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WO2000032736A1 - Additif pour detergent et nettoyant et procede permettant de le preparer - Google Patents

Additif pour detergent et nettoyant et procede permettant de le preparer Download PDF

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Publication number
WO2000032736A1
WO2000032736A1 PCT/EP1999/009011 EP9909011W WO0032736A1 WO 2000032736 A1 WO2000032736 A1 WO 2000032736A1 EP 9909011 W EP9909011 W EP 9909011W WO 0032736 A1 WO0032736 A1 WO 0032736A1
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WIPO (PCT)
Prior art keywords
weight
detergent
cleaning agent
inhibitors
group
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.)
Ceased
Application number
PCT/EP1999/009011
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German (de)
English (en)
Inventor
Andreas Lietzmann
Adolf Wiche
Kathleen Paatz
Birgit Burg
Bernd Larson
Markus Semrau
Christian Block
Hans-Friedrich Kruse
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP99956028.7A priority Critical patent/EP1135455B2/fr
Priority to DE59909136T priority patent/DE59909136D1/de
Priority to ES99956028.7T priority patent/ES2220126T5/es
Priority to AT99956028T priority patent/ATE263830T1/de
Publication of WO2000032736A1 publication Critical patent/WO2000032736A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads

Definitions

  • the present invention relates to particulate additives for detergents and cleaning agents which contain so-called “small components” such as dyes, enzymes, optical brighteners, etc.
  • Modern detergents and cleaning agents are, however, increasingly being manufactured using granulation processes in order to achieve higher bulk densities and thus advantages in packaging, storage and transport. These products have a high degree of compaction and a greatly reduced pore volume. If liquids are sprayed onto such granules, the product is then very sticky.
  • the object of the present invention was to provide a small component compound which can be added directly to the finished detergent and cleaning agent in the preparation of surfactant granules and which shows no tendency to segregate. Furthermore, a manufacturing method for such a small component compound should be provided which is inexpensive, universally applicable and can be carried out without great outlay on equipment and with little cleaning effort.
  • the present invention relates to a detergent and cleaning agent additive which a) 40 to 98.9% by weight of carrier material with an oil absorption capacity of at least 20 g / 100 g, b) 1 to 50% by weight of one or more at temperatures up to 40 ° C liquid binder, c) 0.1 to 40% by weight of a detergent and cleaning agent ingredient from the group of enzymes, pH regulators, fluorescent agents, dyes, foam inhibitors, anti-deposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and contains corrosion inhibitors and mixtures thereof.
  • the carrier material contained in the laundry detergent and cleaning agent additives according to the invention has an oil absorption capacity of at least 20 g / 100 g. However, preference is given to using oil absorption components which have a higher oil absorption capacity. Detergent and cleaning agent additives are preferred in which the carrier material contained therein has an oil absorption capacity of at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular at least 140g / 100g.
  • the oil absorption capacity is a physical property of a substance that can be determined using standardized methods.
  • the British standard methods BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard.
  • the test methods use a balanced sample of the substance in question applied to a plate and added dropwise with refined linseed oil (density: 0.93 "3" ) from a burette. After each addition, the powder is mixed intensively with the oil using a spatula, the addition of oil being continued until a Paste of smooth consistency is reached. This paste should flow or run without crumbling.
  • the oil absorption capacity is now the amount of the added oil, based on 100g absorbent and is given in ml / 100g or g / lOOg, with conversions about the density of linseed oil are easily possible.
  • the oil absorption component preferably has the smallest possible average particle size, since the active surface increases with decreasing particle size.
  • all particles of the carrier material are smaller than 200 ⁇ m, preferably smaller than 100 ⁇ m, particularly preferably smaller than 75 ⁇ m and in particular smaller than 50 ⁇ m.
  • the carrier material is even finer, i.e. that the component with an oil absorption capacity of at least 20 g / 100 g has an average particle size of less than 50 ⁇ m, preferably less than 20 ⁇ m and in particular less than 10 ⁇ m.
  • a large number of substances are suitable as a carrier material.
