EP1053295B1 - Procede pour produire des detergents et nettoyants colores - Google Patents

Procede pour produire des detergents et nettoyants colores Download PDF

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Publication number
EP1053295B1
EP1053295B1 EP99902520A EP99902520A EP1053295B1 EP 1053295 B1 EP1053295 B1 EP 1053295B1 EP 99902520 A EP99902520 A EP 99902520A EP 99902520 A EP99902520 A EP 99902520A EP 1053295 B1 EP1053295 B1 EP 1053295B1
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EP
European Patent Office
Prior art keywords
colored
acid
detergent
spray
detergent particles
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EP99902520A
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German (de)
English (en)
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EP1053295A1 (fr
Inventor
Christian Block
Antoni Machin
Hans-Friedrich Kruse
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/40—Dyes ; Pigments

Definitions

  • the present invention relates to a method for producing washing and Colored particle detergents.
  • Universal detergents sometimes contain colorants in the form of speckles. Frequently The colors used are green and blue. The colorants serve e.g. about that To compensate for yellowing of washed fabrics or to cause the particles to color and make the detergent more appealing to the consumer.
  • European patent application EP 0 138 410 describes a process for producing colored detergent powder, in which a particulate colorant, for example in a screw conveyor, is intensively mixed with a detergent powder and a colored detergent powder can be obtained in this way.
  • Ultramarine blue, Duasyn Acid Blue and Polar Brilliant Blue are used as colorants.
  • US Pat. No. 3,519,054 describes a process for the preparation of multicolored particulate products, in which two streams of liquid in the form of droplets are dried in countercurrent and a colorant is added to one or both streams of liquid, the droplets being converted into dried, multicolored particles.
  • Ultramarine blue for example, is used as the colorant.
  • Other examples include phthalocyanine blue, indigo, rhodamine pigment, azo ruby, chrome orange, alizarin, Indanthren® yellow, phthalocyanine green, wool violet or anthraquinone violet.
  • Powdery detergents are also known from the prior art, which in Powder colored, mostly green or blue, speckles included.
  • powder colored mostly green or blue, speckles included.
  • For the colored particles it is often colored detergent additives, such as. B. Bleach activator.
  • DE-A-195 42 830 discloses colored particles for incorporation in detergents or cleaning agents which contain surfactants, builders and / or bleaches and a colorant which can be partially or completely oxidatively destroyed in the washing process. These colored particles are produced using a process in which the individual components and the colorant are slurried in water to form a slurry and then subjected to spray drying. In this method, however, the washing or cleaning agents are packaged in the presence of the dye solutions. As a result, considerable dye contamination occurs in the production plants, which necessitates a disproportionate cleaning effort.
  • the present invention is accordingly based on the object of a method for Production of colored detergent or cleaning agent particles for incorporation in To provide detergents or cleaning agents that meet the state of the art Technology does not have existing disadvantages.
  • the present invention thus relates to a process for the production of Detergents and cleaning agents made of colored particles, the surfactants, builders and / or Contain bleach and a colorant, characterized in that (A) the Powder and the colorant slurried and spray dried are and (B) then the colored and spray-dried powder on washing or Detergent particles is applied, the process steps (A) and (B) in separate steps are carried out (claim 1).
  • step (A) Spray drying process carried out.
  • powder and colorants are used first slurried and then form a "slurry".
  • This "slurry” is then in the spray tower typically spray dried by blowing hot air from below.
  • the consistency of the "slurry” can also be used to accelerate particle formation to be added.
  • the person skilled in the art is familiar with the suitable procedure.
  • uniformly colored, homogeneous Powder particles are obtained, which are then used to stain washing and Detergents can be used.
  • Uncolored detergent particles are produced in parallel with the production of the colored powder.
  • step (B) of the process the colored powder is finally transferred from the spray drying tower to a separate plant. There the powdering of the undyed detergent particles is then carried out with the separately produced, colored powder agent. The powdering process with the colored powder particles is thus carried out as a separate step from the production of the same.
  • suitable colored particles are those which, in addition to the colorant, have at least one further one Contains component that contributes to the washing or cleaning performance of the washing and Detergent contributes.
  • Particles can be used as components of universal detergents or as Universal detergents themselves are used, the colorants - depending on the choice of Dye - in the wash liquor either very quickly and oxidatively destroyed Do not give color to the laundry even under high washing temperatures or under Color delivery during the washing process can be used to dye laundry. It Color mixtures can also be used which, in addition to being oxidatively destructible Coloring agents suitable for detergents and cleaning agents Blue tones are used to compensate for the yellowing of washed fabrics.
