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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/11—Encapsulated compositions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/38—Percompounds, e.g. peracids
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/08—Preparations for bleaching the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/10—Preparations for permanently dyeing the hair
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/20—After-treatment of capsule walls, e.g. hardening
  • B01J13/22—Coating
• • 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
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • 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
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • 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
  • C11D3/18—Hydrocarbons
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
• • 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
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3937—Stabilising agents
  • C11D3/394—Organic compounds
• • 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
  • C11D3/3945—Organic per-compounds
• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/41—Particular ingredients further characterized by their size
  • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/52—Stabilizers

Definitions

• the present invention relates to a process for the stabilization of peroxycarboxylic acids solid at room temperature, in particular
• Imidoperoxycarbon Acid in surfactant-containing, preferably aqueous dispersions, and the surfactant-containing dispersions obtained in this way and their use in detergents and cleaners, dentifrices, hair dyes and decolorizing or bleaching compositions, especially for technical applications.
• the present invention relates to detergents and cleaners, dentifrices, hair colorants and decolorizing or bleaching compositions, in particular for industrial applications, which contain the stabilized surfactant-containing dispersions of peroxycarboxylic acids according to the invention.
• bleaching (middle) components For liquid, particularly aqueous detergents and cleaners, which are becoming increasingly popular because of their positive product properties, such as better and faster solubility and applicability, the incorporation or incorporation of bleaching (middle) components is problematic for a number of reasons.
• bleaching agents used lose due to decomposition or hydrolysis reactions and incompatibilities with other components of the detergent formulation, such as.
• enzymes or surfactants often already during storage or in the context of the application of the products of their activity.
• the detergent formulation thereby clearly loses washing performance, in particular bleaching capacity, so that, in particular, bleachable soiling can no longer be satisfactorily removed.
• the bleaching components commonly used for solid detergent formulations are sensitive to moisture so that they often lose their bleaching action within a few days in a liquid and especially aqueous detergent or cleaning agent due to the loss of active oxygen.
• peroxycarboxylic acids in particular
• Imidoperoxycarboxylic acids the most important of which is phthalimidoperoxycaproic acid (PAP), more efficiently and less susceptible to hydrolysis, and known in the art as bleaching agents for detergents and cleaners.
• PAP phthalimidoperoxycaproic acid
• their storage stability is far from sufficient to ensure a long-term applicability of the corresponding washing or cleaning agent without concomitant loss of activity. Therefore, the use of peroxycarboxylic acids, in particular imidoperoxycarboxylic acids, in liquid detergents and cleaners is particularly problematical.
• EP 0 334 405 B1 describes aqueous bleach compositions containing solid, particulate, substantially water-insoluble organic peroxycarboxylic acids, wherein for stabilizing the peroxycarboxylic acids against phase separation from the aqueous liquid 1 to 30 wt .-% of a secondary C 8 -C 22 alkanesulfonate and 0.5 to 10 wt .-% of a fatty acid are added. Due to the very special composition of the additives, such a bleaching composition is not generally applicable. On the other hand, the stabilizing effect achieved hereby is not always sufficient.
• Another object is storage-stable surfactant-containing dispersions of peroxycarboxylic acids, in particular imidoperoxycarboxylic acid, such as
• Phthalimidoperoxycaproic acid (PAP), with improved properties compared to the prior art and to provide a corresponding manufacturing method for these dispersions.
• Yet another object of the present invention is to provide surfactant-containing dispersions which have peroxycarboxylic acids in the form of solid particles and lead to good stabilization of the peroxycarboxylic acids and thus to improved storage stability.
• the object of the present invention is to provide dispersions which can be used inter alia as detergents or cleaners, dentifrices, hair dyes, decolorizing or bleaching compositions, in particular for technical applications or the like, or inter alia in detergents or cleaners , Dentifrices, hair dyes, decolorizing or bleaching compositions, in particular for industrial applications or the like can be incorporated stably.
• the peroxycarboxylic acids present in the dispersions in the state of concentrated dispersion should on the one hand have a high storage stability and on the other hand have or have a high active power during application of the product, in particular when diluted with water etc. (eg during the washing process) unfold the full bleaching effect.
