EP0264977B1 - Detergens-Builder und aufgebaute Detergentien - Google Patents

Detergens-Builder und aufgebaute Detergentien Download PDF

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Publication number
EP0264977B1
EP0264977B1 EP87201564A EP87201564A EP0264977B1 EP 0264977 B1 EP0264977 B1 EP 0264977B1 EP 87201564 A EP87201564 A EP 87201564A EP 87201564 A EP87201564 A EP 87201564A EP 0264977 B1 EP0264977 B1 EP 0264977B1
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Prior art keywords
salt
component
succinate
tartrate
weight
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French (fr)
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EP0264977A1 (de
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Ivan Herbots
James Pyott Johnston
Francesco De Buzzaccarini
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Procter and Gamble European Technical Center
Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2089—Ether acids-salts thereof

Definitions

  • the present invention relates to cleaning compositions which contain a mixture of succinate builders.
  • ingredients succinates in combination with certain detergency ingredients is also known; see EPO 70191 and EPO 70190, as well as copending European applications EP-A- 0 232 114 and EP-A- 0 233 010 and German 32 05 791 and 33 17 337.
  • carboxylate materials of various types in solid and liquid cleaners is well-known; see UK 1,514,276 for amine soap mixture; UK 1,429,143 for zeolite/polycarboxylate mixtures: US 2,264,103 for citrate and other carboxylate plus soap mixtures; US 3,634,392 for polysaccharidic carboxylate detergency builders; US 3,898,187 for various sulfur-succinates in dish-washing detergents; and UK 1,400,898 for use with clay softeners.
  • the present invention encompasses detergency builder compositions comprising:
  • compositions are those wherein substituent R in the hydrocarbyl succinate component (b) is C 12 -C 16 , alkyl or alkenyl.
  • substituent R in the hydrocarbyl succinate component (b) is C 12 -C 16 , alkyl or alkenyl.
  • 2-Dodecenyl succinic acid, or water-soluble salts thereof, is most preferred for use as component (b).
  • the weight ratio of component (a):(b) is in the range of 2:1 to 1:3.
  • This invention also encompasses detergent compositions comprising conventional detersive surfactants and detersive ingredients, and a detergency builder composition which comprises a mixture of:
  • Fully-formulated detergent compositions herein typically contain from 1% to 50% by weight of detersive surfactants and from 5% to 45% by weight of the detergency builder composition, the balance comprising conventional detergent ingredients or carriers.
  • Conventional anionic, cationic, and nonionic detersive surfactants may be used in such compositions, as may other detersive surfactants as described more fully, hereinafter.
  • detergent compositions typically comprise:
  • Preferred for laundry detergents are compositions wherein the hydrocarbyl succinate component of the builder is a C12-C16 alkyl or alkenyl succinate; the compound 2-dodecenyl succinic acid, or water-soluble salts thereof, is most preferred.
  • compositions herein may be formulated as liquids; or formulated to be releasably carried on a sheet or other carrier substrate, or releasably contained in pouches; or formulated as bars, powders, granules, tablets, flowable gels, or the like.
  • the essential components of the builder compositions herein are the tartrate succinates and also the hydrocarbyl succinates, all as more fully described hereinafter.
  • the detersive surfactants, optional detersive adjunct ingredients, as well as the carriers fillers, etc., used in the detergent compositions of this invention are all well-known to workers in this field.
  • Tartrate Succinate Components The tartrate succinate compounds used herein may be generically classified as "ether carboxylates.” These include tartrate monosuccinic acid, or salts thereof, having the structural formula: wherein each X is H or a salt-forming cation. This tartrate monosuccinic acid or salt thereof is hereinafter designated as "TMS.” “TMS” is used to designate both the acid and salt forms of this material.
  • the tartrate monosuccinic acid component can be employed in the compositions herein in its free acid form, i.e., wherein X in the structural formula is H.
