JP2005281455A - Detergent composition - Google Patents
Detergent composition Download PDFInfo
- Publication number
- JP2005281455A JP2005281455A JP2004096464A JP2004096464A JP2005281455A JP 2005281455 A JP2005281455 A JP 2005281455A JP 2004096464 A JP2004096464 A JP 2004096464A JP 2004096464 A JP2004096464 A JP 2004096464A JP 2005281455 A JP2005281455 A JP 2005281455A
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- JP
- Japan
- Prior art keywords
- acid
- group
- cleaning composition
- compound
- weight
- 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.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000003599 detergent Substances 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 21
- 150000003855 acyl compounds Chemical class 0.000 claims abstract description 20
- 125000002252 acyl group Chemical group 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001767 cationic compounds Chemical class 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 5
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000006850 spacer group Chemical group 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
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- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 5
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- 235000019482 Palm oil Nutrition 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 239000002540 palm oil Substances 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
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- 239000000344 soap Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- 206010015150 Erythema Diseases 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 206010040880 Skin irritation Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000003704 aspartic acid Nutrition 0.000 description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
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- 125000002091 cationic group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は、特定の構造を有するアシル化合物とシリコーン誘導体とを含む洗浄剤組成物に関する。 The present invention relates to a cleaning composition comprising an acyl compound having a specific structure and a silicone derivative.
従来より、界面活性剤はシャンプー、ボディシャンプー等において洗浄剤、起泡剤として、また乳液、クリーム等の化粧料等の乳化剤、可溶化剤として香粧品組成物や洗浄剤組成物等において重要な構成要素であり、多々用いられている。しかし一方で界面活性剤は皮膚刺激性が強く、タンパク変性作用を有し、長期使用の場合や肌の弱い人が使用した場合には、肌荒れ等を引き起こすことが知られている。
界面活性剤に要求される性能としては、洗浄性・泡立ち等の界面活性能に優れることは勿論のこと、最近では、消費者の要求の多様化や高級品志向に伴い、皮膚などに対する刺激が少ないことに加え、起泡性がよいことや、皮膚などに好ましい感触を付与できることなどの効果が求められている。また、さらには環境への負荷という観点から、生分解性が良いこと、少量で界面活性効果のあることが望まれる傾向がより強くなっている。
Conventionally, surfactants have been important in cosmetic compositions and detergent compositions as detergents and foaming agents in shampoos and body shampoos, and as emulsifiers and solubilizers in cosmetics such as emulsions and creams. It is a component and is often used. However, on the other hand, the surfactant has a strong skin irritation and has a protein denaturing action, and is known to cause rough skin when used for a long time or when a person with weak skin is used.
As the performance required for surfactants, not only is it superior in surface activity such as detergency and foaming, but recently, with the diversification of consumer demand and the trend toward luxury products, there is a stimulus to the skin and the like. In addition to being small, there are demands for effects such as good foaming properties and the ability to impart a favorable feel to the skin. Furthermore, from the viewpoint of environmental load, there is a growing tendency that biodegradability is good and that a small amount of a surface-active effect is desired.
例えば、特許文献1(特公昭50−95303号公報)、特許文献2(特開平7−316589号公報)、特許文献3(特開平8−53694号公報)に開示されているように、従来よりアルキル硫酸塩、ポリオキシエチレンアルキル硫酸塩、アルキルベンゼンスルホン酸塩等が使用されている。しかし、これらの多くは使用時において皮膚への刺激性が強いという問題点がある。また、皮膚などへの刺激性が小さく、生分解性にも優れたアニオン界面活性剤としてN−長鎖アシルアミノ酸塩がある。しかしこの場合には、低濃度での界面活性能、例えば泡立ち、対硬水性等においてはまだ十分とはいえない。
したがって、毛髪、皮膚などに対して低刺激性であり、かつ洗浄性、起泡性に優れるという界面活性剤を含有しており、かつ頭髪、皮膚などに対して良好な感触を付与しうる洗浄剤の開発が熱望されてきた。
Therefore, it contains a surfactant that is hypoallergenic to hair, skin, etc., and has excellent detergency and foaming properties, and can give a good feel to hair, skin, etc. The development of agents has been eagerly desired.
本発明は、毛髪、皮膚などに対して低刺激性であり、かつ起泡性、洗浄性にも優れ、使用時、すすぎ時において指どおりが良く、さらさらとした感触を与えうる洗浄剤組成物の提供を目的とするものである。 The present invention is a detergent composition that is hypoallergenic to hair, skin, etc., has excellent foaming properties and cleanability, is easy to use when used and rinsed, and has a smooth feel. It is intended to provide.
本発明は、特定の化合物、即ち、分子内にアシル基と親水基とを2個以上づつ有する化合物(アシル化合物)の1種以上とシリコーン誘導体の1種以上とを含有する洗浄剤組成物により達成される。
即ち本発明は、下記の通りである。
1.(A)一般式(1)に示すアシル化合物の1種以上、および(B)シリコーン誘導体の1種以上を含有する洗浄剤組成物。
The present invention provides a cleaning composition containing one or more specific compounds, that is, one or more compounds having two or more acyl groups and hydrophilic groups in the molecule (acyl compounds) and one or more silicone derivatives. Achieved.
