EP1981936A1 - Accumulateur de fluides - Google Patents

Accumulateur de fluides

Info

Publication number
EP1981936A1
EP1981936A1 EP06829646A EP06829646A EP1981936A1 EP 1981936 A1 EP1981936 A1 EP 1981936A1 EP 06829646 A EP06829646 A EP 06829646A EP 06829646 A EP06829646 A EP 06829646A EP 1981936 A1 EP1981936 A1 EP 1981936A1
Authority
EP
European Patent Office
Prior art keywords
acid
mixture
fluid
fluid reservoir
agents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06829646A
Other languages
German (de)
English (en)
Other versions
EP1981936B1 (fr
Inventor
Gonzalez Rene-Andres Artiga
Hubert Harth
Mario Sturm
Andreas Bauer
Frank Korber
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
Priority to PL06829646T priority Critical patent/PL1981936T3/pl
Publication of EP1981936A1 publication Critical patent/EP1981936A1/fr
Application granted granted Critical
Publication of EP1981936B1 publication Critical patent/EP1981936B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • 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
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y10T428/249958—Void-containing component is synthetic resin or natural rubbers

Definitions

  • the invention relates to a fluid reservoir based on a polymer substrate, its uses and a method for producing such fluid reservoir.
  • particulate carriers that are capable of receiving and, depending on the application, storing and returning fluids as needed.
  • a particulate fluid reservoir which is constructed from a porous, particulate polymer substrate which is loaded with 5 wt .-% to 95 wt .-%, based on the total weight of the loaded polymer substrate, a guest mixture is, wherein this guest mixture a) is highly viscous or solid as such at temperatures ⁇ 20 ° C, b) contains fluids and at least one flowable at elevated temperatures additive having a melting or pouring point in the range of 25 ° C to 120 0 C. , c) already at temperatures below 120 ° C substantially undecomposed into a molten state.
  • the particulate fluid reservoir is thus meant a porous polymer substrate in which large quantities of liquid, e.g. Perfume, safe and permanently immobilized.
  • the release of the liquid may e.g. be achieved by increasing the temperature and / or mechanical stress. So it is possible to create a kind of liquid depot, which can be opened if necessary.
  • the fluid reservoir can be advantageously incorporated easily into various matrices, even into liquid matrices, without there being any significant disadvantageous interaction with the matrix.
  • the term "essentially undecomposed” takes into account the fact that some materials or compounds or substances can decompose upon the supply of thermal energy, ie that the material in question is so altered in its structure by the influence of temperature, that it is thereby converted into a no longer suitable for its original purpose condition.
  • the guest mixtures are preferably characterized by the fact that they go substantially undecomposed in a molten state. This means that they do not undergo major degradation reactions at the specific temperature load necessary to bring them to the molten state, so that a guest mixture according to the invention, even after its conversion to a flowable state and the subsequent return to the solid state preferably remains largely unchanged.
  • a guest mixture according to the invention even after its conversion to a flowable state and the subsequent return to the solid state preferably remains largely unchanged.
  • there is an object which undergoes decomposition upon being transferred to the molten state so that the object, after being returned to the solid state, is clearly different from its initial state, e.g. in terms of its appearance, its feel, its smell or other aspects.
  • a guest mixture shall preferably be as high viscosity, when the Brookfield viscosity at 20 0 C exceeds a value of 2500 mPas, preferably from 5000 mPas, in particular from 7 500 mPas, with preference 10000 mPas and especially preferably from 25000 mPas. (Viscosity Measurement in a Brookfield Viscometer Model DV II at 20 rpm with Spindle 3)
  • a liquid fragrances perfume oils
  • liquid detergents and cleaning agent ingredients such as preferably surfactants, in particular nonionic surfactants, silicone oils, paraffins and / or c
  • liquid cosmetic ingredients such as preferably oils and / or d) liquid non-pharmaceutical additives or active ingredients and / or e) mixtures of the aforementioned.
  • fragrances and nonionic surfactants especially in admixture.
  • fragrance (s) and “perfume oil (s)” are used synonymously. This means, in particular, all those substances or mixtures thereof that are perceived by humans and animals as odor, in particular perceived by humans as a fragrance.
  • fragrance compounds for example, the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons used become.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate,
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8 -18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellel, 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 and balsams.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • the perfume oils may, of course, also contain natural fragrance mixtures, such as are available from plant or animal sources, e.g. Pine, citrus, jasmine, lily, rose or ylang-ylang oil.
  • Lower volatility volatile oils most commonly used as aroma components, are useful as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, galbanum oil and ladanum oil.
  • fragrances can be used which are selected from fragrances with
  • almond-like odor such as preferably benzaldehyde, pentanal, heptenal, 5-methylfurfural, methylbutanal, furfural and / or acetophenone or
  • apple-like odor preferably (S) - (+) - ethyl-2-methylbutanoate, diethyl malonate, ethyl butyrate, geranyl butyrate, geranyl isopentanoate, isobutyl acetate, linalyl isopentanoate, (E) - ⁇ -damascone, heptyl-2-methyl butyrate, methyl 3-methylbutanoate, 2-hexenal-pentyl-methyl butyrate, ethyl methyl butyrate and / or methyl 2-methyl butanoate or
  • apple peel-like odor such as preferably ethyl hexanoate, hexyl butanoate and / or hexyl hexanoate or
  • apricot-like odor preferably ⁇ -undecalactone, or
  • banana-like odor such as preferably isobutyl acetate, isoamyl acetate, hexenyl acetate and / or pentyl butanoate or
  • bitter almond-like odor such as preferably 4-acetyltoluene or
  • blackcurrant-like odor such as preferably mercaptomethylpentanone and / or methoxymethylbutanethiol or
  • citrusy odor preferably linalyl pentanoate, heptanal, linalyl isopentanoate dodecanal, linalyl formate, ⁇ -p-dimethylstyrene, p-cymenol, nonanal, ⁇ -cubebene, (Z) -lemonone, cis-6-ethenyl-tetrahydro-2,2,6- trimethylpyran-3-ol, cis-pyranoidlinalooloxide, dihydrolinalool, 6 (10) -dihydromyrcenol, dihydromyrcenol, ⁇ -farnesene, (Z) - ⁇ -Farnesen, (Z) - Ocimen, (E) -Limonenoxid, Dihydroterpinylacetat, (+) - limonene, (Epoxymethylbutyl) - methylfuran and / or p-cymene
  • cocoa like odor preferably dimethylpyrazine, butylmethyl butyrate and / or methylbutanal or
  • coconut-like odor such as preferably ⁇ -octalactone, ⁇ -nonalactone, methyl laurate, tetradecanol, methyl nonanoate, (3S, 3aS, 7aR) -3a, 4,5,7a-tetrahydro-3,6-dimethylbenzofuran-2 (3H) -on, 5-butyldihydro-4-methyl-2 (3H) -furanone, ethyl undecanoate and / or ⁇ -decalactone or
  • (k) creamy odor such as preferably diethyl acetal, 3-hydroxy-2-butanone, 2,3-pentadione and / or 4-heptenal, or
  • (I) flower-like odor such as preferably benzyl alcohol, phenylacetic acid, tridecanal, p-anisyl alcohol, hexanol, (E, E) -farnesylacetone, methyl geranate, trans-crotonaldehyde, tetradecylaldehyde, methyl anthranilate, linalooloxide, epoxylinalool, phytol, 10-epi- ⁇ -eudesmol , Nerol oxide, ethyldihydrocinnamate, ⁇ -dodecalactone, hexadecanol, 4-mercapto-4-methyl-2-pentanol, (Z) -oximes, cetyl alcohol, nerolidol, ethyl (E) -cinnamate, elemicin, pinocarveol, ⁇ -bisabolol, ( 2R, 4R) -Tetrahydro-4-methyl-2-