  • this material may be partially or fully neutralized to a tartrate monosuccinate salt.
  • Preferred salt-forming cations useful in forming the neutralized materials are those which yield substantially water-soluble salts of tartrate monosuccinic acid. Examples of such preferred salt-forming cations include alkali metal, e.g., sodium, potassium, lithium, ammonium, C1-C4 alkyl substituted ammonium and C1-C4 alkanolamine. The most preferred salt-forming cations are sodium, potassium, monoethanolamine and triethanolamine.
  • the tartrate monosuccinic component can be used in the builder compositions of this invention in an amount ranging from about 10% to 85% by weight of the builder. More preferably, the tartrate monosuccinate component will comprise from about 15% to 75% by weight of the builder compositions herein. Most preferably, this component is present to the extent of from about 50% to 65% by weight of the builder composition.
  • the second ether carboxylate composition which can be used in this invention is the particular novel polycarboxylate, tartrate disuccinic acid, or a salt thereof, having the structural formula :wherein each X is H or a salt-forming cation.
  • Tartrate disuccinic acid, or a salt thereof, is hereinafter designated as "TDS.”.
  • the TDS component can be utuilzed in either its free acid form or in its partially or fully neutralized form in the builder compositions herein.
  • Neutralizing cations are likewise those which provide TDS in the form of its substantially water-soluble salt.
  • suitable salt-forming cations include the same cations hereinbefore described for formation of the tartrate monosuccinate material.
  • both the acid and salt forms of the TDS material will hereinafter be referred to as the "tartrate disuccinate" or "TDS" component.
  • the TDS component can be used in the builder compositions of this invention in an amount ranging from about 10% to 85% by weight of the builder. More preferably, the TDS component will comprise from about 15% to 75% by weight of the builder compositions herein. Most preferably, TDS is present to the extent of from about 50% to 65% by weight.
  • TMS and TDS can also be used; indeed, mixtures are generally obtained in the method of manufacture disclosed hereinafter.
  • mixtures comprise TMS:TDS in ratios ranging from 97:3 to 20:80.
  • Preferred ratios TMS:TDS are 95:5 to 40:60. These are used at the same levels as mentioned above for the single components to provide the builder compositions of this invention.
  • This component is of the general formual R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid, wherein R is C8 ⁇ 18 hydrocarbyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts, at levels of 15% to 90%, more preferably 35% to 50%, of the present builder compositions.
  • succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like.
  • Detersive Surfactants The detergent compositions of this invention will contain organic surface-active agents ("surfactants") to provide the usual cleaning benefits associated with the use of such materials.
  • Detersive surfactants useful herein include well-known synthetic anonic, nonionic , amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyland alkylether sulfates, paraffin sulfonates, olefin sulfonates, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, ethoxylated alcohols and ethoxylated alkyl phenols, and the like, which are well-known from the detergency art.
  • detersive surfactants contain an alkyl group in the C9-C10 range; the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts.
  • Standard texts such as the McCutcheon's Index contain detailed listings of such typical detersive surfactants.
  • C11-C14 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and C11-C18 alkyl sulfates are especially preferred in the compositions of the present type.
  • Aslo useful herein are the water-soluble soaps, e.g. the common sodium and potassium coconut or tallow soaps well-known in the art.
  • the surfactant component can comprise as little as 1% of the detergent compositions herein, but generally the compositions will contain 5% to 40%, preferably 6% to 30%, of surfactant. Mixtures of the anionics, such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates, with C9-C16 ethoxylated alcohol surfactants are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabric.
  • compositions herein can contain other ingredients which aid in their cleaning performance.
  • laundry compositions herein also contain enzymes to enhance their through-the wash cleaning performance on a variety of soils and stains.
  • Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents.
  • Commercial detersive enzymes preferably a mixtures of amylase and protease are typically used at levels of 0.001% to 2%, and higher, in the present compositions.
  • compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commerical produces to provide aesthetic or additional product performance benefits.
