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WO1994017170A1 - Composition de lavage et de rinçage de la vaisselle en machine - Google Patents

Composition de lavage et de rinçage de la vaisselle en machine Download PDF

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Publication number
WO1994017170A1
WO1994017170A1 PCT/EP1994/000026 EP9400026W WO9417170A1 WO 1994017170 A1 WO1994017170 A1 WO 1994017170A1 EP 9400026 W EP9400026 W EP 9400026W WO 9417170 A1 WO9417170 A1 WO 9417170A1
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WIPO (PCT)
Prior art keywords
mole
formula
monomer units
machine dishwashing
hydrogen atom
Prior art date
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Ceased
Application number
PCT/EP1994/000026
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English (en)
Inventor
Willem Robert Van Dijk
Ezat Khoshdel
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Unilever NV
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Unilever NV
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Filing date
Publication date
Application filed by Unilever NV filed Critical Unilever NV
Priority to EP94904637A priority Critical patent/EP0631609A1/fr
Priority to AU58602/94A priority patent/AU5860294A/en
Priority to BR9403765A priority patent/BR9403765A/pt
Publication of WO1994017170A1 publication Critical patent/WO1994017170A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • This invention relates to machine dishwashing and warewashing compositions. These compositions are used for the cleaning of house and kitchenwares, such as pots, pans, dishes, cups, saucers, bottles, glassware, crockery, cutlery and other kitchen utensils in automatic dishwashing and warewashing machines. For brevity's sake, these compositions are referred to hereinafter as machine dishwashing compositions.
  • the invention also relates to rinse aid compositions for use in the final rinse step of the washing machine operation.
  • Machine dishwashing compositions usually contain, as main components, a builder or builder mixture, buffering and/or alkaline agents, and optionally a surfactant, a bleaching agent which may be a chlorine or oxygen bleach, and lately often also enzymes (e.g. protease, amylase, cellulase. Upases and mixtures thereof) .
  • Rinse aid compositions usually comprise an aqueous liquid containing, as major components, a low-foaming nonionic surfactant and an organic chelating agent, e.g. citric acid.
  • non-phosphate and zero-P formulations inherently contain less effective builders as phosphate replacements, e.g. citrates, carbonates, zeolites, which also have inadequate scale- inhibiting properties, the risk of scaling with these products is higher than with the conventional sodium triphosphate products.
  • Scale formation on dishes and machine parts is thus an important problem that needs to be resolved or at least mitigated in formulating a machine dishwashing product, especially in the case of low-phosphate (e.g. less than the equivalent of 20% by weight, particularly 10% by weight of sodium triphosphate) and phosphate-free machine dishwashing compositions, particularly zero-P machine dishwashing compositions.
  • low-phosphate e.g. less than the equivalent of 20% by weight, particularly 10% by weight of sodium triphosphate
  • phosphate-free machine dishwashing compositions particularly zero-P machine dishwashing compositions.
  • co-builders such as polyacrylic acids or polyacrylates (PAA) , maleic anhydride/ (ineth)acrylic acid copolymers, e.g. Sokalan CP5® ex BASF; and the various organic polyphosphonates, e.g. of the Dequest® range, have been added to phosphate-free machine dishwashinq compositions.
  • PAA polyacrylic acids or polyacrylates
  • maleic anhydride/ (ineth)acrylic acid copolymers e.g. Sokalan CP5® ex BASF
  • the various organic polyphosphonates e.g. of the Dequest® range
  • each of R 1 and R 2 which may be the same or different, represents a hydrogen atom, or a - ⁇ -C- ⁇ Q alkyl group; and M is a hydrogen atom, a solubilising cation or a C ⁇ -C 18 alkyl group; and
  • copolymers usable in this invention are non-phosphorus- containing compounds and are fully biodegradable. They have a weight average molecular weight preferably ranging from 1500 to 50,000, and more preferably from 2000 to 40,000. Detailed description of the invention
  • the invention provides the novel use of a block copolymer as hereinbefore defined (further also referred to as "ITA/VA 11 ) as an anti-scaling agent in machine dishwashing compositions and/or in rinse aid compositions.
  • ITA/VA 11 block copolymer as hereinbefore defined
  • the invention also provides a method for inhibiting calcium carbonate scale formation during a warewashing process by applying a machine dishwashing composition and/or rinse aid composition including the above-defined block copolymer as an anti-scaling agent.
  • the ITA/VA block copolymer is characterised by the presence of monomeric units (i) derived from itaconic acid or a homologue thereof, in acid or salt form, and monomer units (ii) derived from vinyl alcohol or esters thereof.
  • the copolymer comprises from 20 to 95 mole % of units (i) and from 5 to 80 mole % of units (ii) .
  • the copolymer comprises from 20 to 80 mole % of units (i) and from 20 to 80 mole % of units (ii) .
  • the weight average molecular weight ranges from 1000 to not more than 60,000.
  • Copolymers of molecular weight higher than 60,000 are excellent builders, but ineffective as anti-scalants.
  • Preferred copolymers are therefore those having weight average molecular weight of not more than 50,000, more preferably not more than 40,000.
