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EP1991553A1 - Substrats à base de silicium pour des principes actifs contenant des groupes aminoalkyle - Google Patents

Substrats à base de silicium pour des principes actifs contenant des groupes aminoalkyle

Info

Publication number
EP1991553A1
EP1991553A1 EP07703577A EP07703577A EP1991553A1 EP 1991553 A1 EP1991553 A1 EP 1991553A1 EP 07703577 A EP07703577 A EP 07703577A EP 07703577 A EP07703577 A EP 07703577A EP 1991553 A1 EP1991553 A1 EP 1991553A1
Authority
EP
European Patent Office
Prior art keywords
group
acid
silicon
radicals
perfume
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.)
Withdrawn
Application number
EP07703577A
Other languages
German (de)
English (en)
Inventor
Thomas Gerke
Andreas Bauer
Ralf Bunn
Werner Faber
Wolfgang Lahn
Alfred-Michael Lusse
Manuela Materne
Theo Ten Pierik
Frank Rittler
Hubert Smyrek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1991553A1 publication Critical patent/EP1991553A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds releasing perfumes by thermal or chemical activation
    • 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
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • 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
    • C11D3/16—Organic compounds
    • C11D3/162—Organic compounds containing Si
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • 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
    • 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
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring

Definitions

  • the present invention relates to monomeric and oligomeric silicon compounds, wherein the silicon at least one fragrance or Bizidalkoxyrest and at least one optionally chemically modified aminoalkyl or aminoalkoxy radical is bound, and the use of these compounds for scenting or preserving detergents and cleaners or cosmetic means.
  • controlled release is the subject of numerous publications and patent applications.
  • accelerated or delayed releases of ingredients from the group of bleaches, bleach activators, surfactants, etc. are of particular interest.
  • the release of fragrances is of paramount importance in this field, since both the product, as well as the washing and cleaning solution and the articles treated with these agents are to be intensively and long-lasting scented.
  • the siloxane esters tend to degrade the perfume alcohol already during production, i. premature to release. It is therefore a need to provide fragrance offer forms that oduften both the product, as well as the washing and cleaning solution and the treated with the products substrates, the fragrance should continue for as long as possible, especially on textiles.
  • Monomeric orthosilicic esters of perfume alcohols are described, for example, in US3215719 (Dan River Mills). This document also mentions the delayed release of fragrant alcohols from mixed esters such as bis (eugenoxy) diethoxysilane or bis (cinnamoyloxy) diethoxysilane, where the central silicon atom does not necessarily have to be bound only to oxygen. However, radicals comprising aminoalkyl groups are not disclosed.
  • Powdery or granular detergent compositions containing "fragrance-conferring” silicon compounds are described in DE2844789 (Dow Corning).
  • the mono-, oligo- and polymeric silicon compounds disclosed herein do not necessarily have an Si central atom surrounded by four oxygen atoms.
  • amino-alkyl group-containing radicals are enumerated as possible substituents in the specification, no compounds are disclosed which include aminoalkyl group-containing radicals.
  • Liquid or pasty soap compositions containing "fragrance-conferring" silicon compounds are described in DE3003494 (Dow Corning). Also in this document amino-containing groups amino groups are not explicitly disclosed.
  • EP982313 (General Electric) describes monomeric silicon compounds comprising at least one perfume alkoxy group and at least one alkyl group. However, aminoalkyl group-containing radicals are not disclosed.
  • DE19750706 (General Electric) discloses oligomeric and polymeric silicon compounds which, in addition to perfume alkoxy radicals, may also comprise alkyl radicals. However, aminoalkyl group-containing radicals are not disclosed here either.
  • Oligomeric and polymeric silicic acid esters are further disclosed in WO00 / 14091 and WO01 / 68037. However, here too, aminoalkyl-containing radicals are not disclosed.
  • a first object of the present invention was therefore to provide hydrolysis-stable carrier-bound forms of perfume alcohols which can also be incorporated into aqueous detergents and cleaners without already undergoing excessive hydrolysis phenomena in the product. Also, the incorporation of the compounds into granular detergent and cleaner compositions, without causing decomposition in the manufacturing process, is a requirement for the compounds to be provided.
  • the substances to be produced should give the substrates treated with the solution a pleasant and long-lasting fragrance.
  • a further object of the present invention was therefore also to provide preferably such hydrolysis-stable carrier-bound forms of perfume alcohols which make possible the most uniform possible release of the bound perfume.
  • Another object of the present invention was further to provide such carrier-bound forms of perfume alcohols, which are combined because of their release kinetics in a particularly advantageous manner with the already known carrier-bound forms of perfume alcohols and / or non-carrier-bound forms of perfumes can.
  • silicon compounds which, in addition to perfume alcohols bound in alkoxy form, comprise at least one group comprising an aminoalkyl radical, show a particularly advantageous behavior with regard to the release kinetics of the perfume alcohols, and thereby achieve the abovementioned objects.
  • the perfume alcohols are released by these compounds in a uniform manner both in the product and at the site of action. It has also surprisingly been found that these compounds in combination with conventional fragrances also give the fragrances a longer-lasting effect, which are not present in carrier-bound form. Regardless of the chemical composition of the fragrances, the compounds according to the invention can therefore be used in perfume mixtures in order to give the entire perfume composition a prolonged release of fragrance.
  • the compounds according to the invention can advantageously also be used in particular in combination with other carrier-bound forms of fragrances.
  • the combined use of compounds according to the invention and silicic acid esters of perfume alcohols has proved to be particularly advantageous. If the compounds according to the invention are used in combination with silicic acid esters, a uniform release of fragrance which extends over an even longer period of time is made possible.
  • silicon compounds having a group comprising an aminoalkyl radical can also be used to achieve a consistent release of another active substance, to which other active substance alkoxy radicals instead or in addition to perfume alkoxy radicals , in particular biocidalkoxy radicals, are bonded.
  • biocidalkoxy radicals can be achieved about a constant preservative effect.
  • a first subject of the present invention is therefore a silicon compound, characterized in that the silicon is bound to at least one alkoxy group of the formula -OR 'and at least one aminoalkyl group comprising a group, wherein R 1 OH is an active alcohol, in particular a perfume alcohol or biocide alcohol.
  • the silicon compound is preferably a compound of the formula I, R R
  • radicals R is an active alcohol radical, in particular a perfume alcohol radical or biocide alcohol radical which is bonded in alkoxy form to the silicon, and wherein at least one of the remaining radicals R is a straight-chain radical branched, saturated or unsaturated, substituted or unsubstituted and optionally chemically modified aminoalkyl radical group, and wherein those radicals R, which are neither a perfume alcohol or Bizidalkohol residue nor a group comprising an aminoalkyl radical, independently selected are hydrogen, hydroxy and the group of straight-chain or branched, saturated or unsaturated, substituted or unsubstituted alkyl and alkoxy radicals, where two radicals R, which are bonded to different silicon atoms, also an oxygen that bridges these two silicon atoms Atom, and where n is a Value can be from 0 to 20.
  • n is 0, exactly one of the radicals R is a group comprising an aminoalkyl radical and the remaining radicals R are alkoxy radicals, wherein at least one, preferably at least two, of the alkoxy radicals are alkoxy radicals of perfume alcohols.
  • n assumes a value of from 1 to 14, preferably from 1 to 11 and in particular from 2 to 8, with particular preference to the values 3, 4, 5, 6 and 7.
  • the group comprising an aminoalkyl radical is preferably an aminoalkyl radical which is bonded to the silicon atom via an Si-C bond.
  • the group comprising one aminoalkyl radical may also be, for example, an aminoalkoxy radical.
  • the aminoalkyl radical of the group comprising an aminoalkyl radical is preferably a straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C 1-22 -aminoalkyl radical.
  • the aminoalkyl radical here is particularly preferably selected from aminomethyl, aminoethyl, ⁇ -aminopropyl, / so-aminopropyl, ⁇ -aminobutyl, / so-aminobutyl and te / t-aminobutyl, where, if a plurality of aminoalkyl radicals are present in the compound , these can be selected independently of each other.
  • the aminoalkyl radical may optionally also contain further heteroatoms as well as cyclic or aromatic groups.
  • the perfume alcohol radicals contained in the silicon compound can be identical or different, but are identical in a preferred embodiment.
  • the groups comprising aminoalkyl radicals contained in the silicon compound can be identical or different, if several are present. It is also preferred here that all the aminoalkyl radicals contained are identical.
  • the compounds according to the invention can be prepared by simple transesterification of amino-containing silicon compounds bearing alkoxy radicals of lower alcohols with perfume alcohols, with both individual perfume alcohols and perfume alcohol mixtures can be used. Such transesterifications can be carried out, for example, as described in the publication H. Steinmann, G. Tschernko, H. Hamann, Z. Chem. 3, 1977, pp. 89-92. Depending on the reaction time and conditions, the lower alcohols are split off and the perfume alcohols are bonded, whereby the aminoalkyl radicals bonded via an Si-C bond are retained.
  • the transesterification can be controlled exclusively by increasing the temperature and distilling off the readily volatile by-products, but it is preferred if catalysts are used for the transesterification.
  • These are usually Lewis acids, preferably aluminum tetraisopropoxide, titanium tetraisopropylate, silicon tetrachloride or basic catalysts or else preparations such as, for example, of aluminum oxide with potassium fluoride.
  • the silicon compounds thus formed then have at least partially perfume alcohol residues and / or biocide alcohol residues or a combination of both.
  • the resulting compounds usually also contain radicals of lower alcohols. As far as small amounts of water or other H-azide compounds are present in the production, replacement of alcohol residues also takes place against OH groups. Accordingly, the compounds according to the invention optionally also contain, as radical R, hydroxy groups.
  • Aminoalkyl radicals bearing silicon compounds bearing alkoxy radicals of lower alcohols are commercially available, wherein the radicals of lower alcohols are usually selected from radicals of methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and tert butanol.
  • the illustration of silicon compounds not completely reacted with perfume alcohols therefore leads to mixtures in which part of the radicals R is selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy. Such compounds are preferred in the context of the present invention.
  • Suitable starting compounds for the reaction with perfume alcohols are, for example, from Wacker Chemie (Burghausen, Germany) under the names Geniosil® GF 91 (N- (2-aminoethyl) -3-aminopropyltrimethoxysilane), Geniosil® GF 92 (N-cyclohexyl-3 -aminopropyltrimethoxysilane), Geniosil® GF 95 (N- (2-aminoethyl) -3-aminopropyl-methyldimethoxysilane), Geniosil® GF 96 (3-aminopropyltrimethoxysilane) or Geniosil® XL 926 (N-cyclohexylaminomethyltriethoxysilane).
  • the amino group of the aminoalkyl group may be a primary, secondary or tertiary amino group, with primary amino groups being preferred.
  • the amino group is used unmodified in a preferred embodiment, but it may also be modified if necessary.
  • the aldehydes are hereby preferably selected from active substance aldehydes, in particular from fragrance aldehydes or biocidal aldehydes.
  • active alcohol alcohols are to be understood as meaning alcohols which have a certain effect in the composition in which they are contained or else at the site of application to which the composition is applied.
  • Preferred active substance alcohols here are perfume alcohols and biocide alcohols.
  • Perfume alcohols are compounds which comprise at least one hydroxyl group and impart a fragrance impression
  • biocidal alcohols are compounds which comprise at least one hydroxyl group and have biocidal activity or at least inhibit germ growth.
  • perfume alcohols which may be mentioned are the following compounds: IO-undecene-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 1-octen-3-ol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butycyclohexanol, 6,8-dimethyl-2-nonanol, 6-nonene-1-ol, 9-decene-1-ol, alpha-methylbenzyl alcohol, alpha-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, beta-
  • biocide alcohols examples include citronellol, eugenol, farnesol, thymol and geraniol. Further biocide alcohols are phenoxyethanol, 1,2-propylene glycol, glycerol, citric acid and its esters, lactic acid and its esters, salicylic acid and its esters, 2-benzyl-4-chlorophenol and 2,2'-methylenebis (6-bromo) 4-chlorophenol).