That is, the present invention is as follows.
1. (A) A cleaning composition containing at least one acyl compound represented by formula (1) and at least one (B) silicone derivative.
(一般式(1)において、Xはm個の官能基、およびそれ以外の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であるスペーサーであり、Xに結合している、n(m≧n)個のQは、一般式(2)で表される置換基で、それぞれ互いに同一でも異なっていてもよく、一般式(2)において、ZはXの有する官能基に由来する結合部であり、R1COは炭素原子数2〜20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 general formula (1), X is a linear, branched, cyclic or aromatic hydrocarbon chain having a molecular weight of 1 million or less, which may have m functional groups and other substituents. N (m ≧ n) Qs which are a spacer and are bonded to X are substituents represented by the general formula (2), which may be the same as or different from each other. ), Z is a bond derived from a functional group of X, R 1 CO represents a long-chain acyl group derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, and R 2 represents hydrogen Or a lower alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group or a carboxyl group, and Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or a group thereof. Salt, j and k are Are either respectively independently 0, 1, 2, and j, k are not 0 at the same time, n represents an integer from 2 to 20)
2.(A)成分が0.1〜99重量%、(B)成分が0.05〜5重量%であって、かつ(A)成分と(B)成分の重量比((A)/(B))が1/5〜100/1であることを特徴とする1.に記載の洗浄剤組成物。
3.前記1.〜2.のいずれかに記載の洗浄剤組成物であって、さらに、(C)1鎖型アニオン界面活性剤、(D)ノニオン界面活性剤、(E)両性界面活性剤、(F)カチオン性化合物、(G)ポリヒドロキシル化合物から選ばれるいずれか1種以上を含有することを特徴とする1.〜2.のいずれかに記載の洗浄剤組成物。
2. The component (A) is 0.1 to 99% by weight, the component (B) is 0.05 to 5% by weight, and the weight ratio of the component (A) to the component (B) ((A) / (B) ) Is 1/5 to 100/1. The cleaning composition described in 1.
3. 1 above. ~ 2. The detergent composition according to any one of 1), (C) a one-chain anionic surfactant, (D) a nonionic surfactant, (E) an amphoteric surfactant, (F) a cationic compound, (G) It contains any one or more selected from polyhydroxyl compounds. ~ 2. The cleaning composition according to any one of the above.
本発明は、毛髪、皮膚などに対して低刺激性であり、気泡性や洗浄性にも優れ、使用時、すすぎ時において指どおりが良く、さらさらとした感触を与えうる洗浄剤組成物を提供することができる。 The present invention provides a detergent composition that is hypoallergenic to hair, skin, etc., has excellent foamability and cleanability, is easy to follow during use and rinse, and can provide a smooth feel. can do.
以下、本発明について、特にその好ましい形態を中心に、具体的に説明する。
本発明の洗浄剤組成物に含有される(A)成分のアシル化合物は、分子内にアシル基と親水基とを2個以上づつ有するアシル化合物の1種以上を含むものであり、該アシル化合物は一般式(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。
一般式(2)中、R1COで示される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2〜20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。
Hereinafter, the present invention will be specifically described focusing on its preferred form.
The acyl compound of the component (A) contained in the cleaning composition of the present invention contains at least one acyl compound having two or more acyl groups and hydrophilic groups in the molecule, and the acyl compound As shown in the general formulas (1) and (2), the compound has a structure in which compounds having at least one acyl group and a hydrophilic group in the molecule are connected by an appropriate spacer.
In the general formula (2), the acyl groups represented by R 1 CO may be independently, that is, may be different or the same, and are derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms as described above. Any material can be used as long as it is linear, branched or cyclic.
例えば、酢酸、プロピオン酸、酪酸、ペンタン酸、ヘキサン酸、ヘプタン酸、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、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、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;
For example, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid , Linear fatty acids such as 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, methylpentadecanoic acid, ethyltetradecanoic acid, propyltri Canic acid, butyldodecanoic acid, pentylundecanoic acid, hexyldecanoic acid, heptylnonanoic acid, dimethyltetradecanoic acid, butylpentylheptanoic acid, trimethyltridecanoic acid, methylhexadecanoic acid, ethylpentadecanoic acid, propyltetradecanoic acid, butyltridecanoic acid, pentyldodecane Acid, hexylundecanoic acid, heptyldecanoic acid, methylheptylnonanoic acid, dipentylheptanoic acid, methylheptadecanoic acid, ethylhexadecanoic acid, ethylhexadecanoic acid, propylpentadecanoic acid, butyltetradecanoic acid, pentyltridecanoic acid, hexyldodecanoic acid, heptyl Undecanoic acid, octyldecanoic acid, dimethylhexadecanoic acid, methyloctylnonanoic acid, methyloctadecanoic acid, ethylheptadecanoic acid, dimethylheptadecanoic acid, Octyl decanoic acid, Mechirunonadekan acid, Mechirunonadekan acid, dimethyl octadecanoic acid, branched fatty acids such as butyl heptyl nonanoic acid;
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;
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があげられる。
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;
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, tridecic acid, tetradecic acid, pentadecinic acid, heptadecinic 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2〜20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が好ましい。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。これらアシル化合物は2種以上組み合わせて用いても良い。
一般式(2)中、R1COで示されるアシル基は、好ましくは炭素原子数8〜20の飽和または不飽和の脂肪酸から誘導されるものがよい。
Moreover, the acyl group derived from the fatty acid obtained from natural fats and oils may be sufficient, and the acyl group derived from the mixed fatty acid containing 80% or more of the saturated or unsaturated fatty acid having 2 to 20 carbon atoms is preferable. 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. Two or more of these acyl compounds may be used in combination.
