EP0463802B1 - Verfahren zur Verhinderung der Gewebeinkrustation - Google Patents

Verfahren zur Verhinderung der Gewebeinkrustation Download PDF

Info

Publication number
EP0463802B1
EP0463802B1 EP91305580A EP91305580A EP0463802B1 EP 0463802 B1 EP0463802 B1 EP 0463802B1 EP 91305580 A EP91305580 A EP 91305580A EP 91305580 A EP91305580 A EP 91305580A EP 0463802 B1 EP0463802 B1 EP 0463802B1
Authority
EP
European Patent Office
Prior art keywords
acid
water
composition
encrustation
dicarboxylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP91305580A
Other languages
English (en)
French (fr)
Other versions
EP0463802A1 (de
Inventor
Stephen B. Kong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clorox Co
Original Assignee
Clorox Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=24164052&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0463802(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Clorox Co filed Critical Clorox Co
Publication of EP0463802A1 publication Critical patent/EP0463802A1/de
Application granted granted Critical
Publication of EP0463802B1 publication Critical patent/EP0463802B1/de
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/2082—Polycarboxylic acids-salts thereof

Definitions

  • This invention relates to methods for preventing fabric encrustation by decreasing or suppressing the formation of encrustation residue when using detergent applications and formulations during fabric washing operations with "hard water.”
  • this invention relates to the use of certain organic dicarboxylic acids to prevent growth or deposition of insoluble compounds on fabric surfaces during washing operations.
  • the invention is primarily concerned with inhibition of the formation and deposition of insoluble compounds on fabric.
  • the insoluble compounds primarily are calcium and magnesium carbonate precipitates caused by builders, such as sodium carbonate, typically used in non-phosphate detergents. Therefore, the prevention of encrustation or the deposition of insoluble compounds formed during the washing process with "hard water” is strongly desired.
  • Phosphonates and polyacrylates have been shown to be effective in detergent applications for the prevention of encrustation. Phosphonates can function as crystal growth inhibitors which prevents the growth of insoluble calcium and magnesium compounds at substoichiometric concentrations. Polyacrylates can function as sequestering and dispersing agents, as well as crystal growth inhibitors.
  • Heavy-duty laundry detergents typically contain two major ingredients, surfactant and builder, and a number of other ingredients essential to an acceptable product. Although of lesser importance to detergency, these additional ingredients impart certain desirable functions to the total formulated detergent. These miscellaneous ingredients include anti-corrosion agents, anti-soil redeposition agents, fluorescent whitening agents, bleaches, enzymes, perfume and the like. The two major components most essential to detergency are surfactant and builder.
  • the surfactant provides detersive action to the detergent. This is based on their fundamental characteristic to absorb or concentrate at the soil/fiber/water interfaces.
  • the detergent builder functions primarily to prevent divalent calcium and magnesium water-hardness ions from interfering with the surfactant action.
  • the builder also may provide alkalinity thus improve fatty acid saponification and buffering capacity, prevent flocculation, maintain ionic strength, extract metals from soils and remove alkaline-earth metal ions from the washing solutions.
  • Phosphates are extremely effective builders; however, they are in disfavor due to their eutrophication effect on lakes and streams. Many states in the United States have enacted legislation limiting phosphate content.
  • non-phosphate builders such legislation to reduce phosphate content has led to a variety of non-phosphate builders, either proposed and/or employed.
  • examples include silicates, zeolites, carbonates and polycarboxylates, citrates, EDTA and sodium nitrilotriacetate (NTA).
  • Silicates are not preferred because they are not entirely water-soluble and they can therefore deposit onto fabrics, and also can form precipitates with the hardness ions.
  • Zeolites are generally effective co-builders, but not necessarily as the sole builder.
  • Polycarboxylate builders are costly.