• peroxycarboxylic acids in particular PAP
• liquid in particular aqueous media in the presence of surfactants, such as are often present in large quantities, for example in detergents and cleaning compositions z. B. from 0.5 to 30 wt .-%, in particular 5 to 30 wt .-%, are rapidly decomposed, so that their use in surfactant-containing liquid, especially aqueous media has been very limited possible.
• organic peroxycarboxylic acids such as imidoperoxycarboxylic acids (eg PAP) can be incorporated with a high storage stability in surfactant-containing media or dispersions, if they have specific, stabilizing properties, as described in detail below be cited.
• the present invention is thus a method for stabilizing peroxycarboxylic acids solid at room temperature, in particular imidoperoxycarboxylic acids, in a surfactant-containing, preferably aqueous dispersion, wherein the surfactant-containing dispersion is adjusted such that degradation of the present in the surfactant dispersion peroxycarboxylic acids in the state of the dispersion is prevented or at least reduced or slowed down or the solubility of peroxycarboxylic acids in the dispersion is lowered.
• surfactant-containing dispersion is understood in particular to mean a liquid, in particular aqueous system or medium which has a significant content of surfactants (for example in amounts of 0.5 to 30% by weight, in particular 5 to 30 wt .-%, based on the dispersion or continuous phase of the dispersion), as z. B. is required for detergents and cleaners.
• surfactant-containing dispersion is understood to mean a composition which, in the context of its use, has a sufficient content of surfactants, so that, for example, B. a washing or cleaning activity of the composition is present.
• the process according to the invention makes it possible to efficiently stabilize peroxycarboxylic acids (eg PAP) in liquid, in particular aqueous dispersions or media in the presence of surfactants or to efficiently minimize their degradation in such media; this allows their use in such systems.
• peroxycarboxylic acids eg., PAP
• PAP peroxycarboxylic acids
• peroxycarboxylic acids especially imidoperoxycarboxylic acids
• peroxycarboxylic acids are those which (101,325 Pa) present at room temperature (20 0 C) and under normal or atmospheric pressure in the form of solid particles or particles, ie particulate are.
• degradation is understood to mean, in particular, chemical and / or physical degradation processes or degradation reactions of the peroxycarboxylic acids, in particular chemical degradation processes or degradation reactions, such as hydrolysis, reduction, oxidation, decomposition, etc. Such reactions irreversibly lead to a degradation or destruction of the peroxycarboxylic acids and thus to an impairment of their applicability, in particular an impairment of the bleaching performance of the dispersion of such peroxycarboxylic acids.
• the Applicant has now surprisingly found that degradation of peroxycarboxylic acids, in particular imidoperoxycarboxylic acids (eg PAP), in surfactant-containing dispersions, in particular surfactant-containing aqueous dispersions, can be efficiently prevented or at least significantly minimized or reduced if the halide content of these dispersions is minimized is, in particular, these dispersions are at least substantially free of or at least low in halides, in particular chloride and / or bromide.
• peroxycarboxylic acids in particular imidoperoxycarboxylic acids (eg PAP)
• PAP imidoperoxycarboxylic acids
• halide concentration in particular chloride or bromide ion concentration
• a reduction of the halide concentration, in particular of the chloride or bromide ion concentration can lead to a reduced degradation of the peroxycarboxylic acid in the (concentrated) dispersion. Consequently, a reduction or minimization of the halide concentration leads to a drastic reduction in the degradation or to a marked stabilization of the dispersed solid particulate peroxycarboxylic acids.
• a good stabilization of the peroxycarboxylic acids in dispersion is achieved in particular if the total content of halide ions, in particular chloride and / or bromide, based on the continuous phase of the dispersion, 100 ppm, in particular 50 ppm, preferably 30 ppm, particularly preferably 15 ppm, does not exceed (that is, the weight-related Total amount of halides in the continuous phase of the dispersion CHaiogeni d (total) ⁇ 100 ppm, in particular ⁇ 50 ppm, preferably ⁇ 30 ppm, more preferably ⁇ 15 ppm, is).