  • Typical ingredients include pH regulants, perfumes, dyes, bleaches, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach activators and the like.
  • the compositions are typically used at a concentration of 500 ppm, preferably 0.10% to 2.5%, in an aqueous laundry bath, typically at pH 7-11 to launder fabrics.
  • the laundering can be carried out by agitating fabrics with the present compositions over then range from 5°C to the boil, with excellent results.
  • TMS and TDS compounds used in the practice of this invention are not believed to be described in the literature, so their preparation will be described in detail.
  • the first step of the preparation process herein involves the formation a of an aqueous reaction mixture containing particular amounts of a maleate reactant comprising both monovalent cation and calcium salts of maleic acid and a tartrate reactant comprising both monovalent cation and calcium salts of tartaric acid.
  • the total amount of maleate plus tartrate reactants in the reaction mixture will generally range from about 20% to 60% by weight of the mixture, more preferably from about 40% to 55% by weight. Materials which yield these reactants in solution can be dissolved in water to form the reaction mixture used in this process.
  • both the maleate and tartrate reactants in requisite mixed salt form and amounts can be generated in the reaction mixture in situ. This can be done by combining in aqueous solution certain amounts of maleic acid or maleic anhydride, tartaric acid, a source of calcium cations and, as a neutralizing agent, an hydroxide of a monovalent cation in certain amounts.
  • the molar ratio of maleic acid to tartaric acid in such solutions will generally range from about 0.5:1 to 8:1, more preferably from about 0.9:1 to 1.2:1.
  • the ratio of maleic and tartaric acids which is used will depend upon the relative amounts of tartrate monosuccinate and tartrate disuccinate desired in the builder composition to be prepared.
  • a souce of calcium cations which acts as a catalyst for the tartrate succinate-forming reaction, is generally added to such aqueous solutions in an amount such that the ratio of calcium cations to tartaric acid ranges from about 0.1:1 to about 2.0:1, more preferably from about 0.8:1 to 1.5:1.
  • the amount of calcium added should be such that the ratio of moles of calcium cations to total moles of maleic and tartaric acids in solution is less than 1.
  • Any compound which yields calcium cations in solution can be employed as the calcium cation source. Such compounds inlude calcium hydroxide and water-soluble calcium salts. Calcium hydroxide is highly preferred since it acts as both a calcium cation source and a neutralizing agent.
  • An hydroxide of a monovalent cation is also essentially added to the reactant mixture as a neutralizing agent.
  • This neutralizing agent is usually aded in an amount such that the ratio of moles of monovalent cations to total moles of tartaric acid plus the moles of maleic acid minus the mole of calcium cations ranges from about 2.1:1 to about 3.8:1. More preferably this ratio ranges from about 2.2:1 to about 3:1.
  • the monovalent cation-containing neutralizing agent can be any hydroxide which upon addition to water yields monovalent neutralizing cations in solution.
  • Such neutralizing agents include, for example, alkali metal, ammonium or substituted ammonium hydroxide. Sodium hydroxide is highly preferred.
  • Enough neutralizing base e.g. calcium hydroxide and monovalent cation hydroxide
  • the reaction mixtures of this invention will generally have a pH within the range of about 8.5 to 13, more preferably from 9.5 to 12.5.
  • Precursors of the tartrate and maleate mixed salt reactants in solution can take a variety of forms.
  • tartaric acid in either its D-, L- or DL- stereoisomer form is suitable for use as the precursor of the tartrate reactant.
  • the maleate reactant can be derived from maleic acid.
  • Maleic acid itself can be formed in aqueous solution by the addition of maleic anhydride to water.
  • reaction mixture used in the process appropriate by adding the tartrate and maleate reactants in their appropriate salt forms to water and to thereby prepared the reaction mixture without the step of in situ neutralization. If the reaction mixture is formed in this manner, amounts of the tartrate, maleate and calcium materials, as well as added neutralizing agents, should be selected so that the resulting solution corresponds in composition to the hereinbefore described reaction mixtures formed by situ generation of the essential reaction mixture components.
