WO1996019557A2 - Utilisation d'acides hydroxyalkylaminocarboxyliques comme agents complexants - Google Patents

Utilisation d'acides hydroxyalkylaminocarboxyliques comme agents complexants Download PDF

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Publication number
WO1996019557A2
WO1996019557A2 PCT/EP1995/004893 EP9504893W WO9619557A2 WO 1996019557 A2 WO1996019557 A2 WO 1996019557A2 EP 9504893 W EP9504893 W EP 9504893W WO 9619557 A2 WO9619557 A2 WO 9619557A2
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WIPO (PCT)
Prior art keywords
hydroxyalkylaminocarboxylic
hydroxyalkylaminocarboxylic acids
acids according
formulations
alkyl
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PCT/EP1995/004893
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German (de)
English (en)
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WO1996019557A3 (fr
Inventor
Birgit Potthoff-Karl
Beate Ehle
Richard Baur
Günter OETTER
Alfred Oftring
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Basf Aktiengesellschaft
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Priority to EP95942120A priority Critical patent/EP0799296A2/fr
Publication of WO1996019557A2 publication Critical patent/WO1996019557A2/fr
Publication of WO1996019557A3 publication Critical patent/WO1996019557A3/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1042—Use of chelating agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G03C5/44—Bleaching; Bleach-fixing

Definitions

  • the present invention relates to the use of hydroxyalkylaminocarboxylic acids of the general formula I.
  • R 1 is hydrogen, a Ci to C alkyl radical or a grouping of the formula
  • n stands for a number from 1 to 4, preferably 1 or 2,
  • R 2 and R 3 independently of one another are hydrogen, a phenyl radical or an alkyl or alkenyl radical which additionally contains phenoxy groups, carboxylic acid C 1 -C 4 -alkyl ester groups or of triglycerides based on unsaturated C 1 -C 2 -Fatty acid-derived ester groups and can be interrupted by non-adjacent oxygen atoms mean, the sum of the C atoms from both radicals R 2 and R 3 must be at least 4,
  • A stands for a linear or branched Ci to C ⁇ alkylene group, which can additionally carry a hydroxyl group and / or a group of the formula COOM, where R 1 and A together with the N atom form a five- or six-membered ring can form, and
  • M denotes hydrogen, alkali metal, ammonium or substituted ammonium
  • the invention relates above all to the use of these hydroxyalkylaminocarboxylic acids in aqueous lubricant formulations for automatic conveyor systems, in particular as aqueous ones Chain lubricant formulations for belt cleaning in bottle filling and cleaning systems.
  • the present application also relates to an aqueous lubricant or lubricant formulation which contains the hydroxyalkylaminocarboxylic acids mentioned.
  • bottle cleaning, filling and labeling are mostly carried out automatically.
  • semi-automatic systems transport around 2000 bottles per hour.
  • Fully automatic systems can handle up to approximately 80,000 bottles per hour.
  • the bottles are usually transported to the bottling plants on belts, the so-called "plate belts *, which are usually made of stainless steel.
  • These chain-like belts are lubricated with a chain lubricant, also called 'belt lubricant *'. Also have to be lubricated these conveyor belts, usually at more or less regular intervals, are cleaned.
  • the chain lubricant used in breweries is preferably soaps, especially potash lubricating soaps, which e.g. synthetic nonionic or ionic surfactants can be added.
  • a disadvantage of such chain lubricants is that the potash soaps are particularly sensitive to water hardness.
  • sequestering agents such as ethylenediaminetetraacetic acid or nitrilotriacetic acid or their alkali metal salts are also usually added, which partially mask the hardness.
  • EP-B 044 458 (1) discloses lubricants for bottle conveyor belts which contain polyether carboxylates and N-acyl sarcosinates as active substances.
  • WO-A 93/18120 (2) describes clear water-soluble chain conveyor belt lubricants which contain iminodicarboxylates with a long-chain N-alkyl radical.
  • the means from (1) and (2) have considerable disadvantages, with (1) the clear water solubility and the foaming behavior and with (2) the foaming behavior are in need of improvement.
