CN105219527B - 四氢呋喃衍生物作为芳香物质 - Google Patents
四氢呋喃衍生物作为芳香物质 Download PDFInfo
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- CN105219527B CN105219527B CN201510362932.5A CN201510362932A CN105219527B CN 105219527 B CN105219527 B CN 105219527B CN 201510362932 A CN201510362932 A CN 201510362932A CN 105219527 B CN105219527 B CN 105219527B
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- tetrahydrofuran
- fragrance
- compound
- acid
- carboxylic acid
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- 239000000463 material Substances 0.000 claims abstract description 63
- 125000003118 aryl group Chemical group 0.000 claims abstract description 46
- -1 tetrahydrofuran-2-carboxylic acid 2-methylallyl ester Chemical class 0.000 claims description 282
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- IXHZGHPQQTXOKV-UHFFFAOYSA-N methyl oxolane-2-carboxylate Chemical compound COC(=O)C1CCCO1 IXHZGHPQQTXOKV-UHFFFAOYSA-N 0.000 claims description 6
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- WRPMUZXHQKAAIC-ZZEZOPTASA-N stearyl oleate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC WRPMUZXHQKAAIC-ZZEZOPTASA-N 0.000 description 1
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- XMLSXPIVAXONDL-UHFFFAOYSA-N trans-jasmone Natural products CCC=CCC1=C(C)CCC1=O XMLSXPIVAXONDL-UHFFFAOYSA-N 0.000 description 1
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- IMRYETFJNLKUHK-UHFFFAOYSA-N traseolide Chemical compound CC1=C(C(C)=O)C=C2C(C(C)C)C(C)C(C)(C)C2=C1 IMRYETFJNLKUHK-UHFFFAOYSA-N 0.000 description 1
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- 230000001960 triggered effect Effects 0.000 description 1
- HTJNEBVCZXHBNJ-XCTPRCOBSA-H trimagnesium;(2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;diphosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O HTJNEBVCZXHBNJ-XCTPRCOBSA-H 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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- ODHUFJLMXDXVRC-UHFFFAOYSA-N tripropyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCOC(=O)CC(O)(C(=O)OCCC)CC(=O)OCCC ODHUFJLMXDXVRC-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 229940040064 ubiquinol Drugs 0.000 description 1
- QNTNKSLOFHEFPK-UPTCCGCDSA-N ubiquinol-10 Chemical compound COC1=C(O)C(C)=C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)C(O)=C1OC QNTNKSLOFHEFPK-UPTCCGCDSA-N 0.000 description 1
- 229940035936 ubiquinone Drugs 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- WCTNXGFHEZQHDR-UHFFFAOYSA-N valencene Natural products C1CC(C)(C)C2(C)CC(C(=C)C)CCC2=C1 WCTNXGFHEZQHDR-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-M valerate Chemical class CCCCC([O-])=O NQPDZGIKBAWPEJ-UHFFFAOYSA-M 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 235000016788 valerian Nutrition 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229940117960 vanillin Drugs 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- WXETUDXXEZHSCS-MAVITOTKSA-N vertofix coeur Chemical compound C[C@@H]1CC[C@@]2(C(/CC3)=C\C(C)=O)[C@@H]3C(C)(C)[C@@H]1C2 WXETUDXXEZHSCS-MAVITOTKSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001846 viola odorata l. leaf absolute Substances 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
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- 239000011709 vitamin E Substances 0.000 description 1
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- 235000015041 whisky Nutrition 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
- PHXATPHONSXBIL-UHFFFAOYSA-N xi-gamma-Undecalactone Chemical compound CCCCCCCC1CCC(=O)O1 PHXATPHONSXBIL-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 229960003487 xylose Drugs 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229940071566 zinc glycinate Drugs 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- UOXSXMSTSYWNMH-UHFFFAOYSA-L zinc;2-aminoacetate Chemical compound [Zn+2].NCC([O-])=O.NCC([O-])=O UOXSXMSTSYWNMH-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- 235000004835 α-tocopherol Nutrition 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
- 229930007850 β-damascenone Natural products 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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- A—HUMAN NECESSITIES
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Landscapes
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
- Seasonings (AREA)
Abstract
提出特定的式(I)的四氢呋喃衍生物,含有这种四氢呋喃衍生物的芳香物质和香料物质混合物,其在芳香或香料物质(混合物)以及相应的加香产品中的应用。
Description
发明领域
本发明属于芳香和香料物质领域并且涉及首次确定的下式(I)的四氢呋喃衍生物,含有这类四氢呋喃衍生物的芳香物质和香料物质混合物,其在芳香或香料物质(混合物)以及相应的加香产品中的应用。
背景技术
在香水工业存在对新的芳香物质的持续需求,因为一直需要为消费者提供新的流行的具备清新香调(Duftnoten)的香味。具备甜味的、清新的并且自然的香调的新的芳香物质会被大量并且多样的用于香水、芳香物质混合物(香水组合物)和不同应用领域中的加香。由于消费者对于新的甜味的、清新的和自然的香调上涨的需求,香水产业中存在对香料物质持续的需求,借此在香水中实现新效果并以此创造新的流行趋势。因此具备甜味的、清新的并且自然的香调的化合物是香料物质工业,特别是香水组合物中非常重要并且所需的成分。
尽管已经存在大量芳香物质,为了创造新的流行的香水组合物,在香水工业仍然存在对具备特殊的气味性质的新芳香物质的持续需求,这类物质适合作为底物(Grundlage)用于具备复杂特征的新的流行的香水组合物。特别关注的新的香料物质是,除了其基础的,即气味性质外,还具备额外的有利的第二性质,如例如在特定使用条件下的更高稳定性、高的发散性、大的辐射力、良好的扩散性(即好的空间效应)、丰富、力度和/或自然感、气味增强性能,或与具备类似的基础气味性质的芳香物质相比,更好的皮肤感受性能。
特定导向的新的香料物质总是很难确定,因为一方面对于气味感知的机理并未充分已知,并且特定的气味感知与所属芳香物质的化学结构之间的相互关系并未充分研究,通常对已知芳香物质结构组成上细微的改动就会导致感官性能的巨大变化以及损害人体适宜性。因此对于材料作为芳香物质的应用,除了有益的气味谱,材料的其他性质,如例如稳定性,与其他芳香物质的相容性、溶解性、以及毒理学安全性、生物降解性和生物累积性也很重要。
因此在香水工业存在对适用于生产芳香物质组合物或加香产品的芳香物质持续的需求。特别需要一种芳香物质,其由于具备上述技术性能能够提高芳香物质组合物和芳香油的使用。
因此本发明的目标在于,确定具备有益气味谱的新的芳香和香料物质。这种新的芳香和香料物质尤其应当具备一种清新的并且甜味的香调,此外还表现出其他有益的气味特征,赋予其更有益的气味性质和复杂性,尤其是用于含有其他芳香和香料物质的芳香和香料物质混合物。本发明的目标还在于确定芳香和香料化合物,其具备宽的气味谱,而没有不利的旁调或后调,从而可以广泛应用。这种新的香料物质特别还应当适用于香水。本发明的目标特别是提供毒理学安全的芳香和香料物质组合物,使其适用于化妆产品,并且尤其是香水,其中芳香和香料物质组合物与人体皮肤直接接触。这种新的香料物质还应当具备好的稳定性和与(尽可能多的)其他芳香物质的相容性。
发明内容
本发明的主题是式(I)的四氢呋喃衍生物:
其中基团
R1是氢、C1-C3-烷基或O-R2基团,
其中R2是支链或非支链的C1-C5-烷基或支链或非支链的C2-C6-烯基、取代或未取代的环烷基、取代或未取代的(C1-C8)烷基(C3-C7)环烷基、取代或未取代的环烯基、取代或未取代的(C2-C8)烯基(C3-C7)环烷基、取代或未取代的芳基、或取代或未取代的(C1-C8)烷基芳基、取代或未取代的(C2-C8)烯基芳基,
其中包括式(I)化合物的所有立体异构体。
在本发明中定义“支链或非支链的C1-C5-烷基”是指可以直链或支链,例如甲基-、乙基-、正丙基-、异丙基-、正丁基-、异丁基-、叔丁基-或正戊基-、2,2-二甲基丙基-,2-甲基丁基-或3-甲基丁基。优选甲基-或乙基。
在本发明中定义“支链或非支链的C2-C6-烯基”是指含有一个碳碳双键(乙烯结构单元)的基团。形式上由一种烯烃派生出一种烯基。优选烯基为乙烯基、丙烯基、丁烯基(丁-1-烯基、(Z)-丁-2-烯基、(E)-丁-2-烯基、2-甲基丙-1-烯基)、戊烯基(戊-1-烯基、顺式-戊-2-烯基、反式-戊-2-烯基、2-甲基-丁-1-烯基、2-甲基-丁-2-烯基、3-甲基-丁-1-烯基)。
在本发明中定义“环烷基”是指任选由一个或多个卤族元素取代的含有3至7个环上碳原子的饱和环状基团,如例如环丙基、甲基环丙基、环丁基、甲基环丁基、环戊基、甲基环戊基、环己基、甲基环己基、环庚基、甲基环庚基。
在本发明中定义“环烯基”是指任选由一个或多个卤族元素取代的含有3至7个环上碳原子的不饱和环状基团。
“(C1-C8)烷基(C3-C7)环烷基”是指环烷基,其通过直链或支链的(C1-C8)烷基单元与OR2基团的氧原子相连。
“(C2-C8)烯基(C3-C7)环烷基”是指环烷基,其通过直链或支链的(C2-C8)烯基单元与OR2基团的氧原子相连。
“芳基”是含有6至14个碳原子的芳香化或部分芳香化的环碳基团,其含有一个环,如例如苯基或亚苯基或更多稠环如例如萘基或蒽基。实例是苯基、萘基、萘满基、蒽基、茚满基或茚基。芳基可以在任何适于形成稳定的立体异构体的位置由一个或多个选自氢或卤素的基团取代。
在本发明中定义“(C1-C8)烷基芳基”是指如上文所述的芳基基团,其通过直链或支链的(C1-C8)烷基单元与OR2基团的氧原子相连。
在本发明中定义“(C2-C8)烯基芳基”是指芳基基团,如上文所述,该芳基通过直链或支链的(C2-C8)烯基单元与OR2基团的氧原子相连。
定义“取代或未取代”是指各个基团(例如在烷基或环烷基环上)上任选含有其他基团。
式(I)的四氢呋喃衍生物优选自组包括:
化合物1:四氢呋喃-2-羧酸甲酯
化合物2:四氢呋喃-2-羧酸乙酯
化合物3:四氢呋喃-2-羧酸丙酯
化合物4:四氢呋喃-2-羧酸烯丙酯
化合物5:四氢呋喃-2-羧酸异丙酯
化合物6:四氢呋喃-2-羧酸2-甲基烯丙酯
化合物7:四氢呋喃-2-羧酸异丁酯
化合物8:四氢呋喃-2-羧酸丁酯
化合物9:1-(四氢-呋喃-2-基)-乙酮
式(I)的四氢呋喃衍生物的制备
式(I)的四氢呋喃羧酸酯的制备根据US 2,843,607进行,其中反应物(例如呋喃羧酸酯或乙酰基呋喃,参见反应)在H2-气氛中在反应釜中加热并氢化,其中温度保持在为约110℃。反应持续约2小时,其中催化剂使用Raney镍。有利的是在反应中使用其他酯化催化剂,例如对甲苯磺苏氨酸。反应后将Raney镍催化剂分离并蒸发得到反应产物。在US 2,843,607中得到四氢呋喃羧酸乙酯、丙酯和庚酯。已经公开四氢呋喃羧酸丙酯和庚酯可以用作溶剂以及在香水中使用。