  • biocide alcohols in the context of this invention are the lower alcohols, which are already mentioned above as the usual alkoxy of the silicon compounds.
  • biocide alcohols It is explicitly methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl and tert-butyl alcohol, which are not considered according to the invention as biocide alcohols.
  • classical biocides with alcohol functions are expressly regarded as biocide alcohols according to the invention, even if their effect is attributable to other functional groups.
  • biocide alcohols for example, here are various bromphenols and biphenylol and quaternary ammonium compounds having at least one long alkyl radical and at least one alkyl radical which carries a hydroxyl group to call.
  • active substance aldehydes refers to aldehydes which are to have a specific effect in the composition in which they are contained or else at the site of application to which the composition is applied.
  • Preferred active substance aldehydes are fragrance aldehydes and biocidal aldehydes. Fragrance aldehydes are to be understood as meaning aldehydes which convey a scent impression, while biocidal aldehydes are to be understood as meaning aldehydes with biocidal activity.
  • perfume aldehydes which may be mentioned are: adoxal, anisaldehyde, cumyl, ethylvanillin, florhydral, helional, heliotropin, hydroxycitronellal, koavon, laurylaldehyde, lyral, methylnonylacetaldehyde, bucinal, phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl-9-undecenal l 3-dodecene-1-al, alpha-n-amylcinnamaldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) -propanal,
  • aldehydes which can be used according to the invention, reference is further made to the following literature: Steffen Arctander, Aroma Chemicals Vol. 1 (1960, reprinted 2000) ISBN 0-931710-37-5 and Aroma Chemicals Vol. 2 (1969, reprinted 2000) ISBN 0-931710- 38-3.
  • biocidal aldehydes examples include: formaldehyde, paraformaldehyde, propenal (acrolein), glyoxal and glutaraldehyde.
  • Branched, saturated or unsaturated, substituted or unsubstituted alkyl and alkoxy radicals are understood according to the invention to be any type of alkyl and alkoxy radicals which may also contain heteroatoms and also cyclic and aromatic radicals.
  • alkyl and alkoxy radicals which may also contain heteroatoms and also cyclic and aromatic radicals.
  • C ⁇ -alkyl or C 1-4 alkoxy radicals are particularly preferred since these are preferably due to the above-mentioned preferred preparation method, optionally also in addition to hydroxy Residues, may be included.
  • Delayed release of fragrance alcohols is particularly desirable in detergents and cleaners, as well as in cosmetics, since there is a longer fragrance impression on the site of application, i. on the treated textile or on the skin or hair.
  • the silicon compounds according to the invention are distinguished by good hydrolytic stability and can also be used in aqueous media or in production processes for granules, without suffering excessive loss of activity.
  • liquid detergents and cleaners such as liquid detergents, fabric softeners, hand dishwashing detergents, hard surface cleaners, floor wipes, etc. are also conceivable, as are solid detergents and cleaners, for example laundry detergent granules, automatic dishwashing detergents or cleaning and scouring agents.
  • the silicon compounds of the invention can be used in cosmetic products for skin and hair treatment.
  • liquid agents such as shower baths, deodorants and hair shampoo, as well as solid means, such as soap bars meant.
  • Another object of the present invention is therefore also the use of silicon compounds according to the invention as a fragrance in liquid or solid detergents and cleaners and the use of silicon compounds according to the invention as a fragrance in cosmetic compositions for skin or hair treatment.
  • the present invention therefore further includes detergents or cleaners and cosmetic hair or skin treatment compositions containing silicon compounds of the invention.
  • the silicon compound When used in the washing and cleaning agents and in the cosmetic compositions, the silicon compound is preferably used in amounts of 0.001 to 10 wt .-%, particularly preferably from 0.01 to 5 wt .-%, especially from 0.02 to 3 Wt .-% and in particular in amounts of 0.05 to 2 wt .-%, each based on said agent, used.
  • the silicon compounds according to the invention can be used as the sole perfume, but it is also possible to use fragrance mixtures which consist only in part of the silicon compounds according to the invention. Such mixtures have the advantage that the ingredients of the fragrance mixture, which are not present inWstoffalkoxy form, are improved in the durability of the fragrance impression.
  • perfume mixtures which contain 1 to 50 wt .-%, preferably 5 to 40 and in particular at most 30 wt .-% of silicon compounds according to the invention.
  • the use according to the invention advantageously at least 30 wt .-%, preferably at least 40 wt .-% and in particular at least 50 wt .-% of the total contained in the middle Perfumes are introduced into the composition via the silicon compounds according to the invention, while the remaining 70% by weight, preferably 60% by weight and in particular 50% by weight of the total perfume contained in the composition are sprayed on in the usual way or introduced into the composition differently.
  • the use according to the invention can thus be advantageously characterized in that the silicon compounds according to the invention are used together with other fragrances, these being able to be present both in carrier-bound form and not in carrier-bound form.
  • the silicic acid esters are preferably compounds of the general formula II
  • R 1 and R 4 are independently selected from the group of straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C 1-6 -hydrocarbon radicals and the active alcohol radicals, in particular the perfume alcohol radicals and biocide alcohol radicals, each R 2 and R 3 independently of one another is selected from the group of active substance alkoxy radicals, in particular the Walshstoffalkoxy- and Bizidalkoxy radicals, wherein any two radicals R 2 and R 3 , which are bonded to different silicon atoms, can also represent a these two silicon atoms bridging oxygen atom, and n takes values between 2 and 20.
  • preferred silicic acid esters according to the invention, reference is made in particular to the patent specifications WO00 / 14091 and WO01 / 68037.
  • the principle described above can also be reversed by incorporating the more-volatile fragrances in the silicon compounds, and the less volatile, adherent fragrances sprayed on the means or otherwise incorporated. In this way, the loss of the more volatile fragrances from the package during storage and transport is minimized, while the fragrance characteristic of the agents is determined by the more adherent perfumes.
  • fragrances which are to be introduced via the silicon compounds according to the invention originate from the group of perfume alcohols.
  • the fragrances incorporated into the compositions in a conventional manner are not subject to any restrictions.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g.
  • the ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes e.g.
  • the linear alkanals of 8 - 18 C atoms citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, lilial and bourgeonal, to the ketones e.g. the ionones, ⁇ -isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
  • fragrance To be perceptible, a fragrance must be volatile, wherein besides the nature of the functional groups and the structure of the chemical compound also the molecular weight plays an important role , For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note or body” and “base note” (end note or dry out).
  • the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances.
  • more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
  • the above-described embodiment of the present invention in which the more volatile fragrances are present in the silicon compounds of the present invention is one such fragrance-fixing method. In the subsequent classification of the fragrances in "more volatile” or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.
  • Adhesive-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, Champacablütenöl, Edeltannenöl, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, Gurjun Balm Oil, Helichrysum Oil, Ho Oil, Ginger Oil, Iris Oil, Cajeput Oil, Calamus Oil, Chamomile Oil, Camphor Oil, Kanaga Oil, Cardamom Oil, Cassia Oil, Pine Needle Oil, Kopa ⁇ vabalsam Oil, Coriander Oil, Spearmint Oil, Cumin Oil, Cumin Oil, Lavender Oil, Lemongrass Oil, Lime Oil, Tangerine Oil, Melissa Oil, Musk Comer Oil, Myrrh Oil, Clove Oil, Neroli Oil,
  • fragrances of natural or synthetic origin can be used in the context of the present Invention as adherent fragrances or fragrance mixtures, so fragrances are used.
  • These compounds include the following compounds and mixtures thereof: ambrettolide, ambroxan, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate , Borneol, bornyl acetate, Boisambrene forte, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugeno
  • the more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more readily volatile fragrances are diphenyloxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl-n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • the washing or cleaning agent according to the invention may, for example, be a liquid or gel-form agent, in particular a liquid detergent or a liquid dishwashing agent or a cleansing gel, in particular a gel-type cleansing agent for flushing toilets.
  • the liquid washing or cleaning agent may in particular be a cleaning agent which is present in several phases, in particular in two phases.
  • the washing or cleaning agent may, however, also be about a powdery or granular agent. Furthermore, however, the washing or cleaning agent may also be present in the form of shaped bodies, which are preferably tablets which may consist of a single phase or of several, in particular 2 or 3, different phases.
  • the cosmetic agent may be an aqueous preparation which contains surface-active agents and is particularly suitable for the treatment of keratin fibers, in particular human hair, or for the treatment of skin. But it may also be about a shaped body containing surface-active ingredients. In particular embodiments, it can be an agent for influencing body odor, in particular a deodorant, or a hair setting agent which contains polymers, preferably in particular at least one polyurethane, for strengthening.
  • the detergents and cleaners may of course contain conventional ingredients of such agents.
  • these agents are primarily surfactants, builders and bleach, enzymes and other active substances to name.
  • surfactants belong to the essential ingredients of detergents and cleaners.
  • the surfactant content will be higher or lower.
  • the surfactant content of detergents is between 10 and 40 wt .-%, preferably between 12.5 and 30 wt .-% and in particular between 15 and 25 wt .-%, while detergents for automatic dishwashing between 0.1 and 10 wt .-%, preferably between 0.5 and 7.5 wt .-% and in particular between 1 and 5 wt .-% surfactants.
  • anionic surfactants come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants are clearly preferred for economic reasons and because of their power spectrum during washing and cleaning.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9 . 13- Alkylbenzolsulfonate, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci 2 -i 8 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, in consideration.
  • alkanesulfonates which are obtained from C 2 -i ⁇ alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example, the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettcicren are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelhoffreraumester C 2 -C 8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 2 o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and which are commercially obtainable as products of the Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 2 i-alcohols such as 2-methyl-branched C 9-11 alcohols having on average 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8- i 8 fatty alcohol radicals or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium, potassium or magnesium salts, in particular in the form of the sodium salts.
  • anionic surfactants are the freedom from formulation no conditions to be observed in the way.
  • preferred agents have a content of soap which exceeds 0.2% by weight, based on the total weight of the detergent and cleaner produced in step d).
  • Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent form comprising from 2 to 20% by weight, preferably from 2.5 to 15% by weight and in particular from 5 to 10% by weight of fatty alcohol sulfate (s), based in each case on the weight of the funds included
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -i 4 -alcohols with 3 EO or 4 EO, Cg- 11- AlKOhOl with 7 EO, C 13 . 15- alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 . 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -i 4 -alcohol with 3 EO and C 12-1S -AlkOhOl with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • NRE narrow rank ethoxylates
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example, in Japanese Patent Application JP 58/217598, or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) Z , in which R is a linear or branched, especially in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the glycosidation degree z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4.
  • linear alkyl polyglycosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the surfactant granules may preferably contain alkylpolyglycosides, with contents of APG of more than 0.2% by weight, based on the total molding, being preferred.
  • Particularly preferred detergent form bodies contain APG in amounts of 0.2 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.
  • nonionic surfactants of the type of amine oxides for example N-cocoalkyl N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula (III), R 1
  • RCO is an aliphatic acyl group having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)
  • R-CO-N- [Z] (IV) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain with at least two hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • detergent ingredients are the builders. Under this substance class, both organic and inorganic builders are understood. These are compounds which can both perform a carrier function in the compositions according to the invention and also act as a water-softening substance when used.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus, for example in the granules according to the invention, also serve to establish a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. This class of substances has already been described in detail above.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids, such as in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • allylsulfonic acids such as in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers of more than two different monomer units for example those which according to DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C -42 21 381 as monomers containing salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors.
  • Particular preference is given to polyaspartic acids or their salts and derivatives, of which German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European Patent Application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-472 042 and EP-A-0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • Also suitable is an oxidized oligosaccharide according to the German patent application DE-A-196 00 018. A product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Ethylenediamine-N, N'-disuccinate (EDDS) whose synthesis is described for example in US 3,158,615, preferably in the form of its sodium or magnesium salts.