  • hydroxyalkylamino carboxylic acids of the general formula Ia are used
  • R 4 is a C 5 - to Ci ⁇ -alkyl radical, in particular a C ⁇ - to Ci 4 -alkyl radical, or a phenyl radical and M has the meaning given above.
  • hydroxyalkylaminocarboxylic acids of the general formula Ib are used
  • the compounds I are known in principle. In Fette, Seifen, Anstrichstoff 68, No. 11, pp. 964-967 (1966) (3) by E. Ulsperger, some of the compounds Ia and Ib are explicitly described, reference being made to their surface-active properties.
  • the compounds I, Ia and Ib are expediently prepared by reacting the underlying amino acids with the corresponding epoxides, as described in (3).
  • the residual meanings in these starting components described in more detail below apply equally to the definition of the variables in the end products I, Ia and Ib.
  • amino acids Ring structure such as proline or amine acids with a hydroxyl group in the bridge member A such as serine, isoserine or homoserine into consideration.
  • R 1 thus preferably denotes hydrogen or methyl.
  • the carboxyl group COOM can be present as a free acid group or as a salt, in particular as a sodium, potassium, ammonium or substituted ammonium salt (organic amine salt).
  • the bases on which the organic amine salts are based are, in particular, tertiary amines such as trialkylamines having 1 to 4 carbon atoms in the alkyl radical, e.g. Trimethylamine, triethylamine or tri-n-butylamine, and trialkanolamines with 2 or 3 carbon atoms in the alkanol radical, e.g. Triethanolamine, tri-n-propanolamine or triisopropanolamine.
  • terminal epoxides ie those in which R 2 is a C - to usually C3o-alkyl or alkenyl radical or a phenyl radical and R 3 is hydrogen;
  • central epoxides ie those in which R 2 and R 3 each represent a C - to usually C 3 o-alkyl or alkenyl radical or a phenyl radical, where the two radicals can be the same or different;
  • Glycidyl ether ie those compounds in which R 2 is a C 3 to usually C 29 alkyl or alkenyloxymethyl radical or a phenyloxymethyl radical and R 3 is hydrogen.
  • a long-chain radical R 2 or R 3 stands for branched or linear alkyl or alkenyl with 4 to usually 30 C atoms, in particular 6 to 18 C atoms, especially 8 to 14 C atoms.
  • alkyl or alkenyl groups are listed as examples of branched or linear long-chain radicals R 2 and R 3 :
  • n-butyl n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, iso- Tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta-decyl, n-octadecyl, eicosyl, hexadecenyl, hexadecadienyl, hexadecatrienyl, octadecenyl, octadecadienyl and octadecatrienyl.
  • Mixtures of different radicals R 2 or R 3 can also occur, for example mixtures of n-decyl and n-dodecyl or n-dodecyl and n-tetradecyl.
  • Ci to C 4 alkyl ester radicals in (c) are n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and in particular methyl and ethyl.
  • C 3 to C 29 alkyl or alkenyl groups in the alkyl or alkenyloxymethyl radicals in (d) all of the above-mentioned examples for long-chain radicals R 2 or R 3 and n-propyl and isopropyl come into consideration .
  • triglyceride derivatives are triglycerides with, for example, 3 unsaturated fatty acids, the olefinic double bonds of which are partially or preferably completely epoxidized and which, with the amino acids mentioned, give the compounds I via these epoxide groups react.
  • unsaturated fatty acids up to 9, in particular up to 6, amino acid units can normally be bound to a triglyceride molecule.
  • double bonds have not been epoxidized or if the triglyceride carries 1 or 2 saturated fatty acid groups, 1 to 6, in particular 1 to 4, amino acid units are normally bound to a triglyceride molecule.
  • the unsaturated fatty acids in the triglycerides are the usual C 10 to C 22 fatty acids such as oleic acid, linoleic acid or linolenic acid.
  • Triglycerides of vegetable or animal origin are found above all in soybean oil, rapeseed oil, olive oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, rapeseed oil, beef tallow or fish oil, these products, after epoxidation, also being used directly as starting materials for the preparation of the hydroxyalkylamino carboxylic acids I can serve.
  • the sum of the C atoms from the two radicals R 2 and R 3 in the compounds I is usually from 4 to 60 in the absence of triglyceride structures.