  • U.S. Pat. 3,896,056, Benjamin et al. relates to a built detergent compositions which contain as essential ingredients, an organic surface-active agent; a precipitating builder; and a precipitation modifier.
  • This patent describes a functional test to assess the ability of compounds to prevent the formation of precipitation as an indication of its effectiveness as a crystal growth inhibitor.
  • a detergent matrix consisting of an inorganic precipitating builder is used.
  • a number of polycarboxylic acid compounds are disclosed as precipitation modifiers.
  • U.S. Pat. 4,097,016, Brahm, J., et al. relates to a solid composition for washing, cleaning and bleaching, including at least one basic compound, as a solid polylactone is a sequestering agent and can include activators for per-salts, such as anhydrides of organic acids, succinic acid, phthalic acid, and the like.
  • Non-phosphate detergent formulations are disclosed in numerous patents.
  • Larrabee et al., EP 130,640 discloses a laundry detergent comprising a surfactant, 5 to 80% of a non-phosphorus detergent builder which may be a carbonate, and about 0.3 to 5% of a polyacrylate polymer.
  • EP 137,669, Kermode et al. describes a detergent composition including 5 to 60% of a surfactant, 7 to 80% of a polycarboxylate/zeolite builder, and a bleach system.
  • DeRider et al., EP 82 564 discloses machine dishwashing and rinsing compositions having nonionic detergent surfactants, a water-soluble calcium sequestering agent, specific polymeric material and an alkaline detergent material to produce a composition which has improved non-filming, non-spotting or non-streaking properties.
  • the calcium sequestering agents are taught to be an organic builder salt, such as water-soluble citrates, water-soluble salt of nitrilotriacetic acid (NTA), water-soluble salt of carboxymethoxy succinic acid, or other builders such as zeolites, or organic chelating agents.
  • EP 82 564 shows an example of the calcium sequestering agent; dipicolinic acid is disclosed as not causing filming on dishes.
  • dipicolinic acid is disclosed as not causing filming on dishes.
  • Neillie et al. sodium carbonate is combined with polyacrylate, phosphonate, and a calcium sequestering agent.
  • EP 233 730 Sanderson et al. discloses the use of 2,6-pyridine dicarboxylic acid as a chelating stabilizer for potassium sulfoperoxybenzoate in detergent compositions. This is necessary in the situation where inorganic or organic peroxy acids are unstable in the presence of nonionic surfactants. It was not feasible to contemplate storing liquid compositions containing both components without the use of a chelating peroxidic stabilizer such as dipicolinic acid.
  • EP 266 904 relates to machine dishwashing compositions comprising low or zero phosphates using dipicolinic acid derivatives as the builder. Also provided for are enzymes to increase performance.
  • DE-A-2 240 309 ( ⁇ GB 1 398 263), which is said to be based on the finding that a detergent composition with an alkali metal carbonate detergency builder is improved by incorporating therein a calcium sequestering agent and a calcium carbonate anti-deposition agent
  • EP-A-0 094 723 which relates to a method for washing textiles in hard water and to phosphate-free detergent compositions for use therein
  • FR-A-2 396 076 ( ⁇ GB 2 000 177), which concerns a detergent composition wherein the acidic constituent and the alkaline constituent are separately present.
  • the prior art describes polymers of aliphatic polycarboxylic acids as builders in detergent formulations.
  • substoichiometric concentrations of the monomeric forms of some of these compounds alter the kinetics or crystalline morphology of calcium carbonate, and hence can be used to prevent industrial scaling, and reduced fabric encrustation in non-phosphorus detergent formulations.
  • the present invention is primarily effective at preventing encrustation of fabrics in high-carbonate, non-phosphorus detergent. Therefore, the present invention provides an alternative to phosphonate and polyacrylates for prevention of encrustation.
  • the present application relates to the method for using certain organic dicarboxylic acids and water-soluble derivatives thereof as effective fabric encrustation preventatives in detergent applications and formulations.
  • the prior art relates only to the use of certain organic dicarboxylic acids to reduce hardness of water, or as a stabilizer against degradation of peroxy bleaching compounds.