  • EDDS Ethylenediamine-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-AO 150 930 and Japanese Patent Application JP 93/339896.
  • Suitable amounts are in zeolith Wegner and / or silicate-containing formulations at 3 to 15 wt .-%.
  • Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are described, for example, in International Patent Application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • a preferred inorganic builder is fine crystalline, synthetic and bound water-containing zeolite.
  • the finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P.
  • the zeolite P, zeolite MAP is for example Doucil A24 ® (commercially available from Crosfield) was used.
  • zeolite X and mixtures of A, X and / or P for example, a co-crystal of zeolites A and X 1 AX VEGOBOND ® (a product of Condea Augusta SpA).
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 2 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • zeolites are contained in the premix in amounts of from 10 to 94.5% by weight, it being particularly preferred that zeolites are present in amounts of from 20 to 70, in particular from 30 to 60% by weight.
  • Suitable partial substitutes for zeolites are phyllosilicates of natural and synthetic origin.
  • Such layered silicates are known, for example, from the patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here. Also, crystalline, layered sodium silicates of the general formula
  • NaMSi x O 2x + 1 7H 2 O where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4 are suitable for Substitution of zeolites or phosphates.
  • Such crystalline layered silicates are described, for example, in European Patent Application EP-AO 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates having a modulus of Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2,6, which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates are at X-ray diffraction experiments provide no sharp X-ray reflections, as they are typical for crystalline substances, but at best one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle.
  • the silicate particles may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024.
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates, wherein in particular the overdried silicates preferably also occur as a carrier in the granules according to the invention or are used as carriers in the process according to the invention.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished composition.
  • tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.
  • the detergents and cleaners according to the invention may additionally contain one or more substances from the groups of bleaches, bleach activators, enzymes, pH adjusters, fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors, corrosion inhibitors and silver protectants contain. These substances are described below.
  • the sodium perborate tetrahydrate, the sodium perborate monohydrate and the sodium percarbonate have particular significance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the tablets.
  • bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxy
  • Chlorine or bromine releasing substances can also be used as bleaching agents in automatic dishwashing agents.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable. In order to achieve an improved bleaching effect during washing or cleaning at temperatures of 60 ° C.
  • bleach activators can be incorporated into the detergents and cleaners according to the invention.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoyl-succinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts may also be included.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures are of particular interest. Peroxidases or oxidases have also proved suitable in some cases.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • proteases include lipases, amylases, cellulases and proteases.
  • Preferred proteases are, for. B. BLAP®140 from. Biozym, Optimase® M-440 and Opticlean® M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo.
  • Particularly suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk.
  • amylases are found in Duramyl® and Termamyl® 60 T and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades. Other enzymes can also be used.
  • washing and cleaning agents may also contain components that positively influence the oil and Fettauswaschles from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
  • salts of 4.4 l -Bis (2-anilino-4-morpholino-1, 3 l 5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or the like are suitable built compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned brightener can be used.
  • the agents according to the invention can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • Dishwashing agents according to the invention may contain corrosion inhibitors for protecting the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing.
  • silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular.
  • Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, eg.
  • salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V 1 Co and Ce are often used.
  • the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • compositions of the present invention are substances that prevent re-soiling of surfaces and / or facilitate soil release after a single use (so-called "soil release compounds").
  • Useful soil release compounds include all compounds known in the art. Particularly suitable are cationic polymers such as hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino groups, cationic cellulose derivatives, cationic homo- and / or copolymers (monomer units: quaternized ammonium alkyl methacrylate groups).
  • cationic polymers such as hydroxypropyltrimethylammonium guar
  • Copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide polymers with imino groups, cationic cellulose derivatives, cationic homo- and / or copolymers (monomer units: quaternized ammonium alkyl methacrylate groups).
  • the cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups as soil release compounds.
  • Exceptionally preferred within the scope of this application are also natural polyuronic acids and related substances, as well as polyampholytes and hydrophobized polyampholytes, or mixtures of these substances.
  • the agents may also contain organic solvents.
  • it is monohydric or polyhydric alcohols having 1 to 4 carbon atoms.
  • Preferred alcohols in such agents are ethanol, 1, 2-propanediol, glycerol and mixtures of these alcohols.
  • such agents contain from 2 to 12% by weight of such alcohols.
  • the agents can have different states of aggregation.
  • the washing or cleaning agents are liquid or gel-like agents, in particular liquid detergents or liquid dishwashing detergents or cleaning gels, which may in particular also be gel-type cleaners for flushing toilets.
  • Such gel-type cleaners for flush toilets are described, for example, in German Patent Application DE 197 158 72.
  • These are preferably gelatinous, structurally viscous cleaning agents having a viscosity of 30,000-150,000 mPas, which contain as gel former a polysaccharide, as emulsifier and network-active component a C8-C10 alkylpolyglycoside or C12-C14 alkylpolyglycoside and perfume oil.
  • Additional co-surfactants may include fatty alcohol ether sulfates (FAEOS) and fatty alcohol sulfates (FAS).
  • the ratio of APG to cosurfactant is then generally greater than 1, preferably between 50: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1, and most preferably between 5: 1 and 1 , 8: 1.
  • these are stable, gel-like, shear-thinning cleaning compositions containing polysaccharide, a surfactant system and perfume components, which are characterized in that
  • a polysaccharide preferably a xanthan gum, in amounts of between 1 and 5% by weight, preferably 1 to 4% by weight, more preferably 1, 5 to 3.5% by weight and very particularly preferably 1, 8 to 3% by weight,
  • a C8 to C22 alkylpolyglycoside in amounts between 3 and 25 wt .-%, preferably 4 and 20 wt .-%, particularly preferably 5 and 15 wt .-% and most preferably 5 and 12 wt .-% and
  • the perfume component or perfume components up to 15% by weight, preferably in 2 to 12% by weight, more preferably in 3 to 8% by weight
  • the means have a viscosity from 30,000 to 150,000 mPas, measured with a Brookfield rotational viscometer, Type RVT with helipath means and TA spindle at 1 U / min and 23 0 C.
  • Such cleaning gels are usually dosed in containers that can be placed in a toilet bowl or in water boxes.
  • a special container, which is particularly suitable for the gel detergent, is described in the German patent application DE 195 201 45.
  • Bubbles are introduced into the funds, which are stable over a period of several weeks in size and shape and thus represent a visually even more appealing to the consumer product.
  • Production process and control the viscosity of the means can be neither too big nor too small, and the amount of air bubbles are also selected only in a preferred range. So should the presence of air bubbles is desired, not more than 30% by volume of air should be present, preferably 2 and 25% by volume of air and most preferably between 5 and 20% by volume of air.
  • the most preferred embodiments include air bubbles between 0.1 mm and 20 mm in diameter, most preferably between 1 mm and 15 mm in diameter.
  • the viscosity of the preferred means also allows the already entered in the production process air bubbles by brief application of a negative pressure, which may be in a range just below room pressure to near a vacuum. The duration of the vacuum treatment depends on the strength of the negative pressure.
  • the mixture is, as described above, in a suitable container as a function of the viscosity but usually for a short time, for example 15 minutes under reduced pressure or a vacuum.
  • Disinfectants Usually here water in a commercial mixer system such.
  • Isothiazolines benzoates or salicylic acid or salicylates.
  • the filling can in this case z. B. via a bottle rotors in a commercial
  • the common methods of viscosity determination can be used.
  • Brookfield viscometers were used which provided a spindle intended for gels.
  • the preferred gel formulations may contain the following components in a frame formulation:
  • complexing agent 0 to 5.0% by weight of complexing agent to 15% by weight, preferably 2.0 to 12.0% by weight of perfume to 5.0% by weight, preferably 0.01 to 4% by weight of solvent, such as eg ethanol
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate.
  • Xanthan gum is produced by Xanthomonas campestris under aerobic conditions with a molecular weight of 2-15 X 10 6 .
  • xanthan gum is produced in batch cultures and, after killing the culture and precipitated with propanol, dried and ground. Other suitable methods are also described in the literature.
  • Alkyl polyglycosides are the surfactants already mentioned above, which can be obtained by the reaction of sugars and alcohols by the relevant processes of preparative organic chemistry, depending on the nature of the preparation to a mixture of monoalkylated, oligomeric or polymeric sugar.
  • Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol particularly preferably being a long-chain fatty alcohols with alkyl chain lengths between C8 and C22 preferably between C8 and C16 and particularly preferably between C8 and C12 or a mixture of long-chain fatty alcohols.
  • the degree of oligomerization of the sugars which is a calculated and thus generally non-integral quantity, is between 1 and 10, preferably between 1, 1 and 5 and very particularly preferably between 1, 2 and 3 and most preferably between 1, 3 and 2 ; 5.
  • Anionic cosurfactants according to the present invention may be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lignin sulfonates.
  • aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, n-alkyl ether sulfonates, ester
  • fatty acid cyanamides sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • fatty alcohol sulfates and fatty alcohol ether sulfates are used. Less good results have been achieved with alkylbenzenesulfonates.
  • Nonionic co-surfactants can also be used.
  • Nonionic surfactants in the context of the present invention may be alkoxylated alcohols, such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • alkoxylated alcohols such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides and fatty acid polyglycol ethers are also useful.
  • alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably longer-chain alcohols.
  • alkylene oxide preferably ethylene oxide
  • alcohols preferably longer-chain alcohols.
  • n moles of ethylene oxide and one mole of alcohol depending on the reaction conditions, form a complex mixture of addition products of different degrees of ethoxylation.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention.
  • Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.
  • the formulations may preferably contain lime-dissolving acids such as citric acid, acetic acid, lactic acid or their water-soluble salts in an amount of 1-12% by weight. Particular preference is given to contents of 2 to 5% by weight.
  • the gels preferably contain dye, either for the color of the product or for the color of the liquid playing around the container.
  • the content of water-soluble dyes is preferably ⁇ 1% by weight and serves to improve the appearance of the product. If an additional color signal is desired during the flushing process, the content of water-soluble dyes may be up to 5% by weight.
  • the gels already without this component already have an excellent cleaning effect, the hygienic effect can be enhanced by the addition of antimicrobial agents.
  • the amount of these agents depends strongly on the efficacy of the particular compound and can be up to 5% by weight. Preferably, more than 0.01% by weight is incorporated into the gels. Particularly preferred is the range between 0.01 wt .-% and 3 wt .-%. Particularly suitable are isothiazoline mixtures, sodium benzoate or salicylic acid.
  • perfume oils which may be present in preferred gels in amounts of up to 15% by weight and more preferably from 2 to 12% by weight and most preferably from 3 to 8% by weight include those already described above Links. According to the invention, these perfume oils contain the silicon compounds according to the invention. The perfume! consist entirely of such silicon compounds or have these silicon compounds in mixtures with other fragrances.
  • solubilizer such as dyes and perfume oils
  • alkanolamines for example, alkanolamines, polyols such as ethylene glycol, propylene glycol, 1, 2 glycerol and other monohydric and polyhydric alcohols, as well as alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl group
  • Particularly preferred is the group of lower alcohols, especially ethanol.
  • the usual thickening agents which could additionally be used if necessary include urea, sodium chloride, sodium sulfate, magnesium sulfate, ammonium chloride and magnesium chloride, and the combination of these thickeners. However, the use of these additional thickening agents is not preferred.
  • Water-soluble and water-insoluble builders may optionally be present in the gels according to the invention. Water-soluble builders are then preferred because they tend to be less likely to form insoluble residues on hard surfaces. Typical builders which may be present in the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and its salts, the carbonates, phosphates and silicates. Water-insoluble builders include the zeolites, which may also be used, as well as mixtures of the aforementioned builders. Particularly preferred is the group of citrates.