  • inorganic and organic substances that have a sufficiently large oil absorption capacity.
  • examples include finely divided substances that are obtained by precipitation.
  • silicates, aluminosilicates, calcium silicates, magnesium silicates and calcium carbonate are used as substances.
  • Diatomaceous earth (diatomaceous earth) and finely divided cellulose fibers or derivatives thereof can also be used in the context of the present invention.
  • Preferred detergent and cleaning agent additives are distinguished by the fact that the carrier materials they contain with an oil absorption capacity of at least 20 g / 100 g are selected from the group of silicates and / or aluminum silicates, in particular from the group of silicas and / or zeolites.
  • fine-particle zeolites are suitable, but also pyrogenic silica (Aerosil ®) or silicas obtained by precipitation.
  • Detergent and cleaning agent additives preferred in the context of the present invention contain the carrier Germ material in amounts of 50 to 95 wt .-%, preferably from 55 to 85 wt .-% and in particular from 60 to 80 wt .-%, each based on the additive.
  • the detergent and cleaning agent additives according to the invention contain, as second components, 1 to 50% by weight of one or more binders which are liquid at temperatures up to 40 ° C.
  • binders which are liquid at temperatures up to 40 ° C.
  • the term “liquid binder” here refers to the physical state of the binder at temperatures up to 40 ° C. and 1013 mbar. Substances that melt or soften only at higher temperatures or those that boil at temperatures up to 40 ° C. are therefore cannot be used in the context of the present invention.
  • liquid binder (s) Preferred amounts in which the liquid binder (s) are used are within a narrow range, so that preferred detergent and cleaning agent additives contain the liquid binder (s) in amounts of 5 to 47.5% by weight, preferably 7 , 5 to 45 wt .-% and in particular from 10 to 40 wt .-%, each based on the additive.
  • binders contained in the detergent and cleaning agent additives according to the invention that they are liquid at 40 ° C. (and normal pressure).
  • binders from the multitude of binders that can be used, substances from the group of polyethylene glycols and polypropylene glycols, glycerin, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate, as well as perfume oils, paraffins, silicone oils and ethoxylated fatty alcohols have proven to be suitable binders.
  • Polyethylene glycols which can be used according to the invention are polymers of ethylene glycol which have the general formula I
  • n can have values between 1 (ethylene glycol, see below) and approx. 16.
  • the decisive factor in evaluating whether a polyethylene glycol can be used according to the invention is the physical state of the PEG at room temperature, ie the solidification point of the PEG must be below 25 ° C.
  • PEG the average relative molecular weight following the specification "PEG” is customary in technical terms, so that "PEG 200” characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature, the technically customary polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.
  • polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone - Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
  • Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which have the general formula II
  • n values can be between 1 (propylene glycol, see below) and approx. 12.
  • n values can be between 1 (propylene glycol, see below) and approx. 12.
  • Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO contact via the glycide stage.
  • Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-l-propanol), which is converted under pressure in the presence of catalysts with CO to glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1.398 "3 that boils at 125-130 ° C (0.15 mbar).
  • Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113.
  • the freezing point of ethylene glycol is -11, 5 ° C, the liquid boils at 198 ° C.
  • ethylene glycol is obtained from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be based on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
  • 1,3-propanediol trimethylene glycol
  • 1,3-Propanediol can be produced from acrolein and water with subsequent catalytic hydrogenation.
  • 1,2-propanediol propylene glycol
  • 1,2-propanediol propylene glycol
  • Propylene carbonate is a water-bright, easily movable liquid with a density of 1.2057 "3 , the melting point is -49 ° C, the boiling point is 242 ° C 80 bar accessible.
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propalate and styrallyl propalate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • Paraffins suitable as binders in the context of the present invention are liquid mixtures of purified, saturated aliphatic hydrocarbons (paraffins) which contain are odorless and tasteless, easily dissolve in ether and chloroform, do not dissolve in water and 90% alcohol and do not fluoresce.