  • certain organic dicarboxylic acid and their water-soluble salts and anhydrides into detergent compositions in order to decrease and/or suppress the formation of encrustation residue on fabrics from hard water minerals due to the presence of the sodium carbonate builder in the detergent formulation is not contemplated by the prior art.
  • a leading inorganic replacement for phosphate builders is sodium carbonate.
  • high carbonate content non-phosphate builders produce the problem of "hard water” precipitates from the calcium and magnesium ions present in the "hard water.”
  • the growth or deposition of the precipitates on the fabrics during washing application make carbonate-based detergents, otherwise, not preferred.
  • the present invention provides a method for water working a fabric so as to present encrustation characterised in that it comprises using a non-phosphate fabric cleaning composition providing a wash pH range of between 8.0 and 13.00 and comprising:
  • fabric encrustation can be reduced or eliminated when using high carbonate, non-phosphate detergents with water containing calcium and/or magnesium ions.
  • the method is characterized by utilizing certain water-soluble organic dicarboxylic acids, anhydrides, salts and derivatives thereof. More preferably, this invention relates to the use of certain organic dicarboxylic acids, water-soluble salts and anhydrides thereof, especially ketomalonic acid, hydroxymalonic acid and 2,6-pyridine dicarboxylic acid.
  • this invention relates to the use of detergent compositions which contain ketomalonic acid and 2,6-pyridine dicarboxylic acid or a water-soluble salt thereof with monovalent cations in a concentration of from 1 to 20 percent by weight, preferably from 2 to 12 percent by weight.
  • Alkali metal salts can be used as water-soluble salts of the organic dicarboxylic acids of the instant invention having monovalent cations.
  • Ammonium ions also can be regarded as monovalent cations for the purpose of the present invention.
  • the acid or anhydride forms of the organic dicarboxylic acids are equivalent to the salt forms except where the acid has limited solubility. It is understood that the anhydride can hydrolyze to form the diacid in situ. It is also noted that except where explicitly stated or implied from the context, the acid and salt forms are used interchangeably. It is further noted that if the organic dicarboxylic acid derivative is added as a water-soluble salt, the required weight percentage range will be higher than that of the acid, due to the presence of the counter ion.
  • Alkali-metal carbonate is the primary and may be the only builder material of the composition used according to the present invention.
  • the primary builder is defined as that builder which, in total amount, has the higher capacity for hardness ions (e.g., calcium (+2) and magnesium (+2)).
  • the term "co-builder” will refer to any remaining builder which has the lesser capacity (typically less than 30%) for such ions.
  • Alkali metal carbonates, sesquicarbonates and bicarbonates are suitable primary builders; however, the preferred builders are sodium and/or potassium carbonates.
  • a building effective amount of carbonate is present in the compositions used herein, which is defined as that amount of alkali metal carbonates, as the primary builder, which would precipitate in the presence of hardness ions, in solution, during a wash period at 50°C and 250 ppm hardness. Such precipitation is determined by an increase in solution turbidity as indicated by an abrupt change in percent transmittance versus time (defined additionally hereinafter). Generally, in terms of weight percent, and assuming 68 liters of wash water and about 100 g of composition, at least about 30 percent, preferably 40 percent, most preferably 50 percent carbonate is employed. As used herein, unless otherwise stated, all percentages are weight percentages of actives of the total composition.
  • the carbonate acts as the builder to remove divalent metal ions such as calcium, and additionally provides alkalinity and aids in soil removal.
  • the alkali metal carbonate provides good cleaning performance and in situations requiring a high pH, such as oily soils, the carbonate builder may be superior to other builders.
  • the preventative system comprises substoichiometric levels of an organic dicarboxylic acid, water-soluble salt or anhydrides thereof, which act to inhibit fabric encrustation.
  • substoichiometric levels of the certain organic dicarboxylic acid are defined to mean levels which are not able to prevent the precipitation of calcium and magnesium carbonate by sequestering water hardness ions.