然而没有公开详细的气味描述以及作为芳香物质的用途。四氢呋喃羧酸乙酯的阈值在一篇文献中给出(Takeoka,Teranishi and Buttery in Olfaction and TasteXI.Springer-Verlag,pp.271-273),然而没有进一步公开该化合物的气味描述。
本发明的通式(I)的化合物也可以使用醇进行四氢呋喃羧酸甲酯的转酯化。
令人惊异的发现,式(I)的四氢呋喃衍生物具备特定的气味谱,特别是至今未知的所述化合物1至9,因此其作为芳香物质的用途,特别是在芳香油中的应用至今未知。
单个化合物1至9的感官性能如下描述:
在与其他芳香物质的混合物中式(I)的四氢呋喃衍生物并且特别是单个化合物1至9或其混合物在很少的用量下已经能够增强芳香物质混合物的强度并使芳香物质混合物的整体气味圆润,并且赋予该混合物更强的辐射、清新和自然度。因此式(I)的四氢呋喃衍生物及其混合物具备令人惊异的的气味品质。
基于此本发明的另一个主题是香料和/或芳香物质混合物,含有
(i)一种或多种式(I)的四氢呋喃衍生物,
(ii)一种或多种其他芳香或香料物质,
其中式(I)的四氢呋喃衍生物的含量占香料或芳香物质混合物总量的0.00001至40重量%,优选0.001至35重量%并且尤其优选0.2至30重量%,其中所述量为所有式(I)的四氢呋喃衍生物的总量。
本发明的香料和芳香物质混合物能够实现上述优点,并且尤其是提供具备有价值的清新甜味气味和性质的混合物。
本发明的香料和芳香物质混合物,优选一种根据本发明的芳香油,含有用量为0.00001至40重量%,优选0.001至35重量%并且尤其优选0.2至30重量%的式(I)的四氢呋喃衍生物或其混合物,分别基于香料和芳香物质混合物的总量计,其中所述用量为所有式(I)的四氢呋喃衍生物的总量。
本发明的香料和芳香物质混合物,优选芳香油,优选还含有其他芳香物质,其优选自以下给出的出版物中所提到的物质:“Riechstoffe”,Steffen Arctander,“Perfume andFlavor Chemicals”,Eigenverlag,Montclair,N.J.1969;H.Surburg,J.Panten,“CommonFragrance and Flavor Materials”,第五版,Wiley-VCH,Weinheim 2006。
优选地在这类香料和/或芳香物质混合物中使用多种式(I)的四氢呋喃衍生物的混合物,优选两种、三种、四种、五种、六种、七种、八种或九种式(I)的四氢呋喃衍生物,这些化合物优选自化合物1至9,其中同样包括这些化合物的异构体。
在本发明中多种式(I)的四氢呋喃衍生物的混合物是指优选至少一种、两种、三种、四种、五种、六种、七种、八种或九种式(I)的化合物,这些化合物优选自化合物1至9,其中同样包括这些化合物的异构体。
在本发明中定义“式(I)的四氢呋喃衍生物的异构体”是指式(I)的四氢呋喃衍生物的R异构体和S异构体。化合物1至9都具备一个手性中心:
化合物1:四氢呋喃-2-羧酸甲酯
化合物2:四氢呋喃-2-羧酸乙酯
化合物3:四氢呋喃-2-羧酸丙酯
化合物4:四氢呋喃-2-羧酸烯丙酯
化合物5:四氢呋喃-2-羧酸异丙酯
化合物6:四氢呋喃-2-羧酸2-甲基烯丙酯
化合物7:四氢呋喃-2-羧酸异丁酯
化合物8:四氢呋喃-2-羧酸丁酯
化合物9:1-(四氢-呋喃-2-基)-乙酮
相应地化合物1至9的异构体优选是指以下的R和S异构体:
化合物1:
R-四氢呋喃-2-羧酸甲酯(化合物1a),
S-四氢呋喃-2-羧酸甲酯(化合物1b),
化合物2:
R-四氢呋喃-2-羧酸乙酯(化合物2a),
S-四氢呋喃-2-羧酸乙酯(化合物2b),
化合物3:
R-四氢呋喃-2-羧酸丙酯(化合物3a),
S-四氢呋喃-2-羧酸丙酯(化合物3b),
化合物4:
R-四氢呋喃-2-羧酸烯丙酯(化合物4a),
S-四氢呋喃-2-羧酸烯丙酯(化合物4b),
化合物5:
R-四氢呋喃-2-羧酸异丙酯(化合物5a),
S-四氢呋喃-2-羧酸异丙酯(化合物5b),
化合物6:
R-四氢呋喃-2-羧酸2-甲基烯丙酯(化合物6a),
S-四氢呋喃-2-羧酸2-甲基烯丙酯(化合物6b),
化合物7:
R-四氢呋喃-2-羧酸异丁酯(化合物7a),
S-四氢呋喃-2-羧酸异丁酯(化合物7b),
化合物8:
R-四氢呋喃-2-羧酸丁酯(化合物8a),
S-四氢呋喃-2-羧酸丁酯(化合物8b),
化合物9:
R-1-(四氢-呋喃-2-基)-乙酮(化合物9a),
S-1-(四氢-呋喃-2-基)-乙酮(化合物9b)。
化合物1至9的各个异构体以及各个异构体的混合物作为香料和芳香物质的用途,特别是在香料和芳香物质混合物以及消费产品,如例如化妆产品或家居用品中的用途同样是本发明的主题。因此本发明的另一个主题是式(I)的四氢呋喃衍生物或其混合物作为芳香物质的用途。对于作为芳香物质的用途式(I)的四氢呋喃衍生物优选以由至少一种、两种、三种、四种、五种、六种、七种、八种或九种式(I)的化合物构成的混合物使用。
对于化妆产品和家居产品特别涉及洗涤和清洁剂、卫生或护理产品。优选涉及用于身体和/或头发护理、洗发香波、柔软剂或洗衣粉的产品。
本发明的另一个重要方面是式(I)的四氢呋喃衍生物或其混合物
(i)调整、增强、改善和/或改变气味印象,和/或
(ii)用于提高芳香物质或香料和/或芳香物质混合物的附着性或扩散性的用途。
本发明的主题特别是式(I)的四氢呋喃衍生物或其混合物
(i)在纯度、清新度和/或自然度方面用于调整、增强、改善和/或改变气味印象,和/或
(ii)用于香料和/或芳香物质混合物或化妆产品或家居产品气味圆润的用途。
本发明的主题同样是式(I)的四氢呋喃衍生物或其混合物在体积、复杂性、时尚性和/或自然度方面用于调整、增强、改善和/或改变气味印象的用途。
此外本发明的主题是式(I)的四氢呋喃衍生物或其混合物,在香料和/或芳香物质混合物中,用于调整与不含有式(I)的四氢呋喃衍生物或其混合物的混合物相比,舒缓(pflegenderen)、和谐、高品质和/或自然的气味印象的用途。
本发明的的其他方面是本发明的香料和/或芳香物质混合物在化妆产品或家居产品中
(i)用于调整、增强、改善和/或改变气味印象,和/或
(ii)用于提高芳香物质或香料和/或芳香物质混合物的附着性或扩散性,和/或
(iii)在纯度、清新度和/或自然度方面用于调整、增强、改善和/或改变气味印象,和/或
(iv)用于香料和/或芳香物质混合物或化妆产品或家居产品气味圆润的用途。
在本发明的(香料和芳香物质)混合物和(化妆品和家居)产品中式(I)的四氢呋喃衍生物优选与其他芳香和香料物质一起使用。适当的优选可结合芳香物质选自:
·天然原料物质的提取物如精油、浸膏、净油(Absolues)、树脂、香树脂、香膏、酊剂,如例如龙涎香酊、檀香木油、欧白芷油(Angelicasamenl)、当归油、茴芹油、缬草油、罗勒油、树苔-净油、香叶多香果油、北艾油、安息香树脂树脂、拟美国薄荷油、蜂蜡-净油、桦木焦油、苦杏仁油、香薄荷油、布枯油、巴西檀木油、刺桧油、菖蒲油、樟脑油、依兰油、白豆蔻油、苦香树油、決明屬油、決明屬-净油、海狸香-净油、雪松叶油、雪松木油、岩蔷薇油、香茅油、柠檬油、苦配巴香膏、苦配巴香膏油、芫荽油、广木香根油、枯茗油、柏油、印蒿油、莳萝草油、莳萝籽油、Eau de brouts-净油、橡苔-净油、榄香脂油、龙蒿油、柠檬桉油、桉树油、小茴香油、云杉针叶油、白松香油、白松香树脂、天竺葵油、葡萄柚油、愈创木油、羯布罗香膏、羯布罗香膏油、蜡菊-净油、蜡菊油、姜油、鳶尾草根-净油、鳶尾草根油、茉莉-净油、白菖蒲油、蓝母菊油、罗马母菊油、胡萝卜籽油、卡藜油、松针油、绿薄荷油、葛缕子油、岩蔷薇油、岩蔷薇净油、杂薰衣草净油、杂薰衣草油、熏衣草净油、熏衣草油、柠檬草油、圆叶当归油、蒸馏白柠檬油、压榨白柠檬油、沉香油、山苍树油、月桂叶油、肉豆蔻衣油、墨角蘭油、橘子油、Massoirinden油、含羞草-净油、黄葵籽油、黄葵酊、欧丹参油、肉豆蔻油、没药净油、没药油、桃金娘油、石竹叶油、石竹花油、橙花油、乳香净油、乳香油、愈伤草油、橙花净油、橙油、牛至油、玫瑰草油、广藿香油、紫苏子油、秘鲁香脂油、欧芹叶油、欧芹子油、苦橙叶油、胡椒薄荷油、胡椒油、多香果油、松油、Poley油、玫瑰净油、蔷薇木油、玫瑰油、迷迭香油、达尔马提亚鼠尾草油、西班牙鼠尾草油、檀香油、芹菜籽油、穗熏衣草油、八角茴香油、安息香油、万寿菊油、杉针油、茶树油、松节油、百里香油、吐鲁香膏、香豆-净油、晚香玉-净油、香荚兰提取物、紫罗兰叶净油、马鞭草油、岩兰油、刺柏油、葡萄籽油、苦艾油、冬青油、衣兰油、神香草油、灵猫香净油、肉桂叶油、肉桂皮油、以及其馏分,或从其中分离出的成分;
·选自烃类的单个芳香物质,如例如3-蒈烷、α-蒎烯、β-蒎烯、α-松油烯、γ-松油烯、对-伞花烃、甜没药醇、莰烯、石竹烯、柏木烯、金合欢烯、苧烯、长叶烯、月桂烯、罗勒烯、朱栾倍半萜、(E,Z)-1,3,5-十一碳三烯;
·脂肪醇,例如:己醇、辛醇、3-辛醇、2,6-二甲基庚醇、2-甲基庚醇、2-甲基辛醇、(E)-2-己烯醇、(E)-和(Z)-3-己烯醇、1-辛烯-3-醇、3,4,5,6,6-五甲基-3/4-庚烯-2-醇和3,5,6,6-四甲基-4-亚甲基庚-2-醇的混合物、(E,Z)-2,6-壬二烯醇、3,7-二甲基-7-甲氧基辛-2-醇、9-癸烯醇、10-十一(碳)烯醇、4-甲基-3-癸烯-5-醇;
·脂肪族醛及其缩醛,如例如己醛、庚醛、辛醛、壬醛、癸醛、十一醛、十二醛、十三醛、2-甲基辛醛、2-甲基壬醛、(E)-2-己烯醛、(Z)-4-庚烯醛、2,6-二甲基-5-庚烯醛、10-十一烯醛、(E)-4-癸烯醛、2-十二碳烯醛、2,6,10-三甲基-5,9-十一碳二烯醛、庚醛二乙基乙缩醛、1,1-二甲氧基-2,2,5-三甲基-4-己烯、香茅基氧乙醛;
·脂肪族酮及其肟,如例如2-庚酮、2-辛酮、3-辛酮、2-壬酮、5-甲基-3-庚酮、5-甲基-3-庚酮肟、2,4,4,7-四甲基-6-辛烯-3-酮;
·脂肪族含硫化合物,如例如3-甲基硫己醇、3-甲基硫代乙酸己酯、3-巯基己醇、3-巯基乙酸己酯、3-巯基丁酸己酯;3-乙酰基硫代乙酸己酯;1-孟烯-8-硫醇;
·脂肪族腈,如例如2-壬烯酸腈、2-三癸烯酸腈、2,12-三癸二烯酸腈、3,7-二甲基-2,6-辛二烯酸腈、3,7-二甲基-6-辛烯酸腈;
·脂肪族羧酸及其酯,如例如(E)和(Z)-3-己烯基甲酸酯、乙酰乙酸乙酯、乙酸异戊酯、乙酸己酯、3,5,5-三甲基-乙酸己酯、3-甲基-2-乙酸丁烯酯、(E)-2-乙酸己烯酯、(E)和(Z)-3-乙酸己烯酯、乙酸辛酯、3-乙酸辛酯、1-辛烯-3-基乙酸酯、丁酸乙酯、丁酸丁酯、丁酸异戊酯、丁酸己酯、(E)和(Z)-3-异丁酸己烯酯、巴豆酸己酯、异缬草酸乙酯、2-甲基戊酸乙酯、己酸乙酯、己酸烯丙酯、庚酸乙酯、庚酸烯丙酯、辛酸乙酯、(E,Z)-2,4-癸二烯酸乙酯、2-辛烯酸甲酯、2-壬烯酸甲酯、2-异戊基氧乙酸烯丙酯、3,7-二甲基-2,6-辛二烯酸甲酯;
·非环萜烯醇,如例如香茅醇、香叶醇、橙花醇、沉香醇、Lavadulol、橙花叔醇、金合欢醇、四氢里哪醇、四氢香叶醇、2,6-二甲基-7-辛烯-2-醇、2,6-二甲基辛烯-2-醇、2-甲基-6-亚甲基-7-辛烯-2-醇、2,6-二甲基-5,7-辛二烯-2-醇、2,6-二甲基-3,5-辛二烯-2-醇、3,7-二甲基-4,6-辛二烯-3-醇、3,7-二甲基-1,5,7-辛三烯-3-醇、2,6-二甲基-2,5,7-辛三烯-1-醇;及其甲酸酯、乙酸酯、丙酸酯、异丁酸酯、丁酸酯、异戊酸酯、戊酸酯、己酸酯、巴豆酸酯、Tiglinate酯、3-甲基-2-丁烯酸酯;
·非环萜烯醛和酮,如例如香叶醛、橙花醛、香茅醛、7-羟基-3,7-二甲基辛醛、7-甲氧基-3,7-二甲基辛醛、2,6,10-三甲基-9-十一烯醛、香叶基丙酮;和香叶醛的二甲基和二乙基缩醛、橙花醛、7-羟基-3,7-二甲基辛醛;
·环萜烯醇,如例如薄荷醇、异蒲勒醇、α-萜品醇、萜品醇-4、孟-8-醇、孟-1-醇、孟-7-醇、冰片醇、异冰片醇、氧化芳樟醇、诺卜醇、雪松醇、龙涎醇、岩兰草醇、愈创醇、及其甲酸酯、乙酸酯、丙酸酯、异丁酸酯、丁酸酯、异戊酸酯、戊酸酯、己酸酯、巴豆酸酯、Tiglinate酯、3-甲基-2-丁烯酸酯;
·环萜烯醛和酮,如例如薄荷酮、异薄荷酮、8-巯基孟-3-酮、香芹酮、樟脑、葑酮、α-紫罗(兰)酮、β-紫罗(兰)酮、α-n-甲基紫罗兰酮、β-n-甲基紫罗兰酮、α-异甲基紫罗兰酮、β-异甲基紫罗兰酮、α-鸢尾酮、α-二氢大马酮、β-二氢大马酮、β-二氢大马烯酮、γ-二氢大马酮、δ-二氢大马酮、1-(2,4,4-三甲基-2-环己烯-1-基)-2-丁烯-1-酮、1,3,4,6,7,8a-六氢-1,1,5,5-四甲基-2H-2,4a-亚甲基萘甲胺-8(5H)-酮、香柏酮、二氢香柏酮、α-甜橙醛、β-甜橙醛、乙酰基雪松油(甲基柏木酮);
·环醇,如例如4-叔丁基环己醇、3,3,5-三甲基-环己醇、3-异莰基环己醇、2,6,9-三甲基-(Z2,Z5,E9)-环十二碳三烯-1-醇、2-异丁基-4-甲基四氢-2H-吡喃-4-醇;
·环脂族醇,如例如α,3,3-三甲基环己基甲醇、2-甲基-4-(2,2,3-三甲基-3-环戊-1-基)丁醇、2-甲基-4-(2,2,3-三甲基-3-环戊-1-基)-2-丁烯-1-醇、2-乙基-4-(2,2,3-三甲基-3-环戊-1-基)-2-丁烯-1-醇、3-甲基-5-(2,2,3-三甲基-3-环戊-1-基)-戊烯-2-醇、3-甲基-5-(2,2,3-三甲基-3-环戊-1-基)-4-戊烯-2-醇、3,3-二甲基-5-(2,2,3-三甲基-3-环戊-1-基)-4-戊烯-2-醇、1-(2,2,6-三甲基环己基)戊烯-3-醇、1-(2,2,6-三甲基环己基)己-3-醇;
·环醚和环脂族醚,如例如桉树脑、甲基柏木醚、环十二烷基甲基醚、(乙氧基甲氧基)环十二烷、α-环氧柏木烯、3a,6,6,9a-四甲基十二氢萘酚[2,1-b]呋喃、3a-乙基-6,6,9a-三甲基十二氢萘酚[2,1-b]呋喃、1,5,9-三甲基-13-氧杂二环[10.1.0]-十三烷基-4,8-二烯、玫瑰醚、2-(2,4-二甲基-3-环己烯-1-基)-5-甲基-5-(1-甲基丙基)-1,3-二氧杂环己烷;
·环酮,如例如:4-叔丁基环己酮、2,2,5-三甲基-5-戊基环戊酮、2-庚基环戊酮、2-戊基环戊酮、2-羟基-3-甲基-2-环戊烯-1-酮、3-甲基-顺式-2-戊烯-1-基-2-环戊烯-1-酮、3-甲基-2-戊基-2-环戊烯-1-酮、3-甲基-4-环十五烷酮、3-甲基-5-环十五烷酮、3-甲基环十五烷酮、4-(1-乙氧乙烯基)-3,3,5,5-四甲基环己酮、4-叔戊基环己酮、5-环十六烷基-1-酮、6,7-二氢-1,1,2,3,3-五甲基-4(5H)-茚酮、9-环十七烷基-1-酮、环十五烷酮、环十六烷酮;
·环脂族醛,如例如2,4-二甲基-3-环己烯甲醛、2-甲基-4-(2,2,6-三甲基-环己烯-1-基)-2-丁烯醛、4-(4-羟基-4-甲基戊基)-3-环己烯甲醛、4-(4-甲基-3-戊烯-1-基)-3-环己烯甲醛;
·环脂族酮,如例如1-(3,3-二甲基环己基)-4-戊烯-1-酮、1-(5,5-二甲基-1-环己烯-1-基)-4-戊烯-1-酮、2,3,8,8-四甲基-1,2,3,4,5,6,7,8-八氢-2-萘基甲基酮、甲基-2,6,10-三甲基-2,5,9-环十二烷三烯酮、叔丁基-(2,4-二甲基-3-环己烯-1-基)酮;
·环醇的酯,如例如2-叔丁基环己基乙酸酯、4-叔丁基环己基乙酸酯、2-叔戊基环己基乙酸酯、4-叔戊基环己基乙酸酯、十氢-2-萘乙酸酯、3-戊基四氢-2H-吡喃-4基乙酸酯、十氢-2,5,5,8a-四甲基-2-萘乙酸酯、4,7-甲酰氧-3a,4,5,6,7,7a-六氢-5-或-6-茚基乙酸酯、4,7-甲酰氧-3a,4,5,6,7,7a-六氢-5-或-6-茚基丙酸酯、4,7-甲酰氧-3a,4,5,6,7,7a-六氢-5-或-6-茚基异丁酸酯、4,7-甲酰氧八氢-5-或-6-茚基乙酸酯;
·环脂族羧酸酯,如例如3-环己基丙酸烯丙酯、环己氧基乙酸烯丙酯、二氢茉莉酮酸甲酯、茉莉酮酸甲酯、2-己基-3-氧环戊烯羧酸甲酯、2-乙基-6,6-二甲基-2-环己烯羧酸乙酯、2,3,6,6-四甲基-2-环己烯羧酸乙酯、2-甲基-1,3-二氧戊环2-乙酸乙酯;
·芳烃,如例如苯乙烯和二苯基甲烷;
·芳脂族醇,如例如苯甲醇、1-苯乙醇、2-苯乙醇、3-苯丙醇、2-苯丙醇、2-苯氧乙醇、2,2-二甲基-3-苯丙醇、2,2-二甲基-3-(3-甲基苯基)丙醇、1,1-二甲基-2-苯乙醇、1,1-二甲基-3-苯丙醇、1-乙基-1-甲基-3-苯丙醇、2-甲基-5-苯戊醇、3-甲基-5-苯戊醇、3-苯基-2-丙烯-1-醇、4-甲氧基苯甲醇、1-(4-异丙基苯基)乙醇;