  • freshness odor preferably methylhexanoate, undecanone
  • Z -imimonial oxide, benzyl acetate, ethylhydroxyhexanoate, isopropylhexanoate, pentadecanal, ⁇ -elemene, ⁇ -zingiberene
  • E -lownone oxide
  • E -p-mentha- 2,8-dien-1-ol
  • menthone piperitone
  • E -3-hexenol and / or carveol or
  • Fruit odor such as ethylphenylacetate, geranylvalerate, ⁇ -heptalactone, ethylpropionate, diethylacetal, geranylbutyrate, ethylheptylate, ethyloctanoate, methylhexanoate, dimethylheptenal, pentanone, ethyl-3-methylbutanoate, geranylisovalerate, lobutylacetate, ethoxypropanol, methyl-2-butenal, Methylnonanedione, linalyl acetate, methyl geranate, ammonium oxide, hdrocinnamic alcohol, ethylsuccinate, ethylhexanoate, ethylmethylpyrazine, ethyl acetate, cetronellyl butyrate, heyl acetate, nonyl acetate, butylmethyl buty
  • Geranium-like odor such as preferably geraniol, (E, Z) -2,4-nonadienal, octadienone and / or o-xylene or (p) grape-like odor such as preferably ethyl decanoate and / or hexanone or
  • grapefruit-like odor such as preferably (+) - 5,6-dimethyl-8-isopropenylbicyclo [4.4.0] dec-1-en-3-one and / or p-menthenethiol or
  • grassy odor such as preferably 2-ethylpyridine, 2,6-dimethylnaphthalene, hexanal and / or (Z) -3-hexenol or
  • (s) green note preferably 2-ethylhexanol, 6-decenal, dimethylheptenal, hexanol, heptanol, methyl-2-butenal, hexyloctanoates, nonanoic acid, undecanone, methyl geranate, isobornylformiate, butanal, octanal, nonanal, epoxy-2-decenal, cis -Linalool, pyranoxide, nonanol, alpha, Y-dimethylallylalcohol, (Z) -2-penten-1-ol, (Z) -3-hexenylbutanoate, isobutylthiazole, (E) -2-nonenal, 2-dodecenal, (Z) 4-decenal, 2-octenal, 2-hepten-1-al, bicyclogermacrene, 2-octenal, ⁇ -thujene, (Z)
  • herbaceous odor preferably octanone, hexyloctanoate, caryophyllene oxides, methylbutenol, safranal, benzyl benzoate, bornyl butyrate, hexyl acetate, ⁇ -bisabolol, piperitol, ⁇ -selenene, ⁇ -cubebene, p-menth-1-en-9-ol , i. ⁇ . ⁇ . ⁇ -tetramethyl - ⁇ - oxabicyclododeca ⁇ dienes, T-muurolol, (-) - cubenol, levomenol, ocimene, ⁇ -thujene, p-menth-1-en-9-yl acetate , Dehydrocarveol, Artemisia alcohol, ⁇ -Muurolene, Hydroxypentanone, (Z) -Ocimene, ⁇ -
  • honey-like odor preferably ethyl cinnamate, ⁇ -phenethyl acetate, phenylacetic acid, phenylethanal, methyl anthranilate, cinnamic acid, ⁇ -damascenones, ethyl
  • E cinnamate, 2-phenylethyl alcohol, citronellyl valerates, phenylethyl benzoates and / or eugenol or
  • Hyacinth-like odor preferably Hotrienol
  • (x) jasmine-like odor preferably methyl jasmonate, methyldihydroepijasmonate and / or methylepijasmonate or
  • (y) lavender-like odor preferably linalyl valerate and / or linalool or
  • (dd) melon-like odor, preferably dimethylheptenal or
  • minty odor preferably menthone, ethyl salicylate, p-anisaldehyde, 2,4,5,7-tetrahydro-3,6-dimethylbenzofuran, epoxy-p-menthene, geranial, (methylbutenyl) methylfuran, dihydrocarvylacetate , ⁇ -cyclocitral, 1,8-cineole, ⁇ -phellandrene, methylpentanone, (+) - ammonium, dihydrocarveol (-) - carvone, (E) -p-mentha-2,8-dien-1-ol, isopulegyl acetate, Piperitone, 2,3-dehydro-1, 8-cineole, ⁇ -terpineol, DL-carvone and / or ⁇ -phellandrene or
  • (ff) Nutty odor preferably 5-methyl- (E) -2-hepten-4-one, ⁇ -heptalactone, 2-acetylpyrrole, 3-octen-2-one, dihydromethylcyclopentapyrazine, acetylthiazole, 2-octenal, 2,4 Heptadienal, 3-octenone, hydroxypentanone, octanol, dimethylpyrazine, methylquinoxaline and / or acetylpyrroline or
  • (gg) orange-like odor preferably methyloctanoate, undecanone, decyl alcohol, limonene and / or 2-decenal or
  • peach-like odor preferably ⁇ -nonalactone
  • peach-like odor preferably ⁇ -nonalactone
  • Pine-like odor preferably ⁇ -p-dimethylstyrene, ⁇ -pinene, bornyl benzoate, ⁇ -terpinene, dihydroterpinyl acetate and / or ⁇ -pinene or
  • pineapple-like odor preferably propyl butyrate, propyl propanoate and / or ethyl acetate or
  • Rose-like odor preferably ⁇ -phenethyl acetate, 2-ethylhexanol, geranyl valerate, geranyl acetate, citronellol, geraniol, geranyl butyrate, geranyl isovalerate, citronellyl butyrate, citronellyl acetate, isogeraniol, tetrahydro-4-methyl-2- (2-methyl-1-) propenyl) -2,5-cis-2H-pyran, isogeraniol, 2-phenylethyl alcohol, citronellyl valerate and / or citronellyl isobutyrate, or
  • spearmint-like odor preferably carvylacetate and / or carveol, or
  • (rr) sweet odor preferably benzyl alcohol, ethyl phenylacetate, tridecanal, nerol, methylhexanoate, linalyl isovalerate, undecanedehyde, caryophyllene oxide, linalyl acetate, safranal, uncinol, phenylethanal, p-anisaldehyde, eudesmol, ethylmethylpyrazine, citronellylbutyrate, 4-methyl-3-pentene-2 -on, nonyl acetate, 10-epi- ⁇ -eudesmol, ⁇ -bisabolol, (Z) - 6-dodecene- ⁇ -lactone, ⁇ -farnesene, 2-dodecenal, ⁇ -dodecalactone, epoxy- ⁇ -ionone, 2-undecenal , Styrene glycol, methyl furanane, (-) - cis-
  • vanilla-like odor preferably vanillin, methyl vanillate, acetovanillon and / or ethyl vanillate or
  • woody odor preferably ⁇ -muurolens, cadina-1,4-dien-3-ol, isocaryophyllene, eudesmol, ⁇ -ionone, bornyl butyrate, (E) - ⁇ -bergamotene, linalooloxide, ethylpyrazine, 10-epi- ⁇ Eudesmol, ⁇ -ionone, bornyl butyrate, (E) - ⁇ -bergamotene, linalooloxide, ethylpyrazine, 10-epi- ⁇ -eudesmol, germacrene B, trans-sabin hydrate, dihydrolinalool, isodihydrocarveol, ⁇ -farnesene, ⁇ -sesquiphellandrene, ⁇ - Elemene, ⁇ -calacorene, epoxy- ⁇ -ionone, germacrene D, bicyclo mermose, alloaroma
  • the fluid is preferably a substantially hydrophobic liquid.
  • Typical hydrophobic groups are e.g. long-chain or aromatic hydrocarbon radicals.
  • Perfume oils are usually hydrophobic liquids.
  • the fluid may preferably comprise liquid cosmetic ingredients such as e.g. contain oils.
  • oils may advantageously contain fully synthetic oils such as e.g. Silicone oils, vegetable and / or animal fatty oils (triglycerides of medium or unsaturated fatty acids) and / or essential oils (for example of plant parts).
  • the guest mixture may preferably contain one or more skin-care and / or skin-protecting active substances.
  • Skin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage.
  • Skin-care active substances are preferably selected from the following substances: a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others.
  • Hydrophobic plant extracts c) Hydrocarbons such as squalene and / or squalane d) Higher fatty acids, preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or polyunsaturated fatty acids and others.
  • Higher fatty alcohols preferably those having at least 12 carbon atoms, for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others.
  • esters preferably such as cetyloctanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, decyl oleates, cholesterol stearates, glycerol monostearates, glycerol distearates, glycerol tristearates, alkyl lactates, alkyl citrates and / or alkyl tartrates and others.
  • lipids such as cholesterol, ceramides and / or sucrose esters and others.
  • vitamins such as vitamins A and E, vitamin C esters, including vitamin C.
  • the guest mixture may preferably contain antiseptic oil, preferably essential oil, which is in particular selected from the group of Angelica fine - Angelica archangelica, Anis - Pimpinella anisum, Benzoin siam - Styrax tokinensis, Cabreuva - Myrocarpus fastigiatus, Cajeput - Melaleuca leucadendron, Cistus - Cistrus ladaniferus, Copaiba balm - Copaifera reticulata, Costus root - Saussurea discolor, Edeltann needle - Abies alba, Elemi - Canarium luzonicum, Fennel - Foeniculum dulce Spruce needle - Picea abies, Geranium - Pelargonium graveolens, Ho leaves - Cinnamonum camphora , Immortelle Helichrysum ang., Ginger extra - Zingiber off., St.