  • such levels generally comprise less than about 30 percent, more preferably less than about 20 percent, of the total building capacity.
  • organic dicarboxylic acid it is meant an organic compound having at least 2 carboxyl groups.
  • organic dicarboxylic acid compounds used according to this invention relate to the following general formulae wherein
  • Components (a) and (b) are as described previously.
  • Component (c) is further described below.
  • a myriad of surfactants are known to be suitable for laundry applications, including anionic, cationic, nonionic and amphoteric surfactants.
  • Preferred surfactants are anionic, nonionic and mixtures thereof, and if added are present in a cleaning-effective amount.
  • Preferred anionics are selected from surfactants such as alkali metal alkyl sulfates, primary and secondary alkane sulfonates, linear alkyl benzene sulfonates, alkyl ether sulfates, and mixtures thereof. These anionic surfactants will preferably have alkyl chain groups averaging about 8 to 18 carbon atoms.
  • the preferred anionic surfactant is a LAS having an alkyl group averaging 8 to 18 carbons.
  • An additionally preferred anionic surfactant principally for its cleaning effectiveness, is a secondary alkane sulfonate.
  • An example of a particularly preferred secondary alkane sulfonate is HOSTAPUR SAS, a trademarked product manufactured by Farbwerke Hoechst A.G. (Frankfurt, West Germany).
  • the anionic surfactant at least one nonionic, especially C 1-4 alkoxylated aliphatic alcohols and C 1-4 alkoxylated alkyl phenols. Particularly preferred are ethoxylated/propoxylated C 8-14 alcohols. There should be at least about three alkoxy groups per alcohol, preferably at least about nine. Examples of preferred ethoxylated/propoxylated aliphatic alcohols are BASF Corporation's (Parsippany, NJ) trademarked INDUSTROL, and PLURAFAC. Certain C 1-4 alkylene oxide copolymers such as ethylene oxide/propylene oxide copolymers are also preferred as surfactants.
  • NEODOL polyethoxylated alcohols manufactured and marketed by the Shell Chemical Company (Houston, TX) under the trademark NEODOL.
  • NEODOLS are NEODOL 25-7 which is a mixture of 12 to 15 carbon chain length alcohols with about 7 ethylene oxide groups per molecule, NEODOL 23-65, a C 12-13 mixture with about 6.5 moles of ethylene oxide, and NEODOL 25-9, a C 12-15 mixture with about 9 moles of ethylene oxide.
  • Total surfactant content is preferably from 0.1% to about 20%, more preferably from about 2% to 15%.
  • Preferred peroxygen bleaches are available in solid form and include sodium percarbonate, sodium perborate, sodium phosphate peroxyhydrate, potassium permonosulfates and metal peroxides.
  • Bleach activators also known as peracid precursors, can be included with the peroxygen compounds. Examples of activators include tetraacetyl ethylenediamine (TAED), nonanoyloxy benzene-sulfonate (NOBS), and nonanoylglycolate phenol sulfonate (NOGPS).
  • TAED tetraacetyl ethylenediamine
  • NOBS nonanoyloxy benzene-sulfonate
  • NOGPS nonanoylglycolate phenol sulfonate
  • Peracid bleaches may be advantageous in terms of bleaching performance.
  • Suitable peracid bleaching species include C 8-12 alkyl peracids, especially perazelaic and diperazelaic acids, diperoxydodecanedioic acid (DPDDA), and alkyl monoperoxysuccinic acid.
  • DPDDA diperoxydodecanedioic acid
  • Peracid bleaching species, and a method for their production are described in U.S. 4,337,213 to Marynowski et al., the disclosure of which is incorporated herein by reference.
  • the bleach is present in an amount sufficient to provide effective bleaching, e.g., from about 0% to 10% by weight active, more preferably from about 0.05% to 5% by weight active depending on the bleaching species chosen.
  • chlorine bleaches which could be preformed and suspended on a substrate, mitigated or generated in situ.
  • An alkali-metal silicate can be included to provide alkalinity and corrosion resistance.
  • Preferred is one having the formula: M 2 O(SiO 2 ) n where M represents an alkali-metal and n is between about 1 and 4.
  • Preferred alkali-metal silicates are sodium, potassium and lithium silicates, with sodium silicate being the most preferred, and with a preferred n value of 2.0-2.4.
  • a most preferred maximum value for n is about 3.2 in order to minimize insoluble silicates during storage. It is further preferred that at least about 10% of the total silicates have an n value of greater than about 1.6 to impart suitable anti-corrosive properties.