·芳脂族醇和脂肪族羧酸的酯,如例如乙酸苯甲酯、丙酸苯甲酯、异丁酸苯甲酯、异戊酸苯甲酯、乙酸2-苯乙酯、丙酸2-苯乙酯、异丁酸2-苯乙酯、异戊酸2-苯乙酯、乙酸1-苯乙酯、乙酸α-三氯甲基苄酯、乙酸α,α-二甲基苯乙酯、丁酸α,α-二甲基苯乙酯、乙酸肉桂酯、异丁酸2-苯氧基乙酯、乙酸4-甲氧基苄酯;
·芳脂族醚,如例如2-苯乙基甲基醚、2-苯乙基异戊醚、2-苯乙基1-乙氧基乙醚、苯乙醛-二甲基缩醛、苯乙醛二乙基缩醛、龙葵醛-二甲基缩醛、苯乙醛-甘油缩醛、2,4,6-三甲基-4-苯基-1,3-二氧杂环己烷、4,4a,5,9b-四氢茚-[1,2-d]-m-二氧杂环己烯、4,4a,5,9b-四氢-2,4-二甲基茚[1,2-d]-m-二氧杂环己烯;
·芳族和芳脂族醛,如例如苯甲醛、苯乙醛、3-苯丙醛、龙葵醛、4-甲基苯甲醛、4-甲基苯乙醛、3-(4-乙基苯基)-2,2-二甲基丙醛、2-甲基-3-(4-异丙基苯基)丙醛、2-甲基-3-(4-叔丁基苯基)丙醛、3-(4-叔丁基苯基)丙醛、肉桂醛、α-丁基肉桂醛、α-戊基肉桂醛、α-己基肉桂醛、3-甲基-5-苯基戊醛、4-甲氧基苯甲醛、4-羟基-3-甲氧基苯甲醛、4-羟基-3-乙氧基苯甲醛、3,4-亚甲基二氧苯甲醛、3,4-二甲氧基苯甲醛、2-甲基-3-(4-甲氧基苯基)丙醛、2-甲基-3-(4-亚甲基二氧苯基)丙醛;
·芳族和芳脂族酮,如例如苯乙酮、4-甲基苯乙酮、4-甲氧基苯乙酮、4-叔丁基-2,6-二甲基苯乙酮、4-苯基-2-丁酮、4-(4-羟苯基)-2-丁酮、1-(2-萘基)乙酮、苯甲酮、1,1,2,3,3,6-六甲基-5-茚满基甲基酮、6-叔丁基-1,1-二甲基-4-茚满基甲基酮、1-[2,3-二氢-1,1,2,6-四甲基-3-(1-甲基乙基)-1H-5-茚基]乙酮、5’,6’,7’,8’-四氢-3’,5’,5’,6’,8’,8’-六甲基-2-萘乙酮;
·芳族和芳脂族羧酸及其酯,如例如苯甲酸、苯乙酸、苯甲酸甲酯、苯甲酸乙酯、苯甲酸己酯、苯甲酸苄酯、乙酸甲基苯酯、乙酸乙基苯酯、乙酸香叶基苯酯、乙酸苯乙基苯酯、肉桂酸甲酯、肉桂酸乙酯、肉桂酸苄酯、肉桂酸苯乙酯、肉桂酸肉桂酯、乙酸烯丙基苯氧酯、水杨酸甲酯、水杨酸异戊酯、水杨酸己酯、水杨酸环己酯、水杨酸顺式-3-己烯酯、水杨酸苄酯、水杨酸苯乙酯、2,4-二羟基-3,6-二甲基苯甲酸甲酯、-3-苯基缩水甘油乙酯、3-甲基-3-苯基缩水甘油乙酯;
·含氮芳香族化合物,如例如:2,4,6-三硝基-1,3-二甲基-5-叔丁基苯、3,5-二硝基-2,6-二甲基-4-叔丁基乙酰苯、肉桂酸腈、5-苯基-3-甲基-2-戊烯酸腈、5-苯基-3-甲基戊烯酸腈、甲基邻氨基苯甲酸酯、N-甲基邻氨基苯甲酸甲酯、甲基邻氨基苯甲酸酯和7-羟基-3,7-二甲基辛醇的Schiff碱、2-甲基-3-(4-叔丁基苯基)丙醛或2,4-二甲基-3-环己烯甲醛、6-异丙基喹啉、6-异丁基喹啉、6-仲丁基喹啉、吲哚、粪臭素(Skatol)、2-甲氧基-3-异丙基吡嗪、2-异丁基-3-甲氧基吡嗪、4-(4,8-二甲基-3,7-壬二烯基)-吡啶;
·苯酚、苯基醚和苯基酯,如例如:草蒿脑、茴香脑、丁子香酚、丁子香甲基醚、异丁子香酚、异丁子香基甲基醚、麝香草酚、香芹酚、二苯醚、β-萘基甲基醚、β-萘基乙基醚、β-萘基异丁基醚、1,4-二甲氧基苯、乙酸丁子香酯、2-甲氧基-4-甲基苯酚、2-乙氧基-5-(1-丙烯基)苯酚、对甲酚苯基乙酸酯;
·杂环化合物,如例如2,5-二甲基-4-羟基-2H-呋喃-3-酮、2-乙基-4-羟基-5-甲基-2H-呋喃-3-酮、3-羟基-2-甲基-4H-吡喃-4-酮、2-乙基-3-羟基-4H-吡喃-4-酮;
·内酯,如例如1,4-辛内酯、3-甲基-1,4-辛内酯、1,4-壬内酯、1,4-癸内酯、8-癸烯-1,4-内酯、1,4-十一内酯、1,4-十二内酯、1,5-癸内酯、1,5-十二内酯、1,15-十五内酯、顺式和反式-11-十五-1,15-内酯、顺式和反式-12-十五-1,15-内酯、1,16-十六内酯、9-十六-1,16-内酯、10-氧-1,16-十六内酯、11-氧-1,16-十六内酯、12-氧-1,16-十六内酯、乙烯基-1,12-十二烷基-二内酯、乙烯基-1,13-十三烷基-二内酯、香豆素、2,3-二氢香豆素、八氢香豆素。
可以与式(I)的四氢呋喃衍生物有利结合的花香型芳香或香料物质优选自组包括:羟基香茅醛、甲氧基香茅醛、兔耳草醛、[2-甲基-3-(4-异丙基苯基)丙醛]、1-(4-异丙基-环己基)乙醇(Mugetanol(R))、4-叔丁基-a-甲基二氢肉桂醛(Lilial(R))、顺式-六氢枯茗醇(Mayol(R))、3-[4-(1,1-二甲基乙基)苯基]丙醛(Bourgeonal(R))、2,2-二甲基-3-(3-甲基苯基)丙醇(Majantol(R))、3-甲基-3-(3-甲基苄基)-丁-2-醇、2-异丁基-4-甲基四氢-2H-吡喃-4-醇(Florosa(R))、2-甲基-3-(3,4-亚甲基二氧苯基)丙醛(Heliofolal(R))、4-(4-羟基-4-甲基戊基)-3-环己烷基甲醛(Lyral(R))、4-(八氢-4,7-甲撑基-5H-茚-5-亚基-丁醛(Dupical(R))、Vernaldehyd、4-(4-甲基-3-戊烯-1-基)-3-环己烯基甲醛(Vertomugal(R))、八氢-5-(4-甲氧基亚丁基)-4,7-甲撑基-1H-茚(Mugoflor(R))、2,6-二甲基-2-庚醇(Freesiol(R))、1-乙基-1-甲基-3-苯基丙醇(Phemec(R))、2,2-二甲基-3-苯基-1-丙醇(Mugue醇)、Profarnesol、二氢金合欢醇、金合欢醇、橙花叔醇、羟基香茅二甲缩醛、苯甲酸己酯、香叶醇、橙花醇、沉香醇、四氢香叶醇,四氢沉香醇、乙基沉香醇、Geranyltiglinat、苯乙醇(2-苯基乙醇)、香茅醇、氧化玫瑰、2-甲基-5-苯基戊醇(Rosaphen)、3-甲基-5-苯基戊醇(Phenoxanol)、二氢茉莉酸甲酯(Hedion(R)、Hedione(R)高顺式)、2-庚基环戊酮(Projasmon P)、顺式茉莉酮、二氢茉莉酮、肉桂醇(3-苯基-2-丙-1-醇)、二氢肉桂醇(3-苯基丙醇)、2-甲基-4-苯基-1,3-二氧戊烷(Jacinthaflor(R))、二氢月桂烯醇(2,6-二甲基-7-辛烯-2-醇)。
可以与式(I)的四氢呋喃衍生物有利结合的水果型芳香或香料物质优选自组包括:2-甲基-丁酸乙酯、4-(对羟苯基)-2-丁酮、3-甲基-3-苯基缩水甘油酸乙酯、丁酸异戊酯、乙酸异戊酯、乙酸正丁酯、丁酸乙酯、3-甲基-丁酸乙酯、正己酸乙酯、正己酸烯丙酯、2-反式-4-顺式-癸二烯酸乙酯、1,1-二甲氧基-2,2,5-三甲基-4-己烷、2,6-二甲基-5-庚烯-1-醛、γ-十一(碳)烷酸内酯、γ壬内酯、己醛、3Z-己醛、正癸醛、正十二醛、柠檬醛、柠檬萜、香草醛、乙基香草醛、麦芽醇、乙基麦芽醇及其混合物。
如上所述本发明的化合物由于其嗅觉特征特别适合在芳香物质混合物和芳香油中使用。该化合物可以单独或在本发明的混合物中与一种其他的单一芳香物质或多种其他的芳香物质一起在相应的芳香物质混合物中使用。特别有利的是本发明的化合物与其他芳香物质,优选上文提到或下文提到的芳香物质,以不同的用量比例结合得到新的芳香物质混合物或香水。
因此根据本发明提供香料物质混合物和芳香物质混合物(芳香油),其除了其他的香料和芳香物质含有一种或多种式(I)的四氢呋喃衍生物。单一或四氢呋喃衍生物混合物特别优选是R-四氢呋喃-2-羧酸甲酯(化合物1a)、S-四氢呋喃-2-羧酸甲酯(化合物1b)、R-四氢呋喃-2-羧酸乙酯(化合物2a)、S-四氢呋喃-2-羧酸乙酯(化合物2b)、R-四氢呋喃-2-羧酸丙酯(化合物3a)、S-四氢呋喃-2-羧酸丙酯(化合物3b)、R-四氢呋喃-2-羧酸烯丙酯(化合物4a)、S-四氢呋喃-2-羧酸烯丙酯(化合物4b)、R-四氢呋喃-2-羧酸异丙酯(化合物5a)、S-四氢呋喃-2-羧酸异丙酯(化合物5b)、R-四氢呋喃-2-羧酸2-甲基烯丙酯(化合物6a)、S-四氢呋喃-2-羧酸2-甲基烯丙酯(化合物6b)、R-四氢呋喃-2-羧酸异丁酯(化合物7a)、S-四氢呋喃-2-羧酸异丁酯(化合物7b)、R-四氢呋喃-2-羧酸丁酯(化合物8a)、S-四氢呋喃-2-羧酸丁酯(化合物8b)、R-1-(四氢-呋喃-2-基)-乙酮(化合物9a)、S-1-(四氢-呋喃-2-基)-乙酮(化合物9b)。特别优选的单一或四氢呋喃衍生物混合物是R-四氢呋喃-2-羧酸甲酯(化合物1a)、S-四氢呋喃-2-羧酸甲酯(化合物1b)、R-四氢呋喃-2-羧酸乙酯(化合物2a)、S-四氢呋喃-2-羧酸乙酯(化合物2b)、R-四氢呋喃-2-羧酸丙酯(化合物3a)、S-四氢呋喃-2-羧酸丙酯(化合物3b)、R-四氢呋喃-2-羧酸烯丙酯(化合物4a)、S-四氢呋喃-2-羧酸烯丙酯(化合物4b)。尤其特别优选的单一或四氢呋喃衍生物混合物是R-四氢呋喃-2-羧酸甲酯(化合物1a)、S-四氢呋喃-2-羧酸甲酯(化合物1b)、R-四氢呋喃-2-羧酸乙酯(化合物2a)、S-四氢呋喃-2-羧酸乙酯(化合物2b)。
式(I)的四氢呋喃衍生物优选在含有这些物质的组合物中表现其有利的影响。因此根据本发明也提供芳香或加香产品,其含有一种本发明的含有一种或多种式(I)的四氢呋喃衍生物的香料或芳香物质混合物(芳香油)。有利地是至少一种式(I)的四氢呋喃衍生物以感官上足够的量存在从而使各个物质产生根据本发明的有利的气味印象。特别有利的是一种或多种式(I)的四氢呋喃衍生物以足以产生淡淡气味的量存在。
本领域技术人员可以在考虑产品其他成分的基础上通过由8位非嗅觉缺失症的检验员组成的评定组,确定各个式(I)的四氢呋喃衍生物产生气味印象的感官上充足的量,其中在室温下,含有不同浓度的式(I)的四氢呋喃衍生的物相应产品样品从每位检测员前经过三次,检测各种想要的感官性能的存在。当评定组中至少4位组员检测到想要的感官性能的存在,则达到最小浓度。这类评定组测试流行于香水店和花店并且以常规标准进行。
式(I)的四氢呋喃衍生物、根据本发明的其混合物或根据本发明的香料和芳香物质混合物优选用于生产加香产品(加香制品)。本发明化合物的感官性能、材料性能(如在常用溶剂中的溶解性以及和这类产品的其他常用成分的相容性)以及毒理学安全性使其特别适用于所述用途。
在本发明范围内加香产品是例如洗涤剂和清洁剂、化妆产品、香水以及化妆用清洁产品领域的不同产品,优选自组包括:香水提取物、香水(Eau de parfum)、淡香水(Eaude Toilettes)、剃须液、古龙香水(Eau de Colognes)、剃须前产品、古龙水(Splash-Colognes)、加香面巾纸、用于酸性、碱性和中性清洁剂的香水、洗涤剂、清洗片剂、消毒剂和空气清新剂、气溶胶喷雾剂、蜡和上光剂、身体护理产品、沐浴油、化妆乳液例如护肤霜和护肤乳液、防晒霜和防晒乳液、晒后修复霜和晒后修复乳液、护手霜和护手乳液、脚霜和护脚乳液、脱毛霜和脱毛乳液、须后霜和须后液、美黑霜和美黑乳液、护发产品例如头发喷雾剂、发胶、固定头发洗剂、头发漂洗剂、染发剂、毛发定型剂和直发剂、洗发剂、发膏和洗发液、除臭剂和止汗剂、用于美妆的产品,如眼影、指甲油、化妆品、口红、睫毛膏,以及蜡烛、灯油、香烛、杀虫剂、驱虫剂、抛射剂。
本发明的包含本发明的式(I)化合物或如上所定义的本发明混合物的的香料和芳香物质混合物通常(例如,浓缩形式、溶液或以下文所述的经改性形式)可用于生产例如香水提取物,香水(Eau de Parfums)、淡香水(Eau de Toilettes)、剃须液、古龙香水、剃须前产品、古龙水和加香面巾纸、酸性、碱性和中性清洁剂的加香,例如地板清洁剂、窗户清洁剂、洗碗剂、洗浴和卫生清洁剂、去溃产品、固体和液体厕所清洗剂、粉末和泡沫地毯清洁剂、液体洗涤剂、粉状洗涤剂、洗衣预处理剂如漂白剂、浸泡剂和去污剂、织物柔顺剂、洗涤皂、洗涤片剂、消毒剂、表面消毒剂和呈液体或凝胶形式或施用在固体载体上的空气清新剂、气溶胶喷雾剂、蜡和上光剂如家具上光剂、地板腊、鞋油以及身体护理产品例如固体和液体肥皂,淋浴凝胶、香波、剃须皂、剃须泡沫、浴油、水包油型、油包水型和水包油包水型化妆乳液,例如护肤霜和护肤乳液、面霜和面部乳液、防晒霜和防晒乳液、晒后霜和晒后乳液、护手霜和护手乳液、脚霜和护脚乳液、脱毛霜和脱毛乳液、须后霜和须后液、美黑霜和美黑乳液,护发产品例如头发喷雾剂、发胶、固定头发洗剂、头发漂洗剂、永久性和半永久性染发剂、毛发定型剂如冷烫和头发拉直剂、洗发液、护发膏和护发乳液、除臭剂和止汗剂,例如腋下喷雾剂、滚搽式除臭剂(roll-on)、除臭棒、除臭膏,美妆产品例如眼影、指甲油、化妆品、口红、睫毛膏,以及蜡烛、灯油、香烛、杀虫剂、驱虫剂、抛射剂。
根据本发明的含有本发明的化合物或一种如上所定义的本发明的混合物的香料和芳香物质混合物可以以液体形式,未用溶剂稀释或用溶剂稀释用于加香。用于此目的的合适的溶剂例如为乙醇、异丙醇、二甘醇单乙醚、甘油、丙二醇、1,2-丁二醇、二丙二醇、邻苯二甲酸二乙酯、柠檬酸三乙酯、肉豆蔻酸异丙酯等。对于给出溶剂,其适用于本文的上下文中,在存在其自身嗅觉特性的情况下,它们被专门归类为“溶剂”成分而不是“香料”。
在一个优选实施方案中,根据本发明的加香产品中所含有的本发明的化合物、一种如上所定义的本发明的混合物或一种如上所定义的本发明的香料和芳香物质混合物,可以被吸附在一种载体上,所述载体确保芳香物质在产品中的精细分布以及使用过程中的受控释放。这类载体可以是多孔无机材料如轻质硫酸盐、硅胶、沸石、石膏、粘土、粘土颗粒、多孔混凝土等,或者有机材料如基于木材和纤维素的材料。
本发明的加香产品中的所含的化合物、一种如上所定义的本发明的混合物或一种如上所定义的本发明的芳香物质混合物,也可以是微封装的、喷雾干燥的,作为内含复合物或作为挤出产品,并且可以以该形式添加到待加香的产品或制品中。任选地,以此方式改性的香料和芳香物质混合物的性质可以用合适的材料通过所谓的“涂布”而被进一步优化,目的是香料的更具靶向性释放,对此优选使用蜡状塑料,例如聚乙烯醇。
芳香物质混合物的微封装可以例如利用胶囊材料,例如聚氨酯类物质或软明胶,通过所谓的凝聚过程来进行。喷雾干燥的芳香油可以例如通过将含有该芳香油的乳液或分散体喷雾干燥来生产,其中可以使用改性淀粉、蛋白质、糊精和植物胶作为载体。内含复合物可以例如通过将芳香物质混合物与环糊精或脲衍生物的分散系进料至合适的溶剂,例如水中来生产。挤出产品可以通过将芳香物质混合物与合适的蜡状物质一起熔化并通过挤出和后续固化,任选在合适溶剂如异丙醇中,来生产。
如已经提及的,本发明的香料和芳香物质混合物可以随后以浓缩形式、溶液或上述改性形式用于生产本发明的相应的加香制品。
在香料和芳香物质混合物,尤其是芳香油组合物中,式(I)的四氢呋喃衍生物的使用总量优选为0.000001至40重量%,优选0.001至35重量%并且尤其优选0.2至30重量%,均基于香料和芳香物质混合物总量计。
根据本发明的另一方面本发明待使用的式(I)的四氢呋喃衍生物在小剂量下,尤其是以下给出的小剂量浓缩物,优异地适用于改变和/或增强气味或味道,即它可以用作所谓的促进剂或强化剂。
本发明待使用的式(I)的四氢呋喃衍生物主要用于赋予芳香物质和香料物质混合物,尤其是芳香油组合物更多的强度、清新度、(向外)辐射性和/或圆润度和/或增强特定的(芳香物质和香料物质混合物中所含有的其他芳香或香料物质的)香调,特别是清新和甜味方向的香调,式(I)的四氢呋喃衍生物的总量很低并且优选0.00001至5重量%,优选0.0001至3重量%并且尤其优选0.2至2重量%,均基于芳香物质和香料物质混合物总量计。
对于赋予芳香和香料物质混合物,特别是芳香油组合物,更多咖啡和朗姆酒方向的气味印象,优选大量使用本发明的式(I)的四氢呋喃衍生物,如例如6至30重量%,优选6至20重量%并且尤其优选6至15重量%,均基于芳香和香料物质混合物总量计。
如上所述,对于含有表面活性剂的加香产品芳香物质和芳香物质混合物在底物,尤其是头发或纺织纤维上停留的附着性是另一个实际要求。
通过将本发明的化合物或本发明的混合物加入给出的具备较小附着性和/或停留性的芳香物质混合物,该性质将以特别有利的方式被改善。例如一种水果味、花香味和/或芳香味的水性清洗溶剂(或相应的洗涤剂或香波等),由于所含香料物质缺乏附着性,不能用于为清洗物(纺织纤维)或头发带来水果味、花香味和/或芳香味,通过加入本发明的化合物或一种本发明的混合物,转变为给出水果味、花香味和/或芳香味,并且在被处理的底物上(头发或纺织纤维)长时间保持这种水果味、花香味和/或芳香味的溶液。本发明的化合物或含有香料和芳香物质混合物的本发明的混合物优势在于高的附着性。这一效果特别在底物如皮肤、头发和纺织纤维(例如羊毛、棉花、亚麻、合成纤维)上呈现。
