EP0283791B1 - Suspensions de blanchiment aqueuses contenant un acide peroxycarboxylique, leur procédé de préparation et leur application - Google Patents

Suspensions de blanchiment aqueuses contenant un acide peroxycarboxylique, leur procédé de préparation et leur application Download PDF

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Publication number
EP0283791B1
EP0283791B1 EP88103336A EP88103336A EP0283791B1 EP 0283791 B1 EP0283791 B1 EP 0283791B1 EP 88103336 A EP88103336 A EP 88103336A EP 88103336 A EP88103336 A EP 88103336A EP 0283791 B1 EP0283791 B1 EP 0283791B1
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EP
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Prior art keywords
acid
weight
bleaching agent
suspension
hydrate
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EP88103336A
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German (de)
English (en)
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EP0283791A2 (fr
EP0283791A3 (en
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Manfred Dr. Dankowski
Günter Dr. Prescher
Thomas Dr. Lieser
Wolfgang Dr. Leonhardt
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Evonik Operations GmbH
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Degussa GmbH
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Priority to AT88103336T priority Critical patent/ATE63332T1/de
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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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the invention is directed to storage-stable, pourable to paste-like, aqueous bleaching agent suspensions containing a practically water-insoluble peroxycarboxylic acid, preferably a diperoxydicarboxylic acid having 8 to 18 carbon atoms hydrophilized in the presence of a strong acid, in a carrier liquid thickened with a colloidal silica.
  • the invention further relates to a safe process for the production of such bleaching agent suspensions and the use thereof for bleaching and disinfection purposes.
  • Aqueous bleaching agent suspensions containing peroxycarboxylic acids are known from GB-PS 1 535 804, corresponding to US-PS 3 996 152 and US-PS 4 017 412.
  • Such bleaching agent compositions can advantageously be added to alkaline washing liquors in washing machines or used as bleaching agents.
  • bleaching agent suspensions in comparison to solid, generally particulate bleaching agent compositions has the advantage of being able to dispense with complex drying and granulation steps, which are not unproblematic with peroxycarboxylic acids in terms of safety.
  • essential prerequisites for the problem-free and safe handling of bleaching agent suspensions in the commercial and domestic sectors are good chemical resistance and, in particular, physical stability a solid-liquid phase separation and handling safety even in the case of suspension spilled or sprayed from containers.
  • aqueous bleaching agent compositions according to GB-PS 1 535 804 essentially contain water-insoluble peroxycarboxylic acids which are suspended in an aqueous carrier liquid containing a thickener. These compositions are thickened to gelled and their viscosity is 200 to 100,000 mPa.s. Starches, cellulose derivatives, natural gums, synthetic organic polymers and inorganic thickeners from the group of colloidal silicas and hydrophilic clays are claimed as thickeners.
  • a major disadvantage of the known bleaching agent compositions of GB-PS 1 535 804 is, at least insofar as it is not a matter of gelled systems, their generally inadequate storage stability.
  • the suspensions are physically unstable because the solid phase is separated from the liquid phase. This instability generally becomes noticeable quickly after the suspension has been produced, very often within a day or even hours.
  • the professional world demands a higher, preferably several weeks storage stability.
  • EP-A 0 160 342 discloses aqueous bleaching agent suspensions, according to which water-insoluble peroxy acids are suspended in an aqueous liquid containing a surfactant and an electrolyte. Although the limited chemical stability of these surfactant-structured suspensions could be improved according to the teaching of EP-A 0 176 124 and EP-A 0 201 958, their physical stability does not meet the requirements placed on them in any way.
  • GB-PS 1 535 804 indicates the use of colloidal silicas, in particular pyrogenic silicas. In order to obtain the desired thickening, however, an additional amount of 10 to 50% by weight, based on the suspension, is required. However, such a high amount of high-quality, generally very expensive pyrogenic silicas is extremely uneconomical, so that there is still a need for improved bleaching agent suspensions.
  • the object of the invention is thus pourable to pasty bleach suspension with increased storage stability compared to known suspensions.
  • Such systems are understood to mean that even after two weeks of storage there is practically no solid-liquid phase separation and only a slight loss of active oxygen.
  • Other tasks are aimed at increasing the economy of the composition and a technically simple and safely manageable manufacturing process.