  • the preferred process of the present invention employing reactant molar ratios of maleate to tartrate within the range of 0.9:1 to 1.2:1 is especially advantageous from the reactant converion and reaction kinetis standpoint.
  • the improved conversion percentages which can be realized using the preferred process embodiments of the present reaction may be in part due to the inherently greater stability of TMS in the reaction mixture in comparison with oxydisuccinate (ODS) under similar conditions.
  • TMS under conditions used for its formation does not appear to decompose as readily as oxydisuccinate to unreactive by-products such as fumarate, thereby enhancing both TMS formation and subsequent TDS formation from TMS. It should also be noted that irrespective of conversion percentage, production of TMS/TDS mixtures in general can be realized in a relatively short reaction time compared with the extended reaction times which are reported to be required for preaparation of other ether carboxylates such as oxydisuccinate.
  • the TMS/TDS composition forming reaction is carried out by maintaining the aqueous reaction mixture at a temperature of from about 20°C to 120°C, preferably from about 50°C to 80°C, for a period of time sufficient to form a reaction product mixture which contains the desired amounts of the tartrate monosuccinate and tartrate disuccinate compounds of the compositios herein. Reaction times of from about 0.5 to to hours, more preferably from about 1 to 4 hours will generally be suitable for realizing acceptable yields of the compounds used in the builder composition herein.
  • TMS/ TDS are to be used as detergent builders, it is especially important that such compositions contain especially low levels of alkaline earth metals such as calcium.
  • the builder compositions of this invention should generally contain no more than about 10 mole percent of calcium based on the total moles of TMS and TDS present.
  • the calcium content of the aqueous reaction must be reduced. Removal of calcium to effect this reduction can be carried out in a number of ways known in the art. Frequently, calcium can be removed from the product mixture by adding thereto a calcium precipitating material having a greater affinity for reaction with calcium than do the tartrate monosuccinate and tartrate disuccinate reaction products.
  • a calcium precipitating material having a greater affinity for reaction with calcium than do the tartrate monosuccinate and tartrate disuccinate reaction products.
  • Such materials can include, for example, precipitating chelating agents such as ethanehydroxydiphosphonic acid, or salts thereof (EHDP), or calcium precipitating materials such as alkali metal carbonate, pyrophosphate, bicarbonate and/or alkali metal silicate.
  • the resulting calcium precipitate can thereafter be removed from the aqueous reaction product mixture by filtration.
  • An alternate means for removing calcium from the aqueous reaction product mixture involves treatment of the reaction product mixture with an appropriate insoluble ion exchange resin. No matter what technique is employed, calcium content of the aqueous reaction mixture should be reduced to th xtent that the ratio of moles of calcium to total moles of tartrate monosuccinate and tartrate disuccinate is less than about 1:10, preferably less than about 1:20.
  • the reaction product mixture of the present process may also optionally be treated to remove excess reactants or reaction by-products such as maleates, malates, tartrates and fumarates.
  • This can be accomplished by conventional salt separation procedures using a solvent such as methanol in which these excess reactants and reaction by-products are relatively soluble and in which the desired tartrate monosuccinate and tartrate disuccinate are relatively insoluble.
  • the reaction product mixture may be concentrated by a removal of water to the desired extent.
  • Water removal may, for example, involve substantially complete drying of the reaction product mixture, e.g., by spray drying, so that the TMS/TDS mixture is recovered in solid, e.g., granular, form.
  • the TMS/TDS mixture in the form of an aqueous liquid may be utilized directly in the preparation of builder, detergent compositions or laundry additive products of the types more fully described hereinafter.
  • the reaction product mixture After reduction of the calcium content in the reaction product mixture, it is possible, if desired, to acidify the product mixture using conventional acidification or ion exchange techniques to convert the TMS/TDS products therein to their free acid form.