  • DAB9 describes two so-called medical white oils: viscous paraffin (Paraffmum liquidum), an oily liquid with a density of 0.827-0.890 with a viscosity of 110-230 mPas and thin liquid paraffin (Paraffmum perliquidum), an oily liquid with a density of 0.810-0.875 with a viscosity of 25-80 mPas.
  • liquid paraffin forms are often added to mineral oils and are collectively referred to as paraffin oil or white oil.
  • Silicone oils are linear polydimethylsiloxanes in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon are saturated by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups, etc.) ; poly (methylphenylsiloxanes) are also used.
  • the silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids that have molar masses between 1000-150000 Daltons and densities from 0.94 to 0.97 and viscosities between 10 and 1000000 mPas (only slightly dependent on temperature). They are permanently heat-resistant in air up to approx.
  • silicone oils are not very resistant to strong inorganic acids and bases, but to salts, some oxidizing agents and soaps, are gas permeable and water-repellent.
  • Preferred silicone derivatives are, for example, poly-dialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are partially or completely fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 centistokes at 25 ° C., the silicones usually being able to be used in amounts between 0.2 and 1% by weight, based on the ready-made detergent.
  • fatty alcohol alkoxylates can also be used as binders, provided they are or become liquid up to 40 ° C.
  • These compounds also known as fatty alcohol polyglycol ethers or alkyl polyglycol ethers, form a group are nonionic surfactants which are obtained by alkoxylation, but preferably ethoxylation, of primary fatty alcohols or oxo alcohols in the presence of basic or acidic catalysts at temperatures of 150-200 ° and pressures of 1-10 bar.
  • a polyglycol ether mixture of homologs of different degrees of alkoxylation is formed, the distribution of which, depending on the catalyst and the amount of alkoxide, between a Gaussian and the corresponding statistic. of an unselective Schulz-Flory curve can vary. For example, a broad homolog distribution is obtained in the presence of sodium hydroxide and a narrow-range homolog distribution using alkaline earth metal salts.
  • basic catalysts for example sodium methylate in methanol, are preferably used in industry.
  • fatty alcohol ethoxylates are used as binders, preference is given to using products with degrees of ethoxylation below 10, for example with average degrees of ethoxylation of 5, 6, 7 or 8.
  • Medium degrees of ethoxylation can also be fractional numbers, although lower degrees such as 1.5 or medium degrees of 5.5 can also be set.
  • the chain length of the fatty alcohols which are converted to the ethoxylates is usually in the range from 8 to 22, preferably from 10 to 20 and in particular from 12 to 18 carbon atoms.
  • binders mixtures of the named binders with water can also be used as binders.
  • a maximum of 50% by weight of the binder may consist of water, the water content of the binder (more precisely: the binder mixture or the binder solution) preferably being lower, for example below 40% by weight, preferably below 30% by weight and particularly preferably below 20% by weight, in each case based on the binder.
  • the color impression of the compound can be controlled to a considerable extent by the choice of the liquid binder.
  • the dye Sandolan ® Rhodamine gives a violet compound when using glycerin as a binder on zeolite
  • the same carrier material is obtained by using fatty alcohol. lethoxylates as a binder a pink compound.
  • a combination of blue and yellow dyes can result in a blue zeolite-based compound through a mixture of water and glycerin, while the exchange of glycerin with PEG 400 leads to a green compound.
  • the technician will have no difficulty in providing certain color impressions of the compounds to be produced by selecting the binder.
  • the variations described are particularly important in the case of dyes, and processing advantages can be achieved in the case of other “small components” by the choice of the binder.
  • the “small components” that can be used are described below.
  • the third component which is contained in the detergent and cleaning agent additives according to the invention, is a detergent and cleaning agent ingredient from the group mentioned above.
  • Such ingredients the proportion of which in the ready-made detergent and cleaning agent usually makes up no more than 2% by weight, are often referred to as "small components".