• the abovementioned amounts are understood according to the invention as essentially halide-free or halide-poor regions or amounts.
• the term "continuous phase of the dispersion” is understood to mean the dispersant with the constituents or ingredients dissolved therein (for example salts, surfactants, etc.).
• the dispersant is preferably water.
• halide ion content in particular of the chloride or bromide content
• the dispersion according to the invention carried out in the context of the present invention can be achieved by selecting or avoiding certain ingredients, constituents etc. (eg use of essentially halide-free components, for example, halide-free surfactants, halide-free phosphonates, etc.).
• halide ions in particular chloride or bromide
• anionic surfactants preferably only those detergent ingredients, in particular surfactants, should be used which have at least substantially no halide or chloride ions, and only those raw materials are selected which have a particularly low halide or chloride content.
• all of the components used in the process of making the dispersions of the present invention should be selected such that they are substantially halide free or at least low in halide and at least substantially compatible with the peroxycarboxylic acids, ie should not have any unwanted chemical reactions, such as degradation reactions, in particular no reduction, oxidation or hydrolysis reactions, between these components and the peroxycarboxylic acids and no reactions induced by the further components of the peroxycarboxylic occur which lead to their loss of activity, especially degradation.
• the stabilizing effect achieved by the halide minimization with respect to the present in surfactant dispersion Peroxycarbonklaren can be further increased that the surfactant-containing dispersion acidic, preferably slightly to moderately acidic, or at most neutral.
• the dispersion is at a pH of at most 7, in particular a pH in the range of 3.5 to 7, preferably from 4.0 to 6.5, more preferably from 4.5 to 6, most preferably from about 5, set.
• bleaching agents based on peroxycarboxylic acids can surprisingly be effectively stabilized in an acidic surfactant-containing environment
• the peroxycarboxylic acids at such pH values in the dispersant, in particular water have only low solubility and are present as a crystal dispersion, whereas neutral or alkaline pH values, a relatively rapid decomposition of peroxycarboxylic acids, such as PAP, takes place due to the increased solubility.
• the pH of the dispersion, in particular of the washing and cleaning agent should not be adjusted too acidic in order to avoid degeneration or inactivation of any enzymes present in the dispersion.
• the pH given in the context of the present invention represents an area optimized against this background.
• the adjustment, in particular reduction or shift of the pH of the dispersion in the acidic range can be carried out in the context of the inventive method with acids or acidic salts.
• acids or acidic salts which are suitable according to the invention for adjusting the pH are z.
• organic polycarboxylic acids bisulfates and bisphosphates.
• complexing agents used phosphonates as phosphonic acids are then incorporated and then the desired pH value by addition of alkalis are set (pH adjustment method).
• the Applicant was able to show in a surprising manner that the stabilizing effect achieved by the aforementioned measures with respect to the peroxycarboxylic acids in dispersion can be further increased by the surfactants present in the dispersion, as is the case with detergents and cleaners is - converted into an inactivated form, i. H. the dispersion should contain at least substantially no surfactants in active form.
• the total content of active surfactants in the dispersion or the continuous phase of the dispersion should be less than 5%, in particular less than 2.5%, preferably less than 1%, in each case based on the dispersion or the continuous phase of the dispersion ,
• the total content of inactivated surfactants in the dispersion is more than 95%, in particular more than 97.5%, preferably more than 99%, in each case based on the total surfactants.
• the Applicant has been able to show that organic peroxycarboxylic acids, in particular PAP, are rapidly decomposed in the presence of active surfactants (ie surfactants present in free or micellar form in the dispersion or detergent or detergent formulation) since the peroxycarboxylic acids are decomposed by the Surfactants are increasingly dissolved and are extremely unstable in this dissolved state.
• active surfactants ie surfactants present in free or micellar form in the dispersion or detergent or detergent formulation
• nonionic surfactants or nonionic surfactants lead to an accelerated decomposition of the peroxycarboxylic acids.
• the dispersion should therefore have an optimized, preferably a low uncharged surfactant (nonionic surfactant) / charged surfactant ratio.