这一效果随后在应用实施例中进一步说明。
式(I)的四氢呋喃衍生物、其根据本发明的混合物和本发明的香料和芳香物质混合物制成的产品可以含有其他内容物、添加剂和物质,如选自:防腐剂、研磨剂、抗痤疮剂、抗皮肤老化剂、抗菌剂、溶脂剂、去头屑剂、抗炎剂、防刺激剂、抑制刺激剂,抗微生物剂、抗氧化剂、收敛剂、抑汗剂、杀菌剂、抗静电剂、粘合剂、缓冲剂、载体、螯合剂、细胞刺激剂、清洗剂、护理剂、脱毛剂、表面活性物质、除臭剂、止汗剂、增塑剂、乳化剂、酶、精油、纤维、成膜剂、固色剂、泡沫形成剂、泡沫稳定剂、消泡剂、泡沫促进剂、杀真菌剂、胶凝剂、凝胶形成剂、头发护理剂、毛发定型剂、头发拉直剂、保湿剂、增湿剂、润湿剂、漂白剂、加强剂、去污剂、光学增亮剂、浸溃剂、驱污剂、减摩剂、润滑剂、保湿霜、软膏、遮光剂、增塑剂、覆盖剂、上光剂、光泽剂、聚合物、粉末、蛋白质、加脂剂(rückfettende Mittel)、磨蚀剂、硅酮、皮肤舒缓剂、皮肤清洁剂、护肤剂、皮肤愈合剂、皮肤光亮剂、皮肤保护剂、皮肤软化剂、冷却剂、皮肤冷却剂、加温剂、皮肤升温剂、稳定剂、紫外线吸收剂、UV滤光剂、洗涤剂、织物柔顺剂、助悬剂、皮肤美黑剂、增稠剂、维生素、油、蜡、脂肪、磷脂、饱和脂肪酸、单或多不饱和脂肪酸、α-羟基酸、多羟基脂肪酸、液化剂、染料、颜色保护剂、颜料、防蚀剂、芳香物质、调味物质、多元醇、表面活性剂、电解质、有机溶剂或硅酮衍生物。
一些其他内容物、添加剂和物质在下面给出:
I.化妆品内容物、添加剂和物质
1.表面活性剂
可以用作表面活性物质的是阴离子、非离子、阳离子和/或两性或两性离子表面活性剂,其含量通常为约1至70,优选5至50以及特别是10至30重量%。阴离子表面活性剂的典型实例是肥皂、烷基苯磺酸盐、烷烃磺酸盐、烯烃磺酸盐、烷基醚磺酸盐、甘油醚磺酸盐、α-甲酯磺酸盐、磺基脂肪酸、烷基硫酸盐、烷基醚硫酸盐、甘油醚硫酸盐、脂肪酸醚硫酸盐、羟基混合醚硫酸盐、单甘油酯(醚)硫酸盐、脂肪酸酰胺(醚)硫酸盐、单-和二烷基磺基丁二酸盐、单-和二烷基磺基琥珀酰胺酸盐、磺基甘油三酯、酰胺皂、醚羧酸及其盐、脂肪酸羟乙磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、N-酰氨酸如,例如酰基乳酸盐、酰基酒石酸盐、酰基谷氨酸盐和酰基天冬氨酸盐、烷基低聚葡糖苷硫酸盐、蛋白质脂肪酸缩合物(特别是小麦基植物产品)和烷基(醚)磷酸盐。如果阴离子表面活性剂含有聚乙二醇醚链,则它们可具有常规的,但优选窄的同系物分布。非离子表面活性剂的典型实例是脂肪醇聚二醇醚、烷基苯酚聚二醇醚、脂肪酸聚二醇酯、脂肪酸酰胺聚二醇醚、脂肪胺聚二醇醚、烷氧基化三甘油酯、混合醚和混合醛,任选为部分氧化的烷(烯)基低聚糖苷和葡糖酸衍生物、脂肪酸-N-烷基葡糖酰胺、蛋白质水解产物(尤其是基于小麦的植物产品)、多元醇脂肪酸酯、糖酯、山梨聚糖酯、聚山梨酸酯和胺氧化物。如果非离子表面活性剂含有聚二醇醚链时,它们可以具有常规,但优选窄的同系物分布。阳离子表面活性剂的典型实例为季铵化合物,例如二甲基二硬脂基氯化铵、和季铵化酯,尤其是季铵化脂肪酸三烷醇胺酯盐。两性或两性离子表面活性剂的典型实例为烷基甜菜碱、烷基酰胺基甜菜碱、氨基丙酸盐、氨基甘氨酸盐、咪唑啉甜菜碱和磺基甜菜碱。所述表面活性剂均为已知化合物。特别适当的温和,即特别与皮肤相容的表面活性剂的典型实例是脂肪醇聚二醇醚硫酸盐、单甘油醚硫酸盐、单-和/或二烷基磺基丁二酸盐、脂肪酸羟乙磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、脂肪酸谷氨酸盐、α-烯烃磺酸盐、醚羧酸、烷基低聚葡糖苷、脂肪酸谷氨酸盐、烷基酰胺基甜菜碱、两性和/或蛋白脂肪酸浓缩物、最后优选基于小麦蛋白。
2.油体
油体是例如基于含有6至18个,优选8至10个碳原子的脂肪醇的Guerbet醇,直链C6-C22-脂肪酸与直链或支链C6-C22-脂肪醇的酯或支链C6-C13-羧酸与直链或支链C6-C22-脂肪醇的酯,如例如肉豆蔻酸十四烷酯、棕榈酸十四烷酯、硬脂酸十四烷酯、异硬脂酸十四烷酯、油酸十四烷酯、山嵛酸十四烷酯、芥酸十四烷酯、肉豆蔻酸十六烷酯、棕榈酸十六烷酯、硬脂酸十六烷酯、异硬脂酸十六烷酯、油酸十六烷酯、山嵛酸十六烷酯、芥酸十六烷酯、肉豆蔻酸十八烷酯、棕榈酸十八烷酯、硬脂酸十八烷酯、异硬脂酸十八烷酯、油酸十八烷酯、山嵛酸十八烷酯、芥酸十八烷酯、肉豆蔻酸异十八烷酯、棕榈酸异十八烷酯、硬脂酸异十八烷酯、异硬脂酸异十八烷酯、油酸异十八烷酯、山嵛酸异十八烷酯、油酸异十八烷酯、油醇肉豆蔻酸酯、棕榈酸油醇酯、油醇硬脂酸酯、油醇异硬脂酸酯、油酸油醇酯、山嵛酸油醇酯、芥酸油醇酯、肉豆蔻酸二十二烷酯、棕榈酸二十二烷酯、硬脂酸二十二烷酯、异硬脂酸二十二烷酯、油酸二十二烷酯、山嵛酸二十二烷酯、芥酸二十二烷酯、肉豆蔻酸芥醇酯、棕榈酸芥醇酯、硬脂酸芥醇酯、异硬脂酸芥醇酯、油酸芥醇酯、山嵛酸芥醇酯和芥酸芥醇酯。此外适当的是直链C6-C22-脂肪酸与支链醇,特别是2-乙基己醇的酯、C18-C38-烷基羟基羧酸与直链或支链C6-C22-脂肪醇的酯,特别是苹果酸二辛酯、直链和/或支链脂肪酸与多元醇(如例如丙二醇、二聚二元醇(Dimerdiol)或三聚三元醇(Trimertriol))和/或Guerbet醇的酯、基于C6-C10-脂肪酸的甘油三酯、基于C6-C18-脂肪酸的液态单-/二-/三酸甘油酯混合物、C6-C22-脂肪醇和/或Guerbet醇与芳族羧酸,特别是苯甲酸的酯、C2-C12-二羧酸与具有1至22个碳原子的直链或支链醇或者具有2至10个碳原子和2至6个羟基的多元醇的酯、植物油、支链伯醇、取代环己烷、直链和支链C6-C22-脂肪醇的碳酸酯,如例如碳酸二辛酯(CC)、基于具有6至18个优选8至10个碳原子的脂肪醇的Guerbet碳酸酯、苯甲酸与直链和/或支链C6-C22-醇的酯(例如TN)、每个烷基具有6至22个碳原子的直链或支链、对称或非对称的二烷基醚,如例如二辛酰基醚(OE)、环氧化脂肪酸酯与多元醇的开环产物、硅油(环聚二甲基硅氧烷、硅酮甲基硅油等级等)和/或脂肪烃或环烷烃,如例如角鲨烷、角鲨烯或二烷基环己烷。
3.乳化剂
作为乳化剂可以是例如选自以下至少一组的非离子表面活性剂。
·2至30摩尔环氧乙烷和/或0至5摩尔环氧丙烷与具有8-22个碳原子的直链脂肪醇、与具有12-22个碳原子的脂肪酸、与烷基中具有8-15个碳原子的烷基苯酚以及具有8至22个碳原子的烷基胺的加成产物;
·烷(烯)基中具有8至22个碳原子的烷基和/或烯基低聚糖苷,及其乙氧基化的类似物;
·1至15摩尔环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
·15至60摩尔环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
·甘油和/或山梨糖醇与具有12至22个碳原子的不饱和、直链或饱和、支链脂肪酸和/或具有3至18个碳原子的羟基羧酸的偏酯及其与1至30摩尔的环氧乙烷的加成产物;
·聚甘油(平均缩聚度为2至8)、聚乙二醇(分子量400至5000)、三羟甲基丙烷、季戊四醇、糖醇(例如山梨糖醇)、烷基糖苷(例如甲基糖苷、丁基糖苷、月桂基糖苷)以及多元糖苷(例如纤维素)与具有12至22个碳原子的饱和和/或不饱和、直链或支链脂肪酸和/或具有3至18个碳原子的羟基脂肪酸的偏酯及其与1至30摩尔的环氧乙烷的加成产物;
·季戊四醇、脂肪酸、柠檬酸和脂肪醇的混合脂和/或具有6至22个碳原子、甲基葡萄糖和多元醇,优选丙三醇或聚甘油的混合脂;
·磷酸单-、二-和三烷酯类以及磷酸单-、二-和/或三-PEG烷酯类及其盐;
·羊毛蜡醇类;
·聚硅氧烷-聚烷基-聚醚共聚物及相应衍生物;
·嵌段共聚物例如聚乙二醇-30二聚羟基硬脂酸酯;
·聚合物乳化剂,例如Goodrich的Pemulen类(TR-1、TR-2)或Cognis的SP;
·聚二醇类以及
·碳酸甘油酯。
以下给出特别适当的乳化剂:
(i).烷氧基化合物。环氧乙烷和/或环氧丙烷在脂肪醇、脂肪酸、烷基苯酚或蓖麻油上的加成产物是市售可得的产品。在这里是指同系混合物,其平均烷氧基化度相当于进行加成反应的环氧乙烷和/或环氧丙烷和基质的用量比例。环氧乙烷与甘油加成产物的C12/18脂肪酸单酯和二酯已知作为回脂剂用于化妆制剂。
(ii).烷基-和/或烯基低聚苷。烷基-和/或烯基低聚苷的生产和使用在现有技术中已知。尤其通过使用葡萄糖或具有8至18个碳原子的伯醇的低聚糖进行生产。对于糖苷基团,适合的不仅可以是单糖苷,其中环状糖基与脂肪醇通过糖苷键连接,而且也可以是低聚度优选为约8的低聚糖苷。低聚度是统计平均值,是对于这类技术产物常规的同系物分布的基础。
(iii).偏甘油酯。适当的偏甘油酯的典型实例是羟基硬脂酸单甘油酯、羟基硬脂酸二甘油酯、异硬脂酸单甘油酯、异硬脂酸二甘油酯、油酸单甘油酯、油酸二甘油酯、蓖麻酸单甘油酯、蓖麻酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、芥酸单甘油酯、芥酸二甘油酯、酒石酸单甘油酯、酒石酸二甘油酯、柠檬酸单甘油酯、柠檬酸二甘油酯、苹果酸单甘油酯、苹果酸二甘油酯及其仍含有少量源自生产过程的甘油三酯的技术混合物。1至30且优选5至10摩尔环氧乙烷与上述偏甘油酯的加成产物同样适当。
(iv).脱水山梨醇酯。脱水山梨醇酯是脱水山梨醇单异硬脂酸酯、脱水山梨醇倍半异硬脂酸酯、脱水山梨醇二异硬脂酸酯、脱水山梨醇三异硬脂酸酯、脱水山梨醇单油酸酯、脱水山梨醇倍半油酸酯、脱水山梨醇二油酸酯、脱水山梨醇三油酸酯、脱水山梨醇单芥酸酯、脱水山梨醇倍半芥酸酯、脱水山梨醇二芥酸酯、脱水山梨醇三芥酸酯、脱水山梨醇单蓖麻酸酯、脱水山梨醇倍半蓖麻酸酯、脱水山梨醇二蓖麻酸酯、脱水山梨醇三蓖麻酸酯、脱水山梨醇单羟基硬脂酸酯、脱水山梨醇倍半羟基硬脂酸酯、脱水山梨醇二羟基硬脂酸酯、脱水山梨醇三羟基硬脂酸酯、脱水山梨醇单酒石酸酯、脱水山梨醇倍半酒石酸酯、脱水山梨醇二酒石酸酯、脱水山梨醇三酒石酸酯、脱水山梨醇单柠檬酸酯、脱水山梨醇倍半柠檬酸酯、脱水山梨醇二柠檬酸酯、脱水山梨醇三柠檬酸酯、脱水山梨醇单马来酸酯、脱水山梨醇倍半马来酸酯、脱水山梨醇二马来酸酯、脱水山梨醇三马来酸酯及其技术混合物。1至30且优选5至10摩尔环氧乙烷与上述脱水山梨醇酯的加成产物同样适当。
(v).聚甘油酯。适当的聚甘油酯的典型实例是聚甘油-2二聚羟基硬脂酸酯(PGPH)、聚甘油-3-二异硬脂酸酯(TGI)、聚甘油-4异硬脂酸酯(GI 34)、聚甘油-3油酸酯、聚甘油-3二异硬脂酸酯(PDI)、聚甘油-3甲基葡糖二硬脂酸酯(Tego450)、聚甘油-3蜂蜡(Cera)、聚甘油-4癸酸酯(聚甘油癸酸酯T2010/90)、聚甘油-3鲸蜡基醚(NL)、聚甘油-3二硬脂酸酯(GS 32)和聚甘油聚蓖麻酸酯(WOL 1403)、聚甘油二异硬脂酸(polyglyceryl dimerate isostearate)酯及其混合物。其它适当的多元醇酯的实例是任选与1至30摩尔环氧乙烷反应的月桂酸、椰油酸、牛油酸、棕榈酸、硬脂酸、油酸、山嵛酸等与三羟甲基丙烷或季戊四醇的单酯、二酯和三酯。
(vi).阴离子乳化剂。典型的阴离子乳化剂是具有12至22个碳原子的脂肪族脂肪酸,如例如棕榈酸、硬脂酸或山嵛酸,以及具有12至22个碳原子的二羧酸,如例如壬二酸或癸二酸。
(vii).两性和阳离子乳化剂。此外两性离子表面活性剂可以用作乳化剂。两性离子表面活性剂是分子中含有至少一个季铵基团和至少一个羧酸酯基团和一个磺酸酯基团的表面活性化合物。特别适当的两性离子表面活性剂为所谓的甜菜碱,如N-烷基-N,N-二甲基甘氨酸铵,例如椰油烷基二甲基甘氨酸铵、N-酰胺基丙基-N,N-二甲基甘氨酸铵,例如椰油酰胺基丙基二甲基甘氨酸铵、和烷基或酰基中具有8-18个碳原子的2-烷基-3-羧甲基-3-羟乙基咪唑啉和椰油酰胺基乙基羟乙基羧甲基甘氨酸盐。特别优选已知CTFA名为椰油酰胺丙基甜菜碱的脂肪酸酰胺衍生物。同样适当的乳化剂为两性表面活性剂。两性表面活性剂是除了C8/18烷基或酰基外,分子中还含有至少一个游离氨基和至少一个-COOH或-SO3H基团且能形成内盐的表面活性化合物。适当的两性表面活性剂的实例为烷基中具有约8-18个碳原子的N-烷基甘氨酸、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚氨基二丙酸、N-羟乙基-N-烷基酰胺基丙基甘氨酸、N-烷基牛磺酸、N-烷基肌氨酸、2-烷基氨基丙酸和烷基氨基乙酸。特别优选的两性表面活性剂为N-椰油烷基氨基丙酸酯、椰油酰胺基乙基氨基丙酸酯和C12/18酰基肌氨酸。最后也可以使用阳离子表面活性剂作为乳化剂,如季铵盐类,尤其优选甲基季铵化的二脂肪酸三乙醇胺酯-盐。
4.脂肪和蜡
用做脂肪的典型实例是甘油酯,即固体或液体的植物或动物产品,其主要由高级脂肪酸的混合甘油酯构成。作为蜡的是天然蜡,如例如小烛树蜡、巴西棕榈蜡、日本蜡、芦华草腊(Espartograswachs)、软木蜡、小冠椰子腊(Guarumawachs)、米糠油蜡、糖甘蔗蜡、小冠巴西棕蜡(Ouricurywachs)、褐煤蜡、蜂蜡、紫胶蜡(Schellackwachs)、鲸蜡、羊毛脂(Wollwachs)、尾脂脂肪(Bürzelfett)、(纯)地蜡、地蜡(石蜡)、凡士林、石油蜡、微蜡;化学改性的蜡类(硬蜡类)如例如褐煤酯蜡(Montanesterwachse)、德国沙索集团石油蜡(Sasolwachse)、氢化霍霍巴蜡(Jojobawachse)以及合成蜡类如例如聚亚烷基蜡类和聚乙二醇蜡类。除了脂肪,作为添加剂的还可以是类脂肪物质,如卵磷脂和磷脂。卵磷脂是指由脂肪酸、甘油、磷酸和胆碱通过酯化形成的甘油磷脂。因此在专业领域卵磷脂通常被称为磷脂酰胆碱(PC)。天然卵磷脂的实例为脑磷脂,其也被称为磷脂酸并且是1,2-二酰基-sn-甘油基-3-磷酸的衍生物。与之相反磷脂是指磷酸与甘油的常规单酯和优选二酯(甘油磷酸酯),其通常属于脂肪。此外还可以包括鞘氨醇和鞘类脂物。
5.珠光蜡
珠光蜡是例如:烷二醇酯,尤其是乙二醇二硬脂酸酯;脂肪酸烷醇酰胺,尤其是椰油脂肪酸二乙醇酰胺;偏甘油酯,尤其是硬脂酸单甘油酯;多元、任选羟基取代的羧酸与具有6-22个碳原子的脂肪醇的酯,尤其是酒石酸的长链酯;具有总计至少24个碳原子的脂肪物质,如例如脂肪醇、脂肪酮、脂肪醛、脂肪醚和脂肪碳酸酯,尤其是月桂酮和二硬脂醚;脂肪酸如硬脂酸、羟基硬脂酸或山嵛酸、具有12-22个碳原子的环氧烯烃与具有12-22个碳原子的脂肪醇和/或具有2-15个碳原子和2-10个羟基的多元醇的开环产物、及其混合物。
6.清凉剂
清凉剂是在皮肤上产生清凉感受的化合物。一般涉及薄荷醇化合物,除了本体薄荷醇自身,选自例如组包括薄荷醇甲醚、薄荷酮甘油缩醛(FEMA GRAS1 3807)、薄荷酮甘油缩酮(FEMA GRAS 3808)、乳酸薄荷酯(FEMA GRAS 3748)、薄荷醇乙二醇碳酸酯(FEMA GRAS3805)、薄荷醇丙二醇碳酸酯(FEMA GRAS 3806)、乙基草氨酸薄荷酯、琥珀酸单薄荷酯(FEMAGRAS 3810)、谷氨酸单薄荷酯(FEMA GRAS 4006)、薄荷氧基-1,2-丙二醇(FEMA GRAS3784)、薄荷氧基-2-甲基-1,2-丙二醇(FEMA GRAS 3849)以及薄荷烷碳酸酯和酰胺WS-3、WS-4、WS-5、WS-12、WS-14和WS-30及其混合物。
这类物质的第一种重要代表是琥珀酸单薄荷酯(FEMA GRAS 3810)。不仅琥珀酸酯,而且类似物谷氨酸单薄荷酯(FEMA GRAS 4006)也是基于二元或多元羧酸的单薄荷酯的重要代表。
这类物质的使用实例参见例如文献WO 2003 043431(Unilever)或EP1332772A1(IFF)。
本发明优选的下一组重要薄荷醇化合物包括薄荷醇和多元醇,如例如乙二醇、甘油或碳水化合物的碳酸酯,如例如薄荷醇乙二醇碳酸酯(FEMA GRAS 3805=MGC)、薄荷醇丙二醇碳酸酯(FEMA GRAS 3784=MPC)、2-甲基-1,2-丙二醇碳酸薄荷醇酯(FEMA GRAS 3849)或相应的糖衍生物。同样优选薄荷醇化合物是乳酸薄荷酯(FEMA GRAS 3748=ML)并且特别是薄荷酮甘油缩醛(FEMA GRAS 3807)、或薄荷酮甘油缩酮(FEMA GRAS 3808),市场上以名称MGA出售。这类物质中特别有利是薄荷酮甘油缩醛/缩酮和乳酸薄荷酯、薄荷醇乙二醇碳酸酯、薄荷醇丙二醇碳酸酯,被申请人以名称MGA、ML、MGC和MPC市售。