  • the tartrate monosuccinate and tartrate disuccinate materials can be used as builders in their water-soluble salt form, and such acidification is therefore not usually necessary or desirable.
  • TMS and TDS materials are also possible, if desired, to separate the individual components of the resulting builder mixture and recover such compounds as substantially pure TMS and TDS materials.
  • component separation cab be effected, for example, using conventional liquid chromatographic techniques.
  • TMS or TDS it may be desirable to use either TMS or TDS as substantially pure materials. More frequently, however, recovery of the individual TMS and TDS components as substantially pure materials is neither necessary nor particularly advantageous.
  • TMS tartrate monosuccinate
  • TDS tartrate disuccinate
  • the base mixture is then added at a uniform rate over 0.5 hour to the moderately stirred acid solution which is at 70-85°C.
  • the resulting reaction mixture is cooled with warm (ca. 60°C) water in order to maintain a reaction temperature of 90 ⁇ 5°C most of the time.
  • the reaction mixture may, however, boil briefly from time to time. The object is to prevent major losses of water vapor and also to limit the amount of insoluble salt which crystallizes upon the cool reaction vessel walls.
  • the reaction temperature is held at 85°C.
  • the reaction mixture is immediately heated with steam, stirred moderately in a covered reactor, and a 0.40g sample taken with time arbitrarily set at zero.
  • the reaction mixture which is a white suspension, is brough to 90-100°C within 10 minutes. Within 15 to 20 minutes of time zero, the reaction mixture clears.
  • Samples (0.40 + 0.04 g) of the reaction solution are taken every half hour to be dissolved in 100 ml 0.1N sulfuric acid solution and immediately submitted for high pressure liquid chromatography (HPLC) analysis in order to monitor the course of the reaction.
  • HPLC high pressure liquid chromatography
  • HPLC analysis indicates that the composition of the organic portion of the reaction product solution is 11.1% tartrate. 1.7% malate, 12.6% maleate, 10.9% fumarate, 35.0% peak 2A, 19.6% peak 2B, 3.3% peak 3A, and 5.9% peak 3B.
  • Peaks 2A and 2B are isomers of sodium tartrate monosuccinate (TMS) and peaks 3A and 3B are isomers of sodium tartrate disuccinate (TDS). Therefore, the HPLC estimated yield of TMS + TDS based upon all peak areas is 63.7%. The approximate weight ratio of TMS:TDS is 86:14. All yields are based upon HPLC refractive index raw data, i.e., are not corrected to mole%. Calculated yield of this reaction based on tartrate is 4.139g.
  • a second reaction product batch of the same size is made using similar procedures.
  • HPLC analysis indicates that the composition of this second reaction product solution is 9.8% tartrate, 1.7% malate, 12.4% maleate, 10.1% fumarate, 35.0% peak 2A, 18.1% peak 2B, 5.1% peak 3A, and 7.9% peak 3B.
  • peaks 2A and 2B are isomers of sodium tartrate monosuccinate (TMS) and peaks 3A and 3B are isomers of sodium tartrate disuccinate (TDS). Therefore, the HPLC-estimated yield of TMS + TDS based upon all peak areas is 66.1%.
  • the approximate weight ratio of TMS:TDS is 80:20. Yield is 4400g based on calculation.
  • a TMS/TDS reaction product mixture is prepared using procedures similar to those set forth in Reaction Sequence I except that the reactants used to form the reaction mixture are maleic anhydride, tartaric acid, sodium hydroxide and calcium hydroxide in a 1.3:1.0:3.93:0.5 molar ratio.
  • the resulting reaction product mixture is determined by high pressure liquid chromatography to contain 17.2% tartrate, 1.5% malate, 9.9% maleate, 10.3% fumarate, TMS (2A 36.2%, 2B 13.4%) and TDS 3A 5.3%, 3B 6.2%).
