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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

• the invention is directed to storage-stable, pourable to paste-like aqueous bleaching agent suspensions with a pH between about 1 and 6, 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 one with special Polysaccharides thickened carrier liquid.
• 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 British Pat. No. 1,535,804, corresponding to US Pat. No. 3,996,152 and US Pat. No. 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 costly drying and granulation processes which are not unproblematic in terms of safety in the case of peroxycarboxylic acids to be able to do without steps.
• the essential prerequisites for the problem-free and safe handling of bleaching agent suspensions in the commercial and domestic sectors are, in addition to their effectiveness, good chemical resistance and, in particular, physical stability with regard to solid-liquid phase separation and handling safety, even in the case of a suspension that has leaked or sprayed out of 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, but very often within a day or even hours. In contrast, the professional world demands a higher, preferably several weeks storage stability.
• EP-A-0 160 342 discloses aqueous bleach suspensions, according to which water-insoluble peroxyacids are suspended in an aqueous liquid containing a surfactant and an electrolyte. These pourable suspensions preferably contain sodium sulfate and an anionic and / or nonionic surfactant.
• a major disadvantage of these systems namely the very limited chemical stability, could be achieved by using alkali metal salts of alkylbenzenesulfonic acids, cf. EP-A-0 176 124, or by setting a pH value limited to 3.5 to 4.1, cf. EP-A-0 201 958.
• the physical stability of these surfactant-structured bleaching agent suspensions does not meet the requirements placed on such systems, as has been established on the basis of comparative examples.
• the object of the invention is thus pourable to pasty aqueous bleaching agent suspensions with increased storage stability. 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.
• a further object relates to a process for the preparation of the suspensions according to the invention which is technically simple to carry out and preferably allows the use of undried, optionally desensitized, peroxycarboxylic acids.
• 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.
• the suspensions thickened with xanthan or agar, but especially xanthan polysaccharides show pseudoplastic behavior; after the yield point is exceeded, they flow more easily under the influence of shear gradients.
• shear forces as they occur during the pouring process are sufficient up to those as occur when a paste is manually pressed out of a tube.
• Bleach suspensions according to the invention with good storage stability show practically no signs of phase separation even after two to six weeks of storage.
• a slight phase separation occurring in the course of a few weeks in rare cases does not have a disadvantage because the suspension can easily be homogenized again by, for example, 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 between approximately 1 and 500 ⁇ m, preferably 4-100 ⁇ m. 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 optionally 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.
• aliphatic or aromatic diperoxycarboxylic acids with 8 to 18 carbon atoms, for example diperoxyazealic acid, diperoxydodecanedioic acid, in the 2-position C6 to C12-alkyl-substituted diperoxysuccinic or diperoxyglutaric acid, diperoxyphthalic acids and diperoxynaphthalenedicarboxylic acids. Diperoxydodecanedioic acid is particularly preferred.
• the bleaching agent suspensions can contain one, two or more peroxycarboxylic acids, but they preferably contain a peroxycarboxylic acid.
• the bleaching agent suspensions contain 1 to 40% by weight of peroxycarboxylic acid, preferably 5 to 30% by weight and very particularly preferably 15 to 30% by weight, in each case based on the bleaching agent suspension.
• xanthan and agar polysaccharides are suitable for producing the storage-stable bleaching agent suspensions according to the invention from the large number of organic thickeners known from GB-PS 1 535 804 for the production of bleaching agent suspensions.
• the organic thickeners preferred according to GB-PS 1 535 804 such as starches, cellulose derivatives or carboxypolymethylene, did not result in bleaching agent suspensions having a sufficiently long shelf life.
• gum arabic for example, proved completely unsuitable, since bleaching agent suspensions produced therewith are hardly stable for one to two hours.
• xanthan and agar polysaccharides in the presence of a hydrate-forming neutralizing salt, which stabilizes peroxycarboxylic acids, lead to bleaching agent suspensions which are particularly stable in storage.