  • the compounds I described and in particular Ia and Ib are outstandingly suitable as complexing agents for binding the calcium and magnesium water hardness in general in aqueous detergent formulations. In many applications, water hardness is a disruptive factor that must be excluded.
  • the compounds I, Ia and Ib can be used in aqueous lubricant formulations for automatic conveyor systems.
  • the compounds I, Ia and Ib are particularly suitable for aqueous chain lubricant formulations for the belt cleaning of bottle filling and cleaning systems.
  • aqueous chain lubricant formulations for the belt cleaning of bottle filling and cleaning systems.
  • it is for example beer, milk, soft drinks, fruit juice, sweet must, wine or mineral water bottles.
  • Chain lubricant formulations contain as surface active, i.e. cleaning component usually soaps, especially potash soaps, non-ionic or ionic surfactants, e.g. Fatty alcohol ethoxylates, fatty alcohol sulfates or fatty alcohol ether sulfates, or special surface-active agents such as a mixture of polyether carboxylates and N-acyl sarcosinates according to (1) or N-alkylimidodicarboxylates according to (2) or mixtures of the surfactants or surfactant-like compounds mentioned.
  • surface active i.e. cleaning component usually soaps, especially potash soaps, non-ionic or ionic surfactants, e.g. Fatty alcohol ethoxylates, fatty alcohol sulfates or fatty alcohol ether sulfates, or special surface-active agents such as a mixture of polyether carboxylates and N-acyl sarcosinates according to (1) or N-alkylimido
  • the surface-active compounds mentioned are more or less sensitive to water hardness, but especially soaps, and are therefore usually used together with water-hardness-binding agents.
  • the hydroxyalkylaminocarboxylic acids I, Ia and Ib have proven to be particularly advantageous here; they can be advantageously combined with all of the surface-active agents mentioned, their advantage not only in binding water hardness or preventing precipitation of calcium or magnesium salts from formulation components, but also in part in a synergistic interaction with the surfactants with respect to. the cleaning effect is to be sought.
  • the present invention also relates to an aqueous one
  • Lubricant or lubricant formulation for automatic conveyor systems containing, in addition to the lubricant or lubricant component and other customary auxiliaries, surfactants and hydroxyalkylaminocarboxylic acids I.
  • the long-chain fatty acid such as oleic acid or its water-soluble one is used as the lubricant component
  • Salts in particular alkali metal or amine salts, or a long-chain fatty amine such as oleylamine or stearylamine in the form of its inorganic or organic salts.
  • the surfactants mentioned above can be considered.
  • Typical auxiliaries are, for example, defoamers, corrosion inhibitors, solubilizers, viscosity improvers and preservatives or disinfectants.
  • a typical aqueous lubricant or lubricant formulation of this type, for example for chain lubricants, is composed as follows:
  • the compounds I, Ia and Ib described are generally suitable as complexing agents for alkaline earth and heavy metal ions.
  • Electrolytic degreasers especially for steel
  • These cleaning agent formulations generally contain 0.1 to 30% by weight of hydroxyalkylaminocarboxylic acids I.
  • Formulations customary for the individual fields of use are known in principle to the person skilled in the art.
  • such formulations contain, in addition to the complexing agents, 1 to 35% by weight of surfactants of anionic or preferably nonionic nature, which are foaming or low-foaming depending on the intended use, and, if desired, further complexing agents, builders, foam steamers, emulsifiers, as further auxiliaries.
  • organic solvents can largely be dispensed with in the formulations described.
  • hydroxyalkylaminocarboxylic acids I is in alkaline detergent formulations for the beverage and food industry, in particular for bottle cleaning in the beverage industry and for cleaning equipment in dairies, breweries, in canned goods, baked goods, the sugar, fat processing and meat processing industries.
  • Formulations in particular with improved properties in the removal of dirt were sought for the cleaning of containers and apparatus in the beverage and food industry.
  • the present alkaline detergent formulations generally have pH values from 8 to 14, preferably from 9 to 13, in particular from 10 to 12.
  • the cleaning agent formulations described is bottle cleaning in the beverage industry, in particular using automatic bottle washers.