  • the rest of the sample is a mixture of water and calcium salts.
  • Calcium is then removed from this mixture by a precipitation procedure using a combination of carbonate salts.
  • a combination of carbonate salts 26.5 grams of sodium carbonate and 21.0 grams of sodium bicarbonate (0.25 mole of each salt) are dissolved in 204 grams of water.
  • This solution is then added to 250 grams of the above-described reaction product mixture which contains 0.125 moles of calcium.
  • the resulting mixture is placed in a 1 liter flask equipped with a thermometer and stirrer. This mixture is then heated to 80°C and stirred for 3 hours. After cooling to 25°C while stirring is continued, this mixture is filtered through a sintered glass filter. The resulting filter cake is washed with 20ml of water twice.
  • the filtrate is adjusted to a weight of 1000 grams with the addition of water and then is analyzed.
  • the filtrate is found to contain tartrate - 1.48%; malate - 0.14%; maleate - 1.02%; fumarate - 0.83%; TMS (2A 3.3%, 2B 1.3%); TDS -(3A 0.5%, 3B 0.5%); and calcium - 0.009%.
  • the maleate and fumarate salts are then removed using a methanol precipitation procedure as in Reaction Sequence I.
  • a water-softening builder composition is as follows:
  • Example I is added to an aqueous laundry bath at a concentration of 500ppm to reduce water hardness and to enhance the fabric cleaning performance of commercial laundry detergents.
  • a composition of the type described in Example I is prepared as pre-measured, 50-gram sachets, using water-permeable non-woven cloth as the sachet material.
  • the sachets are simply placed in an aqueous bath to provide water softening and detergency builder activity.
  • a heavy-duty, liquid laundry detergent or hard surface cleaner is as follows: Miscellaneous - minors inclusive of enzyme balance to 100 *Diethylene triamine pentamethylene phosphonic acid.
  • the above composition has a pH, (1% in water; 20°C,) of 7.8.
  • the liquid composition of the example is homogeneous, and stable on storage at room temperature.
  • the liquid compositions are prepared by admixing the ingredients, and adjusting pH (1% aqueous solution; 20°C) to the desired level, generally 6.5 to 9.
  • the levels of tartrate succinate typically range from 2-15%, preferably 2-10%, most preferably 3-7%.
  • the level of hydrocarbyl succinate is typically 3-20%, preferably 5-15%.
  • the total of the two components is typically 5-35%, preferably 7-25%.
  • the weight ratios of the tartrated succinate: hydrocarbyl succinate range from 3:1 to 1:6, preferably 2:1 to 1:3.
  • Example V The composition of Example V was tested in a washing machine in a 60°C cycle and compared to VIZIR R , a liquid detergent containing fatty acid builder. The comparative performance on various types of soil on cotton fabrics are reported below. Product concentration during wash was 1.0%.
  • the comparative stain removal performance readings represnt the average of the evaluations by two expert judges.
  • a granular detergent composition comprises the following ingredients:
  • An aqueous crutcher mix is prepared and spray-dried.

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Claims (11)

  1. Detergens-Builder-Zusammensetzung, enthaltend
    (a) eine Tartrat-Succinat-Verbindung, ausgewählt aus der Gruppe, bestehend aus
    Figure imgb0036
     worin X Wasserstoff oder ein salzbildendes Kation ist,
    Figure imgb0037
     worin X Wasserstoff oder ein salzbildendes Kation ist,
    iii) Mischungen hiervon,
    und
    (b) eine Kohlenwasserstoff-Succinat-Verbindung der Formel
    Figure imgb0038
     worin R einen C₈-C₁₈-Kohlenwasserstoffrest bedeutet und X Wasserstoff oder ein salzbildendes Kation ist, und worin das Gewichtsverhältnis von Verbindung (a):(b) im Bereich zwischen 15:1 bis 1:15 liegt.