  • the object on which the invention is based is thus achieved by a pourable to pasty aqueous bleaching agent suspension with a pH between about 1 and about 6, containing an aqueous carrier liquid, a particulate, practically water-insoluble peroxycarboxylic acid, an acidifying agent and a thickening colloidal silica, which thereby is characterized in that it contains 0.5 to 9% by weight of silica, based on the bleaching agent suspension, and a hydrate-forming neutralizing salt which stabilizes peroxycarboxylic acids in an amount of 10 to 400% by weight, calculated hydrate-free and based on the peroxycarboxylic acid used.
  • the bleaching agent suspensions according to the invention can be both pourable and pasty.
  • the viscosity usually increases with increasing concentration of thickener and with increasing amount of suspended peroxycarboxylic acid.
  • shear forces as they occur during the pouring process are sufficient up to those as occur during the manual squeezing out of a tube.
  • Preferred bleach suspensions show pseudoplastic and thixotropic behavior; their flow limit can be in the range around 0.1 to 15 Pa, the viscosity, measured at 20 ° C. in a rotary viscometer at a shear rate of 50 / s, around 20 to 2000 mPa.s.
  • Bleaching agent suspensions according to the invention with good storage stability show practically no signs of phase separation even after two weeks of storage.
  • a minor phase separation occurring in the course of a few weeks in rare cases does not have a disadvantage because the suspension can be homogenized again easily, for example by gentle shaking _ to exceed the flow limit _.
  • Good chemical stability is present if the active oxygen loss after four to six weeks of storage at room temperature is below 5%, based on the active oxygen content determined after the suspension has been produced.
  • the carrier liquid for the practically water-insoluble peroxycarboxylic acids preferably consists of 90-100% by weight of water and 0-10% by weight of an organic solvent, in each case based on the carrier liquid.
  • Water-soluble organic solvents for example lower alcohols, can be used, provided that the peroxycarboxylic acids are practically not dissolved in the carrier liquid. Water as the carrier liquid is preferred.
  • the bleaching agent suspensions according to the invention contain one or more particulate peroxycarboxylic acids which are practically water-insoluble, which means a solubility of less than 1 g per 100 ml of water. Solid peroxycarboxylic acids which have a melting or decomposition point above 40 ° C. are suitable.
  • the grain size of the peroxycarboxylic acids can be in the range from 1 to 500 ⁇ m, preferably 4 to 100 ⁇ m. A narrow grain size distribution is generally preferred, especially in less thickened systems. A narrow grain size distribution is usually also advantageous with regard to the application.
  • Water-insoluble aliphatic or aromatic peroxycarboxylic acids with one, two or possibly three peroxycarboxylic acid groups can be used.
  • the peroxycarboxylic acids can also contain a sulfonic acid group.
  • Aliphatic peroxycarboxylic acids with 6 to 18 carbon atoms and aromatic peroxycarboxylic acids with 7 to 14 carbon atoms are suitable.
  • Preferred are aliphatic diperoxydicarboxylic acids with 8 to 18 carbon atoms, for example diperoxyazelaic acid, diperoxydodecanedioic acid, in the 2-position C6 to C12-alkyl-substituted diperoxy amber or.
  • the bleaching agent suspensions can contain one, two or more peroxycarboxylic acids, but they preferably contain a peroxycarboxylic acid.
  • the bleaching agent suspensions preferably contain 1-40% by weight, in particular 5-30% by weight and very particularly 15-30% by weight, of peroxycarboxylic acid, based on the bleaching agent suspension.
  • the bleaching agent suspensions according to the invention contain thickening colloidal silicas in an amount of 0.5 to 9% by weight, based on the suspension.
  • the silicas are hydrophilic and give the carrier liquids both a higher viscosity and thixotropic flow behavior. Fumed silicas with a specific BET surface area of approximately 50-400 m 2 / g and a particle size in the range of approximately 5 to 50 nm are particularly suitable. Fumed silicas are understood to be those which are produced by flame hydrolysis of silicon compounds, such as silicon tetrachloride and are hydrophilic.
  • silicas produced by precipitation processes with a BET surface area of 100 to 700 m2 / g and a particle size of around 20 nm can also be used.
  • the person skilled in the art will test these silicas for their suitability by producing test suspensions.
  • the suspensions according to the invention generally contain 1 to 40% by weight, preferably 2-20% by weight, based on the suspension, of hydrate-forming neutral salt, the amount being calculated as a hydrate-free salt.