  • the soiled bottles contained, for example, beer, milk, soft drinks, fruit juices, sweet must, wine or mineral water.
  • cleaning agent formulations described Another area of application for the cleaning agent formulations described is apparatus cleaning in the canning industry.
  • cleaning agents When heating the tin cans filled and closed with food, usually in an autoclave, or when cleaning cans, e.g. B. in a continuous spraying machine, cleaning agents must be used that wash off the residues of the filling material without attacking the tinplate or its coating.
  • the cleaning agent is intended to prevent scale deposits on the cans or in the apparatus.
  • Another area of application for the cleaning agent formulations described is apparatus cleaning in the baked goods industry, in particular the cleaning of baking and dough forms which are contaminated with burnt-on shortening and dough residues.
  • the cleaning is usually done by boiling with the alkaline cleaning solutions or by washing in continuous spraying systems.
  • sucrose is obtained from sugar beet or sugar cane
  • calcium salts containing impurities or residues are obtained, for the removal of which the hydroxyalkamino Formulations containing carboxylic acids I are also suitable.
  • Another area of application for the cleaning agent formulations described is apparatus cleaning in the fat-processing industry, which primarily produces lard, tallow, edible oils or fats or fatty oils hardened by catalytic hydrogenation from fats of animal or vegetable origin.
  • products of this type also represent important raw materials for the production of products for textile finishing, paints, leather care products, cosmetic preparations, candles, soaps, surfactants, lubricants, plasticizers, cement and asphalt additives and plastics.
  • alkaline detergent formulations containing the described hydroxyalkylaminocarboxylic acids I can be used largely free of organic solvents. A possible environmental impact is thus largely excluded.
  • (iii) 1 to 30% by weight, preferably 2 to 25% by weight, in particular 3 to 20% by weight of surfactants.
  • Sodium and potassium hydroxide are particularly suitable as component (ii), but also sodium and potassium carbonate, * Mixtures of the alkalis mentioned can also be used.
  • surfactants iii
  • alkyl sulfates, alkyl sulfonates, fatty alcohol alkoxylates, oxo alcohol alkoxylates, alkyl polyglucosides and fatty amine alkoxylates are particularly suitable.
  • This composition constitutes a basic formulation for all of the above-mentioned fields of application.
  • the individual compositions within this basic formulation differ from one another due to the different types of food and beverage soiling, the different amounts of alkaline earth metal ions in these residues and deposits, and the differences to explain the sensitive materials of the containers and apparatus to be cleaned in the various fields of application.
  • the alkaline cleaning agent formulations described which contain the compounds I generally do not cause any corrosion, even with sensitive apparatus materials.
  • the basic formulation from components (i) to (iii) described above can also contain conventional auxiliaries in the concentrations customary here, for example disinfectants to achieve the desired degree of bacteriological purity, wetting agents, loose agents, corrosion inhibitors or preservatives.
  • a further use for hydroxyalkylaminocarboxylic acids I is in dishwashing detergent formulations, in particular in phosphate-free detergents for machine dishwashing in dishwashers in the household or in commercial establishments, for example.
  • hydroxyalkylaminocarboxylic acids I Another use for hydroxyalkylaminocarboxylic acids I is in bleaching baths in the paper industry.
  • complexing agents are used in reductive bleaching, e.g. B. with sodium dithionite, or in the oxidative bleaching, for. B. with hydrogen peroxide, needed to increase the effectiveness of the bleaching process, ie to increase the whiteness of the wooden ship.
  • the complexing agents thus serve to eliminate heavy metal cations, mainly iron, copper and especially manganese, which also have a disruptive effect on resin sizing with alum and sodium resinate due to the formation of insoluble salts.
  • the deposition of iron on paper leads to "hot "spots where the oxidative catalytic destruction of cellulose begins.
  • a typical formulation of such an aqueous reductive bleaching bath in the paper industry for wood pulp contains 0.05 to 0.1% by weight of complexing agent I and about 1% by weight of sodium dithionite, in each case based on the wood grinding.
  • the bath temperature is approx. 60
  • the bleaching time is usually 1 hour
  • the pH is approx. 5.8.