In the general formula (2), the acyl group represented by R 1 CO is preferably derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms.
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。
一般式(1)中、Xに結合したn個の置換基Q(式(2))は、それぞれ互いに、異なっても同一でもよい。また、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 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 sulfuric ester group, a phosphoric ester group, or a salt thereof. To 3 lower alkyl groups such as methyl, ethyl, propyl, isopropyl, hydroxymethyl, hydroxyethyl, hydroxy (iso) propyl, dihydroxy (iso) propyl, carboxymethyl, carboxy Examples include an ethyl group, a carboxypropyl group, and a sulfoethyl group.
In the general formula (1), n substituents Q (formula (2)) bonded to X may be different from each other or the same. Moreover, Formula (2) shows what is called an acidic amino acid 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。 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.
Xに付くn個の置換基(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。
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。
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。
The n substituents (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.
In the general formula (2), Z is a bonding part (—O) derived from m functional groups (hydroxyl group, amino group, thiol group) substituted with X (m ≧ n and an integer of 2 to 20). -, -NR < 3 >-, -S-). Here, R 3 is hydrogen, or an alkyl group, alkenyl group, aryl group or alkylaryl group having 1 to 10 carbon atoms.
In general formula (1), X is a linear or 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. It is a spacer which is an aromatic hydrocarbon chain, and X may have a substituent other than the hydroxyl group, amino group and thiol group.
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。
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;
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。
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. , A compound residue that may have a substituent other than a hydroxyl group, an amino group, or 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.
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;
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、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、
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。
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-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, turanose, 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、一般式(2)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 general formula (2), 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、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.
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 general formula (2), the carboxyl group, sulfonic acid group, sulfate ester group, phosphate ester group represented by Y and the carboxyl group, sulfonate group, sulfate ester group, phosphate ester group, etc. that can be contained in X are: Salts can be formed 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.
このような一般式(1)で示されるアシル化合物の製造方法としては、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 compound represented by the general formula (1), an N-acyl acidic amino acid anhydride represented by the general formula (3) and a hydroxyl group, an amino group, or a thiol group in the molecule 1 By reacting a compound having two or more kinds of m functional groups with water and / or a mixed solvent of water and an organic solvent, or tetrahydrofuran, benzene, toluene, xylene, carbon tetrachloride, chloroform It can be obtained by using an inert solvent such as acetone, or by mixing at -5 ° C. to 200 ° C. at a temperature not lower than any melting point and reacting without solvent.
または一般式(1)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。 Alternatively, the acyl compound represented by the general formula (1) includes an N-acyl acidic amino acid mono-lower ester (for example, methyl ester, ethyl ester) and a polyhydroxyl compound, a polyamino compound, or a polythiol compound, or a hydroxyl group or an amino group in the molecule. , A compound having any two or three of thiol groups is dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and the mixture is heated at -5 ° C to 250 ° C under reduced pressure. After that, it can be obtained by 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.
本発明の洗浄剤組成物に含有されるアシル化合物は、0.1〜99重量%配合するのが好ましく、特に0.1〜80重量%、さらには1〜50重量%配合するのが、起泡性、洗浄性の点から好ましい。 The acyl compound contained in the cleaning composition of the present invention is preferably blended in an amount of 0.1 to 99% by weight, particularly 0.1 to 80% by weight, more preferably 1 to 50% by weight. It is preferable from the viewpoint of foamability and cleanability.
本発明の洗浄剤組成物において配合される(B)成分のシリコーン誘導体としては、例えば次のようなものが挙げられる。
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、環状シリコーンなど公知のシリコーンである。シリコーン誘導体の含有量は、0.05〜5重量%が望ましく、特に0.1〜3重量%が好ましい。0.05重量%よりも少ないと使用感(コンディショニング性)が低下しやすく、5重量%を超えるとそれに見合った効果が得られない場合がある。また、アシル化合物とシリコーン誘導体とは、重量比で1/5〜100/1とすることが好ましい。
Examples of the silicone derivative of the component (B) to be blended in the cleaning composition of the present invention include the following.
Known silicones such as 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 . The content of the silicone derivative is desirably 0.05 to 5% by weight, and particularly preferably 0.1 to 3% by weight. If it is less than 0.05% by weight, the feeling of use (conditioning property) tends to be lowered, and if it exceeds 5% by weight, an effect commensurate with it may not be obtained. The acyl compound and the silicone derivative are preferably 1/5 to 100/1 in weight ratio.