  • suitable silicates include sodium or potassium orthosilicates and metasilicates. As used hereinafter, the term "silicate" will be taken to mean any of these alkali-metal silicates, individually or combined.
  • alkali-metal silicates are also suitable.
  • the alkali-metal silicate is present in an amount of from about 0% to 10%, preferably about 2% to 5%. A minimum of about 1% silicate is preferred to provide adequate corrosion resistance.
  • a commercially available sodium silicate is sold by the Philadelphia Quartz Corporation (Valley Forge, PA) under the trademarks RU (as a 47% solution) and D (as a 44.1% solution).
  • the silicates provide alkalinity and serve as processing aids to increase particle size of the agglomerates.
  • Sodium silicates also aid in cleaning, especially on oil and grease stains.
  • the filler is preferably a salt such as sodium chloride, nitrate or sulfate, and is used to adjust the composition density to achieve desired physical characteristics, e.g., grain size and flowability. Depending on the filler and the process used, the filler can also provide surface area for loading of actives.
  • the filler material additionally assists in solubility under cold water washing conditions.
  • Sodium chloride is preferred due to its low cost and availability.
  • other materials such as puffed borax, bentonite clays and inorganic salts such as sodium or potassium sulfate, chloride, bromide, nitrate, and borate, and organic materials like sugars may also be suitable.
  • Some water may be deliberately added as a filler. Generally, about 0-30% filler will be present, preferably about 5-25%.
  • any non-phosphate builder material known in the art to be compatible with the high carbonate formulation herein may be included as a co-builder selected from the group consisting of silicates, citrates, polymeric polycarboxylic acids such as polyacrylates and malonic anhydride based co-polymers, zeolites, salts of ethylene diaminetetraacetic acid and sodium nitrilotriacetate. Silicates at levels above about 10%, and citrates may be added as co-builders. If added, the co-builder should comprise no more than about 30% of the total weight of the composition, and preferably no more than about 20%. Zeolites are preferred as optional co-builders since they perform well when used in a non-encrustation promoting amount. A non-encrustation promoting amount is that amount which will not contribute to or encourage the encrustation formation when present in a detergent formulation and in the presence of water hardness ions.
  • Zeolite A is available, for example, from the PQ Corp., Valley Forge, PA, under the trademark VALFOR 100. Zeolite A typically includes about 21% moisture.
  • alkali-metal carbonate is generally sufficient to keep the wash pH range within the desired limits, it may be desirable to adjust the pH of the wash water by including an electrolyte/buffer.
  • these are alkali-metal inorganic acid salts, hydroxides or oxides. It may also be suitable to use such materials as aluminates and organic materials, such as gluconates, citrates, succinates, maleates, and their alkali metal salts.
  • the wash pH range must be maintained between 8.0 and 13.0, preferably 9.0 to 12.0. If an electrolyte/buffer is needed, sodium hydroxide is preferred, as it does not interact adversely with any other ingredients and is very cost effective.
  • the amount of electrolyte/buffer added solely for purposes of buffering can vary from 0% to 10%.
  • minor additions can be included in the present invention.
  • dyes such as Monastral blue and anthraquinone dyes (such as those described in Zielske, U.S. 4,661,293 and U.S. 4,746,461).
  • Pigments which are also suitable colorants, can be selected, without limitation, from titanium dioxide, ultramarine blue (see also, Chang et al., U.S. 4,708,816), and colored aluminosilicates.
  • Fluorescent whitening agents are other desirable adjuncts. These include the stilbene,styrene and styrene, and naphthalene derivatives, which upon being impinged by ultraviolet light, emit or fluorescent light in a visible wavelength.
  • fluorescent whitener agents or brighteners are useful for improving the appearance of fabrics which have become dingy through repeated soilings and washings.
  • Preferred fluorescent whitener agents are TINOPAL 5BM-GX and TINOPAL AMS, both from Ciba Geigy A.G., (Tom River, NJ) and PHORWITE RKH, from Mobay Chemicals (Union, NJ).
