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EP1657298A1 - Compositions solides - Google Patents

Compositions solides Download PDF

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Publication number
EP1657298A1
EP1657298A1 EP04026983A EP04026983A EP1657298A1 EP 1657298 A1 EP1657298 A1 EP 1657298A1 EP 04026983 A EP04026983 A EP 04026983A EP 04026983 A EP04026983 A EP 04026983A EP 1657298 A1 EP1657298 A1 EP 1657298A1
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EP
European Patent Office
Prior art keywords
water
acid
soluble
preparations
insoluble
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.)
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Application number
EP04026983A
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German (de)
English (en)
Inventor
Juan-Antonio Asensio
Josep-Lluis Viladot Petit
María De Moragas
Agustin Sanchez
Nuria Bonastre Gilabert
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Priority to EP04026983A priority Critical patent/EP1657298A1/fr
Publication of EP1657298A1 publication Critical patent/EP1657298A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the invention is in the field of detergents and relates to novel solid preparations for the release of active substances, a process for their preparation and their use for the preparation of various preparations.
  • Modern detergents in powder form e.g. Detergents, dishwashing detergents, cleaning agents, softeners or textile treatment agents - which are referred to below as WSR agents - are characterized by increasingly complex formulations that have to meet a wide variety of requirements.
  • An essential aspect of their formulation is that, in particular, sensitive drugs, e.g. Colorants or fragrances but also enzymes, compared with other constituents of the preparations with which they could react, are protected, which often happens by encapsulation.
  • sensitive drugs e.g. Colorants or fragrances but also enzymes
  • encapsulated active ingredients encapsulated dyes, which only serve the visual appearance of the preparations, should as far as possible not be released during the application process in order to prevent discoloration, for example during washing.
  • ingredients such as perfumes should be released throughout the application but delayed and not released in one go.
  • formulation ingredients such as Enzymes that intervene spontaneously, but only after a certain period of time or when a certain temperature has reached the application process.
  • the invention relates to solid preparations which are obtainable by absorbing a water- or oil-soluble active ingredient in a water-soluble or water-insoluble matrix.
  • variant i results in solid preparations which effectively protect the active ingredient (eg a perfume oil) from interacting with other formulation constituents, but dissolve within a short time in the washing process and the active ingredient delayed but completely release. If water-insoluble active ingredients are absorbed in a water-soluble matrix (variant ii), the active ingredients are released, for example, as part of the washing process in the form of a suspension.
  • the variant (iii), ie the combination of water-soluble matrix and water-insoluble active ingredient leads to the formation of a dispersion from which the active ingredient is released; a typical example is the delayed release of enzymes.
  • alternative (iv) has the case where both drug and matrix are water-insoluble. This is used, for example, to include dyes that should not be applied to the textiles.
  • active ingredients are dyes, flavors and fragrances which, depending on their chemical structure, may be water-soluble or water-insoluble.
  • Typical examples of expressly water-insoluble active ingredients are, in addition, fats and waxes, cosmetic oil bodies and enzymes.
  • active ingredients such as e.g. UV filters, plant extracts or biogenic agents in the same way, without the need for additional technical teaching.
  • Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. 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, ethylmethylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal to the ketones such as the ionone, ⁇ -isomethylionone and methylatedryl ketone to the alcohols Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams.
  • fragrance oils are suitable as perfume oils, eg sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
  • bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ -hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, ⁇ -damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, evernyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllat, irot
  • Suitable flavors are, for example, peppermint oil, spearmint oil, aniseed oil, star aniseed oil, caraway oil, eucalyptus oil, fennel oil, citron oil, wintergreen oil, clove oil, menthol and the like.
  • dyes the substances suitable and suitable for cosmetic purposes can be used, as compiled, for example, in the publication "Cosmetic Colorants” of the Dye Commission of the Irish Klastician, Verlag Chemie, Weinheim, 1984, pp. 81-106. Examples are Kochillerot A (CI 16255), Patent Blue V (CI42051), Indigotin (CI73015), Chlorophyllin (CI75810), Quinoline Yellow (CI47005), Titanium Dioxide (CI77891), Indanthrene Blue RS (CI 69800) and Krapplack (CI58000). As a luminescent dye and luminol may be included. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.
  • Typical examples of fats are glycerides, i. solid or liquid vegetable or animal products, consisting essentially of mixed glycerol esters of higher fatty acids, are used as waxes and the like.
  • natural waxes e.g. Candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin, crepe fat, ceresin, ozokerite (ground wax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes), e.g.
  • synthetic waxes such as e.g. Polyalkylene waxes and polyethylene glycol waxes in question.
  • fats come as additives and fat-like substances such as lecithins and phospholipids in question.
  • lecithin those skilled in the art will understand those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the art as Phosphatidylcholine (PC).
  • Examples of natural lecithins include the cephalins, which are also referred to as phosphatidic acids and derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids.
  • cephalins which are also referred to as phosphatidic acids and derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids.
  • phospholipids are usually understood as meaning mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally regarded as fats.
  • sphingosines or sphingolipids are also suitable.