在上世纪七十年代第一次发现薄荷醇化合物,其在3位有一个C-C-键并且同样有一系列可以使用的代表物。这类物质通常被称为WS-类。本体是薄荷醇衍生物,其中羟基被羧基取代(WS-1)。由该结构产生所有其他的WS-类,如例如优选的WS-3、WS-4、WS-5、WS-12、WS-14和WS-30。
7.粘度调节剂和增稠剂
作为粘度调节剂可以首先考虑具有12至22并且优选16至18个碳原子的脂肪醇或羟基脂肪醇以及偏甘油酯、脂肪酸或羟基脂肪酸。优选的是这些物质与烷基低聚苷和/或相同链长的脂肪酸-N-甲基糖胺和/或聚甘油聚-12-羟基硬脂酸酯的结合。适当的增稠剂是如Aerosil-类(亲水性二氧化硅)、多糖,更特别是黄原胶、瓜尔胶、琼脂、藻酸盐和纤基乙酸钠(Tylosen)、羧甲基纤维素和羟乙基和羟丙基纤维素、以及脂肪酸的高分子量聚乙二醇单酯和二酯、聚丙烯酸酯(例如Goodrich的和Pemulen-类;或Sigma的Kelco的Keltrol-类;Seppic的Sepigel-类;Allied Colloids的Salcare-类)、聚丙烯酰胺、聚乙烯醇和聚乙烯吡咯烷酮。特别有效的是膨润土,如例如凝胶VS-5PC(Rheox),其涉及十甲基环戊硅氧烷、二硬脂基二甲基胺锂皂石和碳酸丙烯酯的混合物。其他可以考虑的是表面活性剂如,例如乙氧基化脂肪酸甘油酯、脂肪酸与多元醇如季戊四醇或三羟甲基丙烷的酯、窄同系物分布的脂肪醇乙氧基化物或烷基低聚苷以及电解质如氯化钠和氯化铵。
8.富脂剂和稳定剂
作为富脂剂可以使用物质如例如羊毛脂和卵磷脂以及聚乙氧基化或酰基化羊毛脂和卵磷脂衍生物、多元醇脂肪酸酯、单甘油酯和脂肪酸烷醇酰胺,其中脂肪酸烷醇酰胺也可用作泡沫稳定剂。
作为稳定剂可以使用脂肪酸的金属盐,如例如硬脂酸或蓖麻酸镁、铝和/或锌。
9.聚合物
适当的阳离子聚合物是例如阳离子纤维素衍生物,例如以商品名Polymer JR由Amerchol得到的季铵化羟乙基纤维素、阳离子淀粉、二烯丙基铵盐和丙烯酰胺的共聚物、季铵化乙烯基吡咯烷酮/乙烯基咪唑聚合物如,例如(BASF)、聚乙二醇和胺的缩合产物、季铵化胶原多肽如,例如月桂基二甲基铵羟丙基胺水解胶原(L,Grünau)、季铵化小麦多肽、聚乙烯亚胺、阳离子硅氧烷聚合物,例如氨基二甲聚硅氧烷(Amodimethicone)、己二酸和二甲基氨基羟丙基二亚乙基三胺的共聚物(Sandoz)、丙烯酸与二甲基二烯丙基氯化铵的共聚物(550,Chemviron)、聚氨基聚酰胺及其交联水溶性聚合物、阳离子角质素衍生物例如任选以微晶分布的季铵化壳聚糖、二卤代烷基如二溴丁烷与双二烷基胺的缩合产物,例如双-二甲基氨基-1,3-丙烷、阳离子瓜尔胶,例如Celanese的CBS、C-17、C-16、季铵盐聚合物如,例如Miranol的A-15、AD-1、AZ-1以及各种聚季铵盐类。
阴离子、两性离子、两性和非离子聚合物是例如乙酸乙烯酯/巴豆酸共聚物、乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物、乙酸乙烯酯/马来酸丁酯/丙烯酸异冰片酯共聚物、甲基乙烯基醚/马来酸酐共聚物及其酯、未交联的和与多元醇交联的聚丙烯酸、丙烯酰胺基丙基三甲基氯化铵/丙烯酸酯共聚物、辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁基氨基乙酯/甲基丙烯酸2-羟丙酯共聚物、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、乙烯基吡咯烷酮/甲基丙烯酸二甲基氨基乙酯/乙烯基己内酰胺三元共聚物和任选衍生的纤维素醚和硅氧烷。
10.硅氧烷化合物
适当的硅氧烷化合物是例如二甲基聚硅氧烷、甲基苯基聚硅氧烷、环硅氧烷以及氨基、脂肪酸、醇、聚醚、环氧、氟、糖苷和/或烷基改性的硅氧烷化合物,在室温下它们可以是液态以及呈树脂态。其它适当的是有机硅树脂,其为平均链长为200至300个二甲基硅氧烷单元的二甲基硅油与氢化硅酸盐的混合物。
11.UV-防晒因子
UV-防晒因子是指例如在室温下以液态或晶体存在的有机物质(光保护过滤物质),其能吸收紫外光线并将吸收的能量以长波辐射的形式,例如热,再次放出。通常UV-防晒因子的用量为0.1至5且优选0.2至1重量%。
UVB-过滤物质可以是油溶或水溶的。作为油溶物质可以是,例如:
·3-亚苄基樟脑或3-亚苄基降樟脑及其衍生物,例如3-(4-甲基亚苄基)-樟脑;
·4-氨基苯甲酸衍生物,优选4-(二甲基氨基)苯甲酸-2-乙基己酯、4-(二甲基氨基)苯甲酸-2-辛酯和4-(二甲基氨基)苯甲酸-戊酯。
·肉桂酸酯,优选4-甲氧基肉桂酸2-乙基己酯、4-甲氧基肉桂酸丙酯、4-甲氧基肉桂酸异戊酯、2-氰基-3,3-苯基肉桂酸-2-乙基己酯(Octocrylene);
·水杨酸酯,优选水杨酸2-乙基己酯、水杨酸-4-异丙基苄酯、水杨酸高薄荷酯;
·二苯甲酮衍生物,优选2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4’-甲基二苯甲酮、2,2’-二羟基-4-甲氧基二苯甲酮;
·亚苄丙二酸酯,优选4-甲氧基亚苄丙二酸二-2-乙基己酯;
·三嗪衍生物,如例如2,4,6-三苯胺基-(对-羰基-2’-乙基-1’-己氧基)-1,3,5-三嗪和辛基三嗪酮或二辛基丁酰胺三嗪酮(HEB)
·丙-1,3-二酮如例如1-(4-叔丁基苯基)-3-(4’-甲氧基苯基)丙-1,3-二酮;
·挂式三环(5.2.1.0)癸烷衍生物。
作为水溶性物质可以考虑:
·2-苯基苯并咪唑磺酸及其碱金属盐、碱土金属盐、铵盐、烷基铵盐、烷醇基铵盐和葡糖铵盐;
·1H-苯并咪唑-4,6-二磺酸、2,2-(1,4-亚苯基)双,二钠盐(NeoAP);
·二苯甲酮的磺酸衍生物,优选2-羟基-4-甲氧基二苯甲酮-5-磺酸及其盐
·3-亚苄基樟脑的磺酸衍生物,如例如4-(2-氧-3-冰片烯基甲基)苯甲酰基磺酸和2-甲基-5-(2-氧-3-冰片烯基)磺酸及其盐。
作为适当的UVA过滤物质尤其考虑苯甲酰基甲烷,如例如1-(4’-叔丁基苯基)-3-(4’-甲氧基苯基)丙-1,3-二酮、4-叔丁基-4’-甲氧基二苯甲酰基甲烷(1789)、2-(4-二乙基氨基-2-羟基苯甲酰基)-苯甲酸己酯(A Plus)、1-苯基-3-(4’-异丙基苯基)-丙-1,3-二酮以及烯胺化合物。UVA过滤物质和UVB过滤物质可以单独也可以混合使用。特别有利的是由苯甲酰基甲烷衍生物,例如4-叔丁基-4’-甲氧基二苯甲酰基甲烷(1789)和2-氰基-3,3-苯基肉桂酸-2-乙基己酯(Octocrylene)与肉桂酸酯,优选4-甲氧基肉桂酸-2-乙基己酯和/或4-甲氧基肉桂酸丙酯和/或4-甲氧基肉桂酸异戊酯结合的结合物。有利的是这类结合物与水溶性过滤物质如例如2-苯基苯并咪唑-5-磺酸及其碱金属盐、碱土金属盐、铵盐、烷基铵盐、烷醇基铵盐和葡糖铵盐结合。
除了上述溶解性物质,为实现所述目的也可以考虑不溶性的光保护染料,即精细分散的金属氧化物和盐。适当的金属氧化物实例特别是氧化锌和二氧化钛,以及铁、锆、硅、锰、铝和铈的氧化物及其混合物。可使用的盐为硅酸盐(滑石)、硫酸钡或硬脂酸锌。氧化物和盐以染料的形式用于皮肤护理和护肤乳液,以及修饰性化妆品。颗粒应具有小于100nm,优选5-50nm,特别是15-30nm的平均直径。它们可具有球形,但是也可使用具有椭圆形或以某种其它方法偏离球面形状的那些颗粒。染料也可以以表面处理的形式,即亲水化或疏水化存在。典型实例为涂覆的二氧化钛,例如二氧化钛T805(Degussa)或T-2000、T、T-EC0、T-S、T-Aqua、T-45D(所有Merck)、Uvinul TiO2(BASF)。疏水性涂层主要为聚硅氧烷,具体而言,三烷氧基辛基硅烷或二甲基硅油(Simethicone)。在防晒组合物中优选使用所谓的微细染料或纳米染料。优选使用微粉化氧化锌如或
12.保湿剂
保湿剂用于进一步优化组合物的感官性能并且调节皮肤湿度。同时本发明组合物的温度稳定性,特别是在乳液的情况下,增大。保湿剂的含量通常为0.1至15重量%,优选1至10重量%,并且特别是5至10重量%。
根据本发明适当的是氨基酸、吡咯烷羧酸、乳酸及其盐、乳糖醇、脲和脲衍生物、脲酸、葡糖胺、肌氨酸酐、胶原质水解产物、壳多糖或壳多糖盐/衍生物、特别是多元醇和多元醇衍生物(如丙三醇、二丙三醇、三丙三醇、乙二醇、丙二醇、丁二醇、赤藓醇、1,2,6-己三醇、聚乙二醇如PEG-4、PEG-6、PEG-7、PEG-8、PEG-9、PEG-10、PEG-12、PEG-14、PEG-16、PEG-18、PEG-20)、糖和糖衍生物(如果糖、葡萄糖、麦芽糖、麦芽糖醇、甘露醇、肌醇、山梨糖醇、山梨糖醇硅烷二醇、蔗糖、海藻糖、木糖、木糖醇、葡糖醛酸及其盐)、乙氧基化山梨醇(Sorbeth-6、Sorbeth-20、Sorbeth-30、Sorbeth-40)、蜂蜜和氢化蜂蜜、氢化淀粉水解物以及氢化小麦蛋白混合物和PEG-20-乙酸酯共聚物。根据本发明优选适当的保湿剂是丙三醇、二丙三醇、三丙三醇和丁二醇。
13.生物活性物质和抗氧化剂
生物活性物质是例如生育酚、生育酚乙酸酯、生育酚棕榈酸酯、抗坏血酸、(脱氧)核糖核酸及其碎裂产物、β-葡聚糖、视黄醇、红没药醇、尿囊素、植烷三醇、泛醇、AHA酸、氨基酸、神经酰胺、假神经酰胺、芳香油、植物提取物,如例如桃李提取物、班马纳坚果提取物和维生素络合物。
抗氧化剂打断了UV辐射透过皮肤时触发的光化学反应链。其典型实例为氨基酸(例如甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物、咪唑(例如尿刊宁酸)及其衍生物、肽如D,L-肌肽、D-肌肽、L-肌肽及其衍生物(例如鹅肌肽)、类胡萝卜素、胡萝卜素(例如α-胡萝卜素、β-胡萝卜素、番茄红素)及其衍生物、绿原酸及其衍生物、硫辛酸及其衍生物(例如二氢硫辛酸)、金硫葡糖、丙硫氧嘧啶和其它硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺及其糖基、N-乙酰基-、甲基-、乙基-、丙基-、戊基-、丁基-和月桂基-、棕榈酰基-、油基-、γ-亚油基-、胆甾烯基-和甘油基酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸双十八酯、硫代二丙酸及其衍生物(酯类、醚类、肽类、脂类、核苷酸类、核苷类和盐)以及非常低的耐药剂量(例如pmol至μmol/kg)的亚砜亚胺化合物(例如丁硫氨酸亚砜亚胺、同型半胱氨酸亚砜亚胺、丁硫氨酸砜、五-、六-和七-硫氨酸亚砜亚胺)、以及(金属)螯合剂类(例如α-羟基脂肪酸类、棕榈酸、植酸、乳铁蛋白)、α-羟基酸类(例如柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、胆红素、胆绿素、EDTA、EGTA及其衍生物、不饱和脂肪酸及其衍生物(例如γ-亚麻酸、亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醇及其衍生物、维生素C及其衍生物(例如抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸乙酸酯)、生育酚及衍生物(例如维生素E乙酸酯)、维生素A及衍生物(维生素A棕榈酸酯)以及安息香树脂的苯甲酸松酯、芸香十烯酸及其衍生物、α-糖基芸香苷、阿魏酸、亚糠基葡糖醇、肌肽、丁基羟基甲苯、丁基羟基茴香醚、去甲二氢化愈创木酸(Nordihydroguajakharzsure)、去甲二氢愈创木酸木脂酸(Nordihydroguajaretsure)、三羟基丁酰苯、尿酸及其衍生物、甘露糖及其衍生物、超氧化物歧化酶、锌及其衍生物(例如ZnO、ZnSO4)、硒及其衍生物(例如硒代蛋氨酸)、芪及其衍生物(例如氧化芪、反氧化芪)和根据本发明合适的这些所述活性成分的衍生物(例如盐、酯、醚、糖、核苷酸、核苷、肽和脂类)。
14.除臭剂和抗菌剂
化妆品除臭剂针对体味起作用,遮蔽或去除体味。体味是由于皮肤上的细菌影响分泌汗液所产生,其中产生气味不适的分解产物。因此除臭剂含有有效物质,其被用作抗菌剂、酶抑制剂、气味吸收剂或气味遮蔽剂。
(i)抗菌剂。基本上对革兰氏阳性细菌有效的所有物质都适用作抗菌剂,如例如4-羟基苯甲酸及其盐和酯、N-(4-氯苯基)-N'-(3,4-二氯苯基)脲、2,4,4'-三氯-2'-羟基-二苯基醚(三氯生)、4-氯-3,5-二甲基-苯酚、2,2'-亚甲基双(6-溴-4-氯苯酚)、3-甲基-4-(1-甲基乙基)苯酚、2-苄基-4-氯苯酚、3-(4-氯苯氧基)-1,2-丙二醇、丁基氨基甲酸3-碘-2-丙炔酯、氯己定、3,4,4'-三氯碳酰替苯胺(TTC)、抗菌芳香剂、麝香草酚、麝香草油、丁香酚、丁香油、薄荷醇、薄荷油、金合欢醇、苯氧乙醇、甘油单癸酸酯、单辛酸甘油酯、月桂酸单甘油酯(GML)、双甘油单癸酸酯(DMC)、水杨酸N-烷基胺,例如,正辛基水杨酰胺或正癸基水杨酰胺。
(ii)酶抑制剂。适当的酶抑制剂是例如酯酶抑制剂。这些酶抑制剂优选为柠檬酸三烷酯,例如柠檬酸三甲酯、柠檬酸三丙酯、柠檬酸三异丙酯、柠檬酸三丁酯并且特别是柠檬酸三乙酯(Hydagen CAT)。上述物质抑制酶活性,由此减少气味的生成。适合作为酯酶抑制剂的其它物质为甾醇硫酸酯或甾醇磷酸酯,例如,羊毛甾醇硫酸酯或磷酸酯、胆固醇硫酸酯或磷酸酯、菜油甾醇硫酸酯或磷酸酯、豆甾醇硫酸酯或磷酸酯和谷甾醇硫酸酯或磷酸酯;二羧酸和其酯,例如戊二酸、戊二酸单乙酯、戊二酸二乙酯、己二酸、己二酸单乙酯、己二酸二乙酯、丙二酸和丙二酸二乙酯;羟基羧酸及其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯,以及甘氨酸锌。
(iii)气味吸收剂。适当的气味吸收剂是能够吸收并在很大程度上保留形成味道的化合物的物质。它们降低各成分的分压,由此还可降低其扩散速率。重要的是在该过程中芳香剂必须保持未受损害。气味吸收剂对细菌没有作用。它们含有例如作为主成分的蓖麻油酸的复合锌盐,或作为“固香剂”为本领域技术人员所知晓的特定的主要中和气味的芳香剂,例如,岩蔷薇或苏合香的提取物或一些松香酸衍生物。气味掩蔽剂为芳香剂或芳香油,除了其作为气味掩蔽剂的功能之外,还向除臭剂提供其各自香味。可以提及的芳香油是例如天然和合成芳香物质的混合物。天然芳香物质为花、茎和叶、果实、果皮、根、木材、草本植物和禾本植物、松针和树枝以及树脂和香脂的提取物。还适当的是动物原料,例如麝猫香和海狸香。典型的合成芳香化合物为酯、醚、醛、酮、醇和烃类产物。酯类芳香剂化合物是例如,乙酸苄基酯、乙酸p-叔丁基环己酯、乙酸芳樟酯、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类包括,例如苄基乙基醚;醛类包括,例如含有8至18个碳原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛(Bourgeonal);酮包括,例如紫罗兰酮和甲基柏木酮;醇包括茴香脑、香茅醇、丁香酚、异丁香酚、香叶醇、芳樟醇,苯乙醇和松油醇;烃类主要包括萜烯和香脂。然而,优选使用不同芳香物质的混合物,它们一起产生令人愉快的香味。通常用作芳香成分的挥发性较低的精油也适用作芳香油,例如鼠尾草油、甘菊油、丁香油、蜂花油、薄荷油、肉桂叶油、椴树花油、杜松子油、香根草油、乳香油、白松香油(Galbanuml)、岩蔷薇油和熏衣草油。优选单独使用或以混合物使用佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、α-己基肉桂醛、香叶醇、苄丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷(Boisambrene Forte)、龙涎呋喃、吲哚、二氢茉莉酮酸甲酯、Sandelice、柠檬油、柑橘油、橙油、异戊氧基乙酸烯丙酯、Cyclovertal、熏衣草油、鼠尾草油、β-大马酮、波旁香叶油、水杨酸环己酯、Vertofix Coeur、Iso-E-Super、Fixolide NP、Evernyl、iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、Romilat、2-乙基-己酸乙酯(Irotyl)和2-叔丁基环己基乙基碳酸酯(Floramat)。
(iv)止汗剂。止汗剂通过影响分泌汗腺的活性减少汗液形成,并由此抵抗腋下湿和体味。止汗剂的水性或无水制剂通常含有以下内容物:
·收敛活性成分、
·油成分、
·非离子乳化剂、
·助乳化剂、
·稠度调节剂、
·助剂如增稠剂或络合剂和/或
·非水溶剂如乙醇、丙二醇和或/丙三醇。