• the content of Alkylpolyglykolethem should be as low as possible.
• the inactivation of the surfactants can be carried out by adding sulfates, particularly preferably sodium sulfate.
• a salting out of the surfactants is caused (ie inducing a phase separation in a low-surfactant, continuous phase and a preferably lamellar, generally highly viscous, crystalline or liquid-crystalline surfactant-rich phase), wherein the surfactants are converted from the particular micellar, active form in a preferably lamellar, crystalline or liquid crystalline form (crystal or liquid crystal formation), in a nearly surfactant-free continuous phase is dispersed.
• the dispersed surfactant liquid crystal itself which can be separated, for example, by centrifugation, should be as highly viscous as possible.
• a particularly good stabilization of the peroxycarboxylic acids can be achieved if the content of free surfactants in the washing and cleaning formulations according to the invention in the continuous phase is particularly preferably not more than 1%, based on the dispersion or the continuous phase of the dispersion ,
• the inactivation of the surfactants may preferably be brought about by introducing sodium sulfate into the continuous phase of the dispersion.
• the sodium sulfate in amounts of 5 to 30 wt .-%, in particular 15 to 30 wt .-%, preferably 20 to 30 wt .-%, are introduced into the dispersion.
• introduction is to be understood in particular as dissolution, for example by dissociation, or solubilization of the sodium sulfate introduced into the dispersion.
• the Applicant has now unexpectedly found that a particularly good stabilization of the peroxycarboxylic acids in dispersion is achieved when all of the aforementioned measures are implemented in the dispersion (ie minimizing the halide content, lowering the pH, inactivation of the surfactants, optimized or minimized nonionic surfactant content).
• the abovementioned measures have a surprisingly synergistic effect, which is reflected in a particularly efficient stabilization of the dispersed, solid particulate peroxycarboxylic acids, accompanied by a good storage stability of such dispersions.
• the inventive method for the stabilization of solid at room temperature, particulate peroxycarboxylic acids, in particular Imidoperoxycarboxylic acids, in surfactant-containing dispersions, preferably aqueous dispersions, can thus be carried out overall in such a way that the dispersions are adjusted in such a way that
• halide ions in particular chloride and / or bromide, based on the continuous phase of the dispersion, not exceeding 100 ppm, in particular 50 ppm, preferably 30 ppm, more preferably 15 ppm; and or
• dispersions have a pH of at most 7, in particular a pH in the range of 3.5 to 7, preferably from 4.0 to 6.5, more preferably from 4.5 to 6, most preferably of about 5, have; and or
• dispersions at least substantially no surfactants in active form, in particular wherein the total content of active surfactants in the continuous phase of the dispersions less than 5%, especially less 2.5%, preferably less than 1%, each based on the continuous Phase of the dispersion is.
• the stabilization of the peroxycarboxylic acids in the dispersions according to the invention can be further increased by adding at least one complexing agent, preferably in amounts of from 0 to 10% by weight, to the aqueous dispersions.
• the complexing agent may be selected from the group of quinoline and / or its salts, alkali metal polyphosphonates, picolinic acid and dipicolinic acid, mono- or polyphosphonic acids, in particular 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), ethylenediaminetetraacetic acid (EDTA),
• DTPMP Diethylenetriaminepenta (methylenephosphonic acid)
• Azacycloheptane diphosphonate (AHP), nitrilotriacetic acid (NTA), citrate and / or short chain dicarboxylic acids.
• these complexing agents are used in particular for the complexation of heavy metal ions, which are used in particular as catalysts of Degradation processes act and can thus lead to a degradation of peroxycarboxylic acids, such as PAP, and which can be registered, for example via water pipes or metallic components of the production plants or raw materials in the inventive surfactant-containing dispersion (eg, in a detergent or cleaning agent).
• PAP peroxycarboxylic acids
• At least one catalase can be added to the aqueous dispersion in the context of the process according to the invention for further increasing the stability of the peroxycarboxylic acids.
• the catalase is used in particular for removing any hydrogen peroxide which may be formed or present in the dispersion.