  • esters of linear C 6 -C come based on fatty alcohols having 6 to 18, 22 fatty acids with linear or branched C 6 -C 22 -fatty alcohols or esters of branched C 6 - C 13 -carboxylic acids with linear or branched C 6 -C 22 -fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristylerucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, Ste
  • esters of linear C 6 -C 22 fatty acids with branched alcohols in particular 2-ethylhexanol
  • esters of C 18 -C 38 -alkylhydroxycarboxylic acids with linear or branched C 6 -C 22 fatty alcohols in particular dioctyl malates
  • esters of linear and / or branched fatty acids with polyhydric alcohols such as propylene glycol, dimerdiol or trimer triol
  • polyhydric alcohols such as propylene glycol, dimerdiol or trimer triol
  • Guerbet alcohols triglycerides based on C 6 -C 10 fatty acids, liquid mono- / di- / Triglyceridmisonne based on C 6 -C 18 fatty acids
  • Esters of C 6 -C 22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids in particular benzoic acid
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting Enzyme or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • Typical examples of water-soluble matrices are anionic, amphoteric, nonionic or cationic polymers. When anionic and cationic polymers are used together, typically water-insoluble matrices are formed.
  • anionic, zwitterionic, amphoteric and nonionic polymers are vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked polyols crosslinked with polyols, acrylamidopropyltrimethylammonium chloride / acrylate Copolymers, octylacrylamide / methylmethacrylate / tert.butylaminoethylmethacrylate / 2-hydroxypropylmethacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinylacetate copolymers, vinylpyrrolidone / dimethylaminoethylmethacrylate / vinylcaprolactam terpolymers, copo
  • a first group of particularly preferred anionic polymers are the salts of alginic acid.
  • Alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit: The average molecular weight of the alginic acids or alginates is in the range of 150,000 to 250,000.
  • Salts of alginic acid are to be understood as meaning both their complete and their partial neutralization products, in particular the alkali metal salts and, preferably, the sodium alginate ("algin”) as well as the ammonium and alkaline earth salts.
  • particularly preferred are mixed alginates such as sodium / magnesium or sodium / calcium alginates.
  • a second group of preferred (anionic) polymers are the poly (meth) acrylates having average molecular weights in the range of 5,000 to 50,000 daltons, as well as the various carboxymethylcelluloses and cyclodectrins (e.g., maltodextrins).
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethylcellulose which is obtainable under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF) , Condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers such as amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of Acrylic acid
  • Chitosans or oligochitosans are used as preferred cationic polymers.
  • Chitosans are biopolymers and are counted among the group of hydrocolloids. Chemically, they are partially deacetylated chitins of different molecular weight containing the following - idealized - monomer unit: Unlike most hydrocolloids, which are negatively charged at biological pH levels, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used.
  • For the production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available as cheap raw materials in large quantities.
  • the chitin is thereby used in a process first described by Hackmann et al. has been described, usually initially deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights may be distributed over a broad spectrum. Preference is given to using those types having an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 daltons and / or a Brookfield viscosity (1% strength by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and having an ash content of less than 0.3% by weight.
  • the chitosans are generally used in the form of their salts, preferably as glycolates.
  • Suitable water-insoluble matrices are, for example, starches, modified starches and inorganic compounds such as talc or silicates.
  • the solid preparations of the present invention generally have an average particle diameter in the range of 1 to 300, preferably 10 to 100 and in particular 20 to 50 micras. The particle size depends directly on the grain of the matrix.
  • the preparations may contain the active ingredients in an amount of 10 to 40 and preferably 20 to 30 wt .-%.
  • the matrices are still treated with a crosslinking agent and cured in order to protect the preparations against bleeding on the one hand and to ensure the highest possible loading of the active ingredient on the other hand.
  • the solid preparations according to the invention may contain other typical auxiliaries and additives in addition to the already mentioned active ingredients, for example anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, builders, co-polymers.
  • Builder oil and fat dissolving substances, bleaching agents, bleach activators, grayness inhibitors, optical brighteners, defoamers, disintegrants, inorganic salts and the like, as they are explained in more detail below.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino
  • anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using alkylbenzenesulfonates, alkyl sulfates, soaps, alkanesulfonates, olefinsulfonates, methyl ester sulfonates and mixtures thereof.
  • Preferred alkylbenzenesulfonates follow the formula (II), R 5 -Ph-SO 3 X (II) in which R 5 is a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • R 5 is a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms
  • Ph is a phenyl radical
  • X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Alkyl and / or alkenyl sulfates which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary and / or secondary alcohols which preferably follow the formula (III) , R 6 O-SO 3 X (III) in which R 6 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from the Roelen oxo synthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Particular preference is given to alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
  • alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
  • branched primary alcohols are oxo alcohols, as they are accessible, for example by reaction of carbon monoxide and hydrogen to alpha-olefins by the shop process.
  • Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
  • oxo alcohols as obtained by the classical oxo process of Enichema or the Condea by addition of carbon monoxide and hydrogen to olefins.
  • These alcohol mixtures are a mixture of highly branched alcohols.