  • Enzymes particularly hydrolases such as lipases, proteases and amylases, are useful additives in the compositions used herein.
  • Suitable commercial sources include ESPERASE and SAVINASE, both trademarked products of Novo Industries (Danbury, CT).
  • ESPERASE and SAVINASE both trademarked products of Novo Industries (Danbury, CT).
  • Fragrances are also desirable adjuncts in these compositions.
  • the total composition minors will range from 0% to about 5%.
  • Anti-redeposition agents such as carboxymethyl-cellulose, are potentially desirable.
  • Foam boosters such as appropriate anionic surfactants, may be appropriate for inclusion herein.
  • anti-foaming agents such as alkylated polysiloxanes, e.g., dimethylpolysiloxane
  • Water may be present as free water or as water of hydration of the inorganic salts such as sodium carbonate.
  • the detergent composition used is prepared by a process which yields a dry, free-flowing granular mixture, for example agglomeration or spray drying.
  • the compositions used herein are not limited to such forms, and may also be formulated in other dry forms, such as tablets or beads, or may be formulated as pastes, gels or liquids. An example formulation is shown below as Example A.
  • EXAMPLE A Ingredient Wt.% Active Alkali metal carbonate 30-80 Surfactant 1-20 Bleaching agent 0-10 Alkali metal silicate (SiO 2 /M 2 O) 0-10 Filler 0-30 organic dicarboxylic acid, salt or anhydride 0.1-15 Composition Minors (enzymes, FWA's, fragrances, etc.) 0-5 Co-builder 0-30 Water 0-15
  • compositions used herein were tested for their effectiveness at reducing encrustation in beaker studies.
  • the compounds used and results are given in the following table.
  • the turbidity measurement comprises measuring percent transmittance using a dipping probe and colorimeter.
  • the probe is placed in deionized water and the percent transmittance (%T.) is set to 100%.
  • the final solution hardness was 300 ppm.
  • Percent transmittance is continuously plotted and measured vs time. Results are presented as time before the onset of calcium precipitation (t m ) as determined by an abrupt change in the slope of a graph of %T vs time. The longer the t m , the more effective the crystal growth inhibitor.
  • the t m should be longer than the wash cycle, i.e., about 12-15 minutes in the case of washing conditions in the United States.
  • a t m of greater than about 10, preferably 12 minutes provides commercially-acceptable results, as calcium precipitation will still be inhibited to a degree sufficient to avoid consumer preception thereof.
  • each container of detergent sample has immersed therein a 3.5 x 4 inch 100% cotton swatch, trimmed to 1.0 grams. Slits approximately 2.6 cm (approximately 3 inches) long were made about 0.6 cm (about 0.25 inch) apart for better circulation in the test container. After washing for 10 minutes, the swatch is rinsed twice with 2 L deionized water, and placed in a flask containing 25 ml of water and 10 ml of 1.2M HCl to dissolve the CaCO 3 . Fifteen ml of a standard NH 4 OH hardness buffer and a Calmagite indicator are then added and the solution is titrated with standardized EDTA. Results are reported as mg CaCO 3 per gram of fabric (swatch). Preferably, this value should be below about 4 mg/g, most preferably below about 2 mg/g.
  • the preferred level of calcium carbonate deposits per gram of fabric can be achieved without necessarily extending the t m value.
  • precipitation modifiers will have little or no effect or may actually shorten the t m value and still provide low levels of fabric encrustation.
  • Crystal growth inhibitors will extend the t m value. The presence of either of these compound types in a high carbonate non-phosphate built detergent has been found to result in lower levels of encrustation on the fabric surface. Cmpd. No.
  • Table II shows that using substoichiometric levels of the present encrustation preventative system utilizing an organic dicarboxylic acid according to this invention yielded less calcium residue (as ash) than the base detergent composition at two different treatment levels.
  • an organic dicarboxylic acid used according to this invention could be a direct replacement for polyacrylate which is known for its anti-precipitation nature.
  • the organic dicarboxylic acid and water-soluble salts and anhydrides thereof should be more biodegradable than polyacrylates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Fats And Perfumes (AREA)