  • Preferred weight average molecular weight (Mw) ranges are from 1500 to 50,000, particularly from 2000 to 40,000.
  • M is preferably a hydrogen or a sodium, potassium, ammonium or lower alkyl-substituted ammonium ion, and most preferably a sodium ion.
  • both R 1 and R 2 represent a hydrogen atom, i.e. the units are of the formula III and are derived from itaconic acid itself or a salt thereof:
  • the units (ii) are derived from vinyl acetate. In the polymer, they may be present in the ester form as vinyl acetate units, or in hydrolysed form as vinyl alcohol units.
  • Examples of preferred copolymers are copolymers of itaconic acid and vinyl acetate of the following compositions and Molecular Weights (Mw) .
  • the copolymer may also be a terpolymer of monomer units (i) and (ii) , such as, for example, a terpolymer containing vinyl acetate (48 mole %) , disodium itaconate (48 mole %) , and ono-lauryl itaconate (4 mole %) , having Mw 15,200.
  • the polymers may be prepared by copolymerising from 20 to 95 mole % of a compound of the formula IV, that is to say, itaconic acid or ester or an alkyl substitution product thereof in acid or salt form.
  • the acetate groups may subsequently be hydrolysed but that does not appear to be essential.
  • the polymerisation may conveniently be carried out in aqueous or aqueous/organic solution.
  • the preferred media are water and water/ethanol.
  • Polymers have also been prepared successfully in dilute hydrochloric acid.
  • the copolymerisation is advantageously conducted in the presence of a water-soluble initiator.
  • a water- soluble redox initiator is especially preferred.
  • initiators examples include sodium, potassium or ammonium persulphate, 2,2'-azobis(amidinopropane) hydrochloride, 2,2'-azobis(cyanopentanoic acid); and redox initiators, such as hydrogen peroxide (Fenton's reagent) and other hydroperoxide systems.
  • redox initiator is sodium or potassium persulphate in combination with sodium or potassium bisulphite.
  • the polymerisation may typically be performed under a nitrogen atmosphere in a degassed solvent at ambient pressure, or in a sealed tube under vacuum.
  • the entire monomer charge may be polymerised in a single batch, or alternatively the vinyl acetate may be fed in incrementally as the polymerisation progresses, the latter method being preferred.
  • the polymerisation reaction proceeds steadily at temperatures of 40-100°C; redox initiators are generally used at relatively low temperatures, in the region of 40°C, while other initiators may require temperatures in the 50- 100°C range.
  • a reaction time of 1-5 days is required, typical yields being from 20 to 83%, depending on the reaction time.
  • the level of the block copolymer ITA/VA to be included in the machine dishwashing composition or the rinse aid composition, or in both may range from about 0.1 to about 15% by weight, preferably from 0.25% to about 10%, particularly from 0.5 to 10% by weight of the composition. Usually, an amount of not more than 5% by weight of the compositions will be sufficient.
  • the machine dishwashing composition of the invention will normally also contain a builder or builder mixture, buffering and/or alkaline agents, optionally but preferably also a bleaching agent and an enzyme or mixtures of enzymes.
  • Builder materials are well known in the art and many types of organic and inorganic compounds have been described in literature. They are normally used in all sorts of cleaning compositions to provide alkalinity and buffering capacity, prevent flocculation, maintain ionic strength, extract metals from soils and/or remove alkaline earth metal ions from washing solutions.
  • the builder material usable herein can be any one or mixtures of the various phosphate and non-phosphate builder materials.
  • the present invention has particular applicability to non-phosphate and zero-P compositions containing non-phosphate builder materials, such as, for example, the alkali metal citrates, carbonates and bicarbonates; nitrilotriacetic acid (NTA) ; dipicolinic acid (DPA) ; oxydisuccinic acid (ODS) ; alkyl and alkenyl succinates (AKS) ; zeolites; layered silicas and mixtures thereof.
  • NTA nitrilotriacetic acid
  • DPA dipicolinic acid
  • ODS oxydisuccinic acid
  • AWS alkyl and alkenyl succinates
  • zeolites layered silicas and mixtures thereof.
  • Particularly preferred builders are citrates, DPA, ODS, alkenyl succinates, carbonates, bicarbonates, and also the higher molecular weight block copolymers ITA/VA having Mw greater than 60,000.
  • the invention provides a machine dishwashing composition
  • a machine dishwashing composition comprising, as builder, a block copolymer ITA/VA having Mw > 60,000 and, as anti-sealant, a block copolymer ITA/VA of Mw ⁇ 60,000 as hereinbefore described.
  • the buffering and/or alkaline agent is the buffering and/or alkaline agent
  • This is normally an alkali metal silicate, preferably sodium silicate at a level of from about 1 to about 70% by weight, preferably from 5 to 40% by weight.
  • This material is employed as a cleaning ingredient, source of alkalinity, metal corrosion inhibitor and protector of glaze on china tableware.
  • sodium silicate having a mole ratio of Si ⁇ 2 :Na 2 0 of from about 1.0 to about 3.3., preferably from about 1.8 to about 2.2, normally referred to as sodium disilicate.
  • NaOH and/or KOH are also commonly used to provide alkalinity in compositions for industrial warewashing machines.
  • the amount of bleaching agent will preferably lie in a range from 1 to 30% by weight.