  2. Eine Zusammensetzung gemäß Anspruch 1, worin R in Verbindung (b) ein C₁₂-C₁₆-Alkyl- oder Alkenylrest ist.
  3. Eine Zusammensetzung gemäß Anspruch 2, worin die Verbindung (b) 2-Dodecenylbernsteinsäure oder ein wasserlösliches Salz hiervon ist.
  4. Eine Zusammensetzung gemäß einem der vorangehenden Ansprüche, worin das Gewichtsverhältnis von (a):(b) 2:1 bis 1:3 beträgt.
  5. Eine Zusammensetzung, enthaltend herkömmliche oberflächenaktive Detergentien und Reinigungszusätze und eine Detergens-Builder-Zusammensetzung, welche eine Mischung aus
    (a) einer Tartrat-Succinat-Verbindung, ausgewählt aus der Gruppe, bestehend aus
    Figure imgb0039
     worin X Wasserstoff oder ein salzbildendes Kation ist,
    Figure imgb0040
     worin X Wasserstoff oder ein salzbildendes Kation ist,
    iii) Mischungen hiervon,
    und
    (b) einer Kohlenwasserstoff-Succinat-Verbindung der Formel
    Figure imgb0041
     worin R einen C₈-C₁₈-Kohlenwasserstoffrest bedeutet und X Wasserstoff oder ein salzbildendes Kation ist, und worin das Gewichtsverhältnis von Verbindung (a):(b) im Bereich zwischen 15:1 bis 1:15 liegt, enthält.
  6. Eine Detergens-Zusammensetzung gemäß Anspruch 5, welche 1 bis 50 Gew.-% an oberflächenaktivem Detergens und 5 bis 45 Gew.-% der Detergens-Builder-Zusammensetzung enthält, wobei der Rest herkömmliche Detergens-Zusätze oder Trägerstoffe umfaßt.
  7. Eine Detergens-Zusammensetzung gemäß einem der Ansprüche 5 oder 6, worin das oberflächenaktive Detergens ausgewählt ist aus der Gruppe bestehend aus anionischen, kationischen und nichtionischen oberflächenaktiven Detergentien.
  8. Eine Detergens-Zusammensetzung gemäß einem der Ansprüche 5, 6 oder 7, enthaltend:
    I.A. 0 bis 30 Gew.-% eines anionischen oberflächenaktiven Detergens, ausgewählt aus herkömmlichen Alkylbenzolsulfonat-, Alkylsulfat-, Alkylethersulfat-, Seifen-Detergentien und deren Mischungen,
    B. 0 bis 30 Gew.-% eines nichtionischen oberflächenaktiven Mittels, ausgewählt aus herkömmlichen ethoxylierten Alkoholen und ethoxylierten Alkylphenol-Detergentien und deren Mischungen, oder
    C. Mischungen aus A und B mit der Maßgabe, daß die Zusammensetzung wenigstens 5 Gew.-% des oberflächenaktiven Detergens enthält,
    II. wenigstens 10 Gew.-% einer Detergens-Builder-Komponente, umfassend:
    (a) eine Tartrat-Succinat-Verbindung, ausgewählt aus der Gruppe, bestehend aus
    Figure imgb0042
     worin X Wasserstoff oder ein salzbildendes Kation ist,
    Figure imgb0043
     worin X Wasserstoff oder ein salzbildendes Kation ist,
    iii) Mischungen hiervon,
    und
    (b) eine Kohlenwasserstoff-Succinat-Verbindung der Formel
    Figure imgb0044
     worin R einen C₈-C₁₈-Kohlenwasserstoffrest bedeutet und X Wasserstoff oder ein salzbildendes Kation ist, und worin das Gewichtsverhältnis von Verbindung (a):(b) im Bereich zwischen 15:1 bis 1:15 und vorzugsweise 2:1 bis 1:3 liegt, wobei
    III. der Rest der Zusammensetzung herkömmliche DetergensZusätze enthält.
  9. Eine Zusammensetzung gemäß einem der Ansprüche 5-8, worin die Kohlenwasserstoff-Succinat-Verbindung des Builders ein C₁₂-C₁₆-Alkyl- oder Alkenylsuccinat ist.