  • a typical formulation of such an aqueous oxidative bleaching bath in the paper industry for ground wood contains 0.05 to 0.15% by weight of complexing agent I, approx. 2% by weight of water glass, approx. 0 , 75% by weight NaOH and approx. 1% by weight H 2 O 2 , each based on the wood pulp.
  • the bath temperature is approximately 50 ° C. and the bleaching time is normally 2 hours.
  • hydroxyalkylaminocarboxylic acids I are in photographic bleaching and bleach-fixing baths.
  • these compounds can be used in baths which are prepared with hard water in order to prevent the precipitation of poorly soluble calcium and magnesium salts. The precipitations lead to gray veils on films and images as well as deposits in the tanks, which can thus advantageously be avoided.
  • iron IIII complexing agent solutions they can advantageously be used in bleach-fixing baths, where they can replace the hexacyanoferrate solutions, which are harmful from an ecological point of view.
  • a typical aqueous photographic bleach or bleach-fix bath formulation of this type looks as follows:
  • the pH of such a bath is usually 4 to 8.
  • hydroxyalkylaminocarboxylic acids I is in pretreatment and bleaching baths in the textile industry.
  • Pretreatment baths are to be understood in particular as desizing baths and alkaline pretreatment or mercerization baths.
  • these compounds can thus be used to remove traces of heavy metals during the production process of natural and synthetic fibers such as cotton, Serve wool or polyester. This prevents many disturbances, such as dirt stains and stripes on the textile, loss of gloss, poor wettability, uneven dyeing and color defects.
  • a typical aqueous pretreatment bath of this type in textile production contains:
  • complexing agent I 0.1 to 10% by weight of complexing agent I, 0.5 to 20% by weight of customary wetting or emulsifying agents,
  • a reducing agent such as sodium dithionite
  • auxiliaries such as preservatives or desizing agents, e.g. B. enzymes such as lase.
  • hydroxyalkylaminocarboxylic acids I are in galvanic baths for masking contaminating heavy metal cations. They serve here as a replacement for the highly toxic cyanides.
  • the following copper bath may be mentioned as a typical composition of such an aqueous galvanic bath for the deposition of, for example, copper, nickel, zinc or gold:
  • This bath is usually adjusted to pH 13 with sodium hydroxide solution; it can also contain conventional stabilizers such as amines or sodium cyanide.
  • copper, iron, manganese and zinc complexes of the compounds I are used in plant nutrition to correct heavy metal deficits.
  • the heavy metals are added as chelates in order to prevent the precipitation as biologically inactive, insoluble salts.
  • hydroxyalkylaminocarboxylic acids I can advantageously be used wherever precipitation of calcium, magnesium and heavy metal salts is to be disrupted and prevented in industrial processes, for example to prevent Formation of deposits and incrustations in boilers, pipelines, on spray nozzles or generally on smooth surfaces.
  • the compounds I can be used as a complexing agent or as a builder.
  • conventional formulations debris density approx. 450 g / 1
  • more and more compact and ultra-compact detergents debris density ⁇ 700 g / 1 are becoming increasingly important.
  • Compact detergent formulations are known to have a higher content of detergent (tensides), builders (e.g. zeolites), bleaches and polymers than conventional powder detergents.
  • the compounds I are usually active in amounts of 0.1 to 25% by weight, in particular 1 to 15% by weight.
  • the compounds I can be used as complexing agents in an amount of 0.05 to 20% by weight, based on the total weight of the detergent formulation.
  • the compounds I can also be used as preservatives, advantageously in an amount of 0.05 to 1% by weight, based on the total weight of the detergent formulation.
  • Further applications include, for example, applications in pharmaceuticals, cosmetics and foodstuffs, in order, for. B. the metal-catalyzed oxidation of olefinic double bindings and thus prevent the products from becoming rancid.
  • flue gas scrubbing namely the removal of NO ⁇ from flue gases, H 2 S oxidation, metal extraction and use as catalysts for organic syntheses, eg. B. the air oxidation of paraffins or the hydroformylation of olefins to alcohols.
  • An advantageous effect of the compounds I is bleach stabilization, for example in the bleaching of textiles, cellulose or paper stock. Traces of heavy metals such as iron, copper and manganese occur in the components of the bleaching bath itself, in the water and in the material to be bleached and catalyze the decomposition of the bleaching agent.