Claims (7)

  1. Verfahren zum Waschen eines textilen Flächengebildes bzw. Gewebes mit Wasser, so daß eine Krustenbildung verhindert wird, dadurch gekennzeichnet, daß es die Verwendung einer phosphatfreien Gewebereinigungszusammensetzung umfaßt, die einen Wasch-pH-Bereich von zwischen 8,0 und 13,00 ergibt und folgendes enthält:
    (a) mindestens 20 Gew.-% eines Alkalimetallcarbonat-Detergensbuilders,
    (b) eine die Krustenbildung des Gewebes verhindernde Menge von nicht mehr als 20 Gew.-% einer eine Krustenbildung verhindernden organischen Dicarbonsäure, eines wasserlöslichen Salzes, eines Anhydrids oder Gemischen davon mit der Formel
    Figure 00280001
    worin
    R für 2,3-Pyridenyl, 2,4-Pyridenyl, 2,6-Pyridenyl, 1,2-Phenylen, 1,3-Phenylen oder
    Figure 00290001
    steht, wobei R' und R'' unabhängig voneinander für H, -OH oder C1-C6-Alkyl stehen, oder R' und R'' miteinander Sauerstoff darstellen, n 0 oder eine ganze Zahl von 1 bis 3 ist, m 0, 1 oder 2 ist, und M1 und M2 unabhängig voneinander für Wasserstoff, Natrium, Kalium, Lithium und Ammonium stehen, und
    (c) 0,1 bis 20 Gew.-% eines oberflächenaktiven Mittels, wobei (b) in einer substöchiometrischen Menge bezogen auf die Härteionen im Waschwasser vorliegt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Zusammensetzung weiterhin folgendes enthält:
    (d) 1 bis 10 Gew.-% eines Natriumsilicats mit einem Verhältnis SiO2/M2O von 1:1 bis 4:1, wobei M für ein Alkalimetall steht,
    (e) eine bleichwirksame Menge eines Bleichmittels,
    und daß das oberflächenaktive Mittel (c) in der Zusammensetzung aus anionischen, nichtionischen, kationischen, amphoteren oberflächenaktiven Mitteln und Gemischen davon ausgewählt wird.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Menge des Alkalimetallcarbonatbuilders (a) in der Zusammensetzung 20 bis 80 Gew.-%, vorzugsweise 30 bis 70 Gew.-%, beträgt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Menge der organischen Dicarbonsäure, des wasserlöslichen Salzes oder des Anhydrids davon (b) in der Zusammensetzung 1 bis 20 Gew.-% beträgt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das oberflächenaktive Mittel (c) in der Zusammensetzung aus Alkylsulfaten, primären und sekundären Alkylsulfonaten, linearen Alkylarylsulfonaten, Alkylethersulfaten, alkoxylierten aliphatischen Alkoholen, alkoxylierten Alkylphenolen, Copolymeren von C1-C4-Alkylenoxiden und Gemischen davon ausgewählt wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Zusammensetzung weiterhin eine die nicht-Krustenbildung fördernde Menge eines Cobuilders, ausgewählt aus Silicaten, Citraten, polymeren Polycarbonsäuren, Salzen oder Ethylendiamintetraessigsäure und Natriumnitrilotriacetat, und vorzugsweise Zeolithe enthält.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Alkalimetallcarbonat Natriumcarbonat ist, und daß die organische Dicarbonsäure oder das wasserlösliche Salz aus Phthalsäure, Isophthalsäure, 2,4-Pyridindicarbonsäure, 2,6-Pyridindicarbonsäure, 2,3-Pyridindicarbonsäure, Malonsäure, Hydroxymalonsäure, Ketomalonsäure, Methylmalonsäure, Bernsteinsäure, Adipinsäure, Hydroxybernsteinsäure und Weinsäure, vorzugsweise 2,6-Pyridindicarbonsäure, Ketomalonsäure und Hydroxymalonsäure, ausgewählt wird.
EP91305580A 1990-06-22 1991-06-20 Verfahren zur Verhinderung der Gewebeinkrustation Revoked EP0463802B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US54249390A 1990-06-22 1990-06-22
US542493 1990-06-22