  10. Eine Zusammensetzung gemäß Anspruch 9, worin das Alkenylsuccinat 2-Dodecenylbernsteinsäure oder ein wasserlösliches Salz hiervon ist.
  11. Eine Zusammensetzung gemäß einem der Ansprüche 5-10, die als flüssiges Waschdetergens formuliert ist oder auf einem Streifen oder anderen Trägersubstrat freisetzbar formuliert ist, oder in Beuteln oder als Riegel, Pulver, Granulat, Tablette oder fließfähiges Gel formuliert ist.
EP87201564A 1986-08-27 1987-08-18 Detergens-Builder und aufgebaute Detergentien Expired - Lifetime EP0264977B1 (de)

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AT87201564T ATE61393T1 (de) 1986-08-27 1987-08-18 Detergens-builder und aufgebaute detergentien.

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GB868620733A GB8620733D0 (en) 1986-08-27 1986-08-27 Detergency builders & built detergents
GB8620733 1986-08-27

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EP0264977B1 true EP0264977B1 (de) 1991-03-06

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Publication number Priority date Publication date Assignee Title
EP0326208A3 (de) * 1988-01-26 1990-11-28 The Procter & Gamble Company Zu einem Beutel befindliche körnige Detergentzusammensetzungen die hygroskopische Verstärker enthalten
US4904824A (en) * 1988-08-24 1990-02-27 Horng Liou Liang Chemical process
JPH02113100A (ja) * 1988-10-21 1990-04-25 Kao Corp 液体洗浄剤組成物
DE4224607A1 (de) * 1992-07-25 1994-01-27 Benckiser Knapsack Ladenburg Verfahren zum oxidativen oder reduktiven Bleichen und Mittel zur Stabilisierung bei der Bleiche
JP4864598B2 (ja) * 2006-08-11 2012-02-01 花王株式会社 硬質表面用洗浄剤組成物
EP4065677A1 (de) * 2019-11-27 2022-10-05 The Procter & Gamble Company Verbesserte alkylbenzolsulfonat-tenside

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232114A2 (de) * 1986-01-30 1987-08-12 The Procter & Gamble Company Äthercarboxylatreinigungsverstärker und Verfahren zu deren Herstellung
EP0233010A2 (de) * 1986-01-30 1987-08-19 The Procter & Gamble Company Reinigungsverstärkersystem

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692685A (en) * 1968-05-24 1972-09-19 Lever Brothers Ltd Detergent compositions
GB1528171A (en) * 1975-01-06 1978-10-11 Diamond Shamrock Europ Foaming hard surface cleaner formulations
ZA767282B (en) * 1975-12-15 1978-07-26 Colgate Palmolive Co Laundry detergent composition and use
US4107064A (en) * 1976-05-03 1978-08-15 Ethyl Corporation Metal sequestering method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232114A2 (de) * 1986-01-30 1987-08-12 The Procter & Gamble Company Äthercarboxylatreinigungsverstärker und Verfahren zu deren Herstellung
EP0233010A2 (de) * 1986-01-30 1987-08-19 The Procter & Gamble Company Reinigungsverstärkersystem

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EP0264977A1 (de) 1988-04-27
GB8620733D0 (en) 1986-10-08
ATE61393T1 (de) 1991-03-15
AU7743887A (en) 1988-03-03
DK449087A (da) 1988-02-28
FI873696A (fi) 1988-02-28
DK449087D0 (da) 1987-08-27
AU611092B2 (en) 1991-06-06
JPS63132997A (ja) 1988-06-04
FI873696A0 (fi) 1987-08-26
DE3768415D1 (de) 1991-04-11

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