本発明の洗浄剤組成物において、(C)成分として配合される1鎖型アニオン界面活性剤としては次のようなカルボキシル基含有のものが挙げられる。
例えば、高級脂肪酸塩(石鹸);疎水基部の炭素数8〜20の高級脂肪酸またはそれらの塩が挙げられ、混合脂肪酸としても用いられる。
また、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、が挙げられる。
または、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が挙げられる。
In the cleaning composition of the present invention, examples of the one-chain anionic surfactant blended as the component (C) include the following carboxyl group-containing ones.
For example, higher fatty acid salts (soaps); higher fatty acids having 8 to 20 carbon atoms in the hydrophobic group or salts thereof are also used as mixed fatty acids.
N-acyl amino acid type anionic surfactants; examples of acyl groups include those having 8 to 20 carbon atoms as described above, and examples of 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 -Aminobenzoic acid, amino acids such as p-aminobenzoic acid, and the like.
Or alkyl ether carboxylate, amide ether carboxylate, etc. are mentioned.
また、本発明の洗浄剤組成物において、(C)成分として配合される1鎖型アニオン界面活性剤としては次のようなカルボキシル基含有以外のものが挙げられる。
例えば、アルカンスルホン酸塩、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)、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、ジアルキルスルホコハク酸塩、硫酸化油脂、アルキル硫酸エステル塩(AS)、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、ポリオキシアルキレンアルキルエーテル硫酸エステル塩(AES)、ポリオキシアルキレンスチレン化フェニルエーテル硫酸塩、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等が挙げられる。ここで、これらの1鎖型アニオン界面活性剤の塩の対イオンは、アルカリ金属、アルカリ土類金属、アンモニウムイオン、有機アンモニウムイオンから任意に選択される。
In the cleaning composition of the present invention, examples of the one-chain anionic surfactant blended as the component (C) include those other than the following carboxyl group-containing compounds.
For example, alkane sulfonates, alpha-olefin sulfonates (AOS), alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfonates (SAS), sulfonates of higher fatty acid esters, alpha-sulfonated fatty acid salts, Higher fatty acid amide sulfonate, N-acyl-N-alkyltaurine salt, dialkylsulfosuccinate, sulfated oil, alkyl sulfate ester (AS), alkyl ether sulfate, sulfate of higher fatty acid ester, higher fatty acid alkyl Rollamide sulfate, polyoxyalkylene alkyl ether sulfate (AES), polyoxyalkylene styrenated phenyl ether sulfate, alkyl phosphate, alkyl ether phosphate, polyoxyethylene alkyl ether phosphate, Polyoxyethylene alkyl phenyl ether phosphates, naphthalenesulfonic acid salt formalin condensates and the like. Here, the counter ion of the salt of these one-chain anionic surfactants is arbitrarily selected from alkali metals, alkaline earth metals, ammonium ions, and organic ammonium ions.
これらの(C)成分は、洗浄剤組成物に、(A)成分に対して(A)/(C)の重量比で10/1〜1/10で配合することが好ましく、2種以上混合して用いても良い。中でも、石鹸類、N−アシルアミノ酸塩、N−アシルアルキルタウリン塩、スルホコハク酸塩、ポリオキシエチレンアルキルエーテル硫酸塩を配合することが好ましい。
本発明の洗浄剤組成物において、(D)成分として配合されるノニオン界面活性剤としては、アルキルポリグルコシド、(ポリ)グリセリン脂肪酸エステル、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、ポリオキシエチレンアルキルエーテル(AE)、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、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アルキルエーテル、ポリオキシエチレンポリオキシプロピレングリコール、等の酸化エチレン縮合型、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、アルキルアミンオキサイド、等が挙げられる。これらの(D)成分は、洗浄剤組成物に、(A)成分および(C)成分に対して((A)+(C))/(D)の重量比で20/1〜1/20で配合することが好ましく、2種以上混合して用いても良い。
These components (C) are preferably blended in the cleaning composition at a weight ratio of (A) / (C) of 10/1 to 1/10 with respect to component (A), and two or more types are mixed. May be used. Among these, soaps, N-acyl amino acid salts, N-acyl alkyl taurine salts, sulfosuccinates, and polyoxyethylene alkyl ether sulfates are preferably blended.
In the cleaning composition of the present invention, the nonionic surfactant blended as the component (D) includes alkyl polyglucoside, (poly) glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid ester such as sho, etc. Polyhydric alcohol ester, polyoxyethylene alkyl ether (AE), 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, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene Ruki ether, polyoxyethylene polyoxypropylene glycol, ethylene oxide condensation type, fatty acid alkanolamides and the like, sugars Amin'ashiru products, triethanolamine fatty acid partial esters, alkyl amine oxides, and the like. These components (D) are added to the cleaning composition in a weight ratio of ((A) + (C)) / (D) from 20/1 to 1/20 with respect to the components (A) and (C). It is preferable to mix | blend with 2 or more types, and you may mix and use.