  • detergent and cleaning agent additives include the detergent and cleaning agent ingredient from the group of enzymes, pH adjusters, fluorescent agents, dyes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors and mixtures thereof in amounts from 0.1 to 40% by weight, preferably from 1 to 15% by weight, particularly preferably from 2 to 10% by weight and in particular from 2.5 to 5% by weight, in each case based on the
  • preferred detergent and cleaning agent additives include the detergent and cleaning agent ingredient from the group of enzymes, pH adjusters, fluorescent agents, dyes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors and mixtures thereof in amounts from 0.1 to 40% by weight, preferably from 1 to 15% by weight, particularly preferably from 2 to 10% by weight and in particular from 2.5 to 5% by weight, in each case based on the The small components mentioned above are briefly described below.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and li pase or protease, lipase and cellulase, but especially cellulase-containing mixtures of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the pH adjusting agents have the task of bringing the pH value of the washing and cleaning liquor into the desired range, whereby acidic or alkaline adjusting agents can be used, depending on the other composition of the washing and cleaning agents.
  • acidic or alkaline reacting substances does not pose any difficulties for the person skilled in the art.
  • Fluorescent agents or fluorescent dyes that u./od. Fluorescent in UV light can be used to dye detergents and cleaning agents.
  • Suitable fluorescent dyes for fluorescent colors belong to the acridines, xanthene (e.g. fluorescein, rhodamine), thioxanthenes, pyrenes and other classes.
  • the optical brighteners (whiteners) that are added to detergents also belong to the group of fluorescent dyes, see below.
  • All dyes are preferred as dyes which have a high storage stability and insensitivity to the other ingredients of the agents and to light and have no pronounced substantivity towards textile fibers in order not to dye them. It can be advantageous if the dyes can be oxidatively destroyed in the washing process. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances.
  • anionic colorants for example anionic nitroso dyes, are suitable.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020). Which as a commercial product ® for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes.
  • Pigmosol 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 ® Patent blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol Blue ® GLW
  • white powders can also be used.
  • titanium dioxide and sodium sulfate are suitable as possible substances.
  • the detergent and cleaning agent additives can also contain components as small components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • optical brighteners such as, for example, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • optical brighteners such as, for example, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenyl styrene type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4'- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used
  • Color transfer inhibitors are intended to prevent detached dye from being absorbed onto other textiles and staining them when washing colored textiles.
  • Suitable substances come from the group of polymers, with polyvinylpyrrolidone occupying an outstanding position.
  • the additives according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • 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 urocanoic acid are also suitable.
  • Another object of the present invention is a process for the production of a detergent and cleaning agent additive, in which a detergent and cleaning agent ingredient from the group of enzymes, pH adjusters, fluorescent agents, dyes, visual space inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, bitters, color transfer inhibitors and corrosion inhibitors and mixtures thereof are dissolved or suspended in one or more binders which are liquid at temperatures of up to 40 ° C. and this solution or suspension is applied to moving carrier materials with an oil absorption capacity of at least 20 g / 100 g.
  • the process according to the invention can be carried out in a large number of apparatuses customarily used in the detergent and cleaning agent industry. Suitable mixers are characterized in that they can introduce a certain amount of energy into the mix. Conventional mixers and mixing granulators are suitable for carrying out the process according to the invention. Both high-intensity mixers (“high-shear mixers”) and normal mixers with lower circulation speeds can be used as mixers.
  • high-shear mixers high-intensity mixers
  • normal mixers with lower circulation speeds can be used as mixers.