  • antiseptic oil preferably essential oil, which is in particular selected
  • the guest mixture may preferably contain skin-protecting active substances, advantageously skin-protecting oil.
  • the skin-protecting substance is advantageously a skin-protecting oil, eg. B. also to a carrier oil, in particular selected from the group algae oil Oleum Phaeophyceae, Aloe vera oil Aloe vera brasiliana, apricot kernel oil Prunus armeniaca, Arnica montana oil, avocado Persea americana, borage oil Borago officinalis, calendula oil Calendula officinalis, camellia oil Camellia oleifera, thistle oil Carthamus tinctorius, peanut oil Arachis hypogaea, hemp oil Cannabis sativa, hazelnut oil Corylus avellana, hypericum perforatum, jojoba oil Simondsia chinensis, caraway oil Daucus carota, coconut oil Cocos nucifera, pumpkin seed oil Curcubita pe
  • the guest mixture may preferably contain moisturizing factors, for example those selected from the following group: amino acids, chitosan or chitosan salts / derivatives, ethylene glycol, glucosamine, glycerol, diglycerol, triglycerol, uric acid, honey and hardened honey, creatinine, Cleavage products of collagen, lactitol, polyols and polyol derivatives (for example, butylene glycol, erythritol, propylene glycol, 1,2,6-hexane triol, polyethylene glycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10 , PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), pyrrolidonecarboxylic acid, sugars and sugar derivatives (for example, fructose, glucose, maltose, maltitol, mannitol, inositol
  • the longitudinal diameter of the fluid reservoir measured at its longest point, between 20 .mu.m and 30 cm.
  • Lower limits may also be 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m or 100 ⁇ m or higher values such as 200 ⁇ m, 300 ⁇ m, 400 ⁇ m, 500 ⁇ m, 600 ⁇ m etc.
  • Upper limits may also be 20cm, 15cm, 10cm , 5 cm, 3 cm, 1 cm, 0.5 cm, 0.25 cm, 0.1 cm or 0.01 cm or even lower values, eg 0.005 cm etc.
  • the polymer substrate is at least partially composed of polymers which are selected from polyolefins, fluoropolymers, styrene polymers, copolymers of these polymers and / or mixtures of the abovementioned polymers.
  • Particularly preferred are e.g. Polypropylenes, polyethylenes, etc.
  • hydrophobic polymer substrates are used.
  • Particularly advantageous polyethylenes are HDPE, LDPE, LLDPE or UHMW-PE.
  • Preferred fluoropolymers are, for example, polyvinylidene fluoride and polyvinyl fluoride, and the copolymers poly (tetrafluoroethylene-co-hexafluoropropylene), poly (tetrafluoroethylene-co-perfluoroalkyl vinyl ether) and poly (ethylene-co-tetrafluoroethylene).
  • the styrenic polymers polystyrene and styrene-acrylonitrile copolymers, styrene-butadiene copolymers and acrylonitrile-butadiene-styrene copolymers are preferable.
  • polymer substrates based on polyolefins and in particular based on polypropylene or polyethylene are particularly preferred.
  • crosslinked (co) polymers are also preferred.
  • the polymer substrate prior to loading with the guest mixture, has an at least partially open-pore structure with an average pore diameter of preferably between 1 ⁇ m and 300 ⁇ m.
  • the lower limit can also be at values such as 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m or 30 ⁇ m etc.
  • the upper limit can also be used for values such as z. 280 ⁇ m, 260 ⁇ m, 240 ⁇ m or 220 ⁇ m and so on.
  • An insertable, porous, particulate polymer substrate with at least partially open-pore structure may have a sponge-like cellular or even a network-like or coral-shaped microstructure.
  • the pore structure should be at least partially open pore, i. the pores present in the polymer substrate must be in fluid communication with each other at least in partial regions of the substrate structure, and the particles of the polymer substrate should be open-pored at least in partial regions of their outer surface. As a result, a sufficient permeability for the fluids can be achieved.
  • the use of a particulate polymer substrate with at least partially open-pored structure allows a generous fluid absorption.
  • the polymer substrate used according to the invention has an average pore diameter in the range between 4 and 110 ⁇ m. Particularly preferred is a mean pore diameter in the range of 5 to 50 microns. Polymer substrates with such preferred pore diameters show good loadability.
  • the guest mixture is at temperatures below 100 0 C, advantageously below 9O 0 C, more preferably below 8O 0 C, in particular below 7O 0 C substantially undecomposed in a molten state.
  • the guest mixture is at least 20 wt .-%, preferably at least 30 wt .-%, advantageously at least 40 wt .-%, in a very advantageous manner to at least 50 wt .-%, in a particularly advantageous manner at least 60% by weight, most advantageously at least 70% by weight, most preferably at least 80% by weight, even more preferably at least 90% by weight, especially at least 95% by weight. -%, but most advantageously to 100 wt .-% of the components fluid and additive (s) with melting or pour points in the range of 25 0 C to 12O 0 C.
  • the host mixture at temperatures ⁇ 22 ° C, advantageously to ⁇ 28 ° C, in a very advantageous manner to ⁇ 32 0 C, in a particularly advantageous manner to ⁇ 38 0 C, in a particularly advantageous manner to ⁇ 42 ° C, in a further advantageous manner to ⁇ 48 ° C, even more advantageously up to ⁇ 55 ° C, even more preferably up to ⁇ 6O 0 C highly viscous or especially solid.
  • the pour point of the flowable at elevated temperatures additives or the mixture of these additives is greater than 25 ° C, preferably in the range of 30 to 90 0 C, advantageously in the range of 35 to 70 0 C and in particular in the range from 40 to 60 0 C.
  • the guest mixture contains up to 90 wt .-%, preferably 10 to 80 wt .-%, more preferably but less than 70 wt .-%, namely advantageously 15 to 65 wt .-%, in a very advantageous manner to 55 wt .-%, more preferably 28 to 50 wt .-% of flowable at elevated temperatures additives (ie additives with melting or flow point in the range of 25 0 C to 120 ° C), based on the total guest mixture with which the polymer substrate is loaded.
  • additives ie additives with melting or flow point in the range of 25 0 C to 120 ° C
  • the guest mixture contains more than 5 wt .-% of fluid (s), preferably more than 10 wt .-%, advantageously 15 to 90 wt .-%, very advantageously 20 to 80 wt .-% , More preferably, 25 to 75 wt .-%, in particular 30 to 72 wt .-% of fluid (s), based on the total guest mixture, with which the polymer substrate is loaded.
  • the fluid reservoir contains less than 25% by weight, preferably less than 15% by weight, advantageously less than 10% by weight, more preferably less than 5% by weight of water, based on the total Fluid storage, in particular, it is completely anhydrous.
  • the additives which are contained in the guest mixture whose pour points in the temperature range from 25 ° C to 12O 0 C, selected from the group of fatty alcohols, fatty acids, silicones (silicone oils), paraffins, nonionic surfactants, esterquats, glycerides of fatty acids (natural oils), waxes, mono-, di- or triglycerides, carbohydrates and / or polyalkylene glycols.
  • sugars are advantageously used here, for example, alpha-D-glucose monohydrate (melting point in the range 83-86 ° C), alpha-D-galactose monohydrate (melting point in the range of 118-120 0 C) or maltose, for example Monohydrate (melting point in the range 102-103 ° C), to give a few examples.
  • the derivatives such as, for example, amino sugars, such as D-glucosamine (melting point ⁇ -form: 88 ° C), or such as deoxysugar, such as rhamnose monohydrate (melting point 92-94 ° C).
  • Suitable paraffins may e.g. Octadecane, nonadecane, eicosan, docosan, tricosane, tetracosane, pentacosan, hexacosan, heptacosan, octacosan, nonacosan or triacosane, to name but a few.
  • Suitable fatty alcohols may be, for example, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 9-trans-octadecen-1-ol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol. 1-docosanol, 13-cis-docosen-1-ol, 3-trans-docosen-1-ol, to name just a few examples.
  • waxy coal ie fatty alcohols with about 24-36 carbon atoms, such as triacontanol-1 or melissyl alcohol.
  • unsaturated fatty alcohols such as Elaidyalkohol, Erucaalkohol or Brassidylalkohol.
  • Guerbet alcohols such as C 32 H 66 O or C 36 H 74 O.