  • the complexing agents I bind these metal ions and prevent the undesired decomposition of the bleaching system during storage and during use. This increases the efficiency of the bleaching system and damages to the goods to be bleached are suppressed.
  • a further advantageous effect of the hydroxyalkylaminocarboxylic acids I is the strong bleach-activating effect of complexes of the compounds I with manganese, in particular manganese of oxidation levels II and IV.
  • complexes of the compounds I with manganese, in particular manganese of oxidation levels II and IV can be used as bleaching catalysts in amounts as a replacement for conventional bleach activators in textile detergent formulations use in the ppm range.
  • Hydroxyalkylaminocarboxylic acids I are particularly suitable for the purposes described because they are extremely effective complexing agents for alkaline earth metal ions and for heavy metal ions, in particular for calcium and manganese. Their calcium and manganese binding capacity are exceptionally high.
  • the hydroxyalkylaminocarboxylic acids I, Ia and Ib used according to the invention are largely ecologically harmless since they are to a large extent biodegradable or eliminable. They are also toxicologically safe, which is also important for use in the food sector.
  • hydroxyalkylaminocarboxylic acids I, Ia and Ib used according to the invention have the property profile necessary for the intended use, in particular in lubricant or lubricant formulations for automatic conveyor systems, in particular in particular, they are usually clearly water-soluble and very low-foaming.
  • A was prepared from sarcosine and 1,2-epoxyoctane and B from sarcosine and 2-ethylhexylglycidyl ether in each case according to (3).
  • Ethylene diamine tetraacetic acid tetrasodium salt (EDTA-Na 4 ) served as a comparison.
  • the chain lubricant formulation used was composed as follows:
  • Complexing agent (A, B or EDTA-Na 4 ) 12% by weight of commercially available fatty acid ethoxylate 5% by weight of commercially available carboxylic acid mixture as solubilizer 5% by weight
  • the corresponding oleic acid amine salt acts as a lubricating or sliding component.
  • the complexing agent serves to bind water hard and to stabilize the oleic acid, since it prevents the precipitation of poorly soluble calcium oleate.
  • the three formulations were each reacted with water having a hardness of 30 ° and diluted in a ratio of 1: 100, 1: 200 and 1: 300. After standing at room temperature for 3 hours, the turbidity was determined by nephelometric turbidity measurement.
  • the scattering of light is determined photometrically after irradiating the measurement solution, this scattering being determined by the interaction between the light rays and the particles or droplets in the solution, the number and size of which make up the degree of turbidity.
  • the nephelometric turbidity unit (NTU) which is measured at 25 ° C. in aqueous solution and is determined by calibration on the basis of formazin as an artificial opacifier, serves as the measured variable. The higher the NTU value, the cloudy the solution.
  • Table 1 shows the results of the determinations.
  • Ca-Bmdevermogen for A 35 mg CaC0 3 / g complexing agent
  • Ca-Bmdevermogen for B 25 mg CaC0 3 / g complexing agent
  • C was prepared from sarcosine and styrene oxide and D from sarcosine and 2,3-epoxypropylphenyl ether in each case analogously to A and B.
  • the amino acid component N-oleoylsarcosinate of the comparative example was replaced in the mixture by the same amount of the complexing agents A or B to be used according to the invention, and the measurement was repeated.
  • Table 3 shows the results of the determinations.
  • Example 3 The three mixtures from Example 3 were investigated using the air introduction method (see above). For this purpose, 2 g of the mixture were dissolved in 1 liter of water, 100 ml of this solution were removed and placed in a foam tube. Air was blown in for 10 minutes and then the foam height was read. Table 4 shows the results of the determinations. Table 4
  • Table 5 shows the results of the measurements.
  • An analogous mixture according to (2) with 13% by weight of citric acid (example 3 there) instead of 14% by weight of acetic acid gave the same result.
  • Example 6 5 Foam behavior of the mixtures from Example 5
  • Example 5 The three mixtures from Example 5 were examined analogously to Example 4 using the air introduction method (see above). Table 6 shows the results of the determinations. The analog mixtures with 10 13 wt .-% citric acid gave the same result.