  • Suitable mixers are, for example, Eirich R mixers of the R or RV series (trademark of Maschinenfabrik Gustav Eirich, Hardheim), Schugi ® Flexomix, the Fukae ® FS-G mixers (trademark of Fukae Powtech, Kogyo Co., Japan) Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais series T or KT (trademark of Drais-Werke GmbH, Mannheim).
  • Eirich R mixers of the R or RV series trademark of Maschinenfabrik Gustav Eirich, Hardheim
  • Schugi ® Flexomix the Fukae ® FS-G mixers (trademark of Fukae Powtech, Kogyo Co., Japan)
  • Lödige ® FM, KM and CB mixers trademark of Lödige Maschinenbau GmbH, Paderborn
  • Drais series T or KT trademark of Drais-Werke GmbH, Mannheim
  • the above-mentioned preferred areas of use of the ingredients also apply to the methods according to the invention.
  • Processes are preferred in which, based in each case on the end product of the process, the support material in amounts of 40 to 98.9% by weight, preferably 50 to 95% by weight, particularly preferably 55 to 85% by weight and in particular from 60 to 80% by weight, the binder (s) which are liquid at temperatures up to 40 ° C.
  • washing and cleaning agent ingredient from the group of enzymes, pH regulators, fluorescent agents, dyes, foam inhibitors, anti-redeposition agents, optical brighteners, Graying inhibitors, color transfer inhibitors and corrosion inhibitors and mixtures thereof in amounts from 0.1 to 40% by weight, preferably from 1 to 15 % By weight, particularly preferably from 2 to 10% by weight and in particular from 2.5 to 5% by weight, can be used.
  • Preferred processes are characterized in that one or more substances from the group of silicates and / or aluminum silicates are used as the carrier material, it being preferred that all particles of the carrier material are smaller than 200 ⁇ m, preferably smaller than 100 ⁇ m, particularly preferably smaller than 75 ⁇ m and in particular less than 50 ⁇ m.
  • liquid binders are also preferred.
  • one or more substances from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate, as well as perfume oils, paraffins, silicone oils and ethoxylated fatty alcohols are used as liquid binders.
  • Ingredient preferably substances are used which are soluble in the binders mentioned.
  • the process variant according to the invention described above comprises spraying a solution or suspension of the so-called small component onto a moving solid bed from the particles of the carrier material. This procedure is recommended if the small components are soluble in the selected binder or can be converted into stable suspensions in it. In other cases, it is also possible according to the invention not to spray the small component together with the binder, but rather to present it together with the carrier material as a moving solid bed.
  • a solid detergent and cleaning agent additive in which a solid detergent and cleaning agent ingredient from the group of enzymes, pH adjusters, fluorescent agents, dyes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and Corrosion inhibitors and mixtures with carrier materials with an oil absorption capacity of at least 20 g / 100 g are mixed and one or more binders liquid at temperatures up to 40 ° C. are applied to the agitated mixture.
  • the embodiments identified above as preferred are again preferred.
  • the carrier material in amounts of 40 to 98.9% by weight, preferably 50 to 95% by weight, particularly preferably 55 to 85% by weight and in particular 60 up to 80% by weight, with substances from the group of silicates and / or aluminum silicates being preferred and it being particularly preferred that all particles of the support material be less than 200 ⁇ m, preferably less than 100 ⁇ m, particularly preferably less than 75 ⁇ m and in particular less than 50 ⁇ m, the binder (s) which are liquid at temperatures up to 40 ° C.
  • detergent and cleaning agent additives according to the invention described above which can be obtained by the likewise described inventive processes, can be added to detergents and cleaning agents.
  • Another object of the present invention is therefore the use of detergent and cleaning agent additives which contain 40 to 98.9% by weight of carrier material with an oil absorption capacity of at least 20g / 100g, 1 to 50% by weight of one or more at temperatures up to 40 ° C liquid binder, 0.1 to 40 wt .-% of a detergent ingredient from the group of enzymes, pH adjusters, fluorescent agents, dyes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer agents inhibitors and corrosion inhibitors and mixtures thereof contain, as an additive in detergents.
  • washing and cleaning agent additives according to the invention can be added to the washing and cleaning agents by simple mixing. However, it is preferred according to the invention to use the additives as powdering agents, so that in preferred uses the washing and cleaning agent additives are used as powdering agents for coarse-grained washing and cleaning agent particles.