本発明の洗浄剤組成物において、(E)成分として配合される両性界面活性剤としては、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、レシチン類などが挙げられる、具体的にはラウリン酸アミドプロピルベタインが例示される。(E)成分は、洗浄剤組成物において、0.5〜6重量%配合することが好ましく、2種以上混合して用いても良い。
本発明の洗浄剤組成物において、(F)成分として配合されるカチオン性化合物としては、 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が挙げられ、これらの対イオンとしては塩素、ヨウ素、臭素等のハロゲンイオン、メトサルフェート、エトサルフェート、メトフォスフェート、エトフォスフェート等の有機アニオンが挙げられる。
In the cleaning composition of the present invention, examples of the amphoteric surfactant to be blended as the component (E) include alkylbetaines, alkylamidobetaines, alkylsulfobetaines, imidazolinium betaines, and lecithins. Specific examples include amidopropyl betaine laurate. The component (E) is preferably blended in an amount of 0.5 to 6% by weight in the cleaning composition, and two or more kinds may be mixed and used.
In the cleaning composition of the present invention, the cationic compound blended as the component (F) includes primary to tertiary fatty amine salts, alkylammonium chloride salts, tetraalkylammonium salts, trialkylbenzylammonium salts, alkyls. Cationic surfactants such as pyridinium salts, alkylhydroxyethyl imidazolinium salts, dialkylmorpholinium salts, alkylisoquinolium salts, benzethonium salts, benzalkonium salts, and the like, and counterions of these include chlorine, iodine And halogen ions such as bromine, and organic anions such as methosulfate, ethosulfate, methophosphate, and ethophosphate.
また、本発明の洗浄剤組成物において、(F)成分のカチオン性化合物としては、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ポリマーが挙げられる。これらのカチオン性化合物は、洗浄剤組成物において、0.05〜10重量%配合することが好ましく、2種以上混合して用いても良い。 In the cleaning composition of the present invention, the cationic compound of component (F) includes a cationized cellulose derivative, a cationic starch, a cationized guar gum derivative, a diallyl quaternary ammonium salt / acrylamide copolymer, and a quaternary. Polyvinylpyrrolidone derivative, quaternized vinylpyrrolidone / vinylimidazole polymer, polyglycol / amine condensate, quaternized collagen polypeptide, polyethyleneimine, cationic silicone polymer, adipic acid / dimethylaminohydroxypropyldiethylenetriamine copolymer, polyaminopolyamide, Cationic polymers such as cationic chitin derivatives and quaternized polymers can be mentioned. These cationic compounds are preferably blended in an amount of 0.05 to 10% by weight in the cleaning composition, and two or more kinds may be mixed and used.
本発明の洗浄剤組成物において、(G)成分として配合されるポリヒドロキシル化合物としては、前述したような2価以上のポリヒドロキシル化合物が挙げられる。これらのポリヒドロキシル化合物は、洗浄剤組成物において、0.1〜60重量%配合することが好ましく、2種以上混合して用いても良い。
本発明の洗浄剤組成物は通常の方法によって製造することができ、例えば家庭用(衣料、台所、住居、食器、コンタクトレンズ等)洗剤原料、香粧品原料、食品用、医薬品用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。本発明の洗浄剤組成物は、その形態は液体状、固体状、ゲル状、ペースト、スラリー、ミスト状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。
In the cleaning composition of the present invention, examples of the polyhydroxyl compound blended as the component (G) include divalent or higher polyhydroxyl compounds as described above. These polyhydroxyl compounds are preferably blended in an amount of 0.1 to 60% by weight in the cleaning composition, and two or more kinds may be mixed and used.
The cleaning composition of the present invention can be produced by an ordinary method.For example, for household (clothing, kitchen, house, tableware, contact lens, etc.) detergent raw materials, cosmetic raw materials, foods, pharmaceuticals, etc. It can be widely applied from industrial compositions to industrial cleaning agents. The cleaning composition of the present invention can be used in various forms depending on the purpose such as liquid, solid, gel, paste, slurry, mist and the like. However, it is not limited to this form.
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、
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;
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.
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;
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。
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 and powdered perfume; fragrance, deodorant and deodorant such as gel type, liquid type and ceramic type;
Sunscreen / sunscreen cosmetics such as sunscreen / sunscreen cream, sunscreen / sunscreen lotion, sunscreen / sunscreen oil;
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.