  • alkanediols such as undecanediol-1, 11 or dodecanediol-1, 12th
  • Suitable nonionic surfactants may be, for example, fatty alcohol polyglycol ethers, for example C 14 H 29 -O- (CH 2 CH 2 O) 2 H, C 10 H 21 -O- (CH 2 CH 2 O) 8 H, C 12 H 25 -O- (CH 2 CH 2 O) 6 H, C 14 H 29 -O- (CH 2 CH 2 O) 4 H, C 16 H 33 - 0 - (CH 2 CH 2 O) 12 H, C 18 H 37 -O - (CH 2 CH 2 O) 4 H, to name just a few examples.
  • fatty alcohol polyglycol ethers for example C 14 H 29 -O- (CH 2 CH 2 O) 2 H, C 10 H 21 -O- (CH 2 CH 2 O) 8 H, C 12 H 25 -O- (CH 2 CH 2 O) 6 H, C 14 H 29 -O- (CH 2 CH 2 O) 4 H, C 16 H 33 - 0 - (CH 2 CH 2 O) 12 H, C 18
  • Suitable fatty acids may be, for example, capric, undecanoic, lauric, tridecanoic, tetradecanoic, pentadecanoic, palmitic, margaric, stearic, nonadecanoic, arachidic, behenic, lignoceric, cerotic, crotonic, erucic, elaeostearic or melissic acids, to name but a few.
  • the esters of fatty acids such as the methyl or ethyl esters of behenic acid or arachidic acid, to name examples.
  • mono-, di- or triglycerides e.g. the corresponding glycerides of lauric acid, palmitic acid or capric acid, to give a few examples.
  • Suitable waxes may be natural washes such as e.g. Carnauba wax, candelilla wax, espartowax, guaruma wax, Japan wax, cork wax or montan wax, as well as animal washes, e.g. Beeswax, wool wax, shellac wax or spermaceti, as well as synthetic waxes, e.g. Polyalkylene waxes or polyethylene glycol waxes, as well as chemically modified waxes, e.g. hydrogenated jojoba waxes or montan ester waxes.
  • natural washes such as e.g. Carnauba wax, candelilla wax, espartowax, guaruma wax, Japan wax, cork wax or montan wax
  • animal washes e.g. Beeswax, wool wax, shellac wax or spermaceti
  • synthetic waxes e.g. Polyalkylene waxes or polyethylene
  • the guest mixture may additionally contain other substances which have a melting point above 120 0 C, for example, corresponding carbohydrates, advantageously sugar, eg sucrose (melting point 185-186 ° C).
  • corresponding carbohydrates advantageously sugar, eg sucrose (melting point 185-186 ° C).
  • the guest mixture contains further solids, preferably customary detergents, there is also a preferred embodiment.
  • the solids content of the guest mixture is less than 50%, preferably less than 30%, advantageously less than 25%, in particular less than 15%, most preferably less than 10%, based on the total guest mixture with which the polymer substrate is loaded , so is another preferred embodiment.
  • the solids contained in the guest mixture have a d50 value of less than 0.2 mm, preferably less than 0.1 mm, in particular less than 0.05 mm.
  • guest mixture solids selected from the group of zeolites, bentonites, silicates, phosphates, urea and / or its derivatives, sulfates, carbonates, citrates, citric acid, acetates and / or salts of anionic surfactants, so is a further preferred embodiment.
  • the fluid reservoir has a size such that it can be grasped with a human hand and can be used for the manual treatment of objects. For example, you can rub surfaces with a fluid storage in piece form, for example, in the hand washing of textiles.
  • the fluid reservoir may be of any shape, preferably spherical, oval, cylindrical, or granular or of any other regular or irregular shape.
  • a fluid reservoir which contains at least one, preferably two or more substances normally contained in detergents or cleaners, preferably a substance from the group of surfactants, builders (inorganic and organic builders), bleaches, bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers (e.g.
  • grayness inhibitors include grayness inhibitors, optical brighteners, UV protectants, soil repellents, electrolytes, colorants, fragrances, fragrances, perfume carriers, pH adjusters, complexing agents, fluorescers, foam inhibitors, anti-crease agents, antioxidants, quaternary ammonium compounds, antistatic agents, ironing auxiliaries, UV absorbers, anti redeposition agents, germicides, antimicrobial agents, fungicides, viscosity regulators, pearlescers, color transfer inhibitors, anti-shrinkage agents, corrosion inhibitors, preservatives, plasticizers, fabric softeners, Pr oteinhydrolysate, repellents and impregnating agents, hydrotropes, silicone oils and swelling and anti-squeezing agents constitutes a preferred embodiment of the invention.
  • Porous polymer substrate preferably 40-75% by weight, in particular 40-60% by weight, of fluid in the polymer substrate: preferably 1-30% by weight, in particular 20-30% by weight of additive which can flow at elevated temperatures: preferably 1-30% by weight, in particular 20-30%
  • the fluid reservoir according to the invention is advantageously distinguished by the fact that large quantities of liquid, such as e.g. Perfume, safely and permanently immobilized in the porous polymer substrate and only on external stimulus such. Temperature increase and / or mechanical stress, be released again.
  • liquid such as e.g. Perfume
  • the fluid reservoir according to the invention so loaded with the guest mixture polymer substrate , in addition to provide a coating.
  • the fluid reservoir is coated.
  • Coating agents can be used for the coating. These are fabrics which give the outer surface of the object to be coated a shiny appearance and / or form a coating (an envelope) on the outer surface.
  • coating agent solid and / or liquid substances may be used, preferably those which have a Prevent or delay moisture penetration or prevent or delay flavor loss.
  • Suitable coating agents may contain water-soluble, water-dispersible and / or water-insoluble (co) polymers.
  • the coating layer may be water-soluble or water-insoluble.
  • Water-soluble polymers contain a sufficient number of hydrophilic groups for water solubility and are advantageously not crosslinked.
  • the hydrophilic groups may be nonionic, anionic, cationic or zwitterionic be, for example, -NH 2, -OH, -SH, - O-, -COOH, - COO-M +, - SO3 ⁇ M +, -PO 3 2- M 2 + , -NH 3 + ,
  • the individual polymers may simultaneously contain different hydrophilic groups, e.g. ionic and nonionic and / or anionic besides cationic groups.
  • Preferred water-soluble polymers may be e.g. natural polysaccharides and / or polypeptides, e.g. Starch, alginates, pectins, vegetable gums, caseins, gelatin, etc.
  • Preferred water-soluble polymers may be e.g. semi-synthetic polymers, e.g.
  • Preferred water-soluble polymers may be e.g. biotechnologically produced products, e.g.
  • Preferred water-soluble polymers may be e.g. synthetic polymers, e.g. Homo- and / or
  • Vinylphosphonic acid polyvinyl alcohol, polyethylenimine, polyvinylpyrrolidone, and the like. be.
  • Preferred coating compositions contain water-soluble (co) polymer, in particular with one
  • Suitable water-soluble (co) polymer having a corresponding melting or softening point can advantageously be selected from the group consisting of polyalkylene glycols,
  • Polyethylene terephthalates, polyvinyl alcohols and mixtures thereof can be selected.
  • the coating may comprise, in addition to the actual coating agent or independently thereof, further constituents, for example advantageously textile-softening compounds and / or perfume. It is also possible to coat the fluid reservoir several times, for example by first surrounding the fluid reservoir with a first coating, eg containing a textile-softening compound, and then the resulting object with another covering, eg containing water-soluble polymer and perfume. provides.
  • the coating of the fluid reservoir contains lipids and / or silicone oils.
  • Preferred lipids are
  • lipophilic alcohols such as wax alcohols, retinol or cholesterol, etc.
  • lipophilic esters such as neutral fats - i. Mono-, Di- u. Triacylglycerols (triglycerides), sterol esters, etc.]
  • lipids with more than 2 hydrolysis products e.g. Glycolipids, phospholipids, sphingolipids and / or glycerolipids etc.
  • lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products e.g. Lipoproteins and / or lipopolysaccharides, etc.
  • phosphorus-free glycolipids e.g. Glycosphingolipids (such as, preferably, cerebrosides,
  • carbohydrate-free phospholipids e.g. Sphingophospholipids (such as preferably sphingo- myelins) or e.g. Glycerophospholipids (such as preferably lecithins, cephalins, cardiolipins, phosphatidylinositols and inositol phosphates etc.)
  • Sphingophospholipids such as preferably sphingo- myelins
  • Glycerophospholipids such as preferably lecithins, cephalins, cardiolipins, phosphatidylinositols and inositol phosphates etc.