适当的收敛止汗活性成分主要是铝,锆或锌的盐。这类适当的止汗活性成分是例如氯化铝、氢氯酸铝、二氢氯酸铝、倍半氢氯酸铝及其络合物,例如与1,2-丙二醇的络合物、尿囊素羟基铝(Aluminiumhydroxyallantoinat)、酒石酸氯化铝、三氢氯酸铝锆、四氢氯酸铝锆、五氢氯酸铝锆及其络合物,例如与氨基酸如甘氨酸的络合物。此外在止汗剂中通常含有少量油溶或水溶性的助剂。这类油溶助剂可以是例如:
·抗炎、护肤或芳芳精油、
·合成护肤活性成分和/或
·油溶性芳香油。
水溶性添加剂通常是例如防腐剂、水溶性香料、pH值调节剂,例如缓冲混合物、水溶性增稠剂,例如水溶性天然或合成聚合物如例如黄原胶、羟乙基纤维素、聚乙烯吡咯烷酮或高分子聚氧化乙烯。
15.成膜剂
标准成膜剂是例如壳聚糖、微晶壳聚糖、季铵壳聚糖、聚乙烯吡咯烷酮、乙烯基吡咯烷酮-乙酸乙烯酯共聚物、丙烯酸系聚合物、季铵化纤维素衍生物、胶原、透明质酸及其盐和类似化合物。
16.抗头皮屑剂
适当的抗头皮屑剂是Pirocton Olamin(1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2-(1H)-吡啶酮单乙醇胺盐)、(氯咪巴唑)、(4-乙酰基-1-{4-[2-(2,4-二氯苯基)r-2-(1H-咪唑-1-基甲基)-1,3-二氧戊(dioxylan)-c-4-基甲氧基苯基}-哌嗪、酮康唑、新康唑、二硫化硒、胶体硫、硫聚乙二醇脱水山梨醇单油酸酯、硫蓖麻醇聚乙氧基化物、硫磺焦油馏分、水杨酸(或结合六氯酚)、十一碳烯酸、单乙醇酰胺磺基琥珀酸钠盐、UD(蛋白质/十一烯酸浓缩物)、吡啶硫酮锌、吡啶硫酮铝和吡啶硫酮镁/双吡硫翁硫酸镁。
17.膨胀剂
用于水相的膨胀剂可以是蒙脱石、粘土矿物质、Pemulen以及烷基改性的聚羧乙烯类(Goodrich)。其他适当的聚合物和膨胀剂可以参见R.Lochhead的Cosm.Toil.108,95(1993)。
18.驱虫剂
N,N-二乙基-间甲苯甲酰胺、1,2-戊二醇或丁酰基氨基丙酸乙酯可以作为驱虫剂。二羟基酮适用作自行褐色剂。作为能抑止黑色素的形成并在脱色剂中应用的酪氨酸抑止剂有例如熊果苷、阿魏酸、曲酸、香豆酸和抗坏血酸(维生素C)。
19.用于口腔和牙齿护理剂的内容物
牙膏通常是指由水、增稠剂、保湿剂、磨料、表面活性剂、甜味剂、香料、除臭活性成分以及抵抗口腔和牙齿疾病的活性成分构成的凝胶状或膏状制剂。在本发明的牙膏中可以使用所有常用的磨料,如例如白垩、磷酸二钙、不溶性的偏磷酸钠、硅酸铝、焦磷酸钙、细分散的合成树脂、二氧化硅、氧化铝和三水合氧化铝。
对于本发明的牙膏优选适当的磨料特别是含量占牙膏15至40重量%的细分散的二氧化硅干凝胶、二氧化硅水凝胶、沉淀二氧化硅、三水合氧化铝和细分散的α-氧化铝或这些磨料的混合物。作为保湿剂优选用量至多为50重量%的低分子量聚乙二醇、甘油、山梨糖醇或这些产品的混合物。在已知增稠剂中适当的是增稠的细分散凝胶二氧化硅和水凝胶,如例如羧甲基纤维素、羟乙基纤维素、羟丙基瓜尔胶、羟乙基淀粉、聚乙烯吡咯烷酮、高分子聚乙二醇、植物胶如胺黄树胶、琼脂、卡拉胶、阿拉伯树胶、黄原胶和羧乙烯聚合物(例如-Typen)。除了薄荷呋喃和薄荷醇化合物的混合物,口腔和牙齿护理剂尤其含有表面活性物质,优选阴离子和非离子高泡沫表面活性剂,如上文所述物质,特别是烷基醚硫酸盐、烷基聚葡萄糖苷及其混合物。
其他常用的牙膏添加剂是:
·防腐剂和抗菌剂,如例如羟基苯甲酸甲酯、乙酯或丙酯、山梨酸钠、苯基酸钠、溴氯酚、苯基水杨酸酯、麝香草酚等;
·抗牙石活性成分,例如有机磷酸盐如1-羟基乙烷-1.1-二磷、1-磷丙烷-1,2,3-三羧酸和由US 3,488,419、DE 2224430 A1和DE 2343196 A1已知的其他物质;
·其他抑制龋齿物质如例如氟化钠、单氟磷酸钠、氟化亚锡;
·甜味剂,如例如糖精钠、环己氨基磺酸钠、蔗糖、乳糖、麦芽糖、果糖或(天门冬氨酰-苯丙氨酸-甲酯)或其甜味成分,尤其是莱鲍迪甙;
·另外的芳香物质例如桉叶油、茴香油、小茴香油、藏茴香油、醋酸甲酯、肉桂醛、茴香脑、香草醛、麝香草酚及其混合物以及其他天然和合成芳香物质;
·色素例如二氧化钛;
·染料;
·缓冲物质例如伯、仲或叔磷酸碱金属盐或柠檬酸/柠檬酸钠;
·伤口愈合和抑制炎症的物质例如尿囊素、脲、甘菊环、黄春菊活性成分和乙酰水杨酸衍生物。
化妆品组合物实施方案的优选形式是水性糊状分散体形式的牙膏,其包含抛光剂、保湿剂、粘度调节剂,还任选包含其他常用的成分,以及0.5-2%重量的薄荷呋喃和薄荷醇化合物的混合物。
就嗽口水而言,与不同程度的精油、乳化剂、收敛剂和调色药提取物、结石抑制剂、抗菌添加剂和矫味剂的水醇溶液的组合是十分可能的。本发明的另一个优选实施方案是水或水醇溶液形式的嗽口水,其包含0.5-2%重量的薄荷呋喃和薄荷醇化合物的混合物。在应用前被稀释的嗽口水组合物中,较高浓度可以得到相当于指定稀释比的足够效果。
20.助水溶物
此外助水溶物例如乙醇、异丙醇或多元醇类可以用于改善流动性;这些物质大部分相当于上述载体。适合的多元醇类优选包含2-15个碳原子和至少2个羟基。多元醇类可以包含其他官能团,尤其是氨基或可以被氮修饰。典型的实例是:
·甘油;
·亚烷基二醇例如乙二醇、二乙二醇、丙二醇、丁二醇、己二醇和具有100-1000道尔顿平均分子量的聚乙二醇类;
·具有1.5-10的自我缩合度的专用(technische)寡聚甘油混合物例如具有40-50%重量二甘油含量的专用二甘油混合物;
·羟甲基化合物,特别是例如三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、季戊四醇和二季戊四醇;
·低级烷基糖苷类,特别是在烷基上包含1-8个碳原子的那些,例如甲基和丁基糖苷;
·包含5-12个碳原子的糖醇类例如山梨醇或甘露糖醇;
·包含5-12个碳原子的糖类例如葡萄糖或蔗糖;
·氨基糖类例如葡萄糖胺;
·二醇胺类例如二乙醇胺或2-氨基丙-1,3-二醇。
21.防腐剂
适当的防腐剂是例如苯氧乙醇、甲醛溶液、对羟苯甲酸类、戊二醇或山梨酸以及已知的名称为的银化合物和Kosmetikverordnung附录6中A部分和B部分中列举的其他类型的化合物。
22.芳香油和芳香剂
适当的芳香油是天然芳香剂与合成芳香剂的混合物。天然芳香剂包括花(百合、薰衣草、玫瑰、茉莉、橙花、依兰)、茎和叶(天竺葵、广藿香、苦橙)、水果(茴香、胡荽、香菜、杜松)、果皮(佛手柑、柠檬、橙)、根(肉豆蔻、当归、芹菜、小豆蔻、木香、虹膜、菖蒲)、木材(松木、檀香、愈创木、雪松木、花梨木)、草本植物和禾本植物(龙蒿、柠檬草、鼠尾草、百里香)、松针和树枝(云杉、冷杉、松树、矮松)、树脂和香脂(格蓬、榄香脂、安息香、没药、乳香、红没药)的提取物。还可使用动物原料,例如麝猫香和海狸香。典型的合成芳香剂化合物是酯、醚、醛、酮、醇和烃类产物。酯类芳香剂化合物实例是例如乙酸苄酯,异丁酸苯氧基乙酯、环己基乙酸对叔丁酯、乙酸芳樟酯、乙酸二甲基苄基原酯(dimethyl benzyl carbinylacetate)、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、苯基甘氨酸乙基甲酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类包括,例如苄基乙基醚;醛类包括,例如含有8至18个碳原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛;酮类是例如紫罗兰酮、α-异甲基紫罗酮和甲基柏木酮;醇类是例如茴香脑、香茅醇、丁香酚、异丁香酚、香叶醇、芳樟醇、苯乙醇和松油醇;烃类主要包括萜烯类和香脂类。然而,优选使用不同芳香剂化合物的混合物,它们一起产生令人愉快的香味。其它适当的芳香油为大多用作芳香成分的挥发性较低的精油。实例是鼠尾草油、甘菊油、丁香油、蜂花油、薄荷油、肉桂叶油、莱姆花油、杜松子油、香根草油、乳香油、白松香油、岩蔷薇油和熏衣草油。以下为单独或以混合形式优选使用的物质:佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、α-己基肉桂醛、香叶醇、苄丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷、龙涎呋喃、吲哚、二氢茉莉酮酸甲酯(Hedione)、Sandelice、柑橘类精油、柑橘油、橙油、乙醇酸烯丙基戊酯、Cyclovertal、醒目熏衣草油、鼠尾草油、大马酮、波旁香叶油、水杨酸环己酯、Vertofix Coeur、Iso-E-Super、Fixolide NP、Evernyl、Iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、Romilllat、2-乙基-己酸乙酯(Irotyl)和2-叔丁基环己基乙基碳酸酯(Floramat)。
适合的芳香物质是例如辣薄荷油、荷兰薄荷油、茴香油、日本八角茴香油、藏茴香油、桉叶油、小茴香油、柠檬油、冬青油、丁香油、薄荷醇等。
23.染料
适合的染料是例如德国研究学会染料协会(Farbstoff-kommission derDeutschen Forschungsgemeinschaft)的公开物“Kosmetische”,Verlag Chemie,Weinheim,1984,页81至106中列举的适于并批准用于化妆品的物质中的任何一种。实例包括胭脂红A(C.I.16255)、专利蓝V(C.I.42051)、靛蓝(C.I.73015)、叶绿酸(C.I.75810)、喹啉黄(C.I.47005)、二氧化钛(C.I.77891)、阴丹士林蓝RS(C.I.69800)和茜草红(C.I.58000)。鲁米诺(Luminol)也可用作荧光染料。基于总混合物,这些染料通常的使用浓度在0.001-0.1重量%。
II.用于洗涤和清洁剂的内容物、添加剂和物质
A.表面活性剂
用于制造洗涤和清洁剂的表面活性剂除了非离子表面活性剂还可以使用阴离子、阳离子、两性和/或非离子表面活性剂以及支链烷基硫酸盐。
作为非离子表面活性剂优选使用烷氧基化,有利的是乙氧基化,特别是优选每摩尔醇含有8-18个碳原子以及平均1至12摩尔环氧乙烷(EO)的伯醇,其中醇基是直链或优选为2-甲基支化的或者可以混合含有直链和2-甲基支化的醇基,如通常羰基合成醇基中所存在的。然而尤其优选带有直链基团的醇乙氧基化物,其中该基团源自含有12至18个碳原子的天然醇,例如源自椰子醇、棕榈醇、牛油脂肪醇或油醇,并且平均2至8EO每摩尔醇。优选的乙氧基化醇包括例如具有3EO、4EO或7EO的C12-14-醇,具有3EO、5EO、7EO或8EO的C13-5-醇,具有3EO、5EO或7EO的C12-18-醇,以及如含有3EO的C12-4-醇和7EO的C12-8-醇混合物的这类混合物。给出的乙氧基化度是统计平均值,其可能为整数或分数。优选的醇乙氧基化物具有窄同系物分布(窄范围乙氧基化物,NRE)。除了这些非离子表面活性剂之外,也可使用具有大于12EO的脂肪醇。其实例为具有14EO、25EO、30EO或40EO的牛油脂肪醇。根据本发明,也可使用分子中同时包含EO和PO基团的非离子表面活性剂。在本文中,可使用具有EO-PO结构单元或PO-EO结构单元的嵌段共聚物,也可使用EO-PO-EO共聚物或PO-EO-PO共聚物。应理解的是,也可使用具有混合烷氧基化的非离子表面活性剂,其中EO和PO单元不以嵌段分布,而是随机分布。该产品通过使环氧乙烷和环氧丙烷同时作用于脂肪醇而获得。
其他类别的可以有利的用于生产洗涤或清洁剂的非离子表面活性剂是烷基糖苷(APG)。可以使用的烷基糖苷符合通式RO(G),其中R为直链或支链,尤其是2-甲基支化的,饱和或不饱和的,具有8至22,优选12至18个碳原子的脂族基团,G为代表具有5或6个碳原子的单糖单元,优选葡萄糖。糖基化度z为1.0至4.0,优选1.0至2.0并且尤其是1.2至1.4之间。
胺氧化物类型的非离子表面活性剂,如N-椰油烷基-N,N-二甲基胺氧化物和N-牛油脂烷基-N,N-二羟乙胺氧化物,以及脂肪酸链烷醇酰胺类型的非离子表面活性剂也是适合用于生产洗涤和清洁产品。这些非离子表面活性剂的量优选不大于乙氧基化脂肪醇的量,尤其是不大于其一半的量。
其它适当的表面活性剂为式R-CO-N(R1)-[Z]的多羟基脂肪酸酰胺,其中RCO为具有6至22个碳原子的脂肪酰基,R1为氢、具有1至4个碳原子的烷基或羟烷基,并且[Z]为具有3至10个碳原子和3至10个羟基的直链或支链的多羟基烷基基团。多羟基脂肪酸酰胺为已知的物质,其通常可通过用氨、烷基胺或链烷醇胺还原胺化还原性糖,随后通过使用脂肪酸、脂肪酸烷基脂或脂肪酰氯的酰基化而获得。多羟基脂肪酸酰胺基团也包括式R-CO-N(R1-O-R2)-[Z]的化合物,其中R为具有7至12个碳原子的直链或支链的烷基或烯基,R1为具有2至8个碳原子的线性、支化或环状的烷基或芳基,R2为具有1至8个碳原子的线性、支化或环状的烷基、芳基或氧烷基,优选C1-4-烷基-或苯基基团,并且[Z]为其烷基链被至少两个羟基取代的线性多羟基烷基,或为该基团的烷氧基化、优选乙氧基化或丙氧基化的衍生物。[Z]优选通过糖的还原胺化获得,如葡萄糖、果糖、麦芽糖、乳糖、半乳糖、甘露糖或木糖的还原胺化。N-烷氧基-或N-芳氧基-取代化合物在烷氧化物作催化剂时,通过与脂肪酸甲酯反应可转化为期望的多羟基脂肪酸酰胺。
非离子表面活性剂优选占液态洗涤和清洁剂5至30重量%,优选7至20重量%并且尤其为9-15重量%,以总产品量计。
作为阴离子表面活性剂使用的是例如磺酸盐和硫酸盐。磺酸盐类表面活性剂优选C9-3-烷基苯磺酸盐、烯属磺酸酯,即烯基和羟基烷基磺酸盐以及二磺酸盐的混合物,如由带有端位或中间双键的C12-8-单烯烃通过与气态三氧化硫硫化并随后硫化产物的碱性或酸性水解得到。适当的是烷基磺酸盐,其由C12-8-烷烃例如通过磺化氯化或磺化氧化并随后水解或中和得到。同样适当的是α-磺化脂肪酸(磺酸酯),例如水合椰油酸、棕榈仁油酸或牛油脂肪酸的α-磺化甲酯。
同样适当的不饱和脂肪酸,如少量油酸,优选含量不超过约2至3重量%,的磺化产品。尤其优选α-磺化脂肪酸烷基酯,其具有酯基中不多于4个碳原子的烷基链,例如甲酯、乙酯、丙酯和丁酯。特别有利的是α-磺化脂肪酸甲酯(MES),但是也可以使用其皂化二盐。
其他阴离子表面活性剂是氨基酸,例如N-甲基牛胆碱(Tauride)和/或N-甲基甘氨酸(Sarkoside)的脂肪酸衍生物。特别有利的是N-甲基甘氨酸酯或肌氨酸酯,特别是高级并且任选一元或多元不饱和脂肪酸的肌氨酸酯,如Oleylsarkosinat。
其他适当的阴离子表面活性剂是磺化脂肪酸甘油酯。脂肪酸甘油酯是指单酯、二酯和三酯及其混合物,如在单甘油与1至3摩尔脂肪酸的脂肪化或三甘油酯与0.3至2摩尔甘油的转酯化得到。优选的磺化脂肪酸甘油酯是含有6至22个碳原子的饱和脂肪酸,例如己酸、辛酸、癸酸、肉豆蔻酸、月桂酸、棕榈酸、硬脂酸或山嵛酸的磺化产品。
作为烷(烯)基硫酸盐特别优选C12-C18-脂肪醇的硫酸半酯的碱金属,特别是钠盐,例如椰油脂肪醇、牛油脂肪醇、月桂醇、肉豆蔻醇、鲸蜡醇或硬脂醇或C10-C20-羰基合成醇和这类链长的仲醇半酯。其他优选的是所述链长的烷(烯)基硫酸盐,其含有基于石化生产的合成直链烷基,其具备与基于脂肪化学原料的相应化合物类似的降解性能。基于洗涤技术的利益优选C12-C16-烷基硫酸酯和C12-C15-烷基硫酸酯以及C14-C15-烷基硫酸酯。2,3-烷基硫酸酯,例如以产品名DAN(R)由Shell Oil公司市售可得,也是适当的阴离子表面活性剂。
同样适当的是与1至6摩尔环氧乙烷乙氧基化的直链或支链C7-21-烷醇,如平均3.5摩尔环氧乙烷(EO)的2-甲基C9-11-烷醇或具有1至4个EO的C12-18-脂肪醇的硫酸单酯。这些物质基于其高的成泡性能仅以相对少的量,例如1至5重量%的量在清洁剂中使用。
其他适当的阴离子表面活性剂是烷基磺基琥珀酸盐,也被称为磺基琥珀酸酯,其为磺基琥珀酸与醇,优选脂肪醇并且特别是乙氧基化脂肪醇的单酯和/或二酯。优选的磺基琥珀酸酯含有C8-18-脂肪醇基或其混合物。特别优选的磺基琥珀酸酯含有由作为非离子表面活性剂的乙氧基化脂肪醇衍生出的脂肪醇基(参见下文描述)。特别优选其脂肪醇基由适当的具有窄的同系物分布的乙氧基化脂肪醇衍生的磺基琥珀酸酯。同样也可以使用烷(烯)基量中优选含有8至18个碳原子的烷基磺基琥珀酸盐或其盐。
特别适当的阴离子表面活性剂是皂。适当的是饱和和不饱和脂肪酸皂,如月桂酸盐、肉豆蔻酸盐、棕榈酸盐、硬脂酸盐、(氢化)芥酸盐和山嵛酸盐以及特别是源自天然脂肪酸的盐,如椰油酸盐、棕榈仁酸盐、橄榄油酸盐或牛油脂肪酸盐,衍生的皂混合物。
阴离子表面活性剂含有的皂可以以其钠盐、钾盐或铵盐,以及以有机碱的可溶性盐,如单乙醇胺、二乙醇胺或三乙醇胺的形式存在。优选地阴离子表面活性剂以其钠盐或钾盐,特别是以钠盐的形式存在。