  • the particles powdered in this way can be processed further, for example - optionally after mixing with further detergent and cleaning agent ingredients - in a manner known per se to be pressed into detergent tablets.
  • Another object of the invention is therefore a process for the production of detergents and cleaning agents, in which detergent and cleaning agent particles are produced in a manner known per se, which are mixed with detergent and cleaning agent additives, which are 40 to 98.9% by weight.
  • Carrier material with an oil absorption capacity of at least 20g / 100g, 1 to 50% by weight of one or more binders liquid at temperatures up to 40 ° C, 0.1 to 40% by weight of a detergent and cleaning agent ingredient from the group of enzymes , pH-adjusting agents, fluorescent agents, dyes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors and mixtures thereof are powdered.
  • the detergent and cleaning agent particles have a particle size distribution in which at least 75% by weight, preferably at least 85% by weight and in particular more than 95% by weight of the particles have particle sizes between 200 and 2000 ⁇ m, preferably between 400 and 1600 ⁇ m and in particular between 600 and 1200 ⁇ m.
  • the additives according to the invention, which are used as powdering agents, are preferably finely divided.
  • the detergent and cleaning agent additives have a particle size distribution in which at least 75% by weight, preferably at least 85% by weight and in particular more than 95% % By weight of the particles have particle sizes between 1 and 200 ⁇ m, preferably between 2 and 100 ⁇ m and in particular between 5 and 50 ⁇ m.
  • the binders used in the production of the additive are used as adhesion promoters between detergent and detergent particles and additive (powdering agent), so that preferred processes are characterized in that the detergent and detergent particles are based on their weight , with 0.1 to 10% by weight of one or more binders which are liquid at temperatures up to 40 ° C., preferably from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate, as well as perfume oils, paraffins, silicone oils and ethoxylated fatty alcohols , sprayed or sprayed and then powdered with the detergent and cleaning agent additives.
  • a red dye (Sandolan Rhodamine ® E-RD 400%) were dissolved in 19.5 parts by weight of glycerol (86% strength). (Wessalith XD ®, Degussa, particle size: 100% ⁇ 50 microns) in a 20 liter Lödige ploughshare mixer from 80 parts by weight zeolite X were introduced and sprayed over a period of 5 minutes by the dye solution. A finely divided, violet-red compound was created. 4. Preparation of a dye additive
  • the Lödige mixer chopper was used in all of the examples.
  • the compounds produced under 1 to 4 can be added to conventional washing and cleaning agents, the use of the compounds as powdering agents having particular advantages.
  • extruded particles of a textile detergent were each powdered with 1 or 2% by weight of the compounds according to the invention.
  • the dye additives obtained according to the invention had a homogeneous color distribution and were easy to travel, while spraying a dye solution gave sticky particles with an inhomogeneous color distribution.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des additifs pour détergents et nettoyants pouvant être adjoints à des compositions détergentes et nettoyantes classiques. Ces additifs s'obtiennent par application d'une solution ou d'une suspension de constituants déterminés de détergents et de nettoyants dans des liants liquides à des températures allant jusqu'à 40 DEG C, sur des supports ayant des capacités d'absorption d'huile de plus de 20 g/100 g. Une autre solution consiste à pulvériser un mélange solide de matériau support et de constituants déterminer de détergents et de nettoyants avec les liants mentionnés.
PCT/EP1999/009011 1998-12-02 1999-11-23 Additif pour detergent et nettoyant et procede permettant de le preparer Ceased WO2000032736A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP99956028.7A EP1135455B2 (fr) 1998-12-02 1999-11-23 Additif pour detergent et nettoyant et procede permettant de le preparer
DE59909136T DE59909136D1 (de) 1998-12-02 1999-11-23 Wasch- und reinigungsmitteladditiv und verfahren zu dessen herstellung
ES99956028.7T ES2220126T5 (es) 1998-12-02 1999-11-23 Aditivo para agentes de lavado y de limpieza y procedimiento para su fabricación
AT99956028T ATE263830T1 (de) 1998-12-02 1999-11-23 Wasch- und reinigungsmitteladditiv und verfahren zu dessen herstellung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19855676.4 1998-12-02
DE19855676A DE19855676A1 (de) 1998-12-02 1998-12-02 Wasch- und Reinigungsmitteladditiv und Verfahren zu dessen Herstellung