  • Alkali metal hypochlorite may be incorporated.
  • Other chlorine bleaches are alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids.
  • Preferred bleaches are the peroxygen bleaches, such as sodium perborate (tetra- or monohydrate) or sodium percarbonate. These are preferably used in conjunction with a bleach activator which allows the liberation of active oxygen species at a lower temperature. Numerous examples of activators of this type, often also referred to as bleach or peracid precursors, are known in the art.
  • Preferred bleach activators are tetraacetyl ethylene diamine (TAED) , glucose pentaacetate (GPA) and the mono long-chain acyl tetraacetyl glucoses as disclosed in WO 91/10719, but other activators, such as choline sulphophenyl carbonate (CSPC) , as disclosed in US Patents 4,751,015 and 4,818,426 can be used.
  • TAED tetraacetyl ethylene diamine
  • GPA glucose pentaacetate
  • CSPC choline sulphophenyl carbonate
  • the amounts of sodium perborate or percarbonate and bleach activator in the compositions preferably do not exceed 20% and 10% by weight, respectively, e.g. from 4-20% and from 2-10% by weight, respectively.
  • peroxygen bleach is potassium monopersulphate.
  • Further peroxygen bleaches which may be used are the organic peroxyacids and their metal salts. Typical peroxyacids include:
  • aliphatic and substituted aliphatic monoperoxy acids e.g. peroxylauric acid and peroxystearic acid;
  • DPDA 1, 12-diperoxydodecanedioic acid
  • 1,9-diperoxyazelaic acid e.g. 1,9-diperoxyazelaic acid;
  • a bleach catalyst such as the manganese complexes of EP-A-458,397 and the sulphonimines of US Patents 5,041,232 and 5,047,163 may also be added.
  • Amylolytic and/or proteolytic enzymes are normally used.
  • the amylolytic enzymes usable herein can be those derived from bacteria or fungi.
  • Preferred amylolytic enzymes are those prepared and described in GB Patent N° 1,296,839, cultivated from the strains of Bacillus licheniformis NCIB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11945, ATCC 8480 and ATCC 9945 A.
  • Examples of such amylolytic enzymes are those produced and distributed under the tradenames of SP-95® and Termamyl® by Novo Industri A/S, Copenhagen, Denmark.
  • amylolytic enzymes are generally presented as granules and may have enzyme activities of from about 2 to 10 Maltose Units/milligram. They may be present in the composition of the invention in amounts such that the final composition has amylolytic enzyme activity of from 10 3 to 10 6 Maltose Units/kilogram.
  • amylolytic activity as referred to herein can be determined by the method as described by P.Bernfeld in "Method of Enzymology", Volume I (1955), page 149.
  • the proteolytic enzymes usable herein are, for example, the subtilisins which are obtained from particular strains of B . subtilis and B . licheniformis , such as the commercially available subtilisins Maxatase®, supplied by Gist-Brocades N.V. , Delft, Holland, and Alcalase®, supplied by NOVO Industri A/S, Copenhagen, Denmark.
  • Particularly suitable are proteases obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available from NOVO Industri A/S under the tradenames of Esperase® and Savinase®.
  • the preparation of these and analogue enzymes is described in GB Patent N° 1,243,784.
  • These enzymes are generally presented as granules, e.g. marumes, prills, T-granulates etc., and may have enzyme activities of from 500 to 1700 Glycine
  • proteolytic enzymes may be present in amounts such that the final composition has proteolytic enzyme activity of from about 10 6 to 10 8 Glycine Units/kilogram.
  • lipolytic enzymes may also be incorporated to improve fat removal.
  • Typical examples of commercial lipolytic enzymes are Lipase YL, Amano CE, Wallerstein AW, Lipase My, and Lipolase ex Novo Ind.
  • Surfactants though not strictly essential, may also be present for detergency, soil removal, foam depression and/or as rinse aids. If present, they can be used in an amount of up to about 60% by weight, depending upon their types and properties. Normally, in a properly built or highly built composition as is conventional, only small amounts of low- to non-foaming nonionic surfactant, in the order of 0.1-5% by weight, are used, preferably from 0.1- 4%, to aid detergency and particularly to suppress excessive foaming caused by some protein soil. Higher amounts, i.e.
  • highly detersive surfactants such as the high HLB nonionic surfactants, the anionic sulphate or sulphonate surfactants and the alkyl polyglycoside class of surfactants, may be used in lower builder-containing active/enzyme-based compositions.
  • a surfactant content from 0 to less than 5% by weight is preferred.
  • clay minerals particularly the layered clay minerals to reduce film and spot formation on washed articles.
  • Typical and particularly preferred commercial clay products are the synthetic hectorites manufactured and supplied by Laporte Industries Ltd, England, as Laponite® clays, e.g. Laponite S, Laponite XLS, Laponite RD and Laponite RDS.
  • hydrotalcite compounds especially Zn/Al hydrotalcite, as described in Applicant's co-pending European Application N° 92307241.7.
  • Zinc salts both soluble and insoluble zinc salts, can also be incorporated as adjuncts for minimizing glass corrosion.
  • An inert particulate filler especially sodium sulphate, may also be incorporated, though in compact powdered composition it should desirably be omitted as practically possible.