  • colorants which can be oxidatively destroyed in the washing process are preferred as well as mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants in water or at Room temperature are soluble in liquid organic substances.
  • anionic colorants e.g. anionic nitroso dyes.
  • a possible one Colorant 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 Fa. BASF, Ludwigshafen, is available, as well as mixtures of these 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.
  • colorants When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and in particular for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stability to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of colorants which are readily water-soluble, for example the Basacid® green mentioned above or the Sandolan® blue also mentioned above, colorant concentrations in the range from 10 -2 to 10 -3 % by weight are typically chosen.
  • the suitable concentration of the colorant in washing or cleaning agents is typically 10 -3 to 10 - 4 % by weight.
  • the colorant is stable at temperatures up to 40 ° C.
  • the stability of the the agent containing particles produced by the process according to the invention can be increased by the lowest possible water content. Particularly preferred It is when the colorant is already present to some extent in the presence of water react with atmospheric oxygen or with oxygen present in the water. In this case the presence of bleaching agents can be dispensed with. what especially for Detergent is beneficial.
  • the colorants used in the production should be sufficiently alkaline and be heat-resistant and the laundry or components of the washing machine also after Do not stain multiple washes, at the same time if possible no substantivity compared to textile fibers so that they do not stain the laundry ..
  • the dyes do so on the textile fibers, then they should on the textiles drawn paint can be destroyed by reaction with the oxidizing agent, so that a Dyeing of the textiles, in particular over several washing cycles, is avoided.
  • Colorant is partially or completely destroyed by oxidation in the washing process.
  • the oxidative reaction of the coloring agents with an oxidizing agent should be as fast as possible so that the coloring agent decomposes as soon as it comes into contact with the oxidizing agent. If the particles produced by the process according to the invention come into contact with water, as a rule a colored wash liquor is formed first, which is bleached within a short time by the bleaching agent, which also dissolves on contact with water.
  • the colored wash liquor is decolorized at 60 ° C., preferably within 5 to 10 minutes after dissolving in water, to a degree of at least 50%, particularly preferably at least 80%, in particular at least 90%.
  • the degree of oxidative decomposition of the colorant can be determined, for example, by absorbance measurements by measuring the extinction E 0 of the wash liquor with a known concentration C 0 of colorant and the extinction E 1 of the wash liquor after a defined time. From the determined extinction values, the amount of colorant C 0 still present can be calculated from Lambert-Beer law. The rate of oxidation of the colorant should be greater, the higher the substantivity towards the laundry.
  • the colored particles or produced by the process according to the invention Detergents or cleaning agents containing these particles preferably show one of these low substantivity to textiles that after 25 wash cycles Cotton textiles that have a whiteness according to over 200 that Color deviation number according to Ganz / Grieser is between -1.5 to ⁇ 2.5.
  • Suitable oxidizing agents are, for example, the substances usually present in the washing and cleaning agents as bleaching agents. These include in particular the compounds which supply H 2 O 2 in water. Among them, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. In order to decolorize the colorant as completely as possible and in the period mentioned above, the oxidizing agent should be present in a sufficient amount.
  • the colorant can be used without a separately added oxidizing agent.
  • the colorant and the oxidizing agent can be present in a weight ratio of up to about 1 to 10 4 , preferably 1: 100 to 8 x 10 3 , the amount of oxidizing agent should be kept as low as possible in order to protect the colors of the textiles.
  • the colorant and the bleaching agent for decoloring the colorant are therefore preferably in a weight ratio of up to 1: 500.
  • the washing and cleaning agent produced by the method according to the invention can be a universal, a color or a mild detergent. Is the remedy one Delicates, it should, unless the colorant is in the presence of water is already oxidized by oxygen, in addition to that for the oxidation of the colorant required bleach does not contain any further bleach.
  • the washing and cleaning agents produced by a process according to the invention in which the bleaching agents should also contribute to washing power.
  • how to remove bleachable stains have a total bleach content preferably from 5 to 30% by weight and in particular from 10 to 25% by weight.
  • the process is carried out using colored particles which contain bleach activator.
  • the effect of the oxidizing or bleaching agents can namely be increased considerably by adding so-called bleach activators.
  • detergent or cleaning agent particles which contain bleach activators are therefore preferably colored according to the process and finally incorporated into detergent and cleaning agents containing bleach in order to achieve an improved bleaching action when washing at temperatures of 60 ° C. and below.