  • Such alcohol mixtures are commercially available under the trade name Lial®.
  • Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
  • R 7 CO-OX (IV) Under soaps are further fatty acid salts of the formula (IV) to understand R 7 CO-OX (IV) in which R 7 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and in turn X is alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
  • Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • coconut or palm kernel fatty acids are used in the form of their sodium or potassium salts.
  • nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.
  • the preferred fatty alcohol polyglycol ethers follow the formula (V) , R 8 O (CH 2 CHR 9 O) n 1 H (V) in which R 8 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 9 is hydrogen or methyl and nl is a number from 1 to 20.
  • Typical examples are the addition products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol and Brassidylalkohol as well as their technical mixtures. Particularly preferred are addition products of 3, 5 or 7 moles of ethylene oxide to technical Kokosfettalkohole.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI) , R 10 CO (OCH 2 CHR 11) n 2 OR 12 (VI) in the R 10 CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 11 for hydrogen or methyl, R 12 for linear or branched alkyl radicals having 1 to 4 carbon atoms and n 2 for numbers from 1 to 20 stands.
  • Typical examples are the formal charge products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof.
  • the products are prepared by insertion of the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite.
  • catalysts such as, for example, calcined hydrotalcite.
  • Particularly preferred are reaction products of on average 5 to 10 moles of ethylene oxide in the ester bond of technical Kokosfettklamethylestern.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (VII), R 13 O- [G] p (VII) in which R 13 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or Alkenyloligoglykoside are thus alkyl and / or Alkenyloligo glucoside.
  • alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 13 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
  • Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 13 can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut oil having a DP of 1 to 3.
  • cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyl distearyl ammonium chloride or hydroxyethyl hydroxycetyl dimmonium chloride (Dehyquart E) or esterquats.
  • R 15 and R 16 are each independently hydrogen or R 14 CO
  • R 15 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H Group
  • m1, m2 and m3 are in total 0 or numbers from 1 to 12
  • m4 is numbers from 1 to 12
  • Y is halide, alkylsulfate or alkyl phosphate.
  • esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils.
  • the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used.
  • an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 tallow or palm oil fatty acid (iodine value 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven to be particularly advantageous in which R 14 CO is an acyl radical having 16 to 18 carbon atoms, R 15 is R 15 CO, R 16 is hydrogen, R 17 is a methyl group, m1 , m2 and m3 are 0 and Y is methylsulfate.
  • suitable esterquats are, in addition, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) , in the R 18 CO for an acyl radical having 6 to 22 carbon atoms, R 19 is hydrogen or R 18 CO, R 20 and R 21 are independently alkyl radicals having 1 to 4 carbon atoms, m5 and m6 in total for 0 or numbers from 1 to 12 and Y again represents halide, alkyl sulfate or alkyl phosphate.
  • R 22 CO for an acyl radical having 6 to 22 carbon atoms
  • R 23 is hydrogen or R 22 CO
  • R 24 , R 25 and R 26 are independently alkyl radicals having 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12
  • X again represents halide, alkyl sulfate or alkyl phosphate.
  • esterquats are substances in which the ester is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine, in which R 27 is CO for an acyl radical having 6 to 22 carbon atoms, R 28 is hydrogen or R 27 CO, R 29 and R 30 are independently alkyl radicals having 1 to 4 carbon atoms and Y is again halide, alkyl sulfate or alkyl phosphate.
  • Such Amidesterquats are available for example under the brand Incroquat® (Croda) in the market.
  • alkylbetaines examples include alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • suitable alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII) , R 31 is alkyl and / or alkenyl radicals having from 6 to 22 carbon atoms, R 32 is hydrogen or alkyl radicals having from 1 to 4 carbon atoms, R 33 is alkyl radicals having from 1 to 4 carbon atoms, q 1 is from 1 to 6, and Z is from 1 to 6 Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C 12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C 16/18 tallowalkyldimethylamine, and technical mixtures thereof.
  • R 34 CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • R 35 is hydrogen or alkyl radicals having 1 to 4 carbon atoms
  • R 36 is alkyl radicals having 1 to 4 carbon atoms
  • q 2 is from 1 to 4 6
  • q3 represents numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and technical mixtures thereof, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate.
  • condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.
  • imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • the washing, rinsing, cleaning and softening compositions according to the invention may additionally contain additional inorganic and organic builders, for example in amounts of from 10 to 50 and preferably from 15 to 35% by weight, based on the compositions, of which the main inorganic builders are zeolites crystalline phyllosilicates, amorphous silicates and - as far as permissible - phosphates, such as Tripolyphosphate be used.
  • the amount of co-builder is to be counted towards the preferred amounts of phosphates.
  • the finely crystalline, synthetic and bound water-containing zeolite frequently used as detergent builder is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P as well as Y are also suitable.
  • VEGOBOND AX® commercial product from Condea Augusta SpA
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have a average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 ⁇ yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred. Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • Suitable layered silicates which belong to the group of water-swellable smectites are, for example, those of the general formulas (OH) 4 Si 8-y Al y (Mg x Al 4-x ) O 20 montmorillonite (OH) 4 Si 8-y Al y (Mg 6-z Li z ) O 20 hectorite (OH) 4 Si 8-y Al y (Mg 6-z Al z ) O 20 saponite
  • the phyllosilicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na + and Ca 2+ , due to their ion-exchanging properties.