  • the products of the present invention can be manufactured and presented in any physical form, such as a powder, liquid, paste or solid blocks or tablets, and are preferably formulated such that they provide a wash liquor with a pH of from 8-11, preferably from 9.0-10.5 (measured at a concentration of from 0.1-0.3% by weight in water).
  • the invention is also applicable to conventional rinse aid compositions, which usually comprise an aqueous solution comprising a low-foaming nonionic surfactant, citric acid or sodium citrate and optionally a hydrotrope, such as a lower alcohol or sodium xylene ⁇ ulphonate.
  • aqueous solution comprising a low-foaming nonionic surfactant, citric acid or sodium citrate and optionally a hydrotrope, such as a lower alcohol or sodium xylene ⁇ ulphonate.
  • the copolymer ITA/VA according to the invention may be added to the rinse water as such, or it may be added thereto in the form of a liquid solution in water, or in the form of a composition in any suitable physical form comprising the polymer and other suitable or desirable ingredients as normally used in rinse aid products.
  • Such other suitable ingredients may be low levels of wetting or detergent surfactants; organic acids such as citric acid; hydrotropes; alcohols; perfumes; germicides; anti-corrosion agents; clays, particularly layered clay minerals, such as the Laponite® clays, supplied by Laporte Ind. Ltd etc.
  • Suitable physical forms are powders, liquids, tablets, blocks, granulates etc. However, liquid is a suitable preferred form.
  • the level of the polymer in the rinse liquor may vary, depending upon whether the main wash composition already contains the anti-sealant polymer or not.
  • the rinse liquor may contain the defined polymer in concentrations of from 0.2 ppm to about 30 ppm, preferably from 0.5 ppm to 20 ppm, with about 1-10 ppm being the optimum. These correspond to a level of about 0.1% to about 15%, preferably from 0.25% to 10%, and from 0.5-5% by weight as optimum in rinse aid compositions normally used at a dosage level of about 1-3 ml/6 litre rinse water.
  • the invention provides a process for warewashing in a dishwashing machine comprising washing the articles in a main wash cycle and rinsing them in a rinse cycle, characterised in that in the rinse step there is added to the rinse water a copolymer ITA/VA as hereinbefore defined in an amount such that the rinse liquor contains the defined polymer in a concentration of from 1 ppm to about 20 ppm, preferably from 5 ppm to 15 ppm.
  • the polymers were characterised by infra-red spectrometry and in some cases by nuclear magnetic resonance spectroscopy.
  • the infra-red instrumentation used included the Nicolet (trademark) 1705X Fourier Transform infra-red spectrometer with MCT detector using the Nicolet 1280 processor, and the Nicolet SDXC Fourier Transform infra-red spectrometer with DGS detector using the Nicolet 62 processor.
  • Number-average and weight-average molecular weights of polymeric materials were determined by gel permeation chromatography. This was carried out, using a Hewlett
  • This Example describes the preparation of two copolymers of differing molecular weights, each from 50 mole % vinyl acetate and 50 mole % itaconic acid.
  • R 3 indicates hydrogen (predominant) or an acetyl group
  • indices n and m indicate the numbers of repeating units
  • the copolymer was then neutralised and hydrolysed with sodium hydroxide (5.4 g, 1.35 ol) in hot water (50 ml).
  • the sodium salt of the hydrolysed copolymer was precipitated into a large excess of ethanol (300 ml) .
  • the copolymer was dissolved in water, and freeze-dried. The yield was 17.3 g (32%) .
  • Example II Preparation of the copolymer of Example II The copolymer of Example II was prepared by a similar method, but using sodium persulphate alone as the initiator. The reaction temperature was 60°C. The yield was 25.8 g (48%) .
  • Example I 18,000 31,500 1.7
  • Example II 20,000 34,900 1.7
  • Example III Preparation of Copolvmer (III) ITA/VA (50/50) and Mw 5300 Itaconic acid (22.7 g, 0.174 mol) and vinyl acetate (15.0 g, 0.174 mol) were stirred with degassed 0.5 M hydrochloric acid (80 ml) at 40°C. Sodium persulphate (0.5 g) was added in four portions over a period of 48 hours. The resulting copolymer was isolated by precipitation into acetone. It was then purified further by two more precipitations into acetone from concentrated aqueous solutions.
  • the copolymer was then dissolved in water, neutralised with 6% sodium hydroxide solution to pH 8.5 and then freeze-dried. The yield was 44%.
  • copolymer (IV) - ITA/VA (70/30) and Mw 20.500 This copolymer was prepared using the same method as described in Examples I and II.
  • the copolymer was dissolved in water (200 ml) , neutralised with sodium hydroxide at room temperature to pH 8.5 and then freeze-dried. Yield 11.3 g (31%).
  • a composition is added to 1.5 litre of hard water.
  • This water is made by adding calcium chloride, magnesium chloride and sodium bicarbonate to demineralised water, in such amounts that a total water hardness of 40 degrees French 1 (molar ratio Ca/Mg:4/1) and a temporary (bicarbonate) hardness of 32 degrees French 2 is obtained.
  • the temperature is raised from 20 to 65°C at a rate of 2.5°C per minute, and kept constant at 65°C for 12 minutes. This temperature profile simulates a main wash cycle and is obtained, using a submerged electrical heating element and a programmable temperature controller.
  • 1°FH (Ca and/or Mg) is equivalent to 0.1 mmol/1 CaC0 3 .
  • 1°FH (HC0 3 _) is equivalent to 0.2 mmol/1 NaHC0 3 .
  • Main wash base composition (parts by weight) sodium citrate 43.0 sodium disilicate 34.0 sodium perborate onohydrate 6.8
  • Composit:ion Weight increase (mg/slide)