Publications (1)

Publication Number Publication Date
WO2000032736A1 true WO2000032736A1 (fr) 2000-06-08

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PCT/EP1999/009011 Ceased WO2000032736A1 (fr) 1998-12-02 1999-11-23 Additif pour detergent et nettoyant et procede permettant de le preparer

Country Status (5)

Country Link
EP (1) EP1135455B2 (fr)
AT (1) ATE263830T1 (fr)
DE (2) DE19855676A1 (fr)
ES (1) ES2220126T5 (fr)
WO (1) WO2000032736A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2084256B2 (fr) † 2006-11-10 2017-03-29 The Procter and Gamble Company Composition de traitement de tissus à colorant direct pour tissus
US12365812B2 (en) 2015-04-15 2025-07-22 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19919444B4 (de) * 1999-04-29 2016-06-30 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittelformkörper mit Bindemittelcompound, Verfahren zu seiner Herstellung sowie Verwendung von Bindemittelcompounds
DE10105801B4 (de) * 2001-02-07 2004-07-08 Henkel Kgaa Wasch- und Reinigungsmittel umfassend feine Mikropartikel mit Reinigungsmittelbestandteilen
DE10334045A1 (de) * 2003-07-25 2005-02-10 Clariant Gmbh Additive für Wasch- und Reinigungsmittel
DE102006015837A1 (de) * 2006-04-03 2007-10-04 Henkel Kgaa Partikel mit Schmutz abweisender Wirkung auf Basis von Polyethylenglykol und amphiphilem Polymer

Citations (5)

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Publication number Priority date Publication date Assignee Title
EP0521635A1 (fr) * 1991-06-25 1993-01-07 Unilever Plc Composition détergente ou composition sous forme particulaire
WO1995004124A1 (fr) * 1993-08-02 1995-02-09 Henkel Kommanditgesellschaft Auf Aktien Granule regulateur du moussage et son procede de preparation
EP0737739A2 (fr) * 1995-04-13 1996-10-16 The Procter & Gamble Company Procédé pour la préparation d'une particule détergente
WO1996034082A1 (fr) * 1995-04-27 1996-10-31 The Procter & Gamble Company Procede de production de compositions ou constituants detersifs granulaires
GB2304726A (en) * 1995-09-04 1997-03-26 Unilever Plc Granular adjuncts containing soil release polymers, and particulate detergent compositions containing them

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA962158A (en) † 1971-03-11 1975-02-04 Unilever Limited Detergent compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0521635A1 (fr) * 1991-06-25 1993-01-07 Unilever Plc Composition détergente ou composition sous forme particulaire
WO1995004124A1 (fr) * 1993-08-02 1995-02-09 Henkel Kommanditgesellschaft Auf Aktien Granule regulateur du moussage et son procede de preparation
EP0737739A2 (fr) * 1995-04-13 1996-10-16 The Procter & Gamble Company Procédé pour la préparation d'une particule détergente
WO1996034082A1 (fr) * 1995-04-27 1996-10-31 The Procter & Gamble Company Procede de production de compositions ou constituants detersifs granulaires
GB2304726A (en) * 1995-09-04 1997-03-26 Unilever Plc Granular adjuncts containing soil release polymers, and particulate detergent compositions containing them

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2084256B2 (fr) † 2006-11-10 2017-03-29 The Procter and Gamble Company Composition de traitement de tissus à colorant direct pour tissus
US12365812B2 (en) 2015-04-15 2025-07-22 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers

Also Published As

Publication number Publication date
ES2220126T3 (es) 2004-12-01
EP1135455B2 (fr) 2017-03-08
DE19855676A1 (de) 2000-06-08
ES2220126T5 (es) 2017-07-31
ATE263830T1 (de) 2004-04-15
DE59909136D1 (de) 2004-05-13
EP1135455B1 (fr) 2004-04-07
EP1135455A1 (fr) 2001-09-26

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