  • the optional coating comprises colored substances or dyes, brighteners and / or pigments, advantageously in the nanoscale range or in the micrometer range, preferably white pigments, in particular selected from titanium dioxide pigments, in particular anatase pigments and / or rutile Pigments, zinc sulfide pigments, zinc oxide (zinc white), antimony trioxide (antimony white), basic lead carbonate (lead white) 2PbCO 3 Pb (OH) 2 , lithopone ZnS + BaSO 4 .
  • white auxiliaries such as preferably calcium carbonate, talc 3MgO • 4SiO 2 ⁇ H 2 O and / or barium sulfate may be included.
  • the pigments which may preferably be components of an optional coating, may be
  • colored pigments preferably inorganic colored pigments, in particular iron oxide pigments, chromate pigments, iron blue pigments, chromium oxide pigments, ultramarine pigments, mixed oxide phase pigments and / or bismuth vanadate pigments
  • inorganic colored pigments in particular iron oxide pigments, chromate pigments, iron blue pigments, chromium oxide pigments, ultramarine pigments, mixed oxide phase pigments and / or bismuth vanadate pigments
  • black pigments e.g., aniline black, perylene black, iron oxide pigments, manganese black and / or spinel black
  • luster pigments preferably platelet-shaped effect pigments, metallic effect pigments such as aluminum pigments (silver bronze), copper pigments and copper / zinc pigments (gold bronze) and zinc pigments, pearlescent pigments such as magnesium stearate, zinc stearate, lithium stearate or ethylene glycol distearate or Polyethylene terephthalate, interference pigments such as metal oxide mica pigments) and / or
  • luminescent pigments such as e.g. Azomethine fluorescence yellow, silver-doped and / or copper-doped zinc sulfide pigments act.
  • the optional coating may preferably also comprise the following substances:
  • sulphates such as preferably barite, blanc-fixed and / or calcium sulphates
  • silicates such as preferably talc, pyrophyllite, chlorite, hornblende, mica, kaolin wollastonite, slate, precipitated Ca, Al, Ca / Al, Na / Al silicates, feldspars and / or mullite
  • silicas such as, preferably, quartz, fused silica, cristobalite, diatomaceous earth, Neuburg Siliceous Earth, precipitated silica, fumed silica, glass flour, pumice, perlite, Ca-metasilicates and / or fibers from melts of glass, basalt, slags
  • (E) oxides in particular aluminum hydroxide and / or magnesium hydroxide
  • organic fibers such as in particular textile fibers, cellulose fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyacrylonitrile fibers and / or polyester fibers, preferably with lengths in the nanometer or micrometer range and / or
  • (g) flours e.g. Starch flours.
  • the optional coating of the fluid reservoir according to the invention is pH and / or temperature and / or ionic strength-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials.
  • pH sensitivity temperature sensitivity and / or ionic strength sensitivity is meant that the coating or the materials forming the coating with a change in the pH, the temperature and / or the ionic strength in the environment, which is exposed to the coating (eg a wash liquor), (a) undergoes a change (increase or decrease) in solubility (preferably in water); and or
  • the temperature sensitivity also has the additional option (e) according to which the coating or the materials forming the coating change the physical state from solid to liquid when the temperature changes or vice versa, ie the materials melt or solidify.
  • suitable coating materials for the purposes of the invention may be all those materials whose integrity is a function of the temperature and / or the pH and / or the ionic strength, or also those materials which are subject to mechanical stress as described e.g. occur during an automatic laundry process, lose their integrity.
  • the pH sensitivity of the (optional) coating can be used.
  • the (optional) coating may e.g. be designed so that it dissolves in whole or in part if the pH falls below a critical mark. This can be done in the example of a washing process when the alkaline wash water is removed from the machine and fresh water introduced into the machine, preferably in the rinse cycle of the washing process.
  • the coating On contact with the fresh water, the coating then lose its integrity, in whole or in part, making it possible to penetrate the granules for the water.
  • the pH in question in which the coating is completely or partially disintegrated, can be adjusted as desired, so that the material, for example, loses all or part of its integrity if the pH value is e.g. below 9.0, but remains substantially inert as long as the pH is above 10.0.
  • inert is understood according to the invention in the usual sense, ie in such a way that a physical or chemical reaction of the material of the coating with the surrounding environment does not occur substantially, but the material of the coating is physically and chemically resistant to this, so that the granules from penetration through the environment, eg the wash liquor is substantially protected.
  • Preferred coating agents can be any suitable coating agents.
  • carboxylate-group-containing polymers (polycarboxylates), preferably homopolymers of acrylic acid and / or copolymers of acrylic acid and maleic acid,
  • polyethylene glycols in particular those having molecular weights ⁇ about 25,000 g / mol, preferably ⁇ about 10,000 g / mol, advantageously ⁇ about 6000 g / mol, such as, for example, PEG 4000,
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • coatings which at least partially comprise a polyvinyl alcohol whose degree of hydrolysis is advantageously from 70 to 100 mol%, preferably from 80 to 90 mol%, particularly preferably from 81 to 89 mol% and in particular from 82 to 88 mol% is.
  • the film material used comprises at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol whose Hydrolysis degree 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the entire coating is at least 20 wt .-%, more preferably at least 40th % By weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol whose degree of hydrolysis is from 70 to 100 mol%, preferably from 80 to 90 mol%, particularly preferably from 81 to 89 Mol% and in particular 82 to 88 mol%.
  • Polyvinyl alcohols of a specific molecular weight range are preferably used as coating materials, it being preferred according to the invention that the film material comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol -1 , preferably 11,000 to 90,000 gmol -1 , particularly preferably 12,000 to 80,000 gmol "1 and in particular from 13,000 to 70,000 gmol '1 is located.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and L648, L734, Mowiflex LPTC KSE 221 as well as the ex Compounds of Texas polymer such as Vinex 2034.
  • suitable polyvinyl alcohols are ELVANOL ® 51-05, 52-22, 50-42, 85- 82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ®, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), ® Gonozo ⁇ de NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK). Also suitable are ERKOL types from Wacker.
  • the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
  • the reaction products of PVAL and starch are particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
  • the reaction products of PVAL and starch are also used.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values. Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVP polyvinylpyrrolidone
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of preferably about 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • polyethylene oxides are characterized by comprising polyethylene oxides.
  • H- [O-CH 2 -CH 2 J n -OH which are technically produced by basicly catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • coating materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, and mixtures thereof are also preferred.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight-chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW about 300,000 to 2,000,000).
  • small amounts of lipids, phosphoric acid and cations are still included.
  • the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the 1,4-position bond
  • the amylopectin branch branches off into a branch-like structure after an average of 25 glucose building blocks by 1, 6 binding with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings in the context of the present invention.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • Pure cellulose has the formal gross composition (C 6 HioO 5 ) 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 5,000 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 group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • Another object of the present invention is a method for producing a fluid reservoir according to the invention, wherein a mixture of additive (s), which is highly viscous or solid at T ⁇ 20 ° C, and fluid (s) brings by heating in a liquid state, and mixes this flowable mixture with a porous polymer substrate and then allowed to cool.
  • a mixture of additive (s) which is highly viscous or solid at T ⁇ 20 ° C
  • fluid (s) brings by heating in a liquid state, and mixes this flowable mixture with a porous polymer substrate and then allowed to cool.
  • the accessible pore system of the polymer substrate can be fully loaded if necessary and the pores are preferably also sealed when charged by cooling.
  • a method of making a fluid reservoir wherein a) one or more ordinary fluids at temperatures of 20 to 22 ° C with stirring with additive (s) having a pour point in the range of 20 0 C to 100 0 C, are mixed, and then b) the mixture to temperatures in Range of the pour point of the additives, preferably above the flow range, are heated, so that a flowable mixture results, and then c) while maintaining the elevated temperature optionally further additives, in particular detergent additives, advantageously selected from the group of zeolites, bentonites, silicates, Phosphates, urea and / or its derivatives, sulphates, carbonates, citrates, citric acid, acetates and / or salts of the anionic surfactants, whereby the flowability of the mixture is maintained, and subsequently d) the flowable mixture with a porous polymer substrate at temperatures of 25 ° -150 ° C, and finally, e) the resulting mixture cools, represents a preferred embodiment of the invention.
  • the polymer is pre-tempered before mixing with the flowable mixture to a temperature of 25 ° -150 ° C, so is a preferred embodiment.
  • the cooling of the mixture is accelerated by supply of cold.
  • a guest mixture according to the invention comprising in particular fragrances, and the porous, particulate polymer substrate and optionally further additives in liquid carbon dioxide (CO2), there (further) to mix and then the liquid
  • CO2 liquid carbon dioxide
  • carbon dioxide for example by a simple pressure reduction in the system, so that evaporation can take place.