  • the amount of neutral salt, calculated as the hydrate-free salt is 10 to 400% by weight, preferably 20 to 100% by weight.
  • less than 10% by weight, based on peracid is not recommended according to the invention in view of the then reduced handling safety of the suspension and the reduction of the effect according to the invention _ increase in storage stability due to the joint presence of a silica and a hydrate-forming neutralizing salt that permatifies peroxycarboxylic acids .
  • the neutral salt is partially or completely dissolved in the bleach suspension.
  • Preferred bleaching agent suspensions contain a part of the neutral salt, if necessary as a hydrate of the same, in undissolved form at a conventional storage temperature of around 20 ° C.
  • Advantageous hydrate-forming neutral salts are those of the alkali metals, magnesium or aluminum with sulfuric acid, pyrosulfuric acid, phosphoric acid, pyrophosphoric acid or tripolyphosphoric acid.
  • Alkali metal sulfates, in particular sodium sulfate, are particularly preferred.
  • Different hydrate-forming neutral salts can also be present at the same time.
  • the pH of the bleaching agent suspensions according to the invention is between about 1 and about 6 and preferably between 2 and 5.
  • the chemical stability of the peroxycarboxylic acids decreases at pH values around or above 6.
  • the acidifying agent required to adjust the pH can be a mineral acid compatible with peroxycarboxylic acids, such as sulfuric acid or phosphoric acid, a strongly acidic salt such as sodium hydrogen sulfate or sodium dihydrogen phosphate, or an organic acid such as methanesulfonic acid, citric acid or tartaric acid. Sulfuric acid and / or alkali metal bisulfate are particularly preferred.
  • bleaching agent suspensions according to the invention contains peroxycarboxylic acid which has been hydrophilized in the presence of a strong acid.
  • the wettability of the slightly hydrophilic, water-insoluble peroxycarboxylic acids with the aqueous carrier liquid is obviously improved by the fact that the peroxycarboxylic acid comes into direct contact with a strong acid, preferably sulfuric acid, during or after its preparation.
  • a strong acid preferably sulfuric acid
  • the acidifying agent present in the bleaching agent suspension can be wholly or partly derived from the hydrophilization and / or in-situ phlegmatization of the peroxycarboxylic acid, the hydrate-forming neutral salt come wholly or partly from phlegmatization.
  • the suspensions contain 10-30% by weight of diperoxydodecanedioic acid, 5-20% by weight of sodium sulfate (calculated as Na2SO4) and 2 to 6% by weight of pyrogenic silica, in each case based on the bleaching agent suspensions, and sulfuric acid and / or sodium hydrogen sulfate as an acidulant.
  • the bleaching agent suspensions according to the invention can contain other substances which are compatible with them in order to optimally adapt the bleaching agent suspensions to the particular application.
  • the quantities used for this based on the peroxycarboxylic acid and the neutral salt, will be small.
  • the surfactants and additional desensitizing agents can be present in amounts of up to 20% by weight, the other additives generally less than 1% by weight, based in each case on the suspension.
  • the person skilled in the art will get an idea of whether and to what extent he can add the additives he envisages to the suspensions according to the invention without impairing the chemical and physical stability.
  • the bleaching agent suspensions according to the invention are physically and chemically stable for several weeks and thus allow safe handling during storage, transport and use.
  • a phase separation, floating or settling of the solid or inhomogeneities within the suspension such as occurs after a short storage time in the case of previously known bleaching agent suspensions, does not become apparent in the invention or, in rare cases, only after several weeks and is also easily reversible.
  • the presence of the hydrate-forming desensitizing agent also ensures that a dried bleaching agent suspension remains safe.
  • the bleaching agent suspensions according to the invention are produced by homogeneously suspending a water-insoluble peroxycarboxylic acid in a colloidal silicic acid which has a thickening effect, a hydrate-forming neutral salt which stabilizes peroxycarboxylic acids and an aqueous carrier liquid containing an acidifying agent.
  • the individual components of the suspension are added in the amounts mentioned above Carrier liquid, the neutral salt and acidifying agent being introduced before, after or preferably together with the addition of the peracid, suspended homogeneously and the pH adjusted to 1 to 6.
  • the colloidal silica is first suspended in the carrier liquid and then the other mandatory and optionally optional components of the bleach suspension are added and the mixture is homogenized using shear forces, for example by intensive stirring or shaking.