  • the amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing.
  • phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.
  • the preferred builder substances also include 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 are delay-delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” also "X-ray amorphous" Understood.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances, but at most one or more maxima of the scattered X-rays which are several angstroms in width of the diffraction angle.
  • the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments.
  • densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are especially preferred.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished agent.
  • tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished composition, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.
  • Useful organic builders which are suitable as co-builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is for ecological reasons not to complain about, as well as 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.
  • an acidifying component typically also serve to set a lower and milder pH of detergents or cleaners.
  • 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. Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000.
  • 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 customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100.
  • 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.
  • Suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Glycerol disuccinates and glycerol trisuccinates are also particularly preferred in this context. Suitable amounts are in zeolith City City and / or silicate-containing formulations at 3 to 15 wt .-%.
  • Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight from 800 to 150,000 (based on acid and each measured against polystyrene sulfonic acid).
  • Suitable copolymeric polycarboxylates are, 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 molecular weight relative to free acids is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000 (in each case measured against polystyrene sulfonic acid).
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • Granular polymers are usually added later to one or more basic granules. Also particularly preferred are biodegradable polymers of more than two different monomer units.
  • polymeric aminodicarboxylic acids, their salts or their precursors Particular preference is given to polyaspartic acids or their salts and derivatives.
  • polyacetals which are prepared 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, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • compositions may also contain components that positively affect oil and grease washability from fabrics.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the content of the bleaching agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, it being advantageous to use perborate monohydrate or percarbonate.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-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, 2,5-diacetoxy- 2,5-dihydrofuran, enol ester
  • Such bleach activators are contained in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.
  • sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes can also be present as so-called bleach catalysts.
  • Suitable transition metal compounds include in particular manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their N-analogues, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, , Cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, as well as cobalt, iron, copper and ruthenium amine complexes.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, based in each case on the total agent.
  • 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 carboxylic acids or ether sulfonic acids of starch or of 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.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminooeuvre, a methylamino group, an anilino group or a 2-Methoxyethylaminoxx carry.
  • brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.
  • Uniformly white granules are obtained when the means except the usual brighteners in conventional amounts, for example between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt .-%, even small amounts, for example 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).
  • Suitable soil repellents are those which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. More specifically, the molecular weight of the linking polyethylene glycol units is in the range of 750 to 5,000, that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100.
  • the polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure.
  • Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers comprising linking polyethylene glycol units having a molecular weight of from 750 to 5,000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhöne-Poulenc).
  • waxy compounds can be used as defoamers.
  • "Waxy” is understood as meaning those compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C.
  • the waxy defoamer substances are practically insoluble in water, i. at 20 ° C in 100 g of water they have a solubility below 0.1 wt .-%.
  • Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic esters of monohydric and polyhydric alcohols and paraffin waxes or mixtures thereof.
  • Suitable paraffin waxes are generally a complex mixture without a sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA) and / or its solidification point. This is the temperature at which the paraffin is cooled slowly from the liquid to the solid state. In this case, at room temperature completely liquid paraffins, that is those with a solidification point below 25 ° C, according to the invention not useful.
  • Soft waxes having a melting point in the range of 35 to 50 ° C preferably include the group of petrolates and their hydrogenation products. They are composed of microcrystalline paraffins and up to 70 wt .-% oil, have an ointment-like plastic to solid consistency and represent bitumen-free residues from petroleum processing.
  • distillation residues certain paraffin-based and mixed basic crude oils, which is further processed to Vaseline become.
  • These petrolates represent the most important starting point for the production of microwaxes.
  • These petrolatum are mixtures of microcrystalline waxes and refractory n-paraffins.
  • paraffin wax mixtures of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax having a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C.
  • paraffins or paraffin mixtures are used which solidify in the range of 30 ° C to 90 ° C.
  • paraffin wax mixtures may contain different proportions of liquid paraffin.
  • this liquid fraction is as low as possible and is preferably completely absent.
  • particularly preferred paraffin wax mixtures at 30 ° C have a liquid content of less than 10 wt .-%, in particular from 2 wt .-% to 5 wt .-%, at 40 ° C, a liquid content of less than 30 wt .-%, preferably from 5 Wt .-% to 25 wt .-% and in particular from 5 wt .-% to 15 wt .-%, at 60 ° C, a liquid content of 30 wt .-% to 60 wt .-%, in particular of 40 wt .-%.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is, in the case of particularly preferred paraffin wax mixtures, still below 85 ° C., in particular at 75 ° C. to 82 ° C.
  • the paraffin waxes may be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
  • Suitable bisamides as defoamers are those which are derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic esters as defoamers are derived from carboxylic acids having 12 to 28 carbon atoms. In particular, they are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
  • the alcohol portion of the carboxylic acid ester contains a monohydric or polyhydric alcohol having 1 to 28 carbon atoms in the hydrocarbon chain.
  • suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut oil, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol and also ethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
  • Preferred esters are those of ethylene glycol, glycerol and sorbitan, wherein the acid portion of the ester is selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • Suitable esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate and mixed tallow alkyl sorbitan mono- and diesters.
  • Useful glycerol esters are the mono-, di- or triesters of glycerol and said carboxylic acids, the mono- or diesters being preferred.
  • Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glyceryl distearate are examples of this.
  • suitable natural esters as defoamers are beeswax, which consists mainly of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3
  • carnauba wax which is a mixture of carnaubaic acid alkyl esters, often in combination with low levels of free carnaubaic acid, other long chain acids, high molecular weight alcohols and hydrocarbons.
  • Suitable carboxylic acids as further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, which are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil.
  • Preferred are saturated fatty acids having 12 to 22, in particular 18 to 22 C-atoms. In the same way, the corresponding fatty alcohols of the same C chain length can be used.
  • dialkyl ethers may additionally be present as defoamers.
  • the ethers may be asymmetric or symmetric, i. contain two identical or different alkyl chains, preferably having 8 to 18 carbon atoms.
  • Typical examples are di-n-octyl ethers, di-i-octyl ethers and di-n-stearyl ethers, particularly suitable are dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C.
  • Further suitable defoamer compounds are fatty ketones, which are according to relevant methods of preparative organic chemistry can be obtained.
  • Suitable fatty ketones are those prepared by pyrolysis of the magnesium salts of lauric, myristic, palmitic, palmitoleic, stearic, oleic, elaidic, petroselic, arachidic, gadoleic, behenic or erucic acid.
  • fatty acid polyethylene glycol esters which are preferably obtained by basic homogeneously catalyzed addition of ethylene oxide to fatty acids.
  • the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
  • alkanolamines especially triethanolamine, results in extremely selective ethoxylation of the fatty acids, especially when it comes to producing low ethoxylated compounds.
  • Suitable silicones are customary organopolysiloxanes which may have a finely divided silica content, which in turn may also be silanated. Particularly preferred are polydiorganosiloxanes and especially polydimethylsiloxanes known in the art. Suitable polydiorganosiloxanes have a nearly linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
  • silicones which may be both liquid and resinous at room temperature.
  • simethicones which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates.
  • the silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which may also be silanated.
  • siliceous dimethyl polysiloxanes are particularly suitable for the purposes of the present invention.
  • the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C (spindle 1, 10 rpm) in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
  • the silicones are used in the form of their aqueous emulsions.
  • the silicone is added to the initially charged water with stirring.
  • thickening agents known in the art may be added to increase the viscosity of the aqueous silicone emulsions.
  • nonionic cellulose ethers such as methylcellulose, ethylcellulose and mixed ethers such as methylhydoxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutylcellulose and anionic carboxycellulose types such as the carboxymethylcellulose sodium salt (abbreviation CMC).
  • Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
  • concentrations of approximately 0.5 to 10, in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion use concentrations of approximately 0.5 to 10, in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion.
  • the content of silicones of the type described in the aqueous emulsions is advantageously in the range of 5 to 50 wt .-%, in particular from 20 to 40 wt .-% - calculated as silicones and based on aqueous silicone emulsion.
  • the aqueous silicone solutions as thickener starch which is accessible from natural sources, such as rice, potatoes, corn and wheat.
  • the starch is advantageously present in amounts of from 0.1 to 50% by weight, based on the silicone emulsion, and in particular as a mixture with the thickener mixtures already described thick mixtures of sodium carboxymethylcellulose and a nonionic cellulose ether in the quantities already mentioned.
  • the thickeners if present, are allowed to pre-swell in water before the addition of the silicones takes place.
  • the incorporation of the silicones is expediently carried out with the aid of effective stirring and mixing devices.
  • the paraffin waxes described are particularly preferably used alone as waxy defoamers or in admixture with one of the other waxy defoamers, wherein the proportion of paraffin waxes in the mixture is preferably more than 50% by weight, based on waxy defoamer mixture.
  • the paraffin waxes can be applied to carriers as needed.
  • carrier material all known inorganic and / or organic carrier materials are suitable. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminosilicates, water-soluble phyllosilicates, alkali metal silicates, alkali metal sulphates, for example sodium sulphate, and alkali metal phosphates.
  • the alkali metal silicates are preferably a compound having a molar ratio of alkali metal oxide to SiO 2 of from 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good Komeigenschaften, in particular high abrasion stability and yet high dissolution rate in water.
  • the aluminosilicates referred to as support material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
  • silicates can be used, which are under the name Aerosil® or Sipernat® commercially.
  • Suitable organic support materials are, for example, film-forming polymers, for example polyvinyl alcohols, polyvinylpyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
  • Useful cellulose ethers are, in particular, alkali metal carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose and so-called cellulose mixed ethers, such as, for example, methylhydroxyethylcellulose and methylhydroxypropylcellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethylcellulose and methylcellulose, wherein the carboxymethylcellulose usually has a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methylcellulose has a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali metal carboxymethylcellulose and nonionic cellulose ethers in weight ratios of from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • Native starch composed of amylose and amylopectin is also suitable as the carrier. Starch is starch, as it is available as an extract from natural sources, such as rice, Potatoes, corn and wheat. Native starch is a commercial product and thus easily accessible.