Publications (2)

Publication Number Publication Date
EP0463802A1 EP0463802A1 (de) 1992-01-02
EP0463802B1 true EP0463802B1 (de) 1998-09-09

Family

ID=24164052

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91305580A Revoked EP0463802B1 (de) 1990-06-22 1991-06-20 Verfahren zur Verhinderung der Gewebeinkrustation

Country Status (6)

Country Link
EP (1) EP0463802B1 (de)
JP (1) JPH05132697A (de)
AT (1) ATE170910T1 (de)
CA (1) CA2044947A1 (de)
DE (1) DE69130137T2 (de)
ES (1) ES2121770T3 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8669224B2 (en) 2008-09-16 2014-03-11 Ecolab Usa Inc Use of hydroxycarboxylates for water hardness control

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025019727A1 (en) 2023-07-20 2025-01-23 The Procter & Gamble Company Water-soluble automatic dishwashing detergent pouch
EP4506441A1 (de) 2023-07-20 2025-02-12 The Procter & Gamble Company Wasserlöslicher beutel für geschirrspülmaschinen
EP4506439A1 (de) 2023-07-20 2025-02-12 The Procter & Gamble Company Wasserlöslicher beutel für geschirrspülmaschinen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1342095A (en) * 1971-01-05 1973-12-25 Unilever Ltd Detergent compositions
GB1398263A (en) * 1971-08-17 1975-06-18 Unilever Ltd Detergent compositions
JPS6059280B2 (ja) * 1976-07-09 1985-12-24 ライオン株式会社 粒状洗剤組成物の製造方法
CH639416A5 (de) * 1977-06-27 1983-11-15 Akzo Nv Detergentienzusammensetzung enthaltend alkalicarbonat.
NL8201953A (nl) * 1982-05-12 1983-12-01 Blauwe Lier B V I O De Werkwijze voor het wassen van textiel in hard water en fosfaatvrij wasmiddel ten gebruike daarbij.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8669224B2 (en) 2008-09-16 2014-03-11 Ecolab Usa Inc Use of hydroxycarboxylates for water hardness control

Also Published As

Publication number Publication date
DE69130137D1 (de) 1998-10-15
ATE170910T1 (de) 1998-09-15
ES2121770T3 (es) 1998-12-16
CA2044947A1 (en) 1991-12-23
JPH05132697A (ja) 1993-05-28
EP0463802A1 (de) 1992-01-02
DE69130137T2 (de) 1999-01-28

Similar Documents

Publication Publication Date Title
US4470919A (en) Oxygen-bleach-containing liquid detergent compositions
US5246612A (en) Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymes
EP0504091B1 (de) Phosphatfreies Maschinengeschirrspülmittel
US4988363A (en) Detergent bleach composition and method of cleaning fabrics
US5104584A (en) Composition and method for fabric encrustation prevention comprising a lignin derivative
JPH10505365A (ja) 過酸素漂白組成物
JPS61111400A (ja) 漂白剤組成物
EP0364067B1 (de) Waschmittel für Geschirrspülmaschinen mit hohem Karbonatgehalt und verminderter Kalziumsalzabsetzung
GB2353800A (en) Antibacterial detergent compositions
NZ207300A (en) Anticorrosive detergent compositions containing alkali metal silicates
JPH0625700A (ja) 過酸素漂白剤組成物
US3990983A (en) Builder compositions
EP0612842A2 (de) Wäschewaschmittel
EP0463802B1 (de) Verfahren zur Verhinderung der Gewebeinkrustation
US4139486A (en) Built detergent composition
CA2166277A1 (en) Dishwashing detergents containing a biologically degradable builder component
JPH08245985A (ja) 洗濯漂白組成物
EP0463801A2 (de) Zusammensetzung und Methode zur Verhinderung von Gewebeverkrustung
US4617139A (en) Detergent compositions containing polymers
WO1994024250A1 (en) Composition and process for inhibiting dye transfer
US20240218295A1 (en) Machine dishwash detergent
US20020123447A1 (en) Layered silicate built laundry detergent composition
JPH04227692A (ja) 洗剤組成物
CA2044093A1 (en) Chlorine-free machine dishwashing detergent
EP4347766B1 (de) Maschinengeschirrspülmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GR IT LI NL SE

17P Request for examination filed

Effective date: 19920515

17Q First examination report despatched

Effective date: 19950523

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GR IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980909

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980909

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980909

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980909

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980909

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980909

REF Corresponds to:

Ref document number: 170910

Country of ref document: AT

Date of ref document: 19980915

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69130137

Country of ref document: DE

Date of ref document: 19981015

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981209

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981209

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2121770

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 19990608

Opponent name: UNILEVER PLC/ UNILEVER NV

Effective date: 19990607

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20010709

Year of fee payment: 11

R26 Opposition filed (corrected)

Opponent name: UNILEVER PLC/ UNILEVER NV * 19990608 THE PROCTER &

Effective date: 19990607

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

RTI2 Title (correction)

Free format text: METHOD OF PREVENTING FABRIC ENCRUSTATION

RTI2 Title (correction)

Free format text: METHOD OF PREVENTING FABRIC ENCRUSTATION

R26 Opposition filed (corrected)

Opponent name: UNILEVER PLC/ UNILEVER NV * 19990608 THE PROCTER &

Effective date: 19990607

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20020530

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020620

Year of fee payment: 12

27W Patent revoked

Effective date: 20020122

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070628

Year of fee payment: 17