  • liquid or gel cleaner for hard surfaces, especially so-called all-purpose cleaner, glass cleaner, floor or bathroom cleaners and special embodiments of such cleaner including acidic or alkaline forms of all-purpose cleaners as well as glass cleaner with so-called anti-rain Effect include.
  • These liquid cleaning agents can be present both in one and in several phases. In a particularly preferred embodiment, the cleaners 2 have different phases.
  • Cleaner is in the broadest sense a name for - mostly surfactant-containing - formulations with a very wide range of applications and dependent on very different composition.
  • the main market segments are household cleaners, industrial (technical) and institutional cleaners.
  • According to the pH value a distinction is made between alkaline, neutral and acid cleaners, according to the offer form liquid and solid cleaners (also in tablet form).
  • the so-called cleaners for hard surfaces both in the concentrated state and in dilute aqueous solution, in combination with mechanical energy, show an optimum application profile. Cold cleaners develop their performance without increased temperature.
  • Decisive for the cleaning effect are mainly surfactants and / or alkali carriers, alternatively acids, optionally also solvents such as glycol ethers and lower alcohols.
  • builders are also included in the formulations, bleaches, enzymes, germ-reducing or disinfecting additives as well as perfume oils and dyes, depending on the type of cleaner.
  • Cleaners may also be formulated as microemulsions. The cleaning success depends to a great extent on the - also geographically very different - type of dirt and the properties of the surfaces to be cleaned.
  • Household cleaner can be used as a universal cleaner or as a special cleaner for u. a. Ceramics, tiles, windows, plastics, (carpet) floors, hobs, ovens, microwave ovens, be formulated as sanitary cleaner or toilet cleaner.
  • Pipe cleaners are alkaline and consist z. B. of solid sodium hydroxide and aluminum powder, in the resolution of the resulting hydrogen provides a corresponding turbulence in the tube segments to be freed.
  • Sanitary cleaners contain tenside and builder v. a. anti-corrosive agents wherein the previously used sodium hypochlorite is partially replaced by hydrogen peroxide or other peroxygen compounds.
  • WC cleaners are predominantly acidic, sometimes also alkaline, in the former case, the originally used phosphoric acid and sodium hydrogen sulfate largely by organic acids, v.. a. Citric acid, are replaced.
  • organic acids v.. a. Citric acid
  • Do-it-yourself also includes car, car window, rim, engine and paint applicator cleaners.
  • Institutional cleaners serve the operational cleaning and hygiene z. As in schools, office buildings, hotels, restaurants and hospitals, in the latter case, a safe surface disinfection makes a special demand on the products. These cleaners are delivered in bulk containers (bulk consumer goods). The products and the associated service using specially developed cleaning equipment are offered as a system solution.
  • Technical cleaner Become v. a. used in the beverage, food, cosmetic and pharmaceutical industries, but also in the metal industry for metal degreasing.
  • the product group includes u. a. also cleaner for car washes, tanker and aircraft cleaner. In view of the required productivity z.
  • these cleaners must be formulated with low-foaming surfactants, for which special nonionic surfactants such as ethylene oxide-propylene oxide block copolymers and so-called end-capped alkyl ethoxylates are suitable.
  • a preferred multi-phase all-purpose cleaner is an aqueous liquid multiphase surfactant-containing cleaning agent having at least two continuous phases, which has at least one lower aqueous phase I and a non-miscible with this phase upper aqueous phase II and can be converted by shaking temporarily in an emulsion, and 0 to 5 wt .-% sodium hexametaphosphate.
  • sodium hexametaphosphate is a mixture of condensed orthophosphates of the formula I to understand, where n stands for an average of about 12.
  • this cleaner fragrance contains, wherein at least part of the perfume oils contained in the form of the silicon compounds according to the invention is present.
  • such a means consists of a lower continuous phase, which consists of the entire phase I, and an upper continuous phase, which consists of the entire phase II.
  • one or more continuous phases of the composition may also contain portions of another phase in emulsified form, such that in such agent, for example, there is phase I in one part as continuous phase I, which is the lower continuous phase of the agent, and another Part is emulsified as a discontinuous phase I in the upper continuous phase II.
  • phase II and other continuous phases analogous applies.
  • Such agents are characterized by an unusually good cleaning performance of stubborn grease dirt with undiluted application.
  • the funds show a favorable Residue behavior.
  • the individual phases on average are stable for a long time, without, for example, deposits formed, and the conversion into a temporary emulsion remains reversible even after frequent shaking.
  • the separation of ingredients into separate phases can promote the chemical stability of the agent.
  • the continuous phases I and II are delimited from each other by a sharp interface.
  • one or both of the continuous phases I and II contain parts, preferably 0.1 to 25% by volume, in particular 0.2 to 15% by volume, based on the volume of the respective continuous phase, in each case other phase than dispersing.
  • the continuous phase I or II is then reduced by the volume fraction which is distributed as a dispersant in the respective other phase.
  • Particularly preferred are agents in which phase I in amounts of 0.1 to 25 vol .-%, preferably 0.2 to 15 vol .-%, based on the volume of phase II, is emulsified in phase II.
  • part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion being characterized by two sharp interfaces, one upper and one lower, rather than the emulsion involved parts of phases I and II is delimited.
  • the compositions contain one or more hydrophobic components.
  • Suitable hydrophobic components are, for example, dialkyl ethers having identical or different C 4 - to C 1-4 -alkyl radicals, in particular dioctyl ether; Hydrocarbons having a boiling range of 100 to 300 0 C, in particular 140 to 280 0 C, for example aliphatic hydrocarbons having a boiling range of 145 to 200 0 C, isoparaffins having a boiling range of 200 to 260 0 C; essential oils, especially limonene, and pine OiI extracted from pine roots and stumps; and also mixtures of these hydrophobic components, in particular mixtures of two or three of said hydrophobic components.
  • Preferred mixtures of hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and essential oils, of hydrocarbons and essential oils, of dialkyl ethers and hydrocarbons and of essential oils and of these mixtures.
  • the compositions contain hydrophobic components in amounts, based on the composition, of 0 to 20 wt .-%, preferably 0.1 to 14 wt .-%, in particular 0.5 to 10 wt .-%, most preferably 0.8 to 7 wt .-%.
  • the agents may also contain phase separation aids.
  • Suitable phase separation aids are, for example, the alkali metal and alkaline earth metal chlorides and sulfates, in particular sodium and potassium chloride and sulfate, and ammonium chloride and sulfate or mixtures thereof.
  • the salts mentioned as strong electrolytes support the phase separation by the salt effect.
  • Builder salts also cause this effect as electrolytes and are accordingly also suitable as phase separation aids.
  • the compositions contain phase separation aids in amounts, based on the composition, of from 0 to 30% by weight, preferably from 1 to 20% by weight, in particular from 3 to 15% by weight, very preferably from 5 to 12% by weight.
  • compositions may contain as surfactant anionic, nonionic, amphoteric or cationic surfactants or surfactant mixtures of one, more or all of these classes of surfactants.
  • the compositions contain surfactants in amounts, based on the composition, of 0.01 to 30 wt .-%, preferably 0.1 to 20 wt .-%, in particular 1 to 14 wt .-%, most preferably 3 to 10 wt. -%.
  • nonionic surfactants in such a all-purpose cleaners for example, C 8 -C 8 -Alkylalkoholpoly- glycol ethers, alkyl polyglycosides and nitrogen-containing surfactants or mixtures thereof, in particular the first two.
  • the compositions contain nonionic surfactants in amounts, based on the composition, of 0 to 30 wt .-%, preferably 0.1 to 20 wt .-%, in particular 0.5 to 14 wt .-%, most preferably 1 to 10 wt .-%.
  • C ⁇ -Ci ⁇ -Alkylalkoholpolypropylenglykol / polyethylene known are nonionic surfactants. You can by the formula Rb (CH 2 CH (CH 3) O) P (CH 2 CH 2 O) 8 -H, described in which R 1 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 8 to 18 carbon atoms, p is 0 or numbers from 1 to 3 and e is numbers from 1 to 20.
  • the C ⁇ -C ⁇ -Alalkoholpolyglykolether can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to fatty alcohols.
  • Typical examples are polyglycol ethers in which R 1 is an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7.
  • end-capped C 8 -C 18 -alkyl alcohol polyglycol ethers ie compounds in which the free OH group in the formula II is etherified.
  • the end-capped C 8 -C 18 -alkyl alcohol polyglycol ethers can be obtained by relevant methods of preparative organic chemistry.
  • C 8 -C 18 -alkyl alcohol polyglycol ethers are reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride.
  • Typical examples are mixed ethers in which R 1 KJr is a technical fatty alcohol radical, preferably C 12 / i 4 cocoalkyl radical, p is 0 and e is 5 to 10, which are closed with a butyl group.
  • Preferred nonionic surfactants are furthermore the alkylpolyglycosides already described above.
  • nitrogen-containing surfactants may be contained, e.g. Fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxylic acid amides having alkyl groups having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10.
  • Particularly useful compounds include the lauric, myristic and palmitic monoethanolamides.
  • Suitable anionic surfactants for all-purpose cleaners are C 8 -C 18 -alkyl sulfates, C 8 -C 18 -alkyl ether sulfates, ie the sulfation products of the alcohol ethers of the formula II, and / or C 8 -C 18 -alkylbenzenesulfonates, but also C 8 -C 18 -alkanesulfonates , C 8 -C 18 - ⁇ -olefinsulfonates, sulfonated C 8 -C 18 -fatty acids, in particular dodecylbenzenesulfonate, C 8 -C 22 -carboxylic acid amide ether sulfates, sulfonosuccinic mono- and -di-C 1 -C 12 -alkyl esters, C 8 -C 18 - Alkylpolyglykolethercarboxylate, C 8 -C 18 -N-acyl
  • compositions contain anionic surfactants in amounts, based on the composition, of from 0 to 30% by weight, preferably from 0.1 to 20% by weight, in particular from 1 to 14% by weight, very preferably from 2 to 10% by weight. %.
  • the all-purpose cleaners can also treat soaps, i. Alkali or ammonium salts of saturated or unsaturated C6-C22 fatty acids.
  • the soaps may be used in an amount of up to 5% by weight, preferably from 0.1 to 2% by weight.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R “XR”'XR' V) N + CH 2 COO "in which R" a is optionally interrupted by hetero atoms or hetero atom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R '" and R ' v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular
  • compositions contain amphoteric surfactants in amounts, based on the composition, of 0 to 15 wt .-%, preferably 0.01 to 10 wt .-%, in particular 0.1 to 5 wt .-%.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R V ) (R V ') (R V ") (R VI ") N + X " , in which R v to R""for four identical or different, in particular two long and two short-chain, alkyl radicals and X 'are an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof
  • the compositions contain cationic surfactants in amounts, based on the Composition, from 0 to 10 wt .-%, preferably 0.01 to 5 wt .-%, in particular 0.1 to 3 wt .-%.
  • the cleaners contain anionic and nonionic surfactants side by side, preferably C 8 -C 8 -alkylbenzenesulfonates, C 8 -C 18 -alkyl sulfates and / or C 8 -C 18 -alkyl ether sulfates in addition to C 8 -C 18 -alkyl alcohol polyglycol ethers and / or Alkylpolyglykosiden, in particular C 8 -C 18 alkylbenzenesulfonates in addition to C 8 -C 18 alkyl alcohol polyglycol ethers.
  • anionic and nonionic surfactants side by side, preferably C 8 -C 8 -alkylbenzenesulfonates, C 8 -C 18 -alkyl sulfates and / or C 8 -C 18 -alkyl ether sulfates in addition to C 8 -C 18 -alkyl alcohol polyglycol ethers.
  • the agents according to the invention may contain builders.
  • suitable builders are alkali metal gluconates, citrates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium gluconate, citrate and nitrilotriacetate, and sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium hydroxide, ammonia and amines , in particular mono- and triethanolamine, or mixtures thereof.