• Hydrogen peroxide may be formed in the dispersion optionally by reaction of the peroxycarboxylic acid with water; the addition of a catalase leads to an effective reduction of the content of hydrogen peroxide in the dispersion, so that thereby also oxidation-sensitive, optionally present further ingredients, such as enzymes, are effectively protected.
• At least one peroxidase and / or at least one antioxidant may likewise be added to the detergents or cleaners according to the invention.
• Antioxidants preferred according to the invention are, for example, ascorbic acid, tocopherol, gallic acid or derivatives thereof.
• the Applicant has surprisingly found that the stability of the peroxycarboxylic acids in the surfactant-containing dispersions according to the invention can be increased by adding to the dispersion at least one in particular water-miscible solvent (eg glycerol) or else the water-miscible solvent being the dispersion medium of the dispersion ,
• the solvent should have a low dissolving power for the organic peroxycarboxylic acids, in particular imidoperoxycarboxylic acids.
• this solvent is glycerol.
• the amount of the solvent (eg glycerol) may preferably be more than 20% by weight, more preferably more than 30% by weight, based on the dispersion.
• the water content of the washing or cleaning formulation should Preferably, about 5 wt .-%, based on the dispersion, are, wherein the glycerol content may exceed 70 wt .-%.
• Glycerol has a low dissolving power for organic peroxycarboxylic acids, in particular imidoperoxycarboxylic acids, such as PAP, which can lead to a stabilization of the peroxycarboxylic acid in the dispersions according to the invention. Nevertheless, the amount of optionally used glycerol should be such that no negative effects on the other ingredients result, in particular with regard to their solubility in the dispersion. In general, however, water is the preferred dispersant.
• the peroxycarboxylic acids can be additionally provided with at least one shell or incorporated into at least one matrix, if this is desired or required in terms of process or application.
• B results in a capsule system with a capsule core based on at least one peroxycarboxylic acid.
• the storage stability of the peroxycarboxylic acids is increased by at least substantially preventing or at least substantially reducing direct contact of the peroxycarboxylic acids with the environment, in particular with the dispersion or the dispersing agent and the substances dissolved or dispersed therein.
• the shell or matrix may comprise or consist of at least one inorganic salt, preferably an inorganic sulfate, more preferably sodium sulfate.
• the dispersion according to the invention should be designed such that the sulphate shell is at least substantially not degraded during storage, in particular dissolved or dissolved, which is particularly preferred by adding a salt which influences the solubility of the shell, for example an inorganic sulphate Sodium sulfate, can be accomplished. Release of the peroxycarboxylic acid should then take place during use, in particular in a wash liquor, by appropriate dilution effects with concomitant degradation of the shell.
• the application of the shell or matrix to the peroxycarboxylic acid is advantageously carried out before introduction into the dispersion.
• the shell or matrix may, for example, be a gel, for example based on an oil phase solidified or gelled by a stabilizer, in particular a gelling agent.
• the shell may be a multilayer polyelectrolyte capsule shell, for example.
• the shell or matrix may contain, for example, inorganic salts, in particular sulfates and / or phosphates, inorganic oxides, organic polymers, in particular cellulose ethers, polyvinyl alcohols (PVAI) and polyvinylpyrrolidones (PVP).
• capsule systems are obtained which, in addition to the capsule core based on the peroxycarboxylic acid, have a capsule shell based on the shell material, as stated below.
• both the capsule core and the capsule shell can have further substances for the targeted setting of the capsule system properties, if this is desired or required in terms of process engineering or application.
• the organic peroxycarboxylic acid a substance which at a temperature below 80 0 C 1, in particular below 70 0 C, endothermic reactions with itself, especially Kristalliganabspaltungsre syndrome, may be applied.
• this substance can also be mixed or mixed with the peroxycarboxylic acid.
• this substance may be boric acid.
• the shell or matrix may contain at least one complexing agent, in particular as defined above.
• the dissolution rate of the capsule system and thus the release of the peroxycarboxylic acids during use, in particular in a wash liquor can be set in the desired manner.