  • a targeted slowdown in the expansion of carbon dioxide can produce particularly advantageous fluid storage.
  • Advantageously, can be used up to 70 bar at 2O 0 C and the liquid carbon dioxide in a pressure range of 20 bar.
  • the carbon dioxide can be used in other pressure ranges and temperature ranges, as long as it is liquid under these conditions.
  • a highly preferred object of the present invention are detergents or cleaners containing fluid reservoirs according to the invention and also a cosmetic containing fluid reservoirs according to the invention.
  • the use of the fluid reservoir according to the invention for room, vehicle or cabinet ventilation, in particular in the form of scented stones and / or scented sachets, is likewise a further preferred subject matter of the invention.
  • fluid reservoir according to the invention for scenting articles, preferably detergents, washing and cleaning machines, dry laundry and packaging is likewise a further preferred subject matter of the invention.
  • fluid reservoirs containing ingredients of hand dishwashing detergents e.g. selected from
  • surfactants such as, for example, alkanesulfonates, alkyl ether sulfates, alkyl polyglucosides and / or cocoamidopropyl betaine, advantageously suitable for wetting ware and dirt, detaching grease and other impurities,
  • hydrotropes e.g. Cumene sulphonate, advantageously suitable for preventing phase separation
  • refatting agents e.g. Fatty acid amides, advantageously suitable for moisturizing the skin
  • care components such as Aloe vera extracts, advantageously suitable for the care of the skin,
  • Antibacterial agents e.g. Sodium benzoate or sodium salicylate, advantageously suitable for controlling germs, (i) preservatives.
  • fluid reservoirs containing ingredients of automatic dishwashing detergents e.g. selected from the following:
  • Phosphates such as pentasodium triphosphate, phosphonates, citrates such as sodium citrate, sodium polycarboxylates, sodium metasilicate, soda, sodium bicarbonate, sodium disilicate, Active chlorine, sodium perborate, bleach activator such as TAED, enzymes such as protease and amylase, (low-foaming) nonionic surfactants, silver / glass protection, scents.
  • fluid reservoirs containing ingredients of laundry detergents e.g. selected from the following:
  • Anionic surfactants e.g. preferably alkyl benzene sulphonate and / or alkyl sulphate
  • nonionic surfactants e.g. preferably fatty alcohol polyglycol ethers, alkylpolyglucoside and / or fatty acid glucamide
  • builders such as e.g. preferably zeolite, polycarboxylate and / or sodium citrate, alkalis, e.g. preferably sodium carbonate, alcohols, e.g. preferably ethanol and / or glycerol
  • bleaching agents e.g. preferably sodium perborate and / or sodium percarbonate
  • corrosion inhibitors e.g.
  • preferably sodium silicate stabilizers, e.g. preferably phosphonates, foam inhibitor, e.g. preferably soap, silicone oils and / or paraffins, enzymes, e.g. preferably proteases, amylases, cellulases and / or lipases, grayness inhibitor, e.g. preferably carboxymethylcellulose, discoloration inhibitor such as e.g. preferably polyvinylpyrrolidone derivatives, sizing agents such as e.g. preferably sodium sulfate, fragrances, optical brighteners, e.g. preferably stilbene derivative and / or biphenyl derivative, water.
  • foam inhibitor e.g. preferably soap, silicone oils and / or paraffins
  • enzymes e.g. preferably proteases, amylases, cellulases and / or lipases
  • grayness inhibitor e.g. preferably carboxymethylcellulose
  • discoloration inhibitor such as e.g. preferably polyvinylpyr
  • fluid reservoirs containing ingredients of general purpose cleaners e.g. selected from the following:
  • Surfactants e.g. Alkanesulfonates, alkylbenzenesulfonates, alkylpolyglucosides, fatty alcohol polyglycol ether sulfates, fatty alcohol polyglycol ethers, builders such as e.g. Trisodium citrate, sodium nitrilotriacetic acid salt, sodium phosphonate, pentasodium triphosphate, solvents and hydrotrope (solubilizer), e.g. Ethanol, propylene glycol ether, sodium toluene or - cumenesulfonate, fragrances, dyes, preservatives.
  • Acid all-purpose cleaners contain acids, such as preferably acetic, citric or maleic acid. (Weak) alkaline all-purpose cleaners contain alkalis, preferably caustic soda or soda.
  • An inventive cloister e.g. for hanging in the toilet bowl or cistern, can deliver small amounts of acid, surfactant and / or perfume, thereby slowing down the application of soiling.
  • Another object of the invention is a product, such as preferably household sponge, cloth or cloth, in which at least one surface of the product is firmly adhering to the fluid reservoir.
  • a scouring pad is advantageous, the scouring side is occupied by the fluid reservoir.
  • fluid is released from the reservoir due to the mechanical stress, so in the case of perfume, a fragrance is generated.
  • a fluid reservoir which contains at least one, preferably two or more substances normally contained in detergents or cleaning agents, is a preferred embodiment of the invention.
  • a washing or cleaning agent containing fluid reservoirs according to the invention is a highly preferred article of the invention Therefore, the following ingredients of detergents or cleaning agents are described in more detail, which may be advantageously contained in the fluid reservoir or which may be contained in a detergent or cleaning agent, which contains fluid reservoir according to the invention.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • the usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • zeolite can also be used for "powdering." Suitable zeolites have an average particle size of preferably 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.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from O to 20, and preferred values for x 2, 3 or 4 are.
  • 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.
  • crystalline layered silicates of general formula NaMSi x O 2x + 1 • y H can 2 O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, and y is a number from 0 to 33.
  • the crystalline layered silicates of the formula NaMSi x O 2x + 1 • y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 ⁇ x H 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 • x H 2 O, Maga DiIT), Na-SKS -3 (Na 2 Si 8 O 17 • x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 • x H 2 O, Makatite).
  • crystalline phyllosilicates of the formula NaMSi x O 2x + 1 • y H 2 O, in which x is 2.
  • Na-SKS-5 (X-Na 2 Si 2 O 5 )
  • Na-SKS-7 (B-Na 2 Si 2 O 5 , natrosilite)
  • Na-SKS-9 NaHSi 2 O • 5 H 2 O
  • Na-SKS-10 NaHSi 2 O 5 ⁇ 3 H 2 O, kanemite
  • Na-SKS-11 T-Na 2 Si 2 O 5
  • Na-SKS-13 Na-SKS-13
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus 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 Delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may be caused in various ways, for example by surface treatment, compounding, grain pakt réelle / compression or by overdrying.
  • the term "amorphous" is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it 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 the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared to the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • these silicates preferably alkali metal silicates, more preferably crystalline or amorphous alkali disilicates, to be present in detergents or cleaners in amounts of from 10 to 60% by weight, preferably from 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the detergent or cleaning agent, are included.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons. This applies in particular to the use of agents according to the invention as (automatic) dishwashing detergents.
  • the alkali metal phosphates have, with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the detergents and cleaning agents industry the greatest importance.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) ,, and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH 2 PO 4 , in the form of the dihydrate (density 1, 91 like 3 , melting point 60 ° C.) or in the form of the monohydrate (density 2,04 like '3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na 2 HPO 4 , which is anhydrous or with 2 mol (density 2.066 like "3 , water loss at 95 ° C), 7 mol (density 1, 68 like " 3 , melting point 48 ° C with loss of 5 H 2 O) and 12 mol of water (density 1, 52 like '3 , melting point 35 ° C with loss of 5 H 2 O) can be used, but especially the trisodium phosphate (tertiary sodium phosphate) Na 3 PO 4 , which as dodecahydrate, as decahydrate (corresponding to 19 -20% P 2 O 5 ) and in anhydrous form (corresponding to 39-40%
  • Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 .
  • the tetrasodium diphosphate sodium pyrophosphate
  • Na 4 P 2 O 7 which is in anhydrous form (density 2.534 like "3 , melting point 988 0 C, also indicated 88O 0 C) and as decahydrate (density 1, 815- 1, 836 like '3 , melting point 94 ° C with loss of water)
  • potassium salt potassium diphosphate potassium 4 P 2 O 7 .
  • pentasodium triphosphate Na 5 P 3 Oi 0 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • K 5 P 3 O 10 potassium tripolyphosphate
  • K 5 P 3 O 10 potassium tripolyphosphate
  • Potassium polyphosphates are widely used in the detergents and cleaners industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • phosphates are used as detergents or cleaning agents in the context of the present application
  • preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight, in particular from 20 to 70% by weight, based in each case on the weight of the washing or cleaning agent.
  • potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the alkali metal hydroxides are, if at all, preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight. , Particularly preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • Particularly preferred may be the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30% by weight, respectively be based on the weight of the detergent or cleaning agent.
  • carbonate (s) and / or bicarbonate (s) preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30% by weight, respectively be based on the weight of the detergent or cleaning agent.
  • agents which, based on the weight of the washing or cleaning agent, less than 20 wt .-%, preferably less than 17 wt .-%, preferably less than 13 wt .-% and in particular less than 9 wt .-% Carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • 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 also serve to set 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.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of detergents or cleaning agents on optional (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalic aldehyde 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.
  • Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
  • Suitable amounts used in zeolite-containing and / or silicate-containing formulations may be, for example, from 3 to 15% by weight.
  • 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.
  • the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • preferred nonionic surfactants for example, low-foaming nonionic surfactants can be used.
  • the detergents or cleaners contain nonionic surfactants from the group of alkoxylated alcohols.
  • nonionic surfactants 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) used per mole of alcohol in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • 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 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 H -alkyl with 3 EO or 4 EO 1 Cg-u-alcohol with 7 EO, C 13-15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i 8 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -i 4 alcohol containing 3 EO and C 2-18 alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are Taigfettalkohol with 14 EO, 25 EO 1 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G the symbol is that which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants which can be 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.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also 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
  • R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl 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
  • 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 oxyalkyl radical having 1 to 8 carbon atoms, wherein C ⁇ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof residue.
  • [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-aryl-oxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Surfactants containing one or more tallow fatty alcohols containing from 20 to 30 EO in combination with a silicone defoamer can furthermore be used with particular preference.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • Nonionic surfactants which have a melting point above room temperature.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature.
  • nonionic surfactants used in the Room temperature are highly viscous, it is preferred that they have a viscosity above 20 Pa s, preferably above 35 Pa s and in particular above 40 Pa s.
  • Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • surfactants which are solid at room temperature, come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / poly-oxypropylene ((PO / EO / PO) surfactants ).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred, solid at room temperature nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-2 alcohol), preferably a C 8 alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Of these, the so-called “narrow rank ethoxylates" (see above) are particularly preferred.
  • ethoxylated nonionic surfactants selected from C 6-2 o monohydroxyalkanols or C 6 .
  • 20- alkylphenols or C 16 - 2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained are used.
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight.
  • Non-ionic surfactants that can be used with particular preference are available, for example, under the name Poly Tergent ® SLF-18 from the company Ohn Chemicals
  • R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 OI y CH 2 CH (OH) R 2 , wherein R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof , R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x represents values between 0.5 and 1.5 and y represents a value of at least 15 are further particularly preferred nonionic surfactants
  • nonionic surfactants are the end-capped poly (oxyalkyl ⁇ erten) nonionic surfactants of the formula
  • R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ], OR 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is Values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O his] x [CH 2] k CH (OH) [CH 2] j oR 2 are different R 1 and R 2 are preferably linear or branched, saturated or unsaturated, ahphatician or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, said radicals having 8 to For the R 3 radical, H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket may be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 O [CH 2 CH (R 3 ) O] X CH 2 CH (OH) CH 2 OR 2 simplified.
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • end-capped poly (oxyalkylated) nonionic surfactants are of the formula
  • R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] J OR 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is Values between 1 and 30, k and j are for values between 1 and 12, preferably between 1 and 5, preference being given to surfactants of the type
  • R 1 O [CH 2 CH (R 3 ) O] X CH 2 CH (OH) CH 2 OR 2 , in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, is particularly preferred are.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • nonionic surfactants which have a C 9 . 15 alkyl having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 O [CH 2 CH (R 3 ) O] X R 2 , in which R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and are preferably further functionalized with an ether group, R 3 is H or a methyl, Ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical and x is between 1 and 40.
  • R 3 in the abovementioned general formula is H.
  • R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms
  • R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.
  • radical R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms which is adjacent to a monohydroxylated intermediate group - CH 2 CH (OH) -.
  • x in this formula stands for values between 1 and 90.
  • R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , which in addition to a radical R 1 , for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is a monohydroxyl faced intermediate group -CH 2 CH (OH) - adjacent and where x is between 40 and 80, preferably between 40 and 60.
  • R 1 for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which
  • the corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be prepared, for example, by reacting a terminal epoxide of the formula R 2 CH (O) CH 2 with an ethoxylated alcohol of the formula R 1 O [CH 2 CH 2 O] x-1 CH 2 Obtained CH 2 OH.
  • R 1 O [CH 2 CH 2 O] x [CH 2 CH (CH 3 ) O] y CH 2 CH (OH) R 2 , in which R 1 and R 2 independently of one another represent a linear or branched, saturated or on or is polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 J 2 , but preferably -CH 3 and x and y independently represent values between 1 and 32, with nonionic surfactants having values of x of 15 to 32 and y of 0.5 and 1.5 being very particularly preferred.
  • R and R are each independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably represents -CH 3
  • x and y independently of one another are values between 1 and 32 are preferred according to the invention, wherein nonionic surfactants with values of x from 15 to 32 and y of 0.5 and 1.5 are most preferred.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative but of mixtures, which may result in both the C chain lengths and the degrees of ethoxylation or alkoxylation-averaged mean values and, consequently, fractional numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas .
  • anionic surfactants for example, those of the sulfonate type and sulfates can be used.
  • the surfactants of the sulfonate type are preferably C 9 .
  • 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 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 20 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.
  • the C 12 -C 6 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7-21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 -alcohol with in average 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are 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 fatty alcohol residues 8- i or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • 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 present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the anionic surfactant content of detergents or cleaners according to the invention may be e.g. preferably in the range of 1-60% by weight, advantageously 5-40% by weight, in particular 10-30% by weight.
  • cationic active substances for example, cationic compounds of the following formulas can be used:
  • the content of cationic and / or amphoteric surfactants may preferably be less than 10% by weight, preferably less than 5% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. It may also be preferred that no cationic or amphoteric surfactants are included.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the polymers which act as softeners.
  • the washing or cleaning-active polymers for example the polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • “Cationic polymers” for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula
  • R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms
  • R 2 and R 3 independently represent an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group
  • x and y independently represent integers between 1 and 3.
  • X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • cationic or amphoteric polymers contain a monomer unit of the general formula
  • R1HC CR2-C (O) -NH- (CH 2) - N + R3R "R5
  • R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 - CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 - CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H and x is an integer between 1 and 6.
  • H 2 C C (CH 3 ) -C (O) -NH- (CH 2 ) X -N + (CH 3 ) 3
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred amphoteric polymers which can be used are selected from the group of the alkylacrylamide / acrylic-isocyanic copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / Al-kymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the Copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers methacrylamidoalkyl-trialkylammonium chloride and dimethyl (di-allyl) ammonium chloride.
  • amphoteric polymers are selected from the group of the Methacrylamidoalkyl-tri- alkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the
  • Methacrylami-doalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers Methacrylami-doalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyldiallylammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid Copolymers and their alkali metal and ammonium salts.
  • Washing or cleaning agents may contain the aforementioned cationic and / or amphoteric polymers, preferably in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the washing or cleaning agent.
  • Preferred agents can also be completely free of cationic and / or amphoteric polymers.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which can be used with particular preference.
  • Particularly preferred as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 (R 2 ) C C (R 3 ) COOH, in which R 1 to R 3, independently of one another, denote -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched chain, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1 - propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.
  • Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
  • the content of the polymers which can be used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
  • copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid ii) one or more sulfonic acid group-containing monomers of the formulas:
  • the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • These polymers are prepared by copolymerizing acrylic acid with a sulfonic acid group-containing acrylic acid derivative.
  • acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred.
  • the corresponding copolymers contain the structural units of the formula
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers which can preferably be used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molar mass of the sulfo copolymers which can preferably be used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol '1 , preferably from 4000 to 25,000 gmol ' 1 and in particular from 5000 to 15,000 gmol '1 .
  • the bleaching agents are a substance which can be used with particular preference for washing or cleaning.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further useful bleaching agents are, for example, peroxypyrophosphates, Citratperhy-drate and H 2 O 2 supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • 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 [phthaliminoperoxyhexanoic acid (PAP)] , o-
  • PAP phthaliminoperoxyhexanoic acid
  • chlorine or bromine releasing substances can be used as a bleaching agent and chlorine or bromine releasing substances.
  • 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.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • detergents or cleaners which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleach, preferably sodium percarbonate.
  • the active oxygen content of the washing or cleaning agents in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-% amount.
  • Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1, 0 wt .-% to.
  • Bleach activators are used in detergents or cleaners, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 0 C and below.
  • As 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 the O- and / or N-acyl groups of said carbon atom number and / or optionally bear 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) 1 N-acylimides, in particular N-nonanoylsuccinimide (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 tetraacety
  • bleach activators which can preferably be used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula
  • R 1 is -H 1 -CH 3, a C 2 - 24 alkyl or alkenyl group, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN 1 -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH 1 -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2
  • bleach activators are 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-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acyl-limide, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, Ethylene glycol di-acetate, 2,5-diacetoxy-2,5-dihydrofuran, n
  • bleach activators preference is given to bleach activators from the group of the polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol-sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight. %, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.
  • TAED tetraacetylethylenediamine
  • NOSI N-nonanoylsuccinimide
  • AA
  • bleach catalysts can also be used.
  • 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.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese, the manganese sulfate can optionally in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0 , 25 wt .-%, each based on the total weight of the bleach activator-containing agents, are used. But in special cases, more bleach activator can be used.
  • washing or cleaning enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Washing or cleaning composition preferably contain enzymes in total amounts of I x IO "6th to 5 wt .-% based on active protein. The protein concentration can be known by using methods, for example the BCA method and the biuret method to be determined.
  • subtilisin type examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark, available.
  • subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ® variants are derived.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from S. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners.
  • the enzyme out B. licheniformis is obtainable from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this ⁇ - amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from S. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are for example marketed by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Suitable mannanases are, for example, under the names Available Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, United States.
  • the .beta.-glucanase obtained from B. subtilis is obtainable under the name Cereflo ® from Novozymes.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned.
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
  • the enzymes originate, for example, either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the purification of the relevant enzymes is preferably carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. advantageously, are such granules, for example,
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including, in particular, derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
  • peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • enzyme stabilizers are aminoalcohols, such as up to Ci 2, such as succinic acid, other dicarboxylic acids or salts of said acids, mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.
  • Lower aliphatic alcohols but especially polyols, such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Also used are calcium salts, such as calcium acetate or calcium formate, and magnesium salts.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polyamine N-oxide-containing polymers act as enzyme stabilizers.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkyl polyglycosides can stabilize the enzymatic components and even increase their performance.
  • Crosslinked N-containing compounds also act as enzyme stabilizers. Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation.
  • a sulfur-containing reducing agent is, for example, sodium sulfite.
  • combinatons of stabilizers are used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers is enhanced by the combination with boric acid and / or boric acid derivatives and polyols and further enhanced by the additional use of divalent cations, such as calcium ions.
  • 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.
  • disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • PVP polyvinylpyrrolidone
  • Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents, so that preferred washing and cleaning agents comprise such a disintegrating agent
  • Cellulose base in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 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 group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • 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
  • the cellulose which can be used as a disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • 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.
  • 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 As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used.
  • 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 disintegration aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, can be used in disintegration agent-containing agents 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 .-%, in each case based on the total weight of the disintegrating agent-containing agent to be included.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
  • the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas.
  • the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations.
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
  • the relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred.
  • Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • Sokalan ® DCS commercially available and also preferably usable as Acid manufacturingsstoff in the context of the present invention Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid (max. 33 wt .-%).
  • Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
  • Preferred dyes the selection of which presents no difficulty for the skilled person, have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic tableware do not stain them.
  • the colorants do not have too high an affinity for textile surfaces, and in particular for synthetic fibers, whereas in the case of detergents an excessively high affinity for glass, ceramic or plasticware must be avoided , At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation.
  • water-insoluble colorants are more stable to oxidation than water-soluble colorants.
  • concentration of the colorant in the detergents or cleaners varies.
  • the above-mentioned Basacid ® Green or the above-mentioned Sandolan ® Blue are typically chosen dye concentrations in the range of some 10 '2 to 10 "3 wt .-%.
  • the suitable concentration of the colorant in detergents or cleaning agents is typically some 10 '3 to 10 "4 wt .-%.
  • Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes.
  • Pigmosol come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ® GLW (CAS 12219-32- 8, Cl Acidblue 221)), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ® (Cl Acid Blue 182, CAS 12219-26-0) is used.
  • the detergents and cleaners may also contain other ingredients which further improve the performance and / or aesthetic properties of these compositions.
  • Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the washing or cleaning agents is preferred.
  • pH adjusters In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.
  • Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
  • preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R 2 SiO) X and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa.s.
  • Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as from the state known 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.
  • Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners may be added to laundry detergents or cleaners to eliminate graying and yellowing of the treated fabrics, which will be absorbed by the fiber and cause brightening and replicated bleaching action by rendering invisible ultraviolet radiation into visible long wavelength convert light, wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and produces the yellow shade of the grayed or yellowed laundry pure white Suitable compounds originate for example from the substance classes of 4.4.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • graying inhibitors are cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
  • synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester. Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its washability.
  • Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents may also be included. The antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension.
  • a further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing).
  • the water repellents used for hydrophobization coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups.
  • Suitable hydrophobizing agents are, for example, paraffins, waxes, metal soaps, etc.
  • hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening.
  • silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.
  • Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although it is entirely possible to do without these compounds.
  • compositions may contain anti-oxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are usually substances with at least one hydrophilic molecule ligand and give more or less on the surfaces hygroscopic film. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, wherein additionally a softening effect is achieved.
  • Softeners can be used to care for textiles and to improve the textile properties such as a softer "avivage” and reduced electrostatic charge (increased wearing comfort.)
  • the active ingredients in fabric softening formulations are "esterquats", quaternary ammonium compounds with two hydrophobic radicals, such as Disteraryldimethylammoniumchlorid, which, however, due to its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
  • esters with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents. Further suitable as a finish is dimethylolethyleneurea.
  • Silicone derivatives can be used to improve the water absorbency, rewettability of the treated fabrics, and ease of ironing the treated fabrics. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-CI bonds.
  • silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and also the polyalkylene oxide-modified dimetylpolysiloxanes.
  • UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners.
  • Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
  • protein hydrolysates of both vegetable and animal origin can be used.
  • Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein hydrolysates, which may also be present in the form of salts.
  • Preferred according to the invention is the use of protein hydrolysates of plant origin, for example soybean, almond, rice, pea, potato and wheat protein hydrolysates.
  • protein hydrolysates are preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.
  • the nonaqueous solvents which can be used according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone, butanone, cyclohexanone), esters (acetic esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, Pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethylsulfoxide, sulfolane), nitro compounds (nitrobenzene), halogenated hydrocarbons (dich
  • a solvent mixture which is particularly preferred in the context of the present application is, for example, benzine, a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, more preferably above 80% by weight and in particular above 90 wt .-%, each based on the total weight of the mixture, preferably having a boiling range of 81 to 110 0 C.
  • benzine a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, more preferably above 80% by weight and in particular above 90 wt .-%, each based on the total weight of the mixture, preferably having a boiling range of 81 to 110 0 C.
  • a porous polymer support made of crosslinked polypropylene was placed in Lödige mixer and mixed with a melt of PEG (polyethylene glycol) 4000 and a perfume oil at 80 0 C and mixed. After about 1-2 minutes, the mixture solidified.
  • PEG polyethylene glycol

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Abstract

L'invention concerne un accumulateur de fluides à base de substrats polymères et capable d'accumuler un grand volume de fluides. L'accumulateur est sûr et la sortie des fluides de l'accumulateur est facilement contrôlable, par exemple par la température ou par une action mécanique. Il permet de retarder la libération du fluide. L'invention concerne également un procédé de fabrication d'un tel accumulateur de fluides, ainsi que son utilisation, par exemple dans des agents de lavage ou de nettoyage.
EP06829646.6A 2006-02-08 2006-12-15 Accumulateur de fluides Not-in-force EP1981936B1 (fr)

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DE200610021553 DE102006021553A1 (de) 2006-02-08 2006-05-08 Fluidspeicher
PCT/EP2006/012096 WO2007090451A1 (fr) 2006-02-08 2006-12-15 Accumulateur de fluides

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Also Published As

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US20120077728A1 (en) 2012-03-29
US8093197B2 (en) 2012-01-10
US8349781B2 (en) 2013-01-08
PL1981936T3 (pl) 2013-09-30
US20120093902A1 (en) 2012-04-19
DE102006021553A1 (de) 2007-08-16
ES2405305T3 (es) 2013-05-30
EP1981936B1 (fr) 2013-04-10
WO2007090451A1 (fr) 2007-08-16
US20090035337A1 (en) 2009-02-05

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