  • a propeller stirrer with a stirring speed of about 1000-2000 rpm and a stirring time between 5 and 20 minutes are generally suitable for homogenization.
  • a peroxycarboxylic acid which has been hydrophilized and optionally also desensitized in the presence of a strong acid is suspended in the thickened carrier liquid, the desensitizing agent being a hydrate-forming neutral salt and the acidifying agent from the hydrophilization and / or desensitization step adhering. It is particularly advantageous to use an undried, hydrophilized peroxycarboxylic acid with adhering acidifying agent and adhering moisture, and any hydrate-forming neutral salt present from the desensitization.
  • the last-mentioned preferred embodiments are distinguished by the easy wettability of the per-compound, the increased storage stability of the resulting bleaching agent suspension and, above all, by the simple because peroxycarboxylic acid containing an acid and neutral salt is introduced into the thickened carrier liquid, and safe because the peroxycarboxylic acid is never used is unphlegmatized or has to be dried, suspension preparation.
  • the bleaching agent suspensions according to the invention can be used for bleaching laundry in combination with detergents. Tea, coffee and other stains are removed from textiles, for example during washing at 20 to 60 ° C., if a bleaching agent suspension according to the invention is made into an alkaline washing liquor containing conventional detergent components, in particular detergent surfactants, inorganic polyphosphate and / or zeolite builders , organic chelating agents, sodium silicate, alkalis and sodium sulfate.
  • the bleaching agent suspension is added to the washing liquor in such an amount that the active oxygen which can be released from the peroxycarboxylic acid is 1 to 30 ppm.
  • the detergent constituents are dissolved or evenly distributed in the washing liquor in the usual detergent concentration.
  • the bleach suspensions can also be used as bleach boosters and for the production of cleaning agents and disinfectants.
  • the carrier liquid, water in the examples, is placed in a 250 ml beaker equipped with a three-bladed propeller stirrer. After adding the thickener with stirring, the peroxycarboxylic acid and the other constituents are introduced and homogeneously suspended by intensive stirring.
  • the diperoxydodecanedioic acids (DPDDA) used were prepared in accordance with DE-OS 33 20 497 (hydrophilized DPDDA) or DE-OS 33 20 496 (desensitized, hydrophilized DPDDA); due to the acid adhering to them, the pH of the suspensions was around 3.5 to 4.
  • the suspension is transferred to a graduated 100 ml standing cylinder and stored at room temperature. Instabilities during storage manifest themselves as a little or no solid-containing phase, which can occur “above”, “below” or as a "gap" within the 100 ml layer.
  • the chemical stability is determined by iodometric or potentiometric titratrion, the latter allowing the detection of both the peroxycarboxylic acid and the carboxylic acid on which it is based and which is formed during the decomposition of peracid.
  • DPDDA suspensions are prepared in the usual way by suspending at 1700 rpm for 10 minutes and tested for their storage stability in a 100 ml standing cylinder.
  • Suspensions A and B do not contain a thickener; the peroxycarboxylic acids used have a thickening effect, but different amounts of sodium sulfate originating from the desensitization; the stabilizing effect of the neutral salt becomes clear.
  • the suspension C according to GB-PS 1 535 804 contains 1.5% by weight of the pyrogenic silica Aerosil® 200 (Degussa AG, Frankfurt aM) as a thickening agent, but no hydrate-forming neutral salt which has a desensitizing effect.
  • Suspension D is in accordance with the invention and suspension C is clearly superior.
  • DPDDA suspensions are prepared in a known manner from the feedstocks mentioned below, but suspension is carried out for 15 minutes at 1300 rpm using a half-moon stirrer. Undried or dried, hydrophilized with Na2SO ph in-situ hydrophilized diperoxydodecanedioic acid (DPDDA) is used and the suspensions are stored at room temperature.
  • DPDDA diperoxydodecanedioic acid
  • Suspension B was completely stable and no inhomogeneity was visible within the layer height even after 6 weeks of storage.
  • Suspension B showed a yield point of about 2 Pa, a slightly shear thinning and hardly thixotropic behavior; the viscosity was 380 mPa.s at a shear rate of 10 / s or 180 mPa.s at 50 / s (measured in a Rotovisko RV 3 rotary viscometer from Haake).