• a "controlled release effect" with respect to the peroxycarboxylic acids contained in the capsule system according to the invention can be achieved. Under a controlled-release effect is in particular a slight, preferably between 1 and 15 minutes delaying the dissolution of the Capsule system in its application, for. B. when diluted in a washing and cleaning liquor, or to understand a release of peroxycarboxylic acid from the capsule system.
• the degradation, in particular the dissolution or dissolution, of the capsule shells can generally be due to physical or chemical interactions or reactions, for example solubilization or dissociation processes, in particular as a consequence of dilution effects in the application of the dispersion (for example in a wash liquor) Wash liquor, done.
• the particle size of the organic peroxycarboxylic acids introduced into the dispersion may be ⁇ 3,000 .mu.m, in particular ⁇ 2,500 .mu.m, preferably ⁇ 2,250 .mu.m, preferably .ltoreq.2,000 .mu.m, more preferably ⁇ 1,500 .mu.m.
• the particle size of the organic peroxycarboxylic acids should be 10 to 3,000 ⁇ m, in particular 50 to 2,500 ⁇ m, preferably 100 to 1,500 ⁇ m.
• the content of organic peroxycarboxylic acids, in particular imidoperoxycarboxylic acids, based on the dispersion, in the process according to the invention may be 0.1 to 30% by weight, in particular 0.5 to 25% by weight, preferably 1 to 20% by weight 1 to 15 wt .-%, amount.
• adjustment of the particle size of the solid peroxycarboxylic acid for example prior to introduction of the peroxycarboxylic acid particles into the dispersion, can be carried out by methods known to the person skilled in the art, for example by shearing, vibration and / or ultrasound introduction, comminution, grinding, etc., so that according to the invention a targeted Adjustment of the particle size according to their respective later use is possible.
• organic peroxycarboxylic acids are used as substances to be stabilized in the dispersion according to the invention.
• the latter can be selected from organic mono- and diperoxycarboxylic acids. Examples are, in particular, dodecanediperoxyacid or, preferably, imidoperoxycarboxylic acids, particularly preferably 6-phthalimidoperoxidycaproic acids (6-phthalimidoperoxyhexanoic acid, PAP).
• the peroxycarboxylic acid should advantageously at atmospheric pressure (101,325 Pa) a melting point above 20 0 C, in particular above 25 0 C, preferably above 35 0 C, preferably above 45 0 C, more preferably above 50 0 C, very particularly preferably above 100 ° C, have; This ensures that the peroxycarboxylic acid used is substantially in the form of solid particles, so that degradation of the peroxycarboxylic acid in the dispersion according to the invention is at least reduced.
• a further subject-according to a second aspect of the present invention is the storage-stable surfactant-containing dispersions preparable by the novel process, in particular surfactant-containing aqueous dispersions, of peroxycarboxylic acids, especially imidoperoxycarboxylic acids, solid at room temperature.
• the surfactant-containing dispersion according to the invention is adjusted such that degradation of the peroxycarboxylic acids present in the dispersion in the state of the surfactant-containing dispersion is prevented or at least reduced or slowed down or that the solubility of the peroxycarboxylic acids in the surfactant-containing dispersion is reduced.
• a storage-stable, surfactant-containing dispersion according to the invention can be adjusted in this way
• the content of halide ions, in particular chloride and / or bromide, based on the continuous phase of the dispersion not exceeding 100 ppm, in particular 50 ppm, preferably 30 ppm, more preferably 15 ppm; and or in that the dispersion has a pH of at most 7, in particular a pH in the range from 3.5 to 7, preferably from 4.0 to 6.5, particularly preferably from 4.5 to 6, very particularly preferably from about 5 , having; and or
• the dispersion contains at least substantially no surfactants in active form, in particular wherein the total content of active surfactants in the continuous phase of the dispersion is less than 5%, in particular less than 2.5%, preferably less than 1%, in each case based on the continuous Phase of the dispersion is.
• the dispersions according to the invention have numerous characteristics
• the dispersions according to the invention can be used in or as detergents or cleaning agents, in particular liquid detergent compositions, dentifrices, hair colorants or decolorizing agents. Bleaching compositions for technical applications are used.