• neutral salts in the presence of thickeners other than those used according to the invention generally lead to a deterioration in the suspension stability.
• Xanthan is a high-molecular polysaccharide obtainable by fermentation, the basic building blocks of which are mannose, glucose and glucuronic acid, partly as Na, K or Ca salt.
• the agar polysaccharides _ agar contains agarose and agaropectin _ come from certain red algae.
• the bleaching agent suspensions generally contain 0.01 to 5% by weight, preferably 0.05 to 2% by weight and very particularly preferably 0.1 to 1% by weight, each based on the bleaching agent suspension, xanthan or 0 , 05-0.5 wt% agar. If appropriate, other inorganic or organic thickeners compatible with xanthan or agar and the other components of the bleaching agent suspension can additionally be used; however, xanthan is preferably used alone.
• the bleaching agent suspensions according to the invention contain a peroxycarboxylic acid for the purpose of increasing the storage stability of the suspension and desensitizing hydrate-forming neutral salt in a preferred amount of about 1 to about 40 wt .-%, more preferably 2 to 20 wt .-%, calculated hydrate-free and based on the suspension.
• the amount of neutral salt - as calculated above as hydrate-free neutral salt - is generally 10 to 400% by weight, but preferably 20 to 100% by weight.
• 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.
• the viscosity of the bleaching agent suspension generally increases with increasing amount of the hydrate-forming neutral salt present; this increase in viscosity has an advantageous effect on the physical stability of the suspension. If desired, the amount of xanthan or agar in the suspension can thus be reduced while maintaining the viscosity by increasing the amount of neutral salt.
• 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 1 and 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 for the pH can be a strong inorganic 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 a strong organic acid such as methanesulfonic acid, citric acid or tartaric acid. Sulfuric acid and / or alkali metal bisulfate are particularly preferred.
• the storage stability of bleaching agent suspensions according to the invention is particularly good if they contain 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 from the hydrophilization and / or in-situ desensitization of the peroxycarboxylic acid, the hydrate-forming neutral salt entirely or partly derive from phlegmatization.
• the suspensions contain 10-30% by weight of diperoxydodecanedioic acid, 5-20% by weight of sodium sulfate and 0.1 to 1% by weight of xanthan, based in each case on the bleaching agent suspension, and sulfuric acid and / or sodium hydrogen sulfate as acidifying agent .
• the best storage stability of these suspensions is obtained by using a non-dried diperoxydodecanedioic acid which has been hydrophilized in the preparation by means of sulfuric acid and then by the addition of sodium hydroxide with the formation of sodium sulfate.
• constituents of the bleaching agent suspensions according to the invention discussed above, they can contain other substances compatible with them in order to give the respective bleaching agent suspensions.
• 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 Sedimentation of the solid or inhomogeneities within the suspension does not become apparent, 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 the water-insoluble peroxycarboxylic acid in an aqueous carrier liquid containing a xanthan or agar polysaccharide, into which a hydrate-forming neutral salt and an acidifying agent are introduced before, during or after the addition of the peracid.
• the thickening agent is preferably dissolved in the carrier liquid, if appropriate at elevated temperature, and then the remaining mandatory and optionally optional components of the bleaching agent 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 1000-2000 rpm and a stirring time between 5 and 20 minutes are suitable for homogenization.
• the components are used in the amounts mentioned above.
• a peroxycarboxylic acid which has been hydrophilized and optionally 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 it Production of adhering acidifying agent and adhering moisture and, if appropriate, 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 acidifying agent and neutral salt is introduced into the thickened carrier liquid, and safe because the peracid at no time 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 easily removed from textiles, for example when washing at 20-60 ° 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 or zeolite builders, organic chelating agents, sodium silicate, alkalis and sodium sulfate.
• the bleach suspension is added to the wash 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 in the examples water, is placed in a 250 ml beaker equipped with a three-bladed propeller stirrer. After adding the thickener or surfactant and dissolving the same, 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).