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Abstract

Des acides hydroxyalkylaminocarboxyliques ont la formule générale (I), dans laquelle R1 désigne hydrogène, un résidu alkyle C¿1?-C4 ou un groupe ayant les formules -CHR?3¿-CH(OH)-R2 ou -(CH¿2?)n-COOM, dans lesquelles n vaut de 1 à 4; R?2 et R3¿ désignent indépendamment l'un de l'autre hydrogène, un résidu phényle ou un résidu alkyle ou alcényle qui peuvent en outre porter des groupes phénoxy, des groupes esters d'alkyle C¿1?-C4 d'acide carboxylique ou des groupes esters dérivés de triglycérides à base d'acides gras C10-C22 insaturés et peuvent être interrompus par des atomes d'oxygène non adjacents, la somme des atomes de C des deux résidus R?2 et R3¿ devant s'élever à au moins 4; A désigne un groupe alcylène C¿1?-C6 droit ou ramifié qui peut en outre porter un groupe hydroxyle et/ou un groupe ayant la formule COOM, R?1¿ et A pouvant former ensemble avec l'atome de N un cycle à 5 ou 6 éléments; et M désigne hydrogène, un métal alcalin, ammonium ou ammonium substitué. Ces acides hydroxyalkylaminocarboxyliques sont utiles comme agents complexants d'ions de métaux alcalino-terreux et de métaux lourds.
PCT/EP1995/004893 1994-12-22 1995-12-12 Utilisation d'acides hydroxyalkylaminocarboxyliques comme agents complexants WO1996019557A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997030209A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede de blanchiment de pate haut rendement
WO1997030208A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede applicable au traitement de la pate chimique
US6340683B1 (en) 1999-04-22 2002-01-22 Synaptic Pharmaceutical Corporation Selective NPY (Y5) antagonists (triazines)
CN112143567A (zh) * 2019-06-26 2020-12-29 诺翔新材料(无锡)有限公司 一种定影系统清洁剂及其制备方法

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EP0399133A1 (fr) * 1989-05-23 1990-11-28 The Procter & Gamble Company Compositions détergentes et de nettoyage contenant agents de chelation
EP0411436A2 (fr) * 1989-08-03 1991-02-06 BASF Aktiengesellschaft Utilisation de dérivés de l'acide 2-hydroxy-3-aminopropionique comme complexants, stabilisants pour compositions de blanchissement et adjuvants dans les agents de lavage et de nettoyage
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DE3143726A1 (de) * 1981-11-04 1983-05-11 Degussa Ag, 6000 Frankfurt Optisch aktive prolin-derivate, verfahren zu ihrer herstellung und ihre verwendung
US4602106A (en) * 1984-03-26 1986-07-22 Societe Francaise Hoechst Process for producing hydroxyalkylaminoacetic acids
EP0317542A2 (fr) * 1987-11-13 1989-05-24 The Procter & Gamble Company Composition de nettoyage pour surfaces dures contenant des dérivés de l'acide iminodiacétique
EP0399133A1 (fr) * 1989-05-23 1990-11-28 The Procter & Gamble Company Compositions détergentes et de nettoyage contenant agents de chelation
EP0411436A2 (fr) * 1989-08-03 1991-02-06 BASF Aktiengesellschaft Utilisation de dérivés de l'acide 2-hydroxy-3-aminopropionique comme complexants, stabilisants pour compositions de blanchissement et adjuvants dans les agents de lavage et de nettoyage
DE4340043A1 (de) * 1993-11-24 1995-06-01 Henkel Kgaa Verwendung Stickstoff-haltiger Komplexbildner bei der Holzstoffbleiche

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997030209A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede de blanchiment de pate haut rendement
WO1997030208A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede applicable au traitement de la pate chimique
US6340683B1 (en) 1999-04-22 2002-01-22 Synaptic Pharmaceutical Corporation Selective NPY (Y5) antagonists (triazines)
CN112143567A (zh) * 2019-06-26 2020-12-29 诺翔新材料(无锡)有限公司 一种定影系统清洁剂及其制备方法

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