• the abovementioned formulations or compositions have a high storage stability with respect to the peroxycarboxylic acids, so that they still have a high activity, in particular bleaching performance, even after prolonged storage times.
• Another object of the present invention - according to another aspect of the present invention - are detergents and cleaners, dentifrices, hair dyes or decolorizing or
• the detergents and cleaning agents according to the invention can be used for cleaning hard surfaces and / or softer, in particular textile surfaces.
• the detergents and cleaners according to the invention can be used in particular as dishwashing detergents, all-purpose cleaners, bathroom cleaners, floor cleaners, car washers, glass cleaners, furniture care and cleaners, facade cleaners, detergents or the like, particularly preferably as detergents.
• the washing and cleaning agents according to the invention are preferably suitable for cleaning fibers, textiles, carpets and the like.
• the detergents and cleaners according to the invention contain conventional ingredients known to the person skilled in the art or components (for example surfactants, fragrances, dyes, enzymes, enzyme stabilizers, odorous substances or builders, pH adjusters) , other bleaching agents, bleach activators, silver protectants, stain-resistant substances, optical brighteners, grayness inhibitors,
• a washing or cleaning agent according to the invention in particular a liquid washing or cleaning agent, contains, for example, the following ingredients: (I) at least one solid, particulate organic peroxycarboxylic acid, in particular imidoperoxycarboxylic acid, in amounts of 0.1 to 30% by weight, in particular 0.5 to 25 wt .-%, preferably 1 to 20 wt .-%, preferably 1 to 15% by weight; and or
• surfactants preferably in inactivated form, in particular cationic and / or anionic surfactants, preferably in amounts of from 0 to 30% by weight and / or nonionic surfactants, preferably in amounts of from 0 to 30% by weight; and or
• optionally complexing agents in particular selected from the group of quinoline and / or its salts, alkali metal polyphosphonates, picolinic acid and dipicolinic acid, mono- or polyphosphonic acids, in particular 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), ethylenediaminetetraacetic acid (EDTA) 1 diethylenetriaminepenta (methylenephosphonic acid) (DTPMP),
• Azacycloheptane diphosphonate (AHP), nitrilotriacetic acid (NTA), citrate and / or short chain dicarboxylic acids, preferably in amounts of from 0 to 10% by weight; and or
• enzymes such as proteases, amylases, cellulases and / or lipases, and / or enzyme stabilizers, preferably in amounts of 0 to 10 wt .-%; and or
• builders in particular fatty acids, preferably saturated and / or branched fatty acids, in particular having a melting point below 30 ° C., and / or citric acid and / or citrate, preferably in amounts of from 0 to 15% by weight; and or (vii) optionally perfumes, preferably in amounts of from 0 to 5% by weight; and or
• optionally adjuvants such as defoamers, pH regulators, rheology modifiers (thickeners), solvents, dyes; and or
• the detergent or cleaner formulation according to the invention should be designed such that the stability of the peroxycarboxylic acids is at least substantially not reduced. Therefore, the components employed in the washing or cleaning compositions of the invention should be selected such that they are at least substantially compatible with the peroxycarboxylic acids, i. H. in particular in the washing or cleaning agent itself, in particular in the period before its application (storage time), no undesirable chemical reactions, in particular degradation, oxidation or reduction reactions and / or hydrolysis reactions, occur between these components and the peroxycarboxylic acids, which lead to premature degradation and loss of activity of peroxycarboxylic acids.
• the surfactants should be inactivated in the detergent or cleaner formulation, in particular by salting out, ie inducing a phase separation into a low-surfactant, continuous phase and a preferably lamellar, generally highly viscous, crystalline or liquid-crystalline surfactant-rich phase, preferably by introducing a Sulfate compound, particularly preferably sodium sulfate, in the detergent or cleaner formulation.
• a Sulfate compound particularly preferably sodium sulfate
• the content of free surfactants in the detergent and cleaner formulations according to the invention should preferably not exceed 1% in the continuous phase.