  • one or more of the abovementioned compounds can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulphates, alkali metal phosphates, zeolites, water-soluble phyllosilicates, alkali silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • Particularly suitable are mixtures of alkali metal carbonates, in particular sodium carbonate, alkali metal silicates, in particular sodium silicate, alkali metal sulphates, in particular sodium sulphate and zeolites.
  • the solid preparations may further contain disintegrants or disintegrants. These are substances which are added to the shaped bodies in order to accelerate their decomposition upon contact with water. These substances increase their volume upon ingress of water, whereby on the one hand the intrinsic volume increases (swelling), on the other hand a pressure can be generated by the release of gases which causes the tablet to disintegrate into smaller particles.
  • 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 optionally crosslinked polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • PVP polyvinylpyrrolidone
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 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 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 hydroxyl 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 said cellulose derivatives 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, more preferably below 20% by weight, based on the disintegrating agent on cellulose basis. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
  • microcrystalline cellulose can be used as a further disintegrating agent based on cellulose or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact.
  • Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
  • the disintegrating agents can be homogeneously distributed macroscopically in the molded body, but microscopically they form zones of increased concentration due to their production.
  • Disintegrating agents which may be present within the meaning of the invention are, for example, collidone, alginic acid and their alkali metal salts, amorphous or even partially crystalline layered silicates (bentonites), polyacrylates, polyethylene glycols.
  • the preparations may contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15 wt .-% - based on the moldings.
  • compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which do not have outstanding builder properties, or mixtures of these;
  • alkali metal carbonate and / or amorphous alkali silicate especially sodium silicate with a molar ratio of Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the final preparations is preferably up to 40 wt .-%, advantageously between 2 and 35 wt .-%.
  • the content of sodium silicate (without particular builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • Sodium sulfate in amounts of from 0 to 10, in particular from 1 to 5,% by weight, based on the composition, can furthermore be contained as filling or setting agent
  • the detergents obtainable using the additives according to the invention can be prepared or used in the form of powders, extrudates, granules or agglomerates. It can be both universal and fine or color detergents, optionally in the form of compactates or supercompacts.
  • the agents are prepared by mixing together various particulate components containing detergent ingredients.
  • the particulate components can be prepared by spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation. It is preferred in particular that at least one surfactant-containing component is produced by fluidized bed granulation.
  • aqueous preparations of the alkali silicate and of the alkali carbonate are sprayed together with other detergent ingredients in a drying device, wherein granulation can take place simultaneously with the drying.
  • the drying device in which the aqueous preparation is sprayed, may be any dry equipment.
  • the drying is carried out as spray drying in a drying tower.
  • the aqueous preparations are exposed in a known manner a drying gas stream in finely divided form.
  • Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed therein is hereby expressly also made the subject of the present invention disclosure.
  • a particularly preferred way to prepare the means is to subject the precursors to fluidized bed granulation ("SKET" granulation).
  • SKET fluidized bed granulation
  • the precursors can be used both in the dried state and as an aqueous preparation.
  • Preferably used fluidized bed apparatus have bottom plates with dimensions of 0.4 to 5 m.
  • the granulation is carried out at fluidized air velocities in the range of 1 to 8 m / s.
  • the discharge of the granules from the fluidized bed is preferably carried out via a size classification of the granules.
  • the classification can be done for example by means of a sieve or by an opposite air flow (classifier air), which is regulated so that only particles from a certain particle size of the Fluidized bed removed and smaller particles are retained in the fluidized bed.
  • classifier air an opposite air flow
  • the incoming air is composed of the heated or unheated classifier air and the heated bottom air.
  • the soil air temperature is between 80 and 400, preferably 90 and 350 ° C.
  • a starting material for example a granulate from a previous experimental batch, is initially introduced at the beginning of the granulation.
  • the mixtures are subsequently subjected to a compaction step, with further ingredients being added to the compositions only after the compaction step.
  • the compaction of the ingredients takes place in a preferred embodiment of the invention in a press agglomeration process.
  • the press agglomeration process to which the solid premix (dried base detergent) is subjected, can be realized in various apparatuses. Depending on the type of agglomerator used, different press agglomeration processes are distinguished.
  • the four most common and in the present invention preferred press agglomeration processes are the extrusion, the roll pressing or compaction, the hole pressing (pelletizing) and tableting, so that in the present invention preferred press agglomeration processes extrusion, Walzenkompakt réelles-, pelletizing or Tabletting operations are.
  • binders can be used as an aid for compaction. However, it should be made clear that it is always possible to use several different binders and mixtures of different binders.
  • a binder is used which is completely present as a melt at temperatures up to a maximum of 130 ° C., preferably up to a maximum of 100 ° C. and in particular up to 90 ° C. The binder must therefore be selected according to the process and process conditions or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.
  • the actual compression process is preferably carried out at processing temperatures which correspond at least in the compression step at least the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt.