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un copolymère bloc de faible masse molaire (1000-60 000) se composant de 20 à 95 % en mode d'unités d'acide itaconique, et de 5 à 80 % en mole d'unités d'alcool vinylique ou d'acétate de vinyle utilisées en tant qu'agent anti-calcaire dans les opérations de lavage de vaisselle en machine. Le polymère est biodégradable et peut être incorporé dans les compositions principales de lavage et de rinçage de la vaisselle en machine.
PCT/EP1994/000026 1993-01-19 1994-01-06 Composition de lavage et de rinçage de la vaisselle en machine Ceased WO1994017170A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94904637A EP0631609A1 (fr) 1993-01-19 1994-01-06 Composition de lavage et de rin age de la vaisselle en machine
AU58602/94A AU5860294A (en) 1993-01-19 1994-01-06 Machine dishwashing and rinse aid compositions
BR9403765A BR9403765A (pt) 1993-01-19 1994-01-06 Composições para máquina de lavar pratos e para auxiliar de enxague e processo para inibir a formação de incrustação por carbonato de cálcio durante um procedimento de lavagem de luça por aplicação das mesma

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB939300983A GB9300983D0 (en) 1993-01-19 1993-01-19 Machine dishwashing and rinse aid compositions
GB9300983.5 1993-01-19

