗浄し、水洗した後のかさつきを下記基準に従い、官能評価を実施した。
○:油性ゲル状クレンジングの洗浄でかさつきをほとんど感じない人が、3人以上
△:油性ゲル状クレンジングの洗浄でかさつきをほとんど感じない人が、1または2人
×:油性ゲル状クレンジングの洗浄でかさつきをほとんど感じない人が、0人
[Sensitive sensory evaluation of oily gel cleansing by lipstick cleaning]
Five panelists applied lipstick on the back of the hand (0.009 g, 28.3 cm 2), washed with friction with 0.54 g of the prepared oily gel cleansing, and conducted a sensory evaluation on the roughness after washing with water according to the following criteria.
○: 3 or more people who hardly feel the bulkiness by cleaning the oily gel cleansing △: 1 or 2 people who feel almost no bulkiness by the cleaning of the oily gel cleansing ×: of the oily gel cleansing There are no people who feel almost no washing
[安定性]
各油性ゲル状クレンジングを40℃で保存して、1ヵ月後における状態を観察し、安定性を下記基準に従い評価した。
○:状態変化がなく良好
△:わずかに分離が見られる
×:明らかに分離がみられる。
[外観]
各油性ゲル状クレンジングを目視にて評価した。
[Stability]
Each oily gel cleansing was stored at 40 ° C., the state after 1 month was observed, and the stability was evaluated according to the following criteria.
○: Good with no change in state Δ: Slight separation is observed ×: Clear separation is observed
[appearance]
Each oily gel cleansing was visually evaluated.
[多鎖多親水基型化合物の製造例1]
L−リジン塩酸塩9.1g(0.05mol)を水57gと混合した。この液を25%水酸化ナトリウム水溶液でpH範囲を10〜11に調整しながら、また反応温度を5℃に維持しながら、攪拌下にN−ラウロイル−L−グルタミン酸無水物31.1g(0.1mol)を2時間を要して添加し、反応を実施した。さらに30分攪拌を続けた後、ターシャリーブタノールを液中濃度10質量%となるように添加した後、75%硫酸を滴下して液のpH値を2に、また液の温度を65℃に調整した。滴下終了後、攪拌を停止し、20分間65℃で静置すると有機層と水層とに分層し、これから有機層を分離した。分離した
有機層にターシャリーブタノールおよび水を添加して、温度を65℃にして20分攪拌した。攪拌停止後、静置すると有機層と水層とに分層した。得られた有機層に対して、同じ水洗操作をくり返した後、得られた有機層から溶媒を除去し、水酸化ナトリウムで固形分30質量%、酸価に対する中和度0.95に中和した後乾燥して下記式(4)(Xは、各々独立にH又はNa)の多鎖多親水基型化合物を得た。
[Production Example 1 of multi-chain polyhydrophilic group type compound]
9.1 g (0.05 mol) of L-lysine hydrochloride was mixed with 57 g of water. While this solution was adjusted to a pH range of 10 to 11 with a 25% aqueous sodium hydroxide solution and the reaction temperature was maintained at 5 ° C., 31.1 g of N-lauroyl-L-glutamic anhydride (0. 1 mol) was added over 2 hours to carry out the reaction. After further stirring for 30 minutes, tertiary butanol was added to a concentration of 10% by mass in the liquid, 75% sulfuric acid was added dropwise to bring the pH value of the liquid to 2, and the liquid temperature to 65 ° C. It was adjusted. After completion of the dropwise addition, stirring was stopped and the mixture was allowed to stand at 65 ° C. for 20 minutes, so that the organic layer and the aqueous layer were separated, and the organic layer was separated therefrom. Tertiary butanol and water were added to the separated organic layer, the temperature was raised to 65 ° C., and the mixture was stirred for 20 minutes. After the stirring was stopped, the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After repeating the same water washing operation on the obtained organic layer, the solvent was removed from the obtained organic layer, and neutralized with sodium hydroxide to a solid content of 30% by mass and a neutralization degree of 0.95 with respect to the acid value. And then dried to obtain a multi-chain polyhydrophilic group compound of the following formula (4) (X is independently H or Na).
[多鎖多親水基型化合物の製造例2]
製造例1において、中和条件として水酸化ナトリウムで固形分30質量%、酸価に対する中和度0.3とした以外は製造例1と同じ条件で実施し、多鎖多親水基型化合物を得た。
[多鎖多親水基型化合物の製造例3]
製造例1において、中和条件としてトリエタノールアミンで固形分30質量%、酸価に対する中和度0.9とした以外は製造例1と同じ条件で実施し、多鎖多親水基型化合物を得た。
[Production Example 2 of multi-chain polyhydrophilic group type compound]
In Production Example 1, the neutralization was carried out under the same conditions as in Production Example 1 except that the solid content was 30% by mass with sodium hydroxide and the degree of neutralization with respect to the acid value was 0.3. Obtained.
[Production Example 3 of Multi-Chain Polyhydrophilic Group Type Compound]
In Production Example 1, the neutralization was carried out under the same conditions as in Production Example 1 except that the solid content was 30% by mass with triethanolamine and the degree of neutralization with respect to the acid value was 0.9. Obtained.