  • bleach activators are N-acyl or O-acyl compounds forming H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, alkanoyloxybenzenesulfonates, such as iso- and n-nonanoyloxybenzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239 .
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 2 and 8% by weight.
  • bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN®).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN® acetylated sorbitol-mannitol mixtures
  • the colored, spray-dried Powder and the detergent or cleaning agent particles mixed intimately.
  • the corresponding aggregates for mixing are familiar to the person skilled in the art. hereby the powder adheres to the surface of the detergent or cleaning agent particles and give the detergent the desired color characteristics.
  • the detergent or detergent particles to which the colored powder is added can be granular detergent or detergent particles, spray-dried detergent or detergent particles or solid detergent or detergent particles.
  • the detergent or cleaning agent particles can be produced in a manner known per se, for example by spray drying processes, by granulation or by extrusion.
  • the particles can be produced in particular by granulation with the possibility of drying at the same time, advantageously by a process which takes place in a fluidized bed, as described in international application WO 93/04162 .
  • inorganic builder substances are suitable.
  • zeolite-type aluminosilicates therefor prefers.
  • the fine crystalline, synthetic and bound water used Zeolite containing zeolite is most preferably zeolite NaA, especially Wessalith® P, in detergent quality.
  • zeolite X and zeolite P are also suitable Mixtures of A and X or A and X and / or P.
  • a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX®, is also commercially available and can preferably be used in the context of the present invention and through the formula n Na 2 O (1-n) K 2 O Al 2 O 3 (2 - 2.5) SiO 2 (3.5 - 5.5) H 2 O can be described.
  • 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 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
  • Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred as powdering agents.
  • a weight ratio of washing or Detergent particles to colored powder from 95: 5 to 99.5: 0.5, in particular a weight ratio of 97: 3 to 99: 1. With these weight ratios the resulting detergent has a satisfactory color impression.
  • the detergent and cleaning agent particles used in the process according to the invention can preferably contain those usually contained in washing and cleaning agents Components such as anionic, nonionic and / or amphoteric surfactants and / or Builder included.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 -C 18 monoolefins with an end or internal double bond by sulfonation contains gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 12 -C 18 alkanes, for example by sulfochlorination with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids e.g. B. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example on coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates 2 and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles Glycerin can be obtained.
  • Preferred sulfonated fatty acid glycerol esters are Sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, Palmitic acid, stearic acid or behenic acid.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants which will be described later.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the synthetic anionic surfactants and soaps can be in the form of their sodium, Potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine are present.
  • the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohol with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10, preferably x is 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably those having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as those are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533 .
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I).
  • R 2 -CO for an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 Hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the other ingredients include those already described in detail Surfactants, in particular inorganic and organic builder substances, components, which prevent the textile fabric from being soiled again (soil repellents), and Graying inhibitors, alkaline salts, bleaching agents and bleach activators, Foam inhibitors, fabric softening substances, neutral salts as well as color and Fragrances.
  • Surfactants in particular inorganic and organic builder substances, components, which prevent the textile fabric from being soiled again (soil repellents), and Graying inhibitors, alkaline salts, bleaching agents and bleach activators, Foam inhibitors, fabric softening substances, neutral salts as well as color and Fragrances.
  • suitable inorganic builders are suitable in particular zeolite-type aluminosilicates.
  • the fine crystalline Zeolite containing synthetic and bound water is preferably NaA in zeolite Detergent quality.
  • zeolite X and zeolite P are also suitable Mixtures of A and X and / or P.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layer-like 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 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
  • Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • Usable organic builders are, for example, the preferred ones in the form of their Sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, and mixtures of these.
  • Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on 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 relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 12,000 and in particular 50,000 to 100,000.
  • biodegradable terpolymers for example those which, as monomers, contain salts of acrylic acid and maleic acid and vinyl alcohol or Contain vinyl alcohol derivatives (DE 43 00 772) or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives (DE 42 21 381) .
  • Suitable builder systems are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 , or the preparation of which is described in international patent application WO-A-93/161 10 .
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 .
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the inorganic and / or organic builder substances are preferably in Amounts from about 10 to 60% by weight, in particular from 15 to 50% by weight.
  • the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident when a textile is polluted, which has previously been repeatedly with a manufactured according to the invention Detergent containing this oil and fat-dissolving component is washed.
  • nonionic Cellulose ethers such as methyl cellulose and in particular methyl hydroxypropyl cellulose a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as the polymers of phthalic acid and / or of the known from the prior art Terephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. You can already in small quantities be effective. Their content is therefore preferably 0.2 to 10% by weight and in particular up to 5% by weight.
  • Graying inhibitors are also preferred in the inventive contain detergent or cleaning agent particles to be produced. These have the Task to keep the dirt detached from the fiber suspended in the fleet and so on to prevent the laundry from turning gray.
  • Water-soluble colloids are usually used for this suitable organic nature, for example the water-soluble salts of polymer Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or cellulose or salts of acidic sulfuric acid esters of cellulose or of strength. Polyamides containing water-soluble acidic groups are also for this Suitable purpose. Soluble starch preparations and others other than that can also be used Use the above starch products, e.g. B. degraded starch, aldehyde starches, etc.
  • Polyvinyl pyrrolidone is also suitable.
  • cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and Mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, Methylcarboxmethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the total formulation, used.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • amorphous silicates like some commercially available compounds, are made from Carbonates and amorphous silicates suitable, the usual builder substances like Partly or entirely to replace phosphate, zeolite and crystalline layered silicates. Become If such substances are used, their content can also exceed those specified above Go beyond amounts for carbonates and amorphous silicates. Levels here are up to 40 % By weight or even 60% by weight within the scope of the invention.
  • foam inhibitors are preferably contained in the detergent and cleaning agent particles to be produced according to the invention.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica or bistearylethylenediamide. It has proven advantageous to use mixtures of different foam inhibitors, e.g. B. those made of silicone, paraffins or waxes.
  • Foam inhibitors, in particular silicone- or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylene triamine pentamethylene phosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 wt .-% used.
  • enzymes especially come those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question.
  • Enzymes from bacterial strains or fungi such as those from are particularly well suited Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents.
  • Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing Mixtures of special interest. Peroxidases or oxidases have also become proved suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to prevent them from premature decomposition protect.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can for example about 0.1 to 5% by weight. preferably 0.1 to 2 wt .-%.
  • Components that prevent the textile fabric from being soiled again are, in particular, those compounds that prevent the weaning during the Prevent detached dirt particles and thus the occurrence of a so-called. Avoid gray veils without reducing enzyme activity and washing performance affect.
  • Such components are usually polymeric and copolymeric Compounds, such as polyester from aliphatic and / or aromatic dicarboxylic acids and glycols and / or polyglycols.
  • the particles produced according to the invention can optical brighteners, e.g. B. Derivatives of Diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, which instead of the morpholino group Diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group wear. Brighteners of the type of substituted Diphenylstyryle be present, e.g. B.
  • dye according to Example 4 was used as a powder without further Additional component processed.
  • the colored powder listed under Examples 1 to 4 were as Components of colored detergents examined.
  • White cotton fabrics were made Washed 25 times at 90 ° C using 150 g of the detergent per wash.
  • the discoloration of the textiles was visual and measuring technology according to DIN 5033 and the Guideline RAL-RG 992 "Quality assurance for proper laundry care".
  • the dye concentrations prove to be so high that a complete oxidative decomposition of the colorants is no longer guaranteed.