优选的洗涤和清洁剂中阴离子表面活性剂的含量为1至30重量%,优选4至25重量%,并且尤其是5至22重量%,均基于总量剂。特别优选脂肪酸皂的含量至少为2重量%,尤其优选至少3重量%并且特别优选至少4重量%。
其他可用于生产本发明的洗涤或清洁剂的表面活性剂是所谓的双子表面活性剂。通常是指每分子含有两个亲水基团和两个疏水基团。这些基团通常通过所谓“间隔子”相互分隔。这种间隔子通常是碳链,其长度应足以使亲水基团有充足的距离能够相互独立的起作用。这类表面活性剂的优势通常是非常小的临界浓度并且极大地降低水的表面张力。特殊情况下双子表面活性剂不仅指二聚也指三聚表面活性。
用于生产洗涤或清洁剂的双子表面活性剂是例如德国专利DE-A-43 21022的硫酸化羟基混合醚,或根据德国专利申请DE-A-195 03 061的二聚醇-双-和三聚醇-三-硫酸盐和-醚硫酸盐。根据德国专利申请DE-A-195 13 391,封端的二聚和三聚混合醚的特征是其双官能性和多官能性。因此,这种已知的封端的表面活性剂具有良好的润湿性并且低泡沫,这使得它们尤其适合于在机械洗涤或清洗方法中使用。
出于使用技术方面的考虑优选阴离子和非离子表面活性剂的混合物。水性洗涤或清洁剂的总表面活性剂含量优选40重量%并且尤其优选低于35重量%,基于水性洗涤或清洁剂总量计。
B.助洗剂
作为助洗剂在水性洗涤或清洁剂中含有的尤其是二氧化硅、硅酸铝(特别是沸石)、碳酸盐、有机共助洗剂、磷酸盐、有机二元和多元羧酸盐及其混合物。
适当的结晶、层状硅酸钠具备通式NaMSixO2x+1*H2O,其中M表示钠和氢,x表示1.9至4的数,y是0至20的数,优选x的优选值为2、3或4。优选的上述通式的结晶、层状硅酸盐是其中M表示钠、x表示2或3的那些。优选β-或δ-二硅酸钠Na2Si2O5·yH2O。
可以使用无定形硅酸钠,其模数Na2O:SiO5是1:2至1:3.3,优选1:2至1:2.8,特别优选1:2至1:2.6,其具有延迟溶解和二次洗涤特性。与传统的无定形硅酸钠相比,这种延迟溶解特性可由各种方式获得,例如通过表面处理、复合、压实/压密、或通过过度干燥而获得。在本发明的范围内,术语“无定形”也指“X射线无定形”。意即在X射线衍射试验中,硅酸盐没有明显的、例如对于晶态物质是典型的X射线反射,而是充其量具有一个或多个X射线的散射峰值,其具有几度衍射角的宽度。但是,当在电子衍射试验中,硅酸盐颗粒具有模糊或者甚至清晰的衍射峰值时,那么它们极有可能提供很好的助洗剂特性。这可解释为产品具有10至几百纳米的微晶范围,其中优选该值最大是50纳米,尤其最大为20纳米。这种所谓的X射线无定形硅酸盐与常规水玻璃相比同样具有延迟溶解特性。特别优选的是压密/压实的无定形硅酸盐、复合的无定形硅酸盐和过度干燥的X射线无定形硅酸盐。
使用的细晶的、合成的和含有结合水的沸石优选是沸石A和/或沸石P。特别优选的沸石P是沸石MAP TM(Crosfield公司的销售产品)。然而,沸石X以及沸石A、X和/或P的混合物也是适合的。市售可得并且在本发明范围可以优选使用的是例如沸石X和沸石A的共结晶(约80重量%沸石X),其以商品名VEGOBOND AX(R)由SASOL公司可得并且由公式nNa2O*(1-n)K2O*Al2O3.(2-2,5)*SiO2.(3,5-5,5)*H2O,
描述。既可使用喷雾干燥粉末状的沸石,也可使用未干燥、来自其制备的仍潮湿、稳定的悬浮液形式的沸石。在使用悬浮液形式的沸石的情况下,可添加少量的非离子表面活性剂作为稳定剂,例如基于沸石计1至3重量%的、具有2至5个环氧乙烷基团的乙氧基化C12-18-脂肪醇、具有4至5个环氧乙烷基团的C12-14-脂肪醇或乙氧基化的异十三烷醇。合适的沸石具有的平均颗粒尺寸小于10微米(体积分布;测量方法:Coulter计数器),并优选含有18至22重量%,更优选20至22重量%的结合水。
当然也可使用通常已知的磷酸盐作为助洗剂,只要这种使用不会由于生态方面的原因而受到限制。合适的是正磷酸、焦磷酸以及尤其是三聚磷酸盐的钠盐。
有机共助洗剂,尤其是聚羧酸盐/聚羧酸、聚合物类聚羧酸盐、天冬氨酸、聚缩醛、糊精、以及磷酸盐可以作为助洗剂。
聚合物类聚羧酸盐是例如聚丙烯酸-或聚甲基丙烯酸碱金属盐,例如那些相对分子量为500至70000g/mol的那些的。对于给出的聚合物类聚羧酸盐的摩尔量在本发明中是指各个酸形式的重量平均摩尔量,其通常借助凝胶渗透色谱法(GPC)测定,其中使用UV-检测器。测量相对于外部聚丙烯酸标准进行,该标准基于其结构关联性可以提供被检测聚合物的真实摩尔重量。该结果与使用聚苯乙烯磺酸作为标准得到的摩尔重量明显不同。相对于聚苯乙烯磺酸测定的摩尔量通常比本发明中给出的摩尔量大。
适当的聚合物特别是分子量优选2000至20000g/mol的聚丙烯酸酯。基于其出色的溶解性由本组中优选摩尔量为2000至10000g/mol,且特别优选3000至5000g/mol的短链聚丙烯酸酯。
共聚物聚羧酸酯,尤其丙烯酸与甲基丙烯酸以及丙烯酸或甲基丙烯酸与马来酸的那些共聚物是适当的聚合物。特别适当的是丙烯酸与马来酸的共聚物,其含有50至90重量%丙烯酸和50至10重量%马来酸。其自由酸相对分子量通常为2000至70000g/mol,优选20000至50.000g/mol并且尤其是30000至40.000g/mol。
特别优选的是由多于两个不同单体单元构成的可生物降解聚合物,例如那些含有丙烯酸盐和马来酸盐以及乙烯醇或乙烯醇衍生物作为单体或者丙烯酸和2-烷基烯丙基磺酸以及糖衍生物作为单体。
其他优选的共聚物是那些优选丙烯醛和丙烯酸/丙烯酸盐或丙烯酸和乙酸乙烯酯作为单体的共聚物。
其他优选的助洗剂物质是聚合物类氨基二羧酸,其盐或其前体物质。特别优选的是聚天冬氨酸或其盐和衍生物,它们除了共助洗剂性能也具备漂白稳定作用。
其它适合的共助洗剂是聚缩醛,它们是通过将二醛与具有5至7个碳原子和至少3个羟基的多羟基羧酸进行反应而获得的。优选的聚缩醛是由二醛例如乙二醛、戊二醛、对苯二甲醛及其混合物与多羟基羧酸,例如葡糖酸和/或葡庚糖酸获得的。
其它合适的有机共助洗剂物质是糊精,例如碳水化合物的低聚物或聚合物,它们是通过淀粉部分水解而获得的。水解可以常规方法、例如酸催化或酶催化方法进行。优选的是平均摩尔量是400至500000g/mol的水解产物。为此,优选一种具有葡萄糖当量(DE)为0.5至40、优选2至30的多糖,其中DE是与DE为100的葡萄糖相比,该多糖还原作用的常用衡量尺度。不仅可使用DE是3至20的麦芽糊精和DE是20至37的干燥葡萄糖糖浆,而且可使用所谓的具有2000至30000g/mol的较高分子量的黄糊精和白糊精。
这类糊精的氧化衍生物涉及的是糊精与氧化剂的反应产物,这种氧化剂至少能使糖环的醇官能团氧化成羧酸官能团。一种在糖环的C6上氧化的产物是特别优选的。
优选的糊精是在英国专利申请GB 9,419,091 B1中描述的。这类糊精的氧化衍生物中,涉及的是糊精与氧化剂的反应产物,这种氧化剂至少能使糖环的醇官能团氧化成羧酸官能团。例如欧洲专利申请EP 032202 A、EP0427349 A、EP 0472042 A和EP 0542496 A以及国际专利申请WO1992/018542A、WO 1993/008251A、WO 1994/028030A、WO 1995/007303A、WO 1995/012619A和WO 1995/020608A中公开了这种氧化糊精和其制备方法。一种在糖环的C6上氧化的产物是特别优选的。
其它适合的共助洗剂是氧代二琥珀酸酯和二琥珀酸酯(Disuccinaten)的其它衍生物,优选乙基二胺二琥珀酸酯。优选乙二胺-N,N'-二琥珀酸(EDDS)的钠盐或镁盐形式。
特别优选的是甘油二琥珀酸酯和甘油三琥珀酸酯,如在美国专利说明书US 4,524,009、US 4,639 325、欧洲专利申请EP 0150930A和日本专利申请JP 1993/339896A中描述的。
其它可使用的有机共助洗剂例如是乙酰化的羟基羧酸或其盐,其任选也可以内酯的形式存在,且其含有至少4个碳原子和至少1个羟基以及至多2个酸基,在国际专利申请WO1995/020029A中描述了这种共助洗剂的实例。
具备共助洗剂性能的其他物质是膦酸盐。尤其涉及羟基烷基或氨基烷基膦酸盐。羟基烷基磷酸酯特别是指1-羟基乙烷-1,1-二膦酸盐(HEDP)作为共助洗剂。其优选用作钠盐,其中二钠盐给出中性反应,四钠盐给出碱性反应(PH9)。氨基烷基膦酸盐优选是乙二胺四亚甲基膦酸盐(EDTMP),二亚乙基三胺五亚甲基膦酸盐(DTPMP),以及它们的高级同系物。它们优选以中性的反应钠盐的形式使用,例如EDTMP的六钠盐,或作为DTPMP的七钠盐或八钠盐。膦酸盐中优选使用HEDP作为共助洗剂。氨基烷基膦酸盐也显示出显著的重金属结合力。因此,尤其是当本发明的洗涤和清洁剂也包含漂白剂时,优选使用氨基烷基膦酸盐特别是DTPMP,或所述膦酸盐的混合物生产洗涤和清洁剂。
另外,任何能够与碱土金属离子形成复合物的化合物也可用作共助洗剂。
其他可使用的有机助洗剂例如是可以其钠盐形式使用的多羧酸,多羧酸是指含有多于一个酸性官能团的羧酸。实例是柠檬酸、己二酸、琥珀酸、戊二酸、苹果酸、酒石酸、马来酸、富马酸、糖酸、氨基羧酸、次氮基三乙酸(NTA),只要这种使用不会因生态学原因而受到限制,以及它们的混合物。优选的盐是多羧酸例如柠檬酸、己二酸、琥珀酸、戊二酸、酒石酸、糖酸的盐以及其混合物的盐。
也可使用酸本身。这种酸除了具有典型的助洗剂作用外,也具有酸化组分的特性,由此可用于建立洗涤剂或清洗剂中的低和中等pH值。在这方面,优选柠檬酸、琥珀酸、戊二酸、己二酸、葡糖酸和这些酸的任意混合物。
C.漂白剂和漂白催化剂
作为漂白剂的在水中产生H2O2的化合物中,尤其重要的为高硼酸钠四水合物以及高硼酸钠一水合物。其它可用的漂白剂为,例如,过碳酸钠,过氧焦膦酸盐,柠檬酸盐过氧化氢合物以及产生H2O2的过酸盐或过酸,如过苯甲酸盐、过氧邻苯二甲酸盐、过壬二酸、邻苯二甲亚氨过酸或双过十二烷双酸。为了在60℃温度下清洗并达到改善的漂白作用,可以在洗涤剂和清洗剂中加入漂白活性成分。作为漂白活性剂可以使用在过水解条件下形成优选具有1至10个碳原子、更优选2至4个碳原子的脂族过氧羧酸、和/或任选经取代的过苯甲酸的化合物。合适的是具有所述碳原子数的O-酰基和/或N-酰基和/或任选经取代的苯甲酰基的化合物。优选的是多重酰化的烷二胺,尤其是四乙酰基乙二胺(TAED)、酰化的三嗪衍生物、尤其是1,5-二乙酰基-2,4-二氧代六氢-1,3,5-三嗪(DADHT)、酰化的甘脲、尤其是四乙酰基甘脲(TAGU)、N-酰基酰亚胺、尤其是N-壬酰基琥珀酰亚胺(NOSI)、酰化的苯酚磺酸盐、尤其是正壬酰基-或异壬酰基氧基苯磺酸盐(正-或异-NOBS)、羧酸酐、尤其是邻苯二甲酸酐、酰化的多元醇、尤其是三醋精、二乙酸乙二醇酯、2,5-二乙酸基-2,5-二氢呋喃。作为常规的漂白活性剂的替代或补充,在织物处理剂成形体中也可以使用所谓的漂白催化剂。这些物质是增强漂白的过渡金属盐或过渡金属配合物,例如Mn-、Fe-、Co-、Ru-或Mo-Salen配合物或羰基配合物。同样也可以使用具有含氮三脚配位体(Tripod-Liganden)的Mn-、Fe-、Co-、Ru-、Mo-、Ti-、V-和Cu配合物以及Co-、Fe-、Cu-和Ru-氨配合物作为漂白催化剂。
D.增稠剂
液态洗涤剂和清洁剂可以含有增稠剂。增稠剂可以含有例如聚丙烯酸酯增稠剂、黄原胶、结冷胶、瓜尔胶、海藻酸盐、卡拉胶、羧甲基纤维素、膨润土、Wellan胶、刺槐豆胶、琼脂、黄蓍胶、阿拉伯胶、果胶、多聚糖、淀粉、糊精、明胶和酪蛋白。但是也可以使用改性自然物质如改性淀粉和纤维素,例如羧甲基纤维素和其他纤维素醚、羟乙基和丙级纤维素以及豆粉醚。
属于聚丙烯基-和聚甲基丙烯基-增稠剂的是例如与聚烯基聚醚,尤其是蔗糖的烯丙基醚、季戊四醇或丙烯交联的高分子丙烯酸均聚物(根据“The Cosmetic,Toiletry andFragrance Association(CTFA)”的“International Dictionary of CosmeticIngredients”INCI-名称为Carbomer),其也被称为羧乙烯基聚合物。这类聚丙烯酸可由Fa.3V Sigma以商品名例如Polygel DA,以及由Fa.B.F.Goodrich以商品名例如Carbopol 940(分子量约4000000)、Carbopol 941(分子量约1250000)或Carbopol 934(分子量约3000000)得到。其他是以下的丙烯酸-共聚物:(i)选自丙烯酸、甲基丙烯酸中两个或更多单体的共聚物及其单纯优选与C1-4-烷醇形成的共聚物,酯(INCI丙烯酸酯共聚物),包括甲基丙烯酸、丙烯酸丁酯和甲基丙烯酸甲酯的共聚物(根据化学文摘社(Chemical Abstracts Service)CAS名称:25035-69-2)或丙烯酸丁酯和甲基丙烯酸甲酯的共聚物(CAS25852-37-3),以及由Fa.Rohm and Haas以商品名和以及由Degussa(Goldschmidt)公司以商品名Polymer得到的,例如非离子缔合型聚合物Aculyn 22、Aculyn 28、Aculyn 33(交联)、Acusol 810、Acusol820、Acusol 823和Acusol830(CAS 25852-37-3);(ii)交联高分子丙烯酸共聚物,包括与蔗糖或季戊四醇的烯丙基醚交联的C10-30-烷基烯丙酯共聚物,该C10-30-烷基烯丙酯由选自丙烯酸、甲基丙烯酸及其单纯优选与C1-4-烷醇中的两个或更多单体形成,酯(INCI丙烯酸酯/C10-30烷基丙烯酸酯共聚物),以及例如由Fa.B.F.Goodrich以商品名可得,例如疏水Carbopol ETD2623和Carbopol 1382(INCI丙烯酸酯/C10-30烷基丙烯酸酯交联聚合物)以及CarbopolAqua 30(以前的Carbopol EX 473)。
其他优选使用的聚合物类增稠剂是黄原胶、微生物阴离子杂多糖,其由黄单胞杆菌和一些其他种类在有氧条件下产生并具备2至15百万的摩尔量。黄原胶由一个带侧链β-1,4-结合葡萄糖链(纤维素)构成。亚组结构由葡萄糖、甘露糖、葡糖醛酸、乙酸酯和丙酮酸,其中丙酮酸单元的数量决定了黄原胶的粘度。增稠剂还特别可以是脂肪醇。脂肪醇可以是支链或非支链以及自然源或石油源。优选的脂肪醇含有10至20个,优选12至18个原子的碳链长度。优选使用不同碳链长度的混合物,如牛油脂肪醇或椰油脂肪醇。实例是Spezial(C12-14-ROH)或Technisch(C12-14-ROH)(两个ex Cognis)。优选的液态洗涤剂和清洁剂含有占总量0.01至3重量%且优选0.1至1重量%的增稠剂。增稠剂的用量取决于增稠剂的种类和想要的增稠度。
E.酶
洗涤剂和清洁剂中可以含有胶囊形式的酶和/或直接含有酶。作为酶可以特别是水解酶类如蛋白酶、酯酶、脂肪酶和起到分解脂肪作用的酶、淀粉酶、纤维素酶和其他糖苷水解酶、半纤维素酶、角质酶、β-葡聚糖酶、氧化酶、过氧化酶、水解酶和/或漆酶以及所述酶的混合物。所有这些水解酶在洗涤中用于移除污迹如含有蛋白、脂肪或淀粉的污迹和变色。此外纤维素酶和糖苷水解酶通过移除毛球和微纤维用于保持织物的颜色和提高柔软度。也可以使用氧化还原酶用于漂白和防止染料转移。特别合适的是由细菌菌株或真菌如枯草杆菌(Bacillus subtilis)、地衣芽孢杆菌(Bacillus licheniformis)、灰色链霉菌(Streptomyceus griseus)和特异腐质霉(Humicolainsolens)得到的酶活性物。优选使用枯草杆菌蛋白酶类的蛋白酶并且特别是由迟缓芽孢杆菌(Bacillus lentus)得到的蛋白酶。特别重要的是酶混合物,如由蛋白酶和淀粉酶或蛋白酶和酯酶,特别是起到分解脂肪作用的酶或蛋白酶和纤维素酶构成的混合物,或者由纤维素酶和酯酶,特别是起到分解脂肪作用的酶构成的混合物,或者蛋白酶、淀粉酶和酯酶特别是起到分解脂肪作用的酶或蛋白酶、酯酶特别是起到分解脂肪作用的酶和纤维素酶构成的混合物,然而特别是含有蛋白酶和/或酯酶的混合物以及含有起到分解脂肪作用的酶的混合物。这类起到分解脂肪作用的酶是已知的角质酶。在有些情况下过氧化酶或氧化酶也合适。适当的淀粉酶特别包括α-淀粉酶、异淀粉酶、支链淀粉酶和果胶酶。作为淀粉酶优选使用纤维二糖水解酶、内切葡聚糖酶和也被称为纤维素酶的p-葡糖苷酶及其混合物。由于不同的纤维素酶类型通过CMCase-和Avicelase-活性区别,可以通过有目的的混合纤维素酶调节想要的活性。
酶可以被吸附在载体上,从而保护其免于被提前分解。直接加入洗涤剂和清洁剂中的酶、酶液体制剂或酶颗粒含量例如为约0.01至5重量%,优选0.12至约2.5重量%。
对于特定的针对过敏消费者的洗涤剂和清洁剂也可以优选洗涤剂和清洁剂不含有酶。