[多鎖多親水基型化合物の製造例4]
製造例1において、添加物としてN−ココイル−L−グルタミン酸無水物とした以外は製造例1と同じ条件で実施し、多鎖多親水基型化合物を得た。
[多鎖多親水基型化合物の製造例5]
製造例1において、添加物としてN−ステアロイル−L−グルタミン酸無水物とし、酸価に対する中和度0.9とした以外は製造例1と同じ条件で実施し、多鎖多親水基型化合物を得た。
[Production Example 4 of Multi-Chain Polyhydrophilic Group Type Compound]
In Production Example 1, the reaction was carried out under the same conditions as in Production Example 1 except that N-cocoyl-L-glutamic anhydride was used as an additive to obtain a multi-chain polyhydrophilic group type compound.
[Production Example 5 for multi-chain polyhydrophilic group type compound]
In Production Example 1, N-stearoyl-L-glutamic acid anhydride was used as an additive, and the reaction was carried out under the same conditions as in Production Example 1 except that the degree of neutralization with respect to the acid value was 0.9. Obtained.
[実施例1〜11、比較例1、2]
表1に示す組成の油性ゲル状クレンジングを製造し、それぞれについて、使用時の残油感、かさつき、安定性等を評価した。結果を表1に示す。
[油性ゲル状クレンジングの製造方法]
いずれの油性ゲル状クレンジングも下記の方法で調製した。
油性成分以外の成分を70℃で攪拌しながら混合する。これに、攪拌しながら油性成分をゆっくりと滴下し、更に攪拌した後、冷却して油性ゲル状クレンジングを得た。
[Examples 1 to 11, Comparative Examples 1 and 2]
Oily gel cleansing compositions shown in Table 1 were produced, and the residual oil feeling, bulkiness, stability, etc. were evaluated for each. The results are shown in Table 1.
[Method for producing oil-based gel cleansing]
Any oily gel cleansing was prepared by the following method.
Ingredients other than the oil component are mixed at 70 ° C. with stirring. To this, the oil component was slowly added dropwise with stirring, and the mixture was further stirred and then cooled to obtain an oily gel cleansing.
[実施例12]
下記に示す組成の油性ゲル状クレンジングを製造した。
配合成分 配合量(質量%)
製造例1の界面活性剤 4.3
セスキカプリル酸ポリグリセリル−2 25
ジオレイン酸ポリグリセリル−10 5
グリセリン 2.8
オクタン酸セチル 57
精製水 5.9
得られた油性ゲル状クレンジングは乾燥した手、濡れた手のいずれでも快適に使用することが出来た、外観は透明〜半透明で、安定性、水の接触角評価、残油感の官能評価、かさつきの官能評価の何れもが○であった。
[Example 12]
An oily gel cleansing having the composition shown below was produced.
Compounding ingredients Compounding amount (% by mass)
Surfactant of Production Example 1 4.3
Polyglyceryl-2 sesquicaprylate 25
Polyglyceryl dioleate-10 5
Glycerin 2.8
Cetyl octoate 57
Purified water 5.9
The resulting oily gel cleansing can be used comfortably in both dry and wet hands, the appearance is transparent to translucent, stability, contact angle evaluation of water, sensory evaluation of residual oil feeling Both of the sensory evaluations of the bulkiness were ○.
本発明の油性ゲル状クレンジングは、油性成分を多量に含有しており、皮膚等に塗布、水洗した時に残油感がなく、かさつきがない、使用感に優れたもので、クレンジング化粧
料のような香粧品分野で好適に利用できる。
The oil-based gel cleansing of the present invention contains a large amount of oily components, has no residual oil feeling when applied to the skin and washed with water, has no bulkiness, and has an excellent feeling of use. It can be suitably used in the cosmetic field.
Claims (6)
R1COは炭素原子数8〜20の飽和または不飽和の脂肪酸から誘導される長鎖アシル基を示し、R2は水素であるか、またはヒドロキシル基またはカルボキシル基が置換していてもよい炭素原子数1〜3の低級アルキル基を示し、Yはカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基および/またはそれらの塩を示し、j、kはそれぞれ独立に0,1,2のいずれかであり、かつj、kは同時に0ではなく、nは2〜20の整数を示す)
R 1 CO represents a long-chain acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms, R 2 is hydrogen, or a carbon which may be substituted by a hydroxyl group or a carboxyl group A lower alkyl group having 1 to 3 atoms; Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group and / or a salt thereof; j and k are each independently 0, 1, 2; And j and k are not 0 at the same time, and n is an integer of 2 to 20)
6. The oily gel cleansing composition according to any one of claims 1 to 5, wherein the oily gel cleansing composition is used as a cleansing cosmetic composition that does not have a residual oil feel and is not bulky when washed with water. Oily gel cleansing.
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JP2007186498A (en) * | 2006-12-01 | 2007-07-26 | Asahi Kasei Chemicals Corp | Oily gel-like composition |
JP2008094735A (en) * | 2006-10-10 | 2008-04-24 | Asahi Kasei Chemicals Corp | Cosmetic composition having excellent stability |
JP4358286B1 (en) * | 2008-09-29 | 2009-11-04 | 株式会社ファンケル | Oily liquid cleansing composition |
JP2009256253A (en) * | 2008-04-17 | 2009-11-05 | Pola Chem Ind Inc | Microsphere for cosmetic and cosmetic containing the same |
KR20100061339A (en) * | 2008-11-27 | 2010-06-07 | 가부시키가이샤환케루 | Composition for oil-based liquid cleansing |
JP2010235514A (en) * | 2009-03-31 | 2010-10-21 | Dhc Co | Liquid composition for cleansing |
JP2010254881A (en) * | 2009-04-28 | 2010-11-11 | Kao Corp | Liquid detergent composition |
JP2011245440A (en) * | 2010-05-28 | 2011-12-08 | Asahi Kasei Chemicals Corp | Non-aqueous composition |
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