  • the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder.
  • Such a temperature control has the further advantage that even thermally sensitive raw materials, for example peroxy bleaches such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious losses of active substance.
  • the possibility of precise temperature control of the binder in particular in the decisive step of the compression, ie between the mixing / homogenization of the premix and the shaping, allows an energetically very favorable and extremely gentle for the temperature-sensitive components of the premix process, since the premix for a short time the is exposed to higher temperatures.
  • the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roll compactor and the press roll (s) of the pellet press) have a maximum temperature of 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C and the process temperature is 30 ° C and in particular at most 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the action of temperature in the compression region of the press agglomerators is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • Preferred binders which can be used alone or in admixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a molecular weight of between 600 and 12,000 and in particular between 1,000 and 4,000.
  • polyethylene glycols include polymers in the production of which, in addition to ethylene glycol, C 3 -C 5 glycols and also glycerol and mixtures thereof are used as starting molecules. Also included are ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO.
  • the polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols.
  • Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols having a molecular weight of about 4,000 can be used and Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols having a molecular weight between 3,500 and 5,000.
  • polyethylene glycols which are present in liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech.
  • these per se liquid polyethylene glycols should be used only in a mixture with at least one other binder, said mixture must meet the requirements of the invention again, ie must have a melting point or softening point of at least above 45 ° C.
  • suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of not more than 30,000. Preference is given here to molecular weight ranges between 3,000 and 30,000, for example around 10,000.
  • Polyvinylpyrrolidones are preferably not used as sole binders but in combination with others. especially in combination with polyethylene glycols used.
  • the compacted material preferably has temperatures not exceeding 90 ° C. directly after leaving the production apparatus, temperatures between 35 and 85 ° C. being particularly preferred. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
  • the detergent according to the invention is produced by means of an extrusion.
  • a solid premix under pressure is strand-shaped pressed and the strand after leaving the hole shape by means of a cutting device tailored to the pre-definable granule dimension.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers.
  • the pre-mixture is preferably supplied to a planetary roller extruder or a 2-screw extruder with co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature.
  • the premix under pressure which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally
  • the extrudate is reduced to about spherical to cylindrical granules by means of a rotating bladed knife.
  • the hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules of a substantially uniformly previously determinable particle size succeeds, wherein in detail the absolute particle sizes can be adapted to the intended use.
  • particle diameters of at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 3 mm.
  • the length / diameter ratio of the chopped primary granules is preferably in the range from about 1: 1 to about 3: 1.
  • extrusions / compression can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in Bexx Bextruder.
  • the temperature control is preferred designed in the transition region of the screw, the pre-distributor and the nozzle plate such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least achieved, but preferably exceeded.
  • the duration of the action of temperature in the compression region of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the WSR agents can also be made by roll compaction.
  • the premix is selectively metered between two smooth or provided with wells of defined shape rollers and rolled between the two rollers under pressure to form a sheet-like Kompaktat, the so-called scoop.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rolls smooth, unstructured flake tapes are obtained, while by using structured rolls, correspondingly structured flakes can be produced in which, for example, certain shapes of the later detergent particles can be specified.
  • the sling strip is subsequently broken by a tee and crushing process into smaller pieces and can be processed in this way to granules which can be refined by further known per se surface treatment methods, in particular brought into approximately spherical shape.
  • the temperature of the pressing tools, ie the rolls is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C.
  • Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the action of temperature in the compression region of the smooth rolls or rolls provided with depressions of defined shape amounts to a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • the detergent according to the invention can also be produced by means of pelleting.
  • the premix is applied to a perforated surface and by means of a pressurizing body pressed under plasticization through the holes.
  • the premix is compacted under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted with a knock-off device to granules.
  • pressure roller and perforated die conceivable.
  • flat perforated plates are used as well as concave or convex ring matrices, through which the material is pressed through one or more pressure rollers.
  • the press rollers can also be conically shaped in the plate devices, in the annular devices can matrices and press roller (s) have co-rotating or opposite directions of rotation.
  • the ring matrix press disclosed in this document consists of a rotating ring die interspersed by press channels and at least one press roller operatively connected to its inner surface, which presses the material supplied to the die space through the press channels into a material discharge.
  • ring matrix and press roller are driven in the same direction, whereby a reduced shear stress and thus lower temperature increase of the premix can be realized.
  • pelletizing with heatable or coolable rollers in order to set a desired temperature of the premix.
  • the temperature of the pressing tools is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C.
  • Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the production of moldings is usually carried out by tabletting or press agglomeration.
  • the resulting particulate press agglomerates can either be used directly as a detergent or be aftertreated and / or processed by conventional methods beforehand.
  • the usual post-treatments include, for example, powdering with finely divided ingredients of detergents or cleaners, whereby the bulk density is generally further increased.
  • a preferred aftertreatment is the procedure in which dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particle-shaped process end products according to the invention, which serve as the core, and thus agents are formed which have these so-called fine fractions as outer shell.
  • this is again done by a Melt agglomeration.
  • the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
  • the base of these tablets may, for example, be circular or rectangular.