• an optimized or minimized nonionic surfactant / charged surfactant ratio should also be present in the washing or cleaning agent according to the invention-corresponding to the statements on the dispersion according to the invention or the preparation process.
• the content of Alkylpolyglykolethern should be as low as possible.
• the content of inorganic salt, particularly preferably sodium sulfate should be selected in the detergent or cleaning agent such that the surfactants are at least substantially inactivated in the detergent or cleaning agent, in particular by salting out, preferably by introducing at least one sulfate compound, particularly preferably sodium sulfate.
• the sulfate concentration in the washing or cleaning agent according to the invention should be selected such that when using the washing or cleaning agent in the wash liquor, the surfactants are again in active form, which can be achieved for example by a dilution effect when entering the detergent or cleaning agent in the wash liquor can.
• the concentration should be selected so that - as mentioned above - in the continuous phase of the detergent or cleaning agent, in particular less than 1% active surfactant is present and that no temperature crystallization, especially at temperature drops to 0 0 C, no crystallization of the sulfate ,
• the washing and cleaning agents according to the invention should have at least substantially no increased chloride or Bromidionengehalt, which by the use of methyl sulfate, phosphate, tosylate or Cumolsulfonatitati can be achieved. Furthermore, raw materials should be selected which have a particularly low chloride or bromide content.
• the washing or cleaning agents according to the invention may contain at least one fatty acid.
• saturated and / or branched fatty acids in particular having a melting point below 30 ° C., are preferred according to the invention.
• Isocarb- 16 ® of Sasol be used in the inventive detergents or cleaning agents.
• the washing or cleaning agent according to the invention or the dispersions according to the invention should be formulated in such a way that the peroxycarboxylic acids are activated or released sufficiently quickly during their use, in particular in a wash liquor.
• the activation or release of the peroxycarboxylic acids takes place in particular by physical or physicochemical or by chemical processes.
• dilution of the inorganic salt, more preferably sodium sulfate, in the wash liquor results in conversion of the surfactants from their inactivated form (e.g.
• the washing or cleaning agent should be composed in such a way that it degrades, in particular, a dissolution or detachment of an optionally on the peroxycarboxylic acids applied shell or matrix - in particular as described above - during use, especially in the wash liquor guaranteed.
• a dissolution of the sulphate shell if present, can be achieved by the previously mentioned dilution effects.
• an optionally present gel matrix can be dissolved or solubilized.
• a detachment, in particular solubilization, of an optionally polyelectrolyte shell by the activated surfactants can be promoted or caused. Mechanical forces also play a role here.
• the dispersions of the invention lead to a significant increase in the storage stability of the incorporated therein peroxycarboxylic - especially in connection with a low chloride or Bromidionenkonzentration - so that the effectiveness of peroxycarboxylic acids, especially bleaching performance, even after a long period or a long storage time is guaranteed ,
• the respective measures or adjustments of the dispersion in the context of a synergistic effect lead to a significant increase in the storage stability of the peroxycarboxylic acids in the dispersion.
• the process according to the invention for the preparation of the dispersions is simple and easy to handle, whereby it is possible to dispense with the use of substances which are complicated to prepare and therefore often cost-intensive. Therefore, the method is ideal for use on a large scale industrial scale.
• dispersions can be widely varied or tailored with respect to their composition and their active ingredient content, so that an individual adaptation to the respective requirements, in particular to detergents and cleaners, can take place. Due to their specific formation, the dispersion can be used virtually universally for a wide range of different compositions.
• the dispersion of the invention is also compatible with such capsule systems.
• washing and cleaning agent formulations according to the invention have due to their previously mentioned, coordinated and synergistic acting adjustments, such as in particular a low halide ion content, optimization of pH, addition of complexing agents, inactivation of surfactants, use of special solvents or special enzymes such as catalases or Peroxidases, addition of antioxidants, compared to the prior art, considerable advantages, since degradation of the sensitive peroxycarboxylic acid-based bleaching agent is significantly reduced.

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• 2003
  • 2003-12-22 DE DE10361081A patent/DE10361081A1/de not_active Ceased
• 2004
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