また本発明の洗浄剤組成物においては、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 cleaning composition 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;
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;
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;
アボガド油、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、椿油、パーシック油、ひまし油、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、合成トリグリセライド、ホホバ油等の油脂;
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、キャンデリラロウおよびその誘導体等のロウ;
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;
ミリスチン酸イソプロピル、ステアリン酸ブチル等のその他のエステル油;
金属石鹸、ストレートシリコーン油、変成シリコーン油等のシリコーン類等の揮発性および不揮発性の油分;
トリメチルグリジン、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、セラミド類などの保湿剤;
Polymeric surfactants such as sodium alginate, starch derivatives, tragacanth gum;
Natural surfactants such as lecithin, lanolin, cholesterol, saponin;
Avocado oil, almond oil, olive oil, cacao oil, sesame oil, safflower oil, soybean oil, persimmon oil, persic oil, castor oil, mink oil, cottonseed oil, owl, palm oil, egg yolk oil, palm oil, palm kernel oil, synthetic triglyceride, Fats and oils such as jojoba oil;
Hydrocarbons such as liquid paraffin, petrolatum, ceresin, microcrystalline wax, isoparaffin;
Waxes such as beeswax, whale wax, lanolin, carnauba wax, candelilla wax and derivatives thereof;
Higher fatty acids such as 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;
Higher alcohols such as lauryl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldodecanol;
Other ester oils such as isopropyl myristate and butyl stearate;
Volatile and non-volatile oils such as metal soaps, straight silicone oils, silicones such as modified silicone oils;
Moisturizers such as trimethylglycine, sorbitol, raffinose, pyrrolidone carboxylates, lactates, hyaluronates, ceramides;
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;
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;
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;
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, succinoglucan, curdlan, hyaluronic acid, gelatin, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer, polychlorinated Water-soluble and oil-soluble polymers such as dimethylmethylene piperidinium, polyacrylate copolymer, polyvinyl acetate, nitrocellulose, silicone resin;
Thickening and foam increasing components such as polyethylene glycol fatty acid ester, polyoxyethylene fatty acid ester methyl glycoside, tetradecene sulfonate;
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、ヒノキチール等の防腐剤;
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;
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;
アルブチン、コウジ酸、アスコルビン酸、ヒノキチールおよびその誘導体などの美白剤;
Preservatives such as paraoxybenzoates, benzoic acid and its salts, phenoxyethanol, hinokitile;
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;
Benzophenone derivatives, paraaminobenzoic acid derivatives, paramethoxycinnamic acid derivatives, salicylic acid derivatives and other UV absorbers;
Whitening agents such as arbutin, kojic acid, ascorbic acid, hinokitile and its derivatives;
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;
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、スルホ石炭酸亜鉛、タンニン酸などの収斂剤;
メントール、カンフルなどの清涼剤;
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;
精製水;
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;
Astringents such as zinc oxide, zinc sulfate, allantoin hydroxyaluminum, aluminum chloride, zinc sulfocolate, tannic acid;
Refreshing agents such as menthol and camphor;
Antihistamines;
Antioxidants such as silicone-based materials such as polymer silicone and cyclic silicone, tocopherols, BHA, BHT, gallic acid, NDGA;
purified water;
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などを含むことができる。 In addition, 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, seawater dried product, hydrolyzed wheat powder, hydrolyzed silk, carrot extract, cucumber extract, gentian extract, yeast extract, rice germ oil, comfrey extract, savanna extract, ginger 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 extract, Over Ma chamomile extract, royal jelly extract, seaweed, rice bran, licorice, citrus unshiu peel, angelica, pulverized Momonoha, can contain sphingolipid, guaiazulene, such as vitamin C.
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。
(洗浄剤組成物の皮膚刺激性)
10人のパネラーの前腕屈曲部皮膚に、アシル基含有組成物の1wt%ナトリウム塩水溶液試料0.1gを直径1cmのパッチテスト用絆創膏で24時間貼付後、皮膚刺激性の有無を評価した。評価基準を以下に記す。
紅斑を示した人が1人以下の場合 ○
紅斑を示した人が2〜5人の場合 △
紅斑を示した人が6人以上の場合 ×
The evaluation means used in the examples of the present invention are as follows.
(Skin irritation of cleaning composition)
After applying 0.1 g of a 1 wt% aqueous sodium salt solution of the acyl group-containing composition to the skin of the forearm of 10 panelists for 24 hours using a patch test adhesive bandage having a diameter of 1 cm, the presence or absence of skin irritation was evaluated. The evaluation criteria are described below.
When the number of people showing erythema is 1 or less ○
2 to 5 people showing erythema △
When more than 6 people show erythema ×
(毛髪洗髪後のすすぎにおける感触)
長さ20cm、重さ20gの人毛を束ねたものを用い、これを40℃の温水に浸漬した後、被験物である洗浄剤組成物を固形分として1gを用いて泡立てた。これを流水ですすいだ時の指どおり感を、5名のパネラーにより下記の基準で評価した。
非常によい ◎
普通 ○
やや悪い △
悪い ×
(Feeling during rinsing after hair washing)
A bundle of human hair having a length of 20 cm and a weight of 20 g was used and immersed in warm water at 40 ° C., and then the cleaning composition as a test product was foamed using 1 g as a solid content. The feeling of fingering when rinsing this with running water was evaluated by the five panelists according to the following criteria.
Very good ◎
Normal ○
Somewhat bad △
Bad ×
(さらさら感)
長さ20cm、重さ20gの人毛を束ねたものを用い、これを40℃の温水に浸漬した後、被験物である洗浄剤組成物を固形分として1gを用いて泡立てた。これを流水ですすいだ後、ドライヤー乾燥したものを用い、5名のパネラーにより下記の基準で評価した。
非常にさらさらしている ◎
普通 ○
ややべとつき感がある △
べとつき感がある ×
(Smooth feeling)
A bundle of human hair having a length of 20 cm and a weight of 20 g was used and immersed in warm water at 40 ° C., and then the cleaning composition as a test product was foamed using 1 g as a solid content. This was rinsed with running water and then dried with a dryer, and evaluated by the following standards using five panelists.