• the suspension is transferred to a graduated 100 ml standing cylinder and stored at room temperature. Instabilities during storage manifest themselves as a phase containing little or no solid, which can occur “above”, “below” or as a "gap" within the 100 ml layer.
• the chemical stability is determined by iodometric or potentiometric titration, the latter allowing the detection of both the peracid and the carboxylic acid on which it is based and which is formed during the peracid decomposition.
• Bleaching agent suspensions analogous to EP-A-0 176 124, containing 13.3 or 25% by weight of diperoxydodecanedioic acid (DPDDA) and sodium alkylbenzenesulfonate (Meranil®A from Henkel KGaA, Duesseldorf, or Marlon®A 390 from Chemische Werke Hüls, Marl).
• DPDDA diperoxydodecanedioic acid
• Mileanil®A from Henkel KGaA, Duesseldorf, or Marlon®A 390 from Chemische Werke Hüls, Marl.
• Bleaching agent suspensions analogous to GB-PS 1 535 804, containing 25% by weight DPDDA and 0.1 or 0.5% by weight gum arabic (example 2 A and 2 B) or 0.5% by weight Carboxypolymethylene (Carbopol (R) from BF Goodrich Co.) (Examples 2 C and 2 D).
• the same "DPDDA-dried" as in Example 1 was used, suspension for 10 minutes at 2000 rpm.
• Bleaching agent suspensions according to the invention containing 25% by weight of DPDDA and xanthan (KELZAN® from Kelco Co., Oklahoma / USA).
• the desensitized "DPDDA-dried” according to Example 1 was used.
• Xanthan was dissolved with heating before the peracid was added.
• the suspension was 10 minutes at 2000 rpm at 20 ° C. Layer height in the standing cylinder 18.5 cm.
• Example 3 D The chemical stability is significantly increased by the complexing agent (example 3 D): practically no volume expansion. Due to gas bubbles forming and adhering to the solid, the volume in Examples 3 A and 3 B increased by about 2% per week, in Example 3 C by about 1.5% per week.
• DPDDA suspensions 25% by weight DPDDA suspensions were produced in a known manner in a 2 l beaker, but with one Crescent stirrer was suspended for 15 minutes at 1300 rpm. Xanthan was first dissolved in hot water, after cooling the suspension was prepared using undried and dried phlegmatized, hydrophilized DPDDA.
• Suspension B had a flow limit of 11 Pa, showed pseudoplastic flow behavior with weak thixotropy; Viscosity 400 mPa.s at 50 / s.
• a suspension was prepared as usual from: 39.5 g DPDDA (containing 95% DPDDA, 4% dodecanedioic acid and 1% residual moisture), 0.4 g xanthan, 14 g Na2SO4 and 96.5 g water; the pH was adjusted to 4.5 by adding H2SO4. The suspension showed no change within two weeks.

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• 1987
  • 1987-03-21 DE DE19873709348 patent/DE3709348A1/de not_active Withdrawn
• 1988
  • 1988-01-18 FI FI880198A patent/FI87797C/fi not_active IP Right Cessation
  • 1988-02-19 TR TR88/0125A patent/TR24071A/xx unknown
  • 1988-03-04 AT AT88103337T patent/ATE63333T1/de not_active IP Right Cessation
  • 1988-03-04 DE DE8888103337T patent/DE3862665D1/de not_active Expired - Lifetime
  • 1988-03-04 ES ES88103337T patent/ES2021774B3/es not_active Expired - Lifetime
  • 1988-03-04 EP EP88103337A patent/EP0283792B1/de not_active Expired - Lifetime
  • 1988-03-16 US US07/168,997 patent/US4879057A/en not_active Expired - Fee Related
  • 1988-03-17 DK DK145788A patent/DK145788A/da not_active Application Discontinuation
  • 1988-03-22 JP JP63065962A patent/JPS63249769A/ja active Pending

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