  • alkali metal gluconates, citrates, nitrilotriacetates, carbonates and bicarbonates in particular sodium gluconate, citrate and nitrilotriacetate, and sodium and potassium carbonate and bicarbonate
  • alkali metal and alkaline earth metal hydroxides in particular sodium and potassium hydroxide, ammonia and amines , in particular mono- and triethanolamine, or mixtures thereof.
  • These include the salts of glutaric acid, succinic acid,
  • compositions contain builders in amounts, based on the composition, of from 0 to 20% by weight, preferably from 0.01 to 12% by weight, in particular from 0.1 to 8% by weight, very preferably from 0.3 to 5 Wt .-%, but the amount of sodium hexametaphosphate - except for the means according to the invention - is limited to 0 to 5 wt .-%.
  • the builder salts are at the same time phase separation aids.
  • compositions according to the invention may contain further auxiliaries and additives, as are customary in such compositions.
  • auxiliaries and additives include in particular polymers, soil release agents, solvents (eg, ethanol, isopropanol, glycol ethers), solubilizers, hydrotropes (eg, cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), cleaning enhancers, viscosity regulators (eg, synthetic polymers such as polysaccharides, polyacrylates, in nature occurring polymers and their derivatives such as xanthan gum, other polysaccharides and / or gelatin), pH regulators (eg citric acid, alkanolamines or NaOH), disinfectants, antistatic agents, preservatives, bleach systems, enzymes, dyes and opacifiers or even skin protection agents, as described in EP-A A-522 556 are described.
  • solvents eg, ethanol, iso
  • the amount of such additives is usually not more than 12 wt .-% in the detergent.
  • the lower limit of the use depends on the nature of the additive and can be up to 0.001 wt .-% and below, for example, in the case of dyes.
  • the amount of auxiliaries is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.
  • the pH of the all-purpose cleaners can be varied over a wide range, but preferred is a range of 2.5 to 12, especially 5 to 10.5. Under the pH value of the present invention, the pH of the agent in the form of the temporary emulsion to understand.
  • Such general purpose cleaner formulations can be modified for any purpose.
  • a special embodiment are the glass cleaner.
  • Essential in such cleaners is that stains or edges remain.
  • Betschf Anlagen Likewise, it is undesirable if so-called rain stains remain on glass panes which are exposed to the rain. This effect is known as rain effect or anti-rain effect.
  • WO 96/04358 cleaning agents which can clean glass without leaving stains and / or films to an inconvenient extent and contain an effective amount of a substantive polymer having hydrophilic groups which provides the glass with a long-lasting, higher hydrophilicity , so that at least in the next three new wetting, for example by rain, the water expires flat and left after drying less stains.
  • Noun polymers are in particular polycarboxylates such as poly (vinylpyrrolidone-co-acrylic acid), but also poly (styrenesulfonate), cationic sugar and starch derivatives as well as from ethylene oxide and propylene oxide built block copolymers, the latter polyethers have less substantivity.
  • WO 94/22800 discloses epoxy-capped polyalkoxylated alcohols of the formula A,
  • R' ⁇ [CH 2 CH (CH) 3 ⁇ ] x [CH 2 CH 2 ⁇ ] y [CH 2 CH (R ") O] z H (A) in the R 1 is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms or a mixture of different such radicals,
  • R represents a linear, aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms or a mixture of various such radicals, x is an integer from 1 to about 3, y is a number from 5 to about 30, and z represents a number from 1 to about 3.
  • Die Alcohols of Formula A can be incorporated into powdered and liquid machine dishwashing or hard surface cleaners, and in automatic dishwashing detergents, they reduce stain and filming.
  • R l ⁇ [CH 2 CH (CH) 3 ⁇ ] u [CH 2 CH (R lv ) O] v [CH 2 CH (R v ) O ] w H (B) in the R 1 "is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms or a mixture of various such radicals,
  • R 1 is a hydrogen atom or a lower alkyl radical having 1 to 6 carbon atoms
  • R v represents a linear, aliphatic hydrocarbon radical having from about 2 to about 14 carbon atoms or a mixture of various such radicals, u represents a number from 1 to about 5, v represents a number from 1 to about 30, and w represents a number from 1 to about 3.
  • the alcohols of the formula B can be incorporated, alone or together with alcohols of the formula A, into pulverulent and liquid dishwashing detergents or hard surface cleaners, such as bathroom tiles. Even in automatic dishwashing detergents, they reduce stain and film formation.
  • end-capped polyalkoxylated alcohols of the formula V described in the patent application DE 198 565 29 are
  • R 1 O [CH 2 CH (CH) 3 O] p [CH 2 CH (R 2 ) O] q R 3 (V) in the R 1 is a linear, aliphatic hydrocarbon radical having 1 to about 22
  • R 2 is a hydrogen atom or a lower alkyl radical having 1 to 6 carbon atoms
  • R 3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic, hydrocarbon radical having 1 to about 78 carbon atoms and optionally one or more hydroxy groups and / or ether groups -O- or a mixture of different such radicals
  • p represents a number from 0 to about 15
  • q represents a number from 0 to about 50 and the sum of p and q is at least 1, in a hard surface cleaner for reducing the rain effect and / or the fogging effect.
  • the content of one or more end-capped polyalkoxylated alcohols of the formula I in the glass cleaner is 0.001 to 20% by weight, preferably 0.01 to 10% by weight, in particular 0.05 to 5% by weight, particularly preferably 0, 1 to 2.5 wt .-% and most preferably 0.2 to 2.0 wt .-%.
  • Preferred end-capped polyalkoxylated alcohols are those of the formula I in which p and q are both at least 1 and / or the radical R 2 is a hydrogen atom and / or the radical R 3 is at least one hydroxyl group, in particular in the ⁇ -position, ie R 3 is a Group -CH 2 CH (OH) -R.
  • End-capped polyalkoxylated alcohols of the formula I 1 in which the radical R 3 represents a group -CH 2 CH (OH) -R are known, for example, from DE 37 23 323 A1.
  • Particularly preferred end-capped polyalkoxylated alcohols are epoxy-capped polyalkoxylated alcohols of the formula I in which R 1 is a linear, aliphatic hydrocarbon radical having from about 4 to about 18, preferably from about 4 to about 12, carbon atoms, in particular a butyl, hexyl, octyl or Decylrest or mixtures thereof, or a mixture of different such radicals, R is a hydrogen atom or a lower alkyl radical having 1 to 6 carbon atoms, preferably a hydrogen atom, R 3 is a group [CH 2 CH (R 4 ) O] r H, in the R 4 is a linear aliphatic hydrocarbon radical having from about 2 to about 26, preferably from about 4 to about 18, more preferably from about 6 to about 14, carbon atoms or a mixture of various such radicals and r is from 1 to about 3, preferably 1 to is about 2, in particular 1, p is a number from 1 to about 5, preferably 1 to about 2, in particular 1, and q is
  • Such epoxy-capped polyalkoxylated alcohols and methods for their preparation are known, for example, from WO 94/22800 and WO 96/12001.
  • Preferred end-capped alcohols are available, for example under the trade name Dehypon ® by the company. Henkel KGaA or under the trade name Poly Tergent ® by the company. Olin Corporation, for example Dehypon ® LT 104, Dehypon ® LS 104, Dehypon ® LT 54, Dehypon ® LS 531 or Dehypon ® O 54 or poly Tergent ® SLF 18 B 48, poly Tergent ® SLF 18 B 45, or poly Tergent ® SL 62nd
  • the agents are powdery or granular agents.
  • the compositions according to the invention can have any bulk densities.
  • the range of possible bulk densities ranges from low bulk densities below 600 g / l, for example 300 g / l, over the range of average apparent weights of 600 to 750 g / l up to the range of high bulk densities of at least 750 g / l.
  • the bulk density is even above 800 g / l, bulk densities above 850 g / l being particularly advantageous.
  • compositions are prepared by mixing together various particulate components which contain detergent and / or detergent ingredients and together form at least 60% by weight of the total composition.
  • the particulate components can be prepared by spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation. It is preferred in particular that at least one surfactant-containing component is produced by fluidized bed granulation.
  • aqueous preparations of builder substances are sprayed together with other detergent and / or cleaning agent ingredients in a drying device, wherein granulation can take place simultaneously with the drying.
  • the drying device into which the aqueous preparation is sprayed can be any desired dry apparatus.
  • the drying is carried out as spray drying in a drying tower.
  • the aqueous preparations are exposed in a known manner a drying gas stream in finely divided form.
  • Applicant describes an embodiment of superheated steam spray drying in a series of published references.
  • the working principle disclosed therein is hereby expressly also made the subject of the present invention disclosure.
  • the mixtures are subsequently subjected to a compaction step, with further ingredients being added to the compositions only after the compaction step.
  • the compaction of the ingredients takes place in a preferred embodiment of the invention in a press-agglomeration process.
  • the pressing agglomeration process to which the solid premix is subjected, can be realized in various apparatuses.
  • different Preßagglomerationsvon be distinguished.
  • the four most common and preferred in the present invention Preßagglomerationsclar are the extrusion, the roll pressing or compaction, the hole pressing (pelletizing) and tabletting, so that in the present invention are preferred Preßagglomerationsvor réelle extrusion, Walzenkompakt réelles-, pelletizing or Tabletting operations are.
  • the premix is compacted under pressure and plasticized and the individual particles are pressed together to reduce the porosity and adhere to each other.
  • the tools can be heated to higher temperatures or cooled to dissipate the heat generated by shearing forces.
  • a binder can be used as an aid for compaction.
  • a binder is used, that at temperatures up to 130 ° C, preferably up to 100 ° C and especially to 90 0 C is already completely present as a melt.
  • the binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature must - if a particular binder is desired - be adapted to the binder.
  • the actual compression process is preferably carried out at processing temperatures which correspond at least in the compression step at least the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt.
  • the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder.
  • Such a temperature control has the further advantage that even thermally sensitive raw materials, such as peroxy bleach such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious losses of active substance.
  • thermally sensitive raw materials such as peroxy bleach such as perborate and / or percarbonate, but also enzymes.
  • the working tools of the Preßagglomerators (the worm (s) of the extruder, the roller (s) of the Walzenkompaktors and the press roll (s) of the pellet press) a temperature of at most 150 0 C 1, preferably at most 100 0 C and in particular at most 75 ° C and the process temperature is 30 0 C and in particular at most 2O 0 C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the Temperature effect in the compression region of the pressing agglomerators a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • Preferred binders which can be used alone or in admixture with other binders are polyethylene glycols, 1, 2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn are molecular weights between 600 and 6000, preferably between 1000 and 4000.
  • polyethylene glycols include polymers in the production of which, in addition to ethylene glycol, C 3 -C 5 glycols and also glycerol and mixtures thereof are used as starting molecules. Also included are ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO.
  • the polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols.
  • Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3500 and above 5000, especially in combination with polyethylene glycols having a molecular weight of 4000, can be used and such combinations advantageously to more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols having a molecular weight between 3500 and 5000 have.
  • polyethylene glycols which are present in liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech.
  • these liquid per se polyethylene glycols should be used only in a mixture with at least one other binder, said mixture must again meet the requirements of the invention, ie a melting point or softening point of at least above 45 0 C must have.
  • binders are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of up to 30,000. Preference is given here to molecular weight ranges between 3,000 and 30,000, for example 10,000. Polyvinylpyrrolidones are preferably not used as sole binders but in combination with others, in particular in combination with Polyethylene glycols used.
  • Suitable binders are more raw materials have been found which raw materials having active washing or cleaning properties, thus for example nonionic surfactants with melting points of at least 45 0 C, or mixtures of nonionic surfactants and other binders.
  • the preferred nonionic surfactants include alkoxylated fatty or oxo alcohols, in particular C 12 -C 18 -alcohols.