Very smooth ◎
Normal ○
A little sticky △
There is a sticky feeling ×
(アシル化合物の製造例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20重量%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重量%、pH6.5(25℃)の水溶液に中和調製して式(4)に示すアシル化合物を含有する組成物を得た。
(Production Example 1 of acyl 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 stirring for another 30 minutes, tertiary butanol was added to a concentration of 20% by weight in the liquid, 75% sulfuric acid was added dropwise to bring the liquid pH value 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 an aqueous solution having a solid content of 30% by weight and a pH of 6.5 (25 ° C.). A composition containing an acyl compound represented by formula (4) was prepared.
(アシル化合物の製造例2)
製造例1において、N−ラウロイル−L−グルタミン酸無水物31.1gをN−ココイル−L−グルタミン酸無水物とし、中和をトリエタノールアミンを用い、固形分30重量%、pH5.5(25℃)とした以外は、製造例1の方法と同じ条件で実施し、アシル化合物を含有する組成物を得た。
(Production Example 2 of acyl compound)
In Production Example 1, 31.1 g of N-lauroyl-L-glutamic anhydride was converted to N-cocoyl-L-glutamic anhydride, neutralization was performed using triethanolamine, a solid content of 30% by weight, pH 5.5 (25 ° C. ) Was carried out under the same conditions as in Production Example 1 to obtain a composition containing an acyl compound.
(アシル化合物の製造例3)
製造例2において、中和を水酸化カリウムを用い、固形分30重量%、pH6.3(25℃)とした以外は、製造例1の方法と同じ条件で実施し、アシル化合物を含有する組成物を得た。
(Acyl Compound Production Example 3)
A composition containing an acyl compound, which was carried out under the same conditions as in Production Example 1, except that potassium hydroxide was used for neutralization and the solid content was 30 wt% and pH 6.3 (25 ° C.). I got a thing.
[実施例1〜3、比較例1〜2]
表1の組成の洗浄剤組成物を調製し、毛髪洗浄時、および乾燥後の感触について評価を実施した。本発明の洗浄剤組成物は、すすぎ時の感触、乾燥後のさらさら感ともに優れることを確認した。組成物はトータルが100重量%となるように精製水を添加した。表中の数字は重量%を示す。
[Examples 1-3, Comparative Examples 1-2]
A cleaning composition having the composition shown in Table 1 was prepared and evaluated for the feel when washing the hair and after drying. It was confirmed that the cleaning composition of the present invention was excellent in both the feel during rinsing and the dry feeling after drying. Purified water was added so that the total amount of the composition was 100% by weight. The numbers in the table indicate% by weight.
[実施例4]
下記のような組成の洗浄剤組成物を作成した。トータルが100重量%となるように精製水を添加した。この組成物をシャンプーとして用いると、洗浄・すすぎ時の感触に優れ、洗髪後のさらさら感に優れていた。
(組成) (重量%)
製造例1の化合物(30重量%水溶液) 33
ジメチルポリシロキサン(1万Pa・s) 0.3
ラウリン酸ジエタノールアミド 10
ラウリン酸ナトリウム 2
ヒドロキシエチルセルロース 0.05
精製水 残余
[Example 4]
A cleaning composition having the following composition was prepared. Purified water was added so that the total would be 100% by weight. When this composition was used as a shampoo, it was excellent in feel during washing and rinsing, and was excellent in smoothness after washing.
(Composition) (wt%)
Compound of Production Example 1 (30% by weight aqueous solution) 33
Dimethylpolysiloxane (10,000 Pa · s) 0.3
Lauric acid diethanolamide 10
Sodium laurate 2
Hydroxyethyl cellulose 0.05
Purified water residue
[実施例5]
下記のような組成の洗浄剤組成物を作成した。トータルが100重量%となるように精製水を添加した。この組成物をシャンプーとして用いると、洗浄・すすぎ時の感触に優れ、洗髪後のさらさら感に優れていた。
(組成) (重量%)
製造例2の化合物(30重量%水溶液) 33
N-ココイル-L-グルタミン酸トリエタノールアミン 10
ジメチルポリシロキサン(1万Pa・s) 0.5
ラウリン酸ジエタノールアミド 2
ラウリン酸アミドプロピルベタイン 2
グリセリン 4
精製水 残余
[Example 5]
A cleaning composition having the following composition was prepared. Purified water was added so that the total would be 100% by weight. When this composition was used as a shampoo, it was excellent in feel during washing and rinsing, and was excellent in smoothness after washing.
(Composition) (wt%)
Compound of Production Example 2 (30% by weight aqueous solution) 33
N-cocoyl-L-glutamic acid triethanolamine 10
Dimethylpolysiloxane (10,000 Pa · s) 0.5
Lauric acid diethanolamide 2
Lauric acid amidopropyl betaine 2
Glycerin 4
Purified water residue
[実施例6]
下記のような組成の洗浄剤組成物を作成した。トータルが100重量%となるように精製水を添加した。この組成物をボディシャンプーとして用いると、洗浄・すすぎ時の感触に優れ、洗浄後のさらさら感に優れていた。
(組成) (重量%)
製造例1の化合物(30重量%水溶液) 66
ジメチルポリシロキサン(1万Pa・s) 0.2
ラウリルジメチルアミンオキシド 2
ラウリン酸カリウム 2
グリセリン 4
精製水 残余
[Example 6]
A cleaning composition having the following composition was prepared. Purified water was added so that the total would be 100% by weight. When this composition was used as a body shampoo, it was excellent in feel during washing and rinsing, and was excellent in a smooth feeling after washing.