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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)
  • Detergent Compositions (AREA)

Claims (13)

  1. Procédé de fabrication de détergents et nettoyants constitués de particules colorées, qui contiennent des agents tensio-actifs, des adjuvants de détergence et/ou des agents de blanchiment ainsi qu'un colorant,
    caractérisé en ce que
    (A) on met en suspension le produit de poudrage et le colorant et on les soumet à une atomisation et
    (B) on dépose le produit de poudrage coloré et atomisé sur les détergents et nettoyants,
    les stades (A) et (B) du procédé étant effectués dans des étapes séparées,
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on détruit partiellement ou entièrement par oxydation le colorant dans le processus de lavage.
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce que
    le colorant et l'agent de blanchiment pour la décoloration du colorant se présentent dans un rapport pondéral allant jusqu'à 1:500.
  4. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que
    les particules colorées contiennent un activateur de blanchiment.
  5. Procédé selon l'une des revendications précédentes,
    caractérisé en ce qu'
    on mélange intimement entre eux le produit de poudrage coloré et atomisé et les particules de détergents et de nettoyants dans l'étape (B).
  6. Procédé selon l'une des revendications précédentes,
    caractérisé en ce qu'
    on dépose le produit de poudrage coloré et atomisé sur des particules de détergents et de nettoyants, granulées de façon connue.
  7. Procédé selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    on dépose le produit de poudrage coloré et atomisé sur les particules de détergents et de nettoyants, atomisées de façon connue.
  8. Procédé selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    on dépose le produit de poudrage coloré et atomisé sur les particules de détergents et de nettoyants solides.
  9. Procédé selon l'une des revendications précédentes,
    caractérisé en ce qu'
    on utilise comme produit de poudrage des zéolithes.
  10. Procédé selon la revendication 9,
    caractérisé en ce qu'
    on utilise comme produit de poudrage la zéolithe NaA.
  11. Procédé selon l'une des revendications précédentes,
    caractérisé en ce qu'
    au cours du dépôt du produit de poudrage coloré et atomisé sur les particules de détergents et de nettoyants on établit un rapport pondéral des particules de détergents ou de nettoyants au produit de poudrage coloré de 95 :5 à 99,5 :0,5.
  12. Procédé selon la revendication 11,
    caractérisé en ce qu'
    on établit un rapport pondéral des particules de détergents ou de nettoyants de 97 :3 à 99 :1.
  13. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que
    les particules de détergents ou de nettoyants contiennent des agents tensio-actifs anioniques, non ioniques et/ou amphotères.
EP99902520A 1998-01-15 1999-01-07 Procede pour produire des detergents et nettoyants colores Expired - Lifetime EP1053295B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19801186 1998-01-15
DE19801186A DE19801186A1 (de) 1998-01-15 1998-01-15 Verfahren zur Herstellung gefärbter Wasch- und Reinigungsmittel
PCT/EP1999/000040 WO1999036498A1 (fr) 1998-01-15 1999-01-07 Procede pour produire des detergents et nettoyants colores

Publications (2)

Publication Number Publication Date
EP1053295A1 EP1053295A1 (fr) 2000-11-22
EP1053295B1 true EP1053295B1 (fr) 2002-08-14

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Country Status (7)

Country Link
US (1) US6534471B1 (fr)
EP (1) EP1053295B1 (fr)
JP (1) JP2002509185A (fr)
AT (1) ATE222287T1 (fr)
DE (2) DE19801186A1 (fr)
ES (1) ES2182480T3 (fr)
WO (1) WO1999036498A1 (fr)

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DE19855677A1 (de) * 1998-12-02 2000-06-08 Henkel Kgaa Herstellung Aufheller-haltiger Waschmittel-Granulate
DE10148851A1 (de) * 2001-10-04 2003-04-17 Henkel Kgaa Puder- und Färbehilfsstoffe
USD762486S1 (en) 2015-02-18 2016-08-02 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
USD784819S1 (en) 2015-02-18 2017-04-25 Henkel Us Iv Corporation Container for a solid state detergent
US9512388B2 (en) 2015-02-18 2016-12-06 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
CN113493724B (zh) * 2021-06-22 2023-05-09 广东菁萃生物科技有限公司 一种高效去污洗衣液及其制备方法

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Also Published As

Publication number Publication date
WO1999036498A1 (fr) 1999-07-22
EP1053295A1 (fr) 2000-11-22
US6534471B1 (en) 2003-03-18
DE19801186A1 (de) 1999-07-22
DE59902339D1 (de) 2002-09-19
JP2002509185A (ja) 2002-03-26
ES2182480T3 (es) 2003-03-01
ATE222287T1 (de) 2002-08-15

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