  • degrees of alkoxylation, in particular degrees of ethoxylation averaging 18 to 80 AO 1, in particular EO, per mole of alcohol and mixtures of these have proven to be particularly advantageous.
  • Especially fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO show advantageous binding properties in the sense of the present invention.
  • ethoxylated alcohols having average lower EO units per mole of alcohol may also be present in binder mixtures, for example Taigfettalkohol with 14 EO.
  • binder mixtures for example Taigfettalkohol with 14 EO.
  • the content of the binder in these relatively low ethoxylated alcohols is less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used.
  • nonionic surfactants such as C 12 -C 8 alcohols having an average of 3 to 7 EO, which are liquid at room temperature per se, are preferably present in the binder mixtures only in the amounts that thereby less than 2 % By weight of these nonionic surfactants, based on the final process product.
  • nonionic surfactants are not part of the binder mixture, since these not only reduce the softening point of the mixture, but also the stickiness of the final product and also by their tendency to lead to contact with water to gels, and also do not meet the requirement of rapid dissolution of the binder / the partition in the final product to the desired extent.
  • conventional anionic surfactants used in detergents or cleaning agents or their precursors, the anionic surfactant acids are contained in the binder mixture.
  • nonionic surfactants which are suitable as binders are the non-gelatinous fatty acid methyl ester ethoxylates, in particular those with an average of 10 to 25 EO (for a more detailed description of this substance group, see below).
  • Particularly preferred representatives of this group of substances are predominantly C 16 -C 8 fatty acids based Methylester, for example, hydrogenated beef tallow with an average of 12 EO, or with an average of 20 EO.
  • a mixture is used as a binder, which C 2 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol having a molecular weight of 400 to 4000 used.
  • the binder used is a mixture comprising predominantly C 16 -C 18 fatty acid-based methyl esters having on average 10 to 25 EO, in particular hardened beef tallow methyl ester having an average of 12 EO or an average of 20 EO, and a C 12 - C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and / or polyethylene glycol having a molecular weight of 400 to 4000 contains.
  • binders have been found, either alone on polyethylene glycols having a molecular weight around 4000 or on a mixture of C 12 -C 18 fatty alcohol based coconut or tallow with an average of 20 EO and one of the above-described fatty acid methyl ester or based on a mixture of C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO, one of the above-described fatty acid methyl ester ethoxylates and a polyethylene glycol, in particular having a molecular weight of 4000.
  • the compacted does not have directly after leaving the production apparatus preferably temperatures above 90 0 C, with temperatures between 35 and 85 ° C are particularly preferred. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 0 C, for example up to 70 ° C, are particularly advantageous.
  • the process according to the invention is carried out by means of an extrusion, as described for example in European patent EP-B-486592 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299.
  • a solid premix is extruded under pressure extruded and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers.
  • the premix is preferably fed continuously to a planetary roller extruder or a 2-screw extruder with co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature.
  • the premix under pressure which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally
  • the extrudate is reduced by means of a rotating doctor blade to approximately spherical to cylindrical granules.
  • the hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules of a substantially uniformly predeterminable particle size succeeds, wherein in detail the ab- solute particle sizes may be adapted to the intended use.
  • particle diameters of at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 3 mm.
  • the length / diameter ratio of the chopped primary granules in one important embodiment is in the range of about 1: 1 to about 3: 1.
  • zeolite powder such as zeolite NaA powder
  • This shaping can be done in commercially available Rondierakun. It is important to ensure that only small amounts of fine grain content occur in this stage.
  • a drying which is described in the above-mentioned prior art documents as a preferred embodiment, is then possible, but not necessarily according to the invention. It may just be preferable to stop drying after the compaction step.
  • extrusions / compression can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in Bexx Bextruder.
  • the invention now provides that the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least achieved, but preferably exceeded.
  • the duration of the action of temperature in the compression region of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the method according to the invention is carried out by means of roll compaction.
  • the premix is selectively metered between two smooth or provided with wells of defined shape rollers and rolled between the two rollers under pressure to form a sheet-like Kompaktat, the so-called scoop.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rolls smooth, unstructured flake tapes are obtained, while the use of structured rolls can produce correspondingly structured flakes in which, for example, certain shapes of the later detergent or cleaning agent particles can be predetermined.
  • the sling strip is subsequently broken by a tee and crushing process into smaller pieces and can be processed in this way to granules which can be refined by further known per se surface treatment method, in particular brought into approximately spherical shape.
  • the temperature of the pressing tools ie the rollers, preferably at a maximum of 150 0 C, preferably at a maximum of 100 0 C and preferably at most 75 ° C.
  • Particularly preferred production processes work in the roll compacting process at temperatures which are 10 0 C, in particular at most 5 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the action of temperature in the compression region of the smooth rolls or rolls provided with depressions of defined shape amounts to a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • the method according to the invention is carried out by means of pelleting.
  • the premix is applied to a perforated surface and pressed by means of a pressure-emitting body under plasticization through the holes.
  • the premix is compacted under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted with a knock-off device to granules.
  • flat perforated plates are used as well as concave or convex ring matrices, through which the material is pressed through one or more pressure rollers.
  • the press rollers can also be used with the plate devices may be conically shaped, in the annular devices matrices and press roll (s) have co-rotating or opposite sense of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German Offenlegungsschrift DE 38 16 842.
  • the ring die press disclosed in this document consists of a rotating ring die interspersed by press channels and at least one press roll operatively connected to its inner surface, which presses the material supplied to the die space through the press channels into a material discharge.
  • ring die and pressing roller are drivable in the same direction, whereby a reduced shear stress and thus lower temperature increase of the premix can be realized.
  • the temperature of the pressing tools, so the pressure rollers or press rolls preferably at a maximum of 150 0 C, preferably at a maximum of 100 ° C and in particular at a maximum of 75 ° C.
  • Particularly preferred production processes work in the roll compacting process at temperatures which are 10 0 C, in particular at most 5 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • Preßagglomerations Kunststoffe which can be used according to the invention, is the tableting.
  • detergent tablets are produced.
  • the detergents or cleaners are present in the form of shaped bodies, which are preferably tablets which may consist of a single phase or of several, in particular two or three, different phases.
  • excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
  • the detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the weight of the tablet.
  • Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 Hi 0 Os) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. Washing and
  • Detergent tablets containing disintegrators in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 and DE 197 10 254 and in international patent application WO98 / 40463. Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • the above and described in more detail in the documents cited coarser disintegration aids are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • microcrystalline cellulose can be used as a further disintegrating agent based on cellulose or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact.
  • Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
  • preferred laundry detergent and cleaning product tablets additionally comprise a disintegration assistant, preferably a disintegration assistant based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molding weight.
  • a disintegration assistant preferably a disintegration assistant based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molding weight.
  • the production of the shaped bodies according to the invention takes place firstly by the dry mixing of the constituents, which may be completely or partially pre-granulated, and subsequent informing, in particular pressing into tablets, wherein conventional methods can be used.
  • the premix is compressed in a so-called matrix between two punches to form a solid compressed. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic Deformation With increasing press speed, so high throughputs, the phase of the elastic Deformation further shortened so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • Tableting machines which are suitable for the purposes of the present invention are obtainable, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent.
  • compacts which connect a plurality of such mass units in a compact, wherein in particular by predetermined predetermined breaking points the easy separability portioned smaller units is provided.
  • the formation of the portioned compacts can be useful as tablets, in cylindrical or parallelepiped form, wherein a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process.
  • a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.
  • Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered.
  • This principle of the "wave-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one of their sides.
  • the various components are not pressed into a single tablet, but that moldings are obtained which have multiple phases or layers, ie at least two phases or layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution. Preference is also given to detergent tablets in which at least two phases contain the same active ingredient in different amounts.
  • different amounts does not refer to the absolute amount of the ingredient in the phase, but to the relative amount, based on the phase weight, so represents a weight percentage, based on the individual phases.
  • the silicon compounds according to the invention, and preferably also the entire perfume mixture are in other phases of the shaped bodies than bleaching agents contained in these shaped bodies.
  • alkali carriers such as alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal quicarbonates, alkali metal silicates, alkali metal methacrylates and mixtures of these substances, are present in other phases of the shaped bodies, at least for the most part, but preferably completely, than the silicon compounds according to the invention, or especially prefers the entire perfume mixture.
  • the layer structure of the moldings can be carried out both in a staggered manner, wherein a dissolution process of the inner layer (s) takes place at the edges of the molded body already when the outer layers are not completely dissolved, but it can also be a complete coating of the inner layer (s ) are reached through the respective outer layer (s), which leads to a prevention of premature dissolution of constituents of the inner layer (s).
  • a shaped body consists of at least three layers, ie two outer and at least one inner layer, wherein at least in one of the inner layers, a peroxy-bleach is contained, while the stapeiförmigen shaped body, the two outer layers and the envelope-shaped body
  • outermost layers are free of peroxy bleach.
  • peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other.
  • Such multilayer moldings have the Advantage that they can be used not only via a dispenser or via a metering device, which is added to the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine without stains caused by bleach and the like to be feared.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • the breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.
  • the cosmetic agents according to the invention are aqueous preparations which contain surface-active agents and which are suitable in particular for the treatment of keratin fibers, in particular human hair, or for the treatment of skin.
  • the mentioned hair treatment compositions are in particular means for the treatment of human hair.
  • the most common agents of this category can be classified into shampoos, hair care products, hair hardening and hair styling agents as well as hair dyes and depilatories.
  • Hair-washing and care products include, in particular, hair-care compositions which are preferred according to the invention and contain surfactants.
  • Such a shampoo or hair shampoo consists of 10 to 20, in some cases up to 30 recipe ingredients. These aqueous preparations are usually present in liquid to pasty form.
  • Fatty alcohol polyglycol ether sulfates are predominantly used for the most important ingredient group, the surface-active agents or washing active substances, in some cases in combination with other mostly anionic surfactants.
  • Shampoo surfactants should have except good cleansing power and resistance to water hardness skin and mucous membrane compatibility. According to the legal regulations, good biodegradability must be given.
  • preferred agents may additionally comprise further surfactants, such as alkyl sulfates, alkyl ether carboxylates, preferably having degrees of ethoxylation of from 4 to 10, and surface-active protein-fatty acid condensates.
  • Sulfosuccinic acid esters, amidopropylbetaines, amphoacetates and amphodiacetates, as well as alkyl polyglycosides are also preferred surfactants in hair shampoos.
  • Another group of ingredients is summarized under the term excipients and is very diverse: z.
  • additives of nonionic surfactants such as ethoxylated sorbitan esters or of protein hydrolysates increase the compatibility or have an irritant-reducing effect, eg. In baby shampoos; serve as a refatting to prevent excessive degreasing in the hair wash z.
  • Natural oils or synthetic fatty acid esters are glycerol, sorbitol, propylene glycol (see Propandiole), polyethylene glycols and other polyols.
  • cationic surfactants such as Propandiole
  • B. quaternary ammonium compounds are added.
  • dyes or pearlescent pigments are added.
  • a pH stability is achieved by buffer z.
  • preservatives such.
  • 4-hydroxybenzoic acid ester is added; oxidation-sensitive ingredients can by Addition of antioxidants such as ascorbic acid, butylmethoxyphenol or tocopherol are protected.
  • a third group of ingredients form special ingredients for special shampoos, eg. As oils, herbal extracts, proteins, vitamins and lecithins in shampoos for fast-greasy, especially dry, damaged or damaged hair.
  • Active ingredients in shampoos for controlling dandruff usually have a broad growth-inhibiting effect against fungi and bacteria. In particular, the fungistatic properties z. As of pyrithione salts could be detected as the cause of good anti-dandruff effect.
  • the hair shampoos contain perfume oils.
  • the shampoos may contain only the silicon compounds of the invention, but it is also preferred if the hair shampoos contain not only these, but also other fragrances. In this case, all the usual, and approved in hair shampoos fragrances can be used.