(Composition) (wt%)
Compound of Production Example 1 (30% by weight aqueous solution) 66
Dimethylpolysiloxane (10,000 Pa · s) 0.2
Lauryldimethylamine oxide 2
Potassium laurate 2
Glycerin 4
Purified water residue
[実施例7]
下記のような組成の洗浄剤組成物を作成した。トータルが100重量%となるように精製水を添加した。この組成物を洗顔料として用いると、洗浄・すすぎ時の感触に優れ、洗浄後のさらさら感に優れていた。
(組成) (重量%)
製造例3の化合物(30重量%水溶液) 33
ココイル−L−グルタミン酸カリウム 5
ジメチルポリシロキサン(1万Pa・s) 0.5
ラウリン酸カリウム 2
ミリスチン酸カリウム 3
カチオン化セルロース 0.1
グリセリン 10
精製水 残余
[Example 7]
A cleaning composition having the following composition was prepared. Purified water was added so that the total would be 100% by weight. When this composition was used as a facial cleanser, it was excellent in feel during washing and rinsing and was excellent in a smooth feeling after washing.
(Composition) (wt%)
Compound of Production Example 3 (30% by weight aqueous solution) 33
Cocoyl-L-potassium glutamate 5
Dimethylpolysiloxane (10,000 Pa · s) 0.5
Potassium laurate 2
Potassium myristate 3
Cationized cellulose 0.1
Glycerin 10
Purified water residue
本発明の洗浄剤組成物は、毛髪、皮膚などに対して低刺激性であり、気泡性や洗浄性にも優れ、使用時、すすぎ時において指どおりが良く、さらさらとした感触を与えうる洗浄剤組成物を提供することから、化粧品、医薬部外品等の香粧品、医薬品、洗浄剤の分野で好適に利用できる。 The cleaning composition of the present invention has low irritation to hair, skin, etc., is excellent in foaming properties and cleansing properties, and is easy to follow during use and rinsing, and can give a smooth feel. Since the pharmaceutical composition is provided, it can be suitably used in the fields of cosmetics, cosmetics such as quasi-drugs, pharmaceuticals, and detergents.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005281181A (en) * | 2004-03-29 | 2005-10-13 | Asahi Kasei Chemicals Corp | Irritation emollient |
JP2006137818A (en) * | 2004-11-11 | 2006-06-01 | Asahi Kasei Chemicals Corp | Composition for washing |
JP2006225370A (en) * | 2005-08-19 | 2006-08-31 | Asahi Kasei Chemicals Corp | Hair cosmetic |
JP2007191463A (en) * | 2006-10-10 | 2007-08-02 | Asahi Kasei Chemicals Corp | Bathing agent |
JP2018002609A (en) * | 2016-06-28 | 2018-01-11 | 株式会社ノエビア | Cleansing agent |
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Publication number | Priority date | Publication date | Assignee | Title |
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JPH0881354A (en) * | 1994-09-12 | 1996-03-26 | Kao Corp | Cleaning agent composition for body |
JPH10231500A (en) * | 1997-02-18 | 1998-09-02 | Kanebo Ltd | Detergent composition |
JP2002167313A (en) * | 2000-07-24 | 2002-06-11 | Asahi Kasei Corp | Surface active agent |
WO2004020394A1 (en) * | 2002-08-27 | 2004-03-11 | Asahi Kasei Chemicals Corporation | Novel composition containing acyl group |
-
2004
- 2004-03-29 JP JP2004096464A patent/JP2005281455A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0881354A (en) * | 1994-09-12 | 1996-03-26 | Kao Corp | Cleaning agent composition for body |
JPH10231500A (en) * | 1997-02-18 | 1998-09-02 | Kanebo Ltd | Detergent composition |
JP2002167313A (en) * | 2000-07-24 | 2002-06-11 | Asahi Kasei Corp | Surface active agent |
WO2004020394A1 (en) * | 2002-08-27 | 2004-03-11 | Asahi Kasei Chemicals Corporation | Novel composition containing acyl group |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005281181A (en) * | 2004-03-29 | 2005-10-13 | Asahi Kasei Chemicals Corp | Irritation emollient |
JP4684567B2 (en) * | 2004-03-29 | 2011-05-18 | 旭化成ケミカルズ株式会社 | Irritation relief agent |
JP2006137818A (en) * | 2004-11-11 | 2006-06-01 | Asahi Kasei Chemicals Corp | Composition for washing |
JP2006225370A (en) * | 2005-08-19 | 2006-08-31 | Asahi Kasei Chemicals Corp | Hair cosmetic |
JP2007191463A (en) * | 2006-10-10 | 2007-08-02 | Asahi Kasei Chemicals Corp | Bathing agent |
JP2018002609A (en) * | 2016-06-28 | 2018-01-11 | 株式会社ノエビア | Cleansing agent |
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