  • hydrophilized DPDDA with a content of 95% DPDDA, approx. 4% dodecanedioic acid and 1% residual moisture was converted into 2.5% by weight fumed silica (Aerosil® 200), 9.3% by weight sodium sulfate and 25 %
  • fumed silica Admed silica
  • sodium sulfate sodium sulfate
  • the carrier liquid was water, anhydrous sodium sulfate was stirred into the suspension after the peracid.

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Claims (13)

1. Suspension aqueuse fluide à pâteuse d'agent de blanchiment, stable au stockage, ayant un pH compris entre 1 et 6, contenant un liquide aqueux de support, un acide peroxocarboxylique particulaire, pratiquement insoluble dans l'eau, un agent d'acidification et un acide silicique colloïdal à effet épaississant, caractérisée en ce qu'elle contient de 0,5 à 9% en poids d'acide silicique, par rapport à la suspension d'agent de blanchiment, et un sel neutre formant un hydrate, stabilisant les acides peroxocarboxyliques du point de vue anti-explosif, en une quantité de 10 à 400% en poids, exprimée sans hydrate et par rapport à l'acide peroxocarboxylique utilisé.
2. Suspension d'agent de blanchiment selon la revendication 1, caractérisé en ce qu'elle contient de 1 à 7% en poids, par rapport à la suspension, d'acide silicique pyrogèné et le liquide de support est constitué de 90 à 100% en poids d'eau et de 0 à 10% en poids, par rapport au liquide de support, d'un solvant organique.
3. Suspension d'agent de blanchiment selon la revendication 1 ou 2, caractérisée en ce qu'elle contient un acide peroxocarboxylique rendu hydrophile en présence d'un acide fort, pouvant de préférence être obtenu lors de la préparation de l'acide peroxocarboxylique à partir de l'acide carboxylique de base ou de son anhydride et de peroxyde d'hydrogène en présence d'acide sulfurique.
4. Suspension d'agent de blanchiment selon l'une quelconque des revendications 1 à 3, caractérisée en ce qu'elle contient de 1 à 40% en poids, de préférence de 5 à 30% en poids, par rapport à la suspension, d'acide peroxocarboxylique.
5. Suspension d'agent de blanchiment selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle contient un sel neutre, formant un hydrate, des métaux alcalins, du magnésium ou de l'aluminium avec l'acide sulfurique, l'acide pyrosulfurique, l'acide phosphorique, l'acide pyrophosphorique ou l'acide tripolyphosphorique.
6. Suspension d'agent de blanchiment selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'elle contient un acide diperoxodicarboxylique aliphatique ou aromatique ayant de 8 à 14 atomes de carbone.
7. Suspension d'agent de blanchiment selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'elle contient en tant qu'agent d'acidification de l'acide sulfurique et/ou un hydrogénosulfate de métal alcalin et, en tant que sel neutre formant un hydrate, un sulfate de métal alcalin.
8. Suspension d'agent de blanchiment selon l'une quelconque des revendications 1 à 7, caractérisée en ce qu'elle contient, en outre, d'autres agents de stabilisation anti-explosive neutres ou acides, tels que l'acide borique, et/ou des agents chélateurs, tels que ceux choisis parmi les alkylènepolyamines substituées par le groupe N-méthylènephosphonate, et/ou des stabilisants, tels que l'acide dipicolinique ou des trialkyle-phosphanoxydes et/ou des agents tensioactifs anioniques et/ou non anioniques.
9. Suspension d'agent de blanchiment selon les revendications 2 et 3 et l'une quelconque des revendications 4 à 8, caractérisée en ce qu'elle contient de 10 à 30% en poids d'acide diperoxododécanedioïque, de 5 à 20% en poids de sulfate de sodium et de 2 à 6% en poids d'acide silicique pyrogèné, chacun par rapport à la suspension d'agent de blanchiment, et de l'acide sulfurique et/ou de l'hydrogéno sulfate de sodium en tant qu'agent d'acidification.
10. Procédé pour la préparation d'une suspension d'agent de blanchiment selon l'une quelconque des revendications 1 à 9, par mise en suspension homogène d'un acide peroxocarboxylique particulaire, pratiquement insoluble dans l'eau, dans un liquide aqueux de support contenant un acide silicique colloïdal à effet épaississant, un agent d'acidification et des additifs, caractérisé en ce que l'on utilise de 0,5 à 9% en poids d'acide silicique colloïdal, par rapport à la suspension d'agent de blanchiment et, avant, pendant ou après l'addition de l'acide peroxocarboxylique au liquide de support on introduit dans celui-ci de 10 à 400% en poids, de préférence de 20 à 100% en poids, exprimé non hydraté et par rapport à l'acide peroxocarboxylique utilisé, d'un sel neutre, formant un hydrate, stabilisant du point de vue anti-explosif les acides peroxocarboxyliques.