  • the aim of hair care products is to maintain the natural state of the newly regrown hair as long as possible and to restore it when damaged. Characteristics that characterize this natural state are silky shine, low porosity, elastic yet soft body and pleasantly smooth feeling. An important prerequisite for this is a clean, dandruff-free and not over-greasy scalp.
  • pre-treatment means hair lotions, Frisieryskar, hair rinses and Kurpackungen, and whose composition as with the shampooing agents roughly into basic materials, auxiliary materials and special active substances is divided.
  • the basic substances used are fatty alcohols, v. a. Cetyl alcohol (1-hexadecanol) and stearyl alcohol (1-octadecanol), waxes such as beeswax, wool wax (lanolin), spermaceti and synthetic waxes, paraffins, petrolatum, paraffin oil and as Lsm. v. a. Ethanol, 2-propanol and water. Excipients are emulsifiers, thickeners, preservatives, antioxidants, dyes and perfume oils. The most important group of special active ingredients in hair care products today are the quaternary ammonium compounds.
  • quaternary cellulose ether derivatives or poly (N, N-dimethyl-3,4-methylenepyrrolidinium chloride) quaternary cellulose ether derivatives or poly (N, N-dimethyl-3,4-methylenepyrrolidinium chloride).
  • Their effect in hair care products is based on the fact that the positive charge of the nitrogen atoms of this compound can attach to the negative charges of hair keratin; Damaged hair contains more negatively charged acid groups due to its higher cysteic acid content and therefore can absorb more quaternary ammonium compounds.
  • cationic care substances because of their cationic character also referred to as "cationic care substances", have a smoothing effect on the hair, improve combability, reduce the electrostatic charge, improve grip and shine.
  • the polymeric quaternary ammonium compounds adhere so well to the hair that their effect can be detected even after several washes.
  • Organic acids such as citric acid, tartaric acid or lactic acid are often used to set an acidic environment.
  • the water-soluble protein hydrolysates attract well on the hair keratin because of their close chemical relationship.
  • the largest group of special active ingredients in hair care products form various plant extracts and vegetable oils, which have been used for a long time, without their effectiveness being scientifically proven in all cases to the stated effect. Likewise, the effectiveness of vitamins used in hair care products is only proven in isolated cases.
  • hair lotions contain substances such as certain tar ingredients, cysteic acid derivatives or glycyrrhizin; the intended reduction in sebaceous gland production is also not yet clearly established.
  • the effectiveness of anti-dandruff agents is well documented. They are therefore in appropriate hair lotions u. a. Care agents used.
  • aqueous preparations for the treatment of skin are, in particular, preparations for the care of human skin.
  • This care begins with the cleansing for which soaps are primarily used.
  • soaps are primarily used.
  • the cosmetic agents are in the form of shaped bodies containing surface-active ingredients.
  • the most important ingredients of such shaped bodies are in a preferred embodiment, the alkali metal salts of the fatty acids of natural oils and fats, preferably with chains of 12-18 carbon atoms. Since lauric acid soaps foam particularly well, the lauric acid-rich coconut and palm kernel oils are preferred raw materials for the Toilet soap production.
  • the Na salts of the fatty acid mixtures are solid, the K salts soft-pasty.
  • the dilute sodium or potassium hydroxide solution is added to the fatty raw materials in a stoichiometric ratio so that in the finished soap, a lye excess of max. 0.05% is present.
  • the soaps are no longer produced directly from the fats, but from the fatty acids obtained by lipolysis.
  • Typical soap additives are fatty acids, fatty alcohols, lanolin, lecithin, vegetable oils, partial glycerides and other fatty substances to restore the cleansed skin, antioxidants such as ascorbyl palmitate or tocopherol to prevent the autoxidation of the soap (rancidity), complexing agents such as nitrilotriacetate for binding heavy metal - Traces that could catalyze the autoxidative spoilage, perfume oils to achieve the desired fragrance notes, dyes for coloring the soap bars and possibly special additives.
  • Cream soaps with especially high levels of moisturizing and creaming the skin are especially high levels of moisturizing and creaming the skin
  • Soaps can also be provided with abrasive additives to clean heavily soiled hands.
  • the pH of the wash liquor is 8-10. This alkalinity neutralises the natural acid mantle of the skin (pH 5-6). Although this is regressed relatively quickly in normal skin, it can cause irritation in sensitive or damaged skin.
  • Another disadvantage of the soaps is the formation of insoluble lime soaps in hard water. These disadvantages are not present in syndet soaps. They are based on synthetic anionic surfactants, which can be processed with builders, refills and other additives to soap-like pieces. Their pH can be varied within wide limits and is usually adjusted to neutral pH 7 or the acid mantle of the skin adjusted to pH 5.5. They have excellent cleaning power, foam in any water hardness, even in seawater, the proportion of lubricating additives must be significantly higher than normal soaps because of their intensive cleaning and degreasing effect. Their disadvantage is the relatively high price.
  • Liquid soaps are based on both K-salts of natural fatty acids and on synthetic anionic surfactants. They contain in aqueous. Solution, less detergent substances than solid soaps, have the usual additives, possibly with viscosity-regulating ingredients and pearlescent additives. Because of their convenient and hygienic application from dispensers, they are preferably used in public washrooms and the like.
  • Detergent lotions for particularly sensitive skin are based on mild-acting synthetic surfactants with additives of skin-care substances, pH-neutral or slightly acidic (pH 5.5).
  • Face packs serve z. T. the cleaning, but mainly the refreshment and care of the facial skin.
  • Facial waters are mostly aqueous-alcoholic solutions with low surfactant levels and other skin-care substances.
  • Cleansing lotions, milks, creams and pastes are usually based on O / W emulsions with relatively low levels of fat components with cleansing and nourishing additives.
  • So-called Scruffing and exfoliating preparations contain mild keratolytic substances for the removal of the upper dead skin-horn layers, z. T. with Adding abrasive powder.
  • Almond bran which has long been used as a mild skin cleanser, is still a component of such preparations today.
  • Anti-bacterial and anti-inflammatory agents are also included in cleansing skin cleansing products as the sebum collections in comedones are a breeding ground for bacterial infections and prone to inflammation.
  • the offered wide range of different skin cleansing products varies in composition and content of various active ingredients, tailored to the different skin types u. on special treatment goals.
  • Bath salts and bath tablets are intended to soften, dye and perfume the bath water and generally do not contain any washing-active substances. By softening the bath water, they promote the cleansing power of soaps, but are primarily intended to have a refreshing effect and enhance the bathing experience. Of greater importance are the bubble baths. With a higher content of moisturizing and skin-caring substances one speaks also of cream baths.
  • the following skincare has two main goals: Firstly, it should lead the skin uncontrollably withdrawn during washing ingredients such as horny cells, skin fat lipids, acidifier and water in the natural state of equilibrium, on the other u. v. a. It should counteract as far as possible the natural aging process of the skin and the possible damage caused by weather and environmental influences.
  • Skin care and skin protection products are available in large numbers and in many forms of preparation. The most important are skin creams, lotions, oils and gels. The creams and lotions are based on emulsions in GTW (oil in water) or W / O (water in oil) form.
  • the main components of the oil or fat or lipid phase are fatty alcohols, fatty acids, fatty acid esters, waxes, petrolatum, paraffins and other fatty and oil components mainly of natural origin.
  • fatty alcohols fatty acids, fatty acid esters, waxes, petrolatum, paraffins and other fatty and oil components mainly of natural origin.
  • aqueous phase besides water, mainly moisture-regulating and moisture-retaining substances are contained as essential skin-care active substances, furthermore consistency- or viscosity-regulating agents.
  • Other additives such as preservatives, antioxidants, complexing agents, perfume oils, colorants and special agents are added depending on their solubility and their stability properties of one of the two aforementioned phases.
  • Essential for the emulsion type and its properties is the selection of the emulsifier system. Its selection can be made according to the HLB system.
  • the creams or lotions can be divided into “day creams” and "night creams".
  • Day creams are usually designed as O / W emulsions, they quickly penetrate the skin, without leaving a greasy finish; one calls it therefore z. T. also as dry creams, matte creams or Vanishing Creams.
  • Night creams are mostly W / O emulsions, they are absorbed by the skin more slowly and often contain special ingredients that are supposed to cause a regeneration of the skin during the night.
  • Some of these preparations are also referred to as "nutritional creams", although a "nutrition” of the cell metabolism in the skin can only be done through the bloodstream; The term “nutritional cream” is therefore controversial.
  • CoId Creams are mixed emulsions of the O / W and W / O type, with the oil phase predominating in terms of quantity.
  • the classic CoId Cream the z. T. only unstable emulsified water released and produced by evaporation a cooling effect, which gave this preparation form its name.
  • Skin gels are semi-solid transparent products that are stabilized by appropriate gelling agents.
  • a distinction is made between oleogels (anhydrous), hydrogels (oil-free) and oil / water gels.
  • the type selection depends on the desired application purpose.
  • the oil / water gels contain high levels of emulsifier and have certain advantages over emulsions in both aesthetic and application. -Gesichtsddlingen.
  • Foot baths are said to have a good cleansing, refreshing, circulation-promoting and invigorating effect as well as deodorising and softening the cornea.
  • Foot bath additives are available as bath salts and bubble baths. They exist z. B. from basic mixtures of Na carbonate, Na bicarbonate and Na-perborate or Na-hexametaphosphate (see condensed phosphates), Na sulfate, Na-perborate and 1% Na lauryl sulfate as a foam component with antihidrotic, deodorizing, possibly bactericidal and / or fungicidal additives and fragrances and dyes.
  • Foot powders should be used after foot washing and / or sprinkled in stockings and shoes, skin smoothing, cooling, moisturizing, antiperspirant, antiseptic, deodorant and possibly behave kerhauterend. They usually consist of 85% talc (see Talk) with additions of silica powder, aluminum hydroxychloride, salicylic acid and possibly bactericides, fungicides, deodorants and fragrances. Foot creams or foot balms are used for skin care and for massage of the foot and lower leg muscles. Foot creams are usually O / W emulsions from z. 30% isopropyl myristate, 10% polysorbate, 4.2% aluminum metahydroxide and 55.8% water as the base formulation; Foot balms are mostly anhydrous and.
  • a frame formulation consists of 25% paraffin, 2% stearic acid, 2% beeswax, 2% spermaceti, 2% glycerol monostearate, 0.5% 2,2 1 , 2 "nitrilotriethanol, 1% perfume oil, 0.2% 4-hydroxybenzoic acid and 65.3% water, nail fold tinctures are used to soften keratinization in the nail folds and to soften the nail margins of ingrowing toenails, mainly on the big toes,
  • a frame formulation is 10% 2,2 ', 2 "nitrilotriethanol, 15% urea , 0.5% fatty alcohol polyglycol ether and 74.5% water
  • deodorants are meant here. Such deodorants can cover, remove or destroy odors. Unpleasant body odors are caused by bacterial decomposition of sweat, especially in the moist, warm armpits, where microorganisms find good living conditions. Accordingly, the most important ingredients of deodorants are germ-inhibiting substances. In particular, those germ-inhibiting substances are preferred which have a substantial selective activity against the bacteria responsible for the body odor. However, preferred active ingredients have only a bacteriostatic effect and kill the bacterial flora under any circumstances. In general, all suitable preservatives with specific action against Gram-positive bacteria can be directed to the antimicrobial agent. For example, these are Irgasan DP 300 (trichloro, 2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine
  • fragrances with antimicrobial properties are preferably used in deodorants, in particular farnesol and phenoxyethanol It is particularly preferred for the deodorants according to the invention to contain such self-bacteriostatically effective fragrances, whereby the fragrances may preferably be present again in the form of silicon compounds according to the invention.
  • the fragrances may preferably be present again in the form of silicon compounds according to the invention.