  • Multi-layer tablets, especially tablets with 2 or 3 layers, which may also be different in color, are especially preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
  • the tablets may also contain pressed and unpressed portions. Moldings having a particularly advantageous dissolution rate are obtained when the granular constituents before pressing have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight.
  • a mixing device 100 g of a polyacrylate powder having an average molecular weight of 10,000 daltons and an average particle size of 15 micras were introduced and added in portions with 30 g of phenoxyethyl isobutyrate. The resultant resulting powder was treated with a 10 wt% aqueous solution of hexamethylenediamine over a period of 10 hours and then dried.
  • a mixing device 100 g of a polycondensation product of acrylic acid and chitosan were presented an average particle size of 50 micras and added in portions with 35 g of limonene. Subsequently, the preparation was treated over a period of 5 hours each first with a 10 wt .-% solution of hexamethylenediamine and then a 2 wt .-% solution of glutaraldehyde and then dried.
  • a mixing device 50 g of a water-soluble maltodextrin (N-Zorbitol M, National Starch) were introduced and added in portions with 50 g of a perfume oil.
  • a water-soluble maltodextrin N-Zorbitol M, National Starch
  • a mixing device 70 g of a modified starch (Natrasorb, National Starch) were added and added portionwise with 30 g of a perfume oil.
  • a modified starch Natrasorb, National Starch

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Dispersion Chemistry (AREA)
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EP04026983A 2004-11-12 2004-11-12 Compositions solides Withdrawn EP1657298A1 (fr)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1935711A1 (de) * 1969-02-19 1970-08-20 Boehringer Mannheim Gmbh Wasserunloesliches,traegergebundenes Protein
DE1695662A1 (de) * 1967-12-27 1971-04-22 Roehm & Haas Gmbh Traegergebundene proteinartige Wirkstoffe
EP0049385A1 (fr) * 1980-10-02 1982-04-14 BASF Aktiengesellschaft Polymère sous forme de perles utilisé pour immobiliser les enzymes
DE3228477A1 (de) * 1982-07-30 1984-02-02 UOP Inc., 60016 Des Plaines, Ill. Magnetisches immobilisiertes enzymsystem und traegergrundmaterial hierfuer
EP0294711A1 (fr) * 1987-06-10 1988-12-14 Kali-Chemie Aktiengesellschaft Procédé de préparation d'enzymes fixées sur un support
DE19735783A1 (de) * 1997-08-18 1999-02-25 Henkel Kgaa Hochdosierte Duftstoff-Formkörper
WO1999021955A1 (fr) * 1997-10-23 1999-05-06 Henkel Kommanditgesellschaft Auf Aktien Procede servant a preparer un produit lavant ou detergent au parfum renforce
US20030087788A1 (en) * 1998-02-02 2003-05-08 Giles Guerin Water-dispersible granules comprising a fragrance in a water-soluble or water-dispersible matrix, and process for their preparation
DE10156880A1 (de) * 2001-11-20 2003-06-12 Henkel Kgaa Löslichkeitsverbesserte Polymere
DE10164137A1 (de) * 2001-12-30 2003-07-10 Henkel Kgaa Mittel enthaltender Formkörper mit erhöhter Lagerstabilität
US20040097386A1 (en) * 2000-09-08 2004-05-20 Norbert Trage Care gents

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1695662A1 (de) * 1967-12-27 1971-04-22 Roehm & Haas Gmbh Traegergebundene proteinartige Wirkstoffe
DE1935711A1 (de) * 1969-02-19 1970-08-20 Boehringer Mannheim Gmbh Wasserunloesliches,traegergebundenes Protein
EP0049385A1 (fr) * 1980-10-02 1982-04-14 BASF Aktiengesellschaft Polymère sous forme de perles utilisé pour immobiliser les enzymes
DE3228477A1 (de) * 1982-07-30 1984-02-02 UOP Inc., 60016 Des Plaines, Ill. Magnetisches immobilisiertes enzymsystem und traegergrundmaterial hierfuer
EP0294711A1 (fr) * 1987-06-10 1988-12-14 Kali-Chemie Aktiengesellschaft Procédé de préparation d'enzymes fixées sur un support
DE19735783A1 (de) * 1997-08-18 1999-02-25 Henkel Kgaa Hochdosierte Duftstoff-Formkörper
WO1999021955A1 (fr) * 1997-10-23 1999-05-06 Henkel Kommanditgesellschaft Auf Aktien Procede servant a preparer un produit lavant ou detergent au parfum renforce
US20030087788A1 (en) * 1998-02-02 2003-05-08 Giles Guerin Water-dispersible granules comprising a fragrance in a water-soluble or water-dispersible matrix, and process for their preparation
US20040097386A1 (en) * 2000-09-08 2004-05-20 Norbert Trage Care gents
DE10156880A1 (de) * 2001-11-20 2003-06-12 Henkel Kgaa Löslichkeitsverbesserte Polymere
DE10164137A1 (de) * 2001-12-30 2003-07-10 Henkel Kgaa Mittel enthaltender Formkörper mit erhöhter Lagerstabilität

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