Publications (1)

Publication Number Publication Date
WO1994017170A1 true WO1994017170A1 (fr) 1994-08-04

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PCT/EP1994/000026 Ceased WO1994017170A1 (fr) 1993-01-19 1994-01-06 Composition de lavage et de rinçage de la vaisselle en machine

Country Status (6)

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EP (1) EP0631609A1 (fr)
AU (1) AU5860294A (fr)
BR (1) BR9403765A (fr)
GB (1) GB9300983D0 (fr)
WO (1) WO1994017170A1 (fr)
ZA (1) ZA94158B (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723418A (en) * 1996-05-31 1998-03-03 Ecolab Inc. Alkyl ether amine conveyor lubricants containing corrosion inhibitors
US5807438A (en) * 1994-11-24 1998-09-15 Diversey Lever, Inc. Detergent composition and method for warewashing
US5863874A (en) * 1996-05-31 1999-01-26 Ecolab Inc. Alkyl ether amine conveyor lubricant
US5932526A (en) * 1997-06-20 1999-08-03 Ecolab, Inc. Alkaline ether amine conveyor lubricant
EP0851022A3 (fr) * 1996-12-23 2000-01-12 Unilever N.V. Compositions de rincage contenant des polymères antitartres
US6247478B1 (en) 1996-11-15 2001-06-19 Ecolab Inc. Cleaning method for polyethylene terephthalate containers
WO2001096514A1 (fr) * 2000-06-12 2001-12-20 Unilever Plc Compositions de lavage de vaisselle mecanique contenant des polymeres inhibiteurs de tartre
US6554005B1 (en) 1996-11-15 2003-04-29 Ecolab Inc. Cleaning method for polyethylene terephthalate containers
WO2003068899A1 (fr) * 2002-02-11 2003-08-21 Rhodia Chimie Composition detergente comprenant un copolymere sequence
US8114343B1 (en) 2010-12-21 2012-02-14 Ecolab USA, Inc. Corrosion inhibition of hypochlorite solutions using Zn and Ca
US8496853B2 (en) 2010-12-21 2013-07-30 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions
US8557178B2 (en) 2010-12-21 2013-10-15 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions in saturated wipes
US8603392B2 (en) 2010-12-21 2013-12-10 Ecolab Usa Inc. Electrolyzed water system
JP2020502307A (ja) * 2016-12-16 2020-01-23 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 自動食器洗浄システムにおける斑点形成を制御するための添加剤
JP2020532608A (ja) * 2017-08-30 2020-11-12 ダウ グローバル テクノロジーズ エルエルシー 分散剤ポリマーを含む自動食器洗浄用組成物
JP2021503019A (ja) * 2017-11-15 2021-02-04 ダウ グローバル テクノロジーズ エルエルシー 自動食器洗浄用配合物のための分散剤ポリマー

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2054548A (en) * 1979-06-19 1981-02-18 Sanyo Chemical Ind Ltd Scale removal
EP0425068A2 (fr) * 1989-10-25 1991-05-02 ENICHEM AUGUSTA INDUSTRIALE S.r.l. Procédé de préparation d'agents empêchant la formation de tartre

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2054548A (en) * 1979-06-19 1981-02-18 Sanyo Chemical Ind Ltd Scale removal
EP0425068A2 (fr) * 1989-10-25 1991-05-02 ENICHEM AUGUSTA INDUSTRIALE S.r.l. Procédé