  • Another group of key ingredients of deodorants are enzyme inhibitors that inhibit the degradation of sweat by enzymes, such as triethyl citrate or zinc glycinate.
  • Essential ingredients of deodorants are enzyme inhibitors that inhibit the degradation of sweat by enzymes, such as triethyl citrate or zinc glycinate.
  • the cosmetic agent is a hair setting agent which contains polymers for strengthening. It is particularly preferred if among the polymers at least one polyurethane is included.
  • the agents according to the invention may contain water-soluble polymers from the group of nonionic, anionic, amphoteric and zwitterionic polymers.
  • Water-soluble polymers are to be understood as meaning those polymers which are soluble in water at room temperature in excess of 2.5% by weight.
  • Water-soluble polymers preferred according to the invention are nonionic. Suitable nonionic polymers are, for example:
  • Polyvinylpyrrolidones such as those sold for example under the name Luviskol R (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the invention.
  • Vinylpyrrolidone / vinyl ester copolymers such as, for example, under the trademark
  • LuviskoP (BASF). Luviskol ⁇ VA 64 and Luviskol 1 ⁇ VA 73, in each case vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
  • Cellulose ethers such as hydroxypropylcellulose, hydroxyethylcellulose and M meetthhyyllhhyyddrrooxxyypprrooppyyllcceelllluulloossee, are sold, for example, under the trademarks Culminal® and Benecel R (AQUALON).
  • Suitable amphoteric polymers are, for example, those under the names Amphomer R and
  • Amphomer R LV-71 (DELFT NATIONAL) available Octylacrylamide / methyl methacrylate / tert. Butylaminoethyl ⁇ -Hydroxypropylmethacrylat copolymers.
  • Suitable zwitterionic polymers are, for example, the polymers disclosed in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451.
  • Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers.
  • Further suitable zwitterionic polymers are Methacroylethylbetain / methacrylate copolymers, which under the
  • suitable anionic polymers include:
  • Vinyl acetate / crotonic acid copolymers such as, for example, under the names Resyn R (NATIONAL STARCH) 1 Luviset R (BASF) and Gafset R (GAF) in the trade.
  • Vinyl pyrrolidone / vinyl acrylate copolymers available, for example, under the trademark
  • Luviflex R (BASF).
  • a preferred polymer is the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex R VBM-35 (BASF).
  • BASF Ultrahold strong R
  • the hair treatment compositions according to the invention contain water-soluble polymers, depending on the type of hair treatment agent, which is not restricted, preferably in amounts of 0.01 to 20 wt .-%, in particular 0.1 to 10 wt .-%, based on the total agent.
  • the polyurethanes and the water-soluble polymers are preferably present in a ratio of 1:10 to 10: 1 in the inventive compositions.
  • a ratio of 2: 1 to 1: 1 has proven to be particularly suitable in many cases.
  • the hair-setting compositions according to the invention are in particular hair-setting agents, hair sprays and hair-drying waves. Hairsprays are a particularly preferred embodiment of the hair setting agents of the invention.
  • agents according to the invention can furthermore, in a likewise preferred embodiment, also be formulated as foam aerosol with the aid of a propellant.
  • agents according to the invention can be, for example: anionic surfactants such as fatty alkyl sulfates and ether sulfates, cationic surfactants such as quaternary ammonium compounds, zwitterionic surfactants such as betaines, ampholytic surfactants, nonionic surfactants such as alkylpolyglycosides and ethoxylated fatty alcohols, structurants such as glucose and maleic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and silicone oils,
  • anionic surfactants such as fatty alkyl sulfates and ether sulfates
  • cationic surfactants such as quaternary ammonium compounds
  • zwitterionic surfactants such as betaines
  • ampholytic surfactants such as alkylpolyglycosides and ethoxylated fatty alcohols
  • structurants such as glucose and male
  • Protein hydrolysates in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
  • Perfume oils containing the silicon compounds according to the invention solubilizers, such as ethylene glycol, propylene glycol, glycerol and diethylene glycol, dyes,
  • Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine, other pH adjusters,
  • Active substances such as panthenol, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins, light stabilizers,
  • Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes, such as spermaceti, beeswax, montan wax, paraffins and fatty alcohols, fatty acid alkanolamides,
  • Swelling and penetration materials such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air and
  • the hair setting agents according to the invention preferably also contain polymers from the class of polyurethanes.
  • the polyurethanes consist of at least two different monomer types, a compound (A) having at least 2 active hydrogen atoms per molecule and a di- or polyisocyanate (B).
  • the compounds (A) may be, for example, diols, triols, diamines, triamines, polyetherols and polyesterols.
  • the compounds having more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds having 2 active hydrogen atoms.
  • Examples of compounds (A) are ethylene glycol, 1, 2 and 1, 3-propylene glycol, butylene glycols, di-, tri-, tetra- and poly-ethylene and -Propylenglykole, copolymers of lower alkylene oxides such as Ethylene oxide, propylene oxide and butylene oxide, ethylenediamine, propylenediamine, 1, 4-diaminobutane, hexamethylenediamine and ⁇ , ⁇ ü-diamines based on long-chain alkanes or polyalkylene oxides.
  • lower alkylene oxides such as Ethylene oxide, propylene oxide and butylene oxide
  • ethylenediamine, propylenediamine 1, 4-diaminobutane
  • hexamethylenediamine and ⁇ , ⁇ ü-diamines based on long-chain alkanes or polyalkylene oxides.
  • Polyurethanes in which the compounds (A) are diols, triols and polyetherols may be preferred according to the invention.
  • polyethylene glycols and polypropylene glycols having molecular weights between 200 and 3000, in particular between 1600 and 2500, have proven to be particularly suitable in individual cases.
  • Polyesterols are usually obtained by modifying the compound (A) with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid.
  • compounds (B) predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate are used.
  • polyurethanes used in the invention may contain other building blocks such as diamines as chain extenders and hydroxycarboxylic acids.
  • Dialkylolcarboxylic acids such as dimethylolpropionic acid are particularly suitable hydroxycarboxylic acids.
  • further building blocks there is no fundamental restriction as to whether they are nonionic, anionic or cationic building blocks.
  • Polyurethanes which can be characterized as follows have proven particularly suitable according to the invention in many cases.
  • compositions according to the invention when the polyurethanes were not mixed directly with the other components, but introduced in the form of aqueous dispersions.
  • aqueous dispersions usually have a solids content of about 20-50%, in particular about 35-45% and are also commercially available.
  • the hair setting agents according to the invention preferably contain the polyurethane in amounts of from 0.1 to 15% by weight, in particular from 0.5 to 10% by weight, based on the total composition.
  • KSE stands for silicic acid ester
  • APSV aminopropyl silicon compound.
  • the aminopropyl-silicon compound is a silicon compound in which an aminopropyl group is bonded to the silicon via a Si-C bond and which further comprises said perfume allyl moieties.
  • a laundry detergent / detergent A laundry detergent / detergent:
  • Isoraldein 70 10 10 10 10 10 10
  • Dehyquart ® AU46 Dipalmitoleyloxyethyl-hydroxyethyl-methylammonium-methoxy-sulfate, 90% strength in isopropanol, a product of Henkel KGaA, Dusseldorf
  • B Cleaning agent B1 Acid cleaner
  • Perfume oils were prepared with compositions according to Table 5.
  • 5A is an inventive perfume oil
  • FIG. 5B is a comparative example.
  • perfume oils were incorporated into an acidic detergent having a formulation according to Table 6.
  • Table 9 shows the perfume oil compositions used in the shower bath with a formulation according to Table 10.
  • Table 9 Perfume oils with a fresh, floral scent
  • a bar of soap was made with a composition according to Table 12. It contained the fragrance composition 11A or 11B in the example according to the invention.
  • Perfume oil compositions for a deodorant spray are given in Table 13, the formulation of the deodorant in Table 14.
  • APG 600 Plantacare 1200 UP (Henkel KGaA) Active ingredient: 50-53% by weight of alkyl-Ci 2 -C 6 -oligo (1,4) -glucoside
  • APG 220 Plantacare 220 UP (Henkel KGaA) Active substance: 62-65 % By weight of alkyl C 8 -C 10 -oligo (1, 5) -glucoside
  • Cetiol OE dioctyl ether (Henkel KGaA) Eutanol G: 2-octyl-dodecanol (Henkel KGaA)
  • Compositions 15A and 15B represent a perfume oil for a hair spray of the present invention. These fragrance compositions were incorporated into a hairspray according to the recipe given in Table 16.
  • Alberdingk U 500 anionic polyether polyurethane dispersion (40% in water) (Fa.
  • Luviskol VA64 vinyl acetate-vinylpyrrolidone copolymer (BASF)
  • Table 17 Composition of softener concentrate [wt%]:
  • Dehyquart ® AU46 Dipalmitoleyloxyethyl-hydroxyethyl-methylammonium-methoxy-sulfate, 90% strength in isopropanol, a product of Henkel KGaA, Dusseldorf
  • Each fragrance expert judged the intensity of the fragrance impression of the laundry according to the following scale:
  • a commercial perfume-free detergent was added with about 0.4% each citronellol, monomeric citronellyl-KSE, polymeric citronellyl-KSE and citronellylsilylaminopropane (APSV-Citronellylester), taking care that the amount of perfume units contained is equal in each case.
  • the laundry was washed at 60 ° and rinsed 3 times with clear water. After spinning, the smell of wet laundry was judged, then the laundry dried on a leash. The smell of the dry laundry was evaluated immediately and after 7 days, with the laundry stored in plastic bags.
  • polymeric menthyl KSE and menthylsilylaminopropane were incorporated into a fabric softening concentrate with 15% esterquat, whose composition is given in Table 20, taking care that the amount of perfume units contained in each case the same is.
  • Washed with perfume-free universal detergent laundry was treated with 40g of each fabric softener in the last rinse. After spinning, the smell of the wet laundry was judged, then hung the laundry to dry on a leash. The smell of the dry laundry was judged after removal from the leash and every 7 days, with the laundry stored in plastic bags.
  • Table 20 Composition of softener concentrate [wt%]:
  • Dehyquart ® AU46 Dipalmitoleyloxyethyl-hydroxyethyl-methylammonium-methoxy-sulfate, 90% strength in isopropanol, a product of Henkel KGaA, Dusseldorf
  • Each fragrance expert judged the intensity of the fragrance impression of the laundry according to the following scale:

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Abstract

La présente invention concerne des composés de silicium monomères et oligomères, dans lesquels au moins un résidu de substance odorante ou un résidu alcoxy biocide et au moins un résidu aminoalkyle ou aminoalcoxy le cas échéant modifié chimiquement sont liés au silicium, ainsi que l'utilisation de ces composés pour parfumer ou conserver des produits de lavage et de nettoyage ou des produits cosmétiques.
EP07703577A 2006-03-08 2007-03-02 Substrats à base de silicium pour des principes actifs contenant des groupes aminoalkyle Withdrawn EP1991553A1 (fr)

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DE102006011087A DE102006011087A1 (de) 2006-03-08 2006-03-08 Aminoalkyl-Gruppen enthaltende Wirkstoffträger auf Silizium-Basis
PCT/EP2007/001788 WO2007101612A1 (fr) 2006-03-08 2007-03-02 Substrats à base de silicium pour des principes actifs contenant des groupes aminoalkyle

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JP4878035B2 (ja) * 2008-02-19 2012-02-15 花王株式会社 機能性物質放出剤
JP5133092B2 (ja) * 2008-03-06 2013-01-30 花王株式会社 機能性物質放出剤
JP5364305B2 (ja) * 2008-06-23 2013-12-11 花王株式会社 香り持続性マイクロカプセル
DE102009003088A1 (de) * 2009-05-13 2010-11-18 Henkel Ag & Co. Kgaa Kugelförmige WC-Steine, Verfahren zu ihrer Herstellung und WC-Reinigungskörpchen mit kugelförmigen WC-Steinen
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