11. Procédé selon la revendication 10, caractérisé en ce que l'on utilise un acide peroxocarboxylique rendu hydrophile en présence d'un acide fort et éventuellement stabilisé du point de vue anti-explosif.
12. Procédé selon la revendication 11, caractérisé en ce que l'on utilise l'acide peroxocarboxylique rendu hydrophile avec un agent d'acidification adhérant et de l'humidité adhérante provenant de sa préparation, et éventuellement un sel neutre formant un hydrate, provenant de la stabilisation anti-explosive.
13. Utilisation d'une suspension d'agent de blanchiment selon l'une quelconque des revendications 1 à 9, pour le blanchiment et la désinfection, de préférence en tant qu'agent de blanchiment en association avec des détergents ou en tant qu'adjuvant de blanchiment.
EP88103336A 1987-03-21 1988-03-04 Suspensions de blanchiment aqueuses contenant un acide peroxycarboxylique, leur procédé de préparation et leur application Expired - Lifetime EP0283791B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88103336T ATE63332T1 (de) 1987-03-21 1988-03-04 Peroxycarbonsaeure enthaltende waessrige bleichmittelsuspensionen, verfahren zu ihrer herstellung und ihre verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3709347 1987-03-21
DE19873709347 DE3709347A1 (de) 1987-03-21 1987-03-21 Peroxycarbonsaeure enthaltende waessrige bleichmittelsuspensionen, verfahren zu ihrer herstellung und ihre verwendung

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EP0283791A2 EP0283791A2 (fr) 1988-09-28
EP0283791A3 EP0283791A3 (en) 1989-06-07
EP0283791B1 true EP0283791B1 (fr) 1991-05-08

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US (1) US4790949A (fr)
EP (1) EP0283791B1 (fr)
JP (1) JPS63249770A (fr)
AT (1) ATE63332T1 (fr)
DE (2) DE3709347A1 (fr)
DK (1) DK145588A (fr)
ES (1) ES2021773B3 (fr)
FI (1) FI880199A (fr)
TR (1) TR23984A (fr)

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DE3740899A1 (de) * 1987-12-03 1989-06-15 Degussa Peroxycarbonsaeure-phosphanoxid-komplexe, verfahren zu ihrer herstellung und verwendung
US5358654A (en) * 1988-06-22 1994-10-25 Akzo Nobel N.V. Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
US5126066A (en) * 1988-06-22 1992-06-30 Akzo N.V. Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
EP0350449A3 (fr) * 1988-07-08 1990-10-24 Ciba-Geigy Ag Composition détergente liquide contenant des azurants optiques
ES2081912T3 (es) * 1989-08-08 1996-03-16 Akzo Nobel Nv Composiciones acuosas de peroxidos con perfil de seguridad mejorado.
ES2090118T3 (es) * 1990-10-22 1996-10-16 Procter & Gamble Composiciones detergentes liquidas y estables que contienen blanqueador.
GB9109928D0 (en) * 1991-05-08 1991-07-03 Interox Chemicals Ltd Thickened compositions
US5733474A (en) * 1991-05-08 1998-03-31 Solvay Interox Limited Thickened aqueous peracid compositions
DE4303320C2 (de) * 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
EP0666307A3 (fr) * 1994-02-03 1996-07-03 Procter & Gamble Composition de blanchiment liquide emballée.
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EP0283791A2 (fr) 1988-09-28
DK145588D0 (da) 1988-03-17
EP0283791A3 (en) 1989-06-07
DE3862664D1 (de) 1991-06-13
TR23984A (tr) 1991-01-14
ES2021773B3 (es) 1991-11-16
ATE63332T1 (de) 1991-05-15
DK145588A (da) 1988-09-22
FI880199A0 (fi) 1988-01-18
DE3709347A1 (de) 1988-10-06
US4790949A (en) 1988-12-13
FI880199A (fi) 1988-09-22
JPS63249770A (ja) 1988-10-17

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