F.电解质
无机盐中大量不同的盐都可以用作电解质。优选的阳离子是碱金属和碱土金属,优选阴离子是卤化和硫酸根。出于生产技术的考虑在洗涤和清洁剂中优选使用NaCl或MgCl2。洗涤剂和清洗剂中电解质的含量通常为0.1至5重量%。
G.溶剂
在液态洗涤剂和清洗剂中使用的非水溶剂可以是,例如源自一元或多元醇、烷醇氨或乙二醇醚,只要它们在给定的浓度范围内能与水互溶。优选地溶剂选自乙醇、正丙醇或异丙醇、丁醇、乙二醇、丙二醇或丁二醇、丙三醇、二乙二醇、丙基二乙二醇或丁基二乙二醇、己二醇、乙二醇甲醚、乙二醇乙醚、乙二醇丙醚、乙二醇单正丁醚、二乙二醇甲醚、二乙二醇乙醚、丙二醇甲醚、丙二醇乙醚或丙二醇丙醚、二丙二醇单甲醚或二丙二醇单乙醚、二异丙二醇单甲醚或二异丙二醇单乙醚、甲氧基、乙氧基或丁氧基三丙二醇、1-丁氧基乙氧基-2-丙醇、3-甲基-3-甲氧基丁醇、丙烯-乙二醇-叔丁醚以及这些溶剂的混合物。洗涤剂和清洗剂中使用的非水溶剂的含量为0.5至15重量%,优选低于12重量%并且尤其是低于9重量%。
H.粘度
液态形式的洗涤剂和清洗剂的粘度可以采用常规方法(例如粘度计LVT-II在20℃下20转/分钟,转轴3)测定并且对于液态洗涤剂粘度优选为500至5000mPas。优选地洗涤剂和清洁剂的粘度为700至4000mPas,其中尤其优选1000至3000mPas之间的数值。柔软剂的粘度优选为20至4000mPas,其中尤其优选40至2000mPas之间的数值。柔软剂的粘度尤其优选40至1000mPas。
I. pH-调节剂
为了将液态洗涤剂和清洗剂的pH值调节至想要的区域,可以使用pH-调节剂。此处可以使用所有已知的酸和碱,只要其使用不会由于使用技术或环境保护的原因或消费者保护的原因被禁止。通常这类调节剂的用量不超过总制剂的7重量%。液态洗涤剂和清洁剂的pH值优选4至10之间并且优选5.5至8.5之间。液态柔软剂的pH值优选1至6之间并且优选1.5至3.5之间。
J.染料
为了改善织物处理剂的审美印象可以使用适当的染料着色。优选的染料,其选择对于本领域技术人员不存在任何困难,具备高的储存稳定性和相对于洗涤剂和清洗剂其他内容物以及光的非敏感性,以及对纺织纤维不显著的附着性,从而不会使其染色。
K.抗再沉积剂
适当的去污聚合物,其也被称为“抗再沉积剂”,是例如非离子纤维素醚如甲基纤维素和甲基羟丙基纤维素,含有分别基于非离子纤维素醚计15至30重量%的甲氧基和1至15重量%的羟丙基,以及由现有技术已知的邻苯二甲酸和/或对苯二甲酸或其衍生物的聚合物,特别是对苯二甲酸乙二醇酯聚合物和/或聚对苯二甲酸乙二醇酯和/或聚对苯二甲酸丙二醇酯或其阴离子和/或非离子改性衍生物。适当的衍生物含有邻苯二甲酸和对苯二甲酸聚合物的磺化衍生物。
L.荧光增白剂
可以向洗涤剂和清洗剂中加入荧光增白剂(也称为增白剂),从而消除被处理的纺织面料的变棕和变黄。这类物质在纤维上聚集并产生增亮以及伪装的漂白作用,其中它将不可见的紫外光线转变为可见长波光,由此由太阳光中被吸收的紫外光以淡蓝色荧光被发射并与变棕或变黄的清洗物的黄色调产生纯白色。适当的化合物源自例如4,4'-二氨基-2,2'-芪二磺酸(Flavonsuren)、4,4'-联苯乙烯-联苯、甲基伞形酮、氧杂萘邻酮、二氢喹啉酮、1,3-二芳基吡唑啉、萘二甲酸酰亚胺、苯并噁唑、苯并异噁唑和苯并咪唑-体系以及通过杂环取代的芘衍生物。基于成品洗涤剂和清洁剂计荧光增白剂使用量通常为0%至0.3重量%。
M.变褐抑制剂
变褐抑制剂的任务是,使由纤维脱离的污物保持悬浮在液体中,并从而避免污物的再次吸附。为此大部分水溶性溶胶,例如胶料、明胶、淀粉或纤维素磺酸醚的盐或纤维素或淀粉的酸性硫酸酯的盐是有机环境适宜的。同样适用于此目的的是含有聚酰胺的水溶酸性组。此外可溶解的淀粉制剂等,例如水解淀粉、醛淀粉等可以用作上述淀粉产品。同样可以使用的是聚乙烯吡咯酮。然而优选纤维素醚是如羧甲基纤维素(钠盐)、甲基纤维素、羟甲基纤维素和混合醚如甲基羟乙基纤维素、甲基羟丙基纤维素、甲基羧甲基纤维素及其混合物,使用量为0.1至5重量%,基于洗涤剂和清洗剂计。
N.抗皱剂
纺织面料,尤其由尼龙、粘胶短纤维、棉花及其混合物构成,易于起皱,这是因为单纤维对垂直于纤维方向的弯曲、折叠、挤和压很敏感,因此洗涤剂和清洁剂含有合成抗皱剂。例如包括基于脂肪酸、脂肪酸酯、脂肪酸酰胺、烷醇酯、烷醇酰胺或脂肪醇——其大多与环氧乙烷反应——的合成产品,或基于卵磷脂或改性磷酸酯的产品。
O.抗微生物剂
为了抵抗微生物洗涤剂和清洁剂可以含有抗微生物剂。可以根据抗微生物谱和作用机理分为细菌生长抑制剂和杀菌剂、抑真菌剂和杀真菌剂等。这类物质中重要的是例如苯扎氯铵、烷芳基磺酸盐、卤代酚和乙酸苯酚汞,其中在本发明的洗涤剂和清洁剂也可以完全不使用这些化合物。
P.防腐剂
本发明的洗涤剂和清洁剂可以含有防腐剂,其中优选仅使用不具有或仅少量具有皮肤致敏可能性的防腐剂。实例是山梨酸及其盐、苯甲酸及其盐、水杨酸及其盐、苯氧基乙醇、氨基甲酸-3-碘-2-丙炔丁酯、N-(羟甲基)甘氨酸钠、联苯-2-醇及其混合物。适当的防腐剂是双咪唑烷基脲、苯甲酸钠和山梨酸钾的不含溶剂的水性结合物(以名称K500ex Schülke and Mayr可得),其可以在最大为7的pH范围内使用。基于有机酸和/或其盐的防腐剂特别适合用于本发明的皮肤友好的洗涤剂和清洁剂的防腐。
Q.抗氧化剂
为了避免不想要的,由于酸性物质的影响以及其他氧化过程导致的洗涤剂和清洁剂和/或处理的纺织面料的变化,洗涤剂和清洁剂可以含有抗氧化剂。这类化合物包括例如取代苯酚、对苯二酚、邻苯二酚和芳香胺以及有机硫化物、多硫化物、二硫代氨基甲酸盐、亚磷酸盐、膦酸盐和维生素E。
R.抗静电剂
更高的穿着舒适性可以通过额外使用加入洗涤剂和清洁剂中的抗静电剂实现。抗静电剂增大了表面导电性并从而能够更好的将形成的充电导走。抗静电剂通常是具备至少一个亲水分子配体的物质并且在表面或多或少形成湿膜。大多表面活性的抗静电剂分为含氮(胺、酰胺、季铵化合物)、含磷(磷酸酯)和含硫(烷基磺酸盐、烷基硫酸盐)抗静电剂。月桂基(或硬脂基)二甲基苄基氯化铵适合作为抗静电剂用于纺织面料或作为洗涤剂和清洁剂的助剂,由此实现额外的柔软效果。
S.泡沫抑制剂
为了改善处理的纺织面料的再润湿性并且简化处理的纺织面料的熨烫可以在织物处理剂中使用例如硅衍生物。它们通过其抑制泡沫的能力额外地改善洗涤剂和清洗剂的冲洗性能。优选的硅衍生物是例如聚二烷基或烷芳基硅氧烷,其中烷基含有1至5个碳原子并且全部或部分氟化。优选的硅氧烷是聚二甲基硅氧烷,其可以任选衍生的并随后氨基功能化或季氨化或含有Si-OH-、Si-H-和/或Si-Cl-键。这类优选硅氧烷的粘度在25℃下为100至100000mPas,其中硅氧烷使用量为0.2至5重量%,基于洗涤剂和清洁剂总量计。
T. UV-吸收剂
洗涤剂和清洁剂还可以含有UV-吸收剂,其接触处理的纺织面料并改善纤维的耐光性。具备这种想要的性能的化合物是例如通过非辐射失活的有效化合物以及2位和/或4位取代的二苯甲酮衍生物。其他适当的是取代的苯并三唑、3位苯基取代的丙烯酸酯(肉桂酸衍生物),任选2位含有氰基、水杨酸酯、有机Ni络合物以及天然产物如伞形酮以及本体尿刊酸。
U.重金属络合剂
为了避免重金属催化的特定洗涤剂内容物的分解,可以使用络合重金属的物质。适当的重金属络合剂是例如乙二胺四乙酸(EDTA)或次氮基三乙酸(NTA)的碱金属盐以及阴离子聚电解质如聚马来酸酯和聚磺酸酯的碱土金属盐。一类优选的络合剂是磷酸盐,其在优选织物处理剂中用量为0.01至2.5重量%,优选0.02至2重量%并且特别是0.03至1.5重量%。这类优选化合物特别包括有机膦酸盐,如例如1-羟基乙烷-1,1-膦酸(HEDP)、氨基三(亚甲基膦酸)(ATMP)、二乙烯三胺-五(亚甲基膦酸)(DTPMP或DETPMP)以及2-膦酸丁烷-1,2,4-三羧酸(PBS-AM),其中大部分以其铵盐或碱土金属盐的形式使用。
工业应用性
本发明的式(I)的四氢呋喃衍生物或其混合物优选在香料和芳香物质混合物中使用,其反过来优选制成加香产品。
特别优选的本发明的加香产品是洗涤剂和清洗剂,卫生或护理产品,尤其是在身体和头发护理,化妆品和家居领域。
因此本发明的一个方面是化妆产品,含有
a)一种或多种式(I)的四氢呋喃衍生物
或
b)香料或芳香物质混合物,含有
(i)一种或多种式(I)的四氢呋喃衍生物,
(ii)一种或多种其他芳香或香料物质,
其中所含式(I)的四氢呋喃衍生物的总量基于香料或芳香物质混合物总量计为0.00001至40重量%,优选0.1至15重量%,尤其优选0.2至10重量%,并且香料或芳香物质混合物(i+ii)的用量基于化妆产品计为2至6重量%。
本发明的另一个方面因此是家居产品,含有
a)一种或多种式(I)的四氢呋喃衍生物
或
b)香料或芳香物质混合物,包括
(i)一种或多种式(I)的四氢呋喃衍生物,
(ii)一种或多种其他芳香或香料物质,
其中所含式(I)的四氢呋喃衍生物的总量基于香料或芳香物质混合物总量计为0.00001至40重量%,优选0.1至15重量%,尤其优选0.2至10重量%,并且香料或芳香物质混合物(i+ii)的用量基于化妆产品计为2至6重量%。
这类产品优选是弱酸性、碱性或中性清洁产品,其特别选自组包括多用途清洁剂、地板清洁剂、窗户玻璃清洁剂、洗涤剂、浴室和卫生清洁剂、液体冲刷清洁剂、固体和液体的卫生间清洗液、粉末和泡沫地毯清洁剂、液体洗涤剂、粉状洗涤剂、洗衣预处理剂如漂白剤、浸泡和去污剂、洗衣漂洗剤、洗涤皂、洗衣片、消毒剂、表面消毒剂,液体或凝胶形式或负载在固体载体上或作为喷雾的空气清新剂,
蜡或抛光剂,尤其选自家具上光剂、地板抛光剂和鞋油,
或
身体护理产品,尤其选自沐浴露和洗发水。
本发明的芳香物质混合物根据本发明制备,其中本发明的化合物或一种如上所定义的本发明的混合物与其他香料物质以及任选其他香料物质混合物的组分混合。
根据一个优选实施方案本发明的香料物质混合物如上所述制备,其中本发明的化合物的用量足以调整、改变和/或加强香料物质混合物中朗姆、威士忌、咖啡香调中的一种或优选两种。
上文所述除了本发明的化合物也适用于优先选择的成分或香料物质。
实施例
以下实施例解释本发明,只要不另作说明部分和百分率涉及重量。
使用的缩略语:
二丙二醇(DPG)、邻苯二甲酸二乙酯(DEP)、柠檬酸三乙酯(TEC)。
香料物质产品名称的解释参见例如S.Arctander,Perfume and FlavorMaterials,卷I和II,Montclair,N.J.,1969,Selbstverlag或H.Surburg,J.Panten,CommonFragranceand Flavor Materials“,第五版,Wiley-VCH,Weinheim 2006。
制备实施例:呋喃-2-羧酸乙酯的氢化
将3010g(21.5mol)呋喃-2-羧酸乙酯,500ml乙醇(1%MEK)和20g催化剂(A-木炭负载钯,5%钯,K-0227T类)混合并在20bar氢气压力下加热。30-40℃开始反应并相对强烈地放热。1-1.5小时后在60-70℃下氢气吸附结束。缓慢加热至140-150℃并在该温度下再搅拌2-3小时。GC-监控:不再存在反应物。
滤除催化剂并在旋转蒸发仪上浓缩滤液(水浴60-70℃,200-20mbar)。原始产物为3055g。
蒸发的原始产物在加入0.1重量%Na2CO3下在短柱上蒸发(Kp.:91-93℃/40mbar)。
产物:2999g(96.9%d.Th.)
1H NMR(400MHz,Chloroform-d)δ4.44(dd,J=8.4,5.2Hz,1H),
4.20(qd,J=7.1,1.7Hz,2H),4.05 3.98(m,1H),3.95 3.88(m,
1H),2.30 2.19(m,1H),2.06 1.85(m,3H),1.29(t,J=7.1Hz,3H)
13C NMR(101MHz,CDCl3)δ173.38,76.80,69.33,60.87,30.20,25.27,14.24
实施例1-3:芳香油混合物
芳香油混合物1:
通过加入0.2%的四氢呋喃衍生化合物1至9花香的前味不仅被推动并赋予整个组合物一种额外的丰富感。
芳香油混合物2:
通过加入1%的四氢呋喃衍生化合物1至9混合物具备清新、自然并且柠檬的味道,其具备好的奶油咖啡香调。
芳香油混合物3:
通过加入2%的四氢呋喃衍生化合物1至9,香草并且自然的前味进一步加强了蜂蜜咖啡的香调。
制剂实施例A至K
芳香油混合物1,2和3分别加工为以下制剂。
针对上述各个芳香油混合物所述的气味效果也在以下制剂中观察到。
实施例A:洗衣粉
实施例B:多用途清洁剂
实施例C:洗发香波
实施例D:沐浴液
实施例E:柔软剂
实施例F:古龙水/淡香水
内容物 | 重量% | 重量% |
芳香油混合物1、2和3 | 5 | 10 |
乙醇 | 加至100 | 加至100 |
水 | 18 | 10 |
实施例G:气溶胶喷雾剂
内容物 | 重量% | 重量% |
芳香油混合物1、2和3 | 1,0 | 1,5 |
乙醇 | 加至100 | 加至100 |
水 | 5,0 | 8,0 |
α-生育酚 | 0,20 | 0,20 |
羟丙基纤维素 | 0,20 | - |
迷迭香浓缩物,溶于乙醇 | 0,22 | - |
十六烷醇 | 1,00 | 0,50 |
实施例H:洗发香波
实施例I:洗衣粉
实施例J:液体洗涤剂
实施例K:液体洗涤剂浓缩物
内容物 | 重量% |
去离子水 | 13,4 |
椰油脂肪酸(C12-C18) | 10,0 |
脂肪醇C12-C15,8EO | 26,0 |
仲烷基磺酸钠盐(C13-C17) | 26,5 |
三乙醇胺 | 8,5 |
C12-C14脂肪醇硫酸钠盐 | 3,0 |
乙醇 | 5,5 |
脲 | 4,5 |
酶 | 0,9 |
柠檬酸 | 1,0 |
芳香油混合物1、2和3 | 0,7 |
Claims (10)
1.至少一种式(I)的四氢呋喃衍生物的用途,
所述式(I)的四氢呋喃衍生物选自:
化合物1:四氢呋喃-2-羧酸甲酯,
化合物2:四氢呋喃-2-羧酸乙酯,
化合物4:四氢呋喃-2-羧酸烯丙酯,
化合物5:四氢呋喃-2-羧酸异丙酯,
化合物6:四氢呋喃-2-羧酸2-甲基烯丙酯,
化合物7:四氢呋喃-2-羧酸异丁酯,和
化合物8:四氢呋喃-2-羧酸丁酯,
其用于赋予香料和芳香物质混合物更多的强度、清新度、辐射性和/或圆润度,和/或用于增强存在于所述香料和芳香物质混合物中的其他香料或芳香物质的清新和甜味方向的香调,
其中所述式(I)的四氢呋喃衍生物的量是0.2重量%至2重量%。
2.根据权利要求1所述的用途,其中所述香料和芳香物质混合物是芳香油组合物。
3.至少一种式(I)的四氢呋喃衍生物的用途,
所述式(I)的四氢呋喃衍生物选自:
化合物1:四氢呋喃-2-羧酸甲酯,
化合物2:四氢呋喃-2-羧酸乙酯,
化合物4:四氢呋喃-2-羧酸烯丙酯,
化合物5:四氢呋喃-2-羧酸异丙酯,
化合物6:四氢呋喃-2-羧酸2-甲基烯丙酯,
化合物7:四氢呋喃-2-羧酸异丁酯,和
化合物8:四氢呋喃-2-羧酸丁酯,
其(i)用于化妆产品或家居产品中在纯度、清新度和/或自然度方面提供、增强、改善和/或改变气味印象,和/或
(ii)用于化妆产品或家居产品的气味圆润,
其中所述式(I)的四氢呋喃衍生物的量是0.2重量%至2重量%。
4.根据权利要求3所述的用途,其中所述家居产品是洗涤剂、清洗剂、卫生产品或护理产品。
5.根据权利要求3所述的用途,其中所述化妆产品是身体护理产品、头发护理产品、洗发香波、柔软剂或洗衣粉。
6.一种香料或芳香物质组合物,其包括(i)至少一种式(I)的四氢呋喃衍生物
所述式(I)的四氢呋喃衍生物选自:
化合物1:四氢呋喃-2-羧酸甲酯,
化合物2:四氢呋喃-2-羧酸乙酯,
化合物4:四氢呋喃-2-羧酸烯丙酯,
化合物5:四氢呋喃-2-羧酸异丙酯,
化合物6:四氢呋喃-2-羧酸2-甲基烯丙酯,
化合物7:四氢呋喃-2-羧酸异丁酯,
化合物8:四氢呋喃-2-羧酸丁酯,和
(ii)一或多种其他香料或芳香物质,
其中所述式(I)的四氢呋喃衍生物的量是0.2重量%至2重量%。
7.如权利要求6所述的香料或芳香物质组合物,其中所述香料或芳香物质组合物是芳香油组合物。
8.一种化妆品或家居组合物,其包含如权利要求6或7所述的香料或芳香物质组合物。
9.一种用于使化妆品或家居组合物充满香气的方法,其通过向所述化妆品或家居组合物施加有效量的权利要求6的香料或芳香物质组合物来实施。
10.根据权利要求9所述的方法,其中施加包括至少一种、两种、三种、四种或更多种所述式(I)的化合物的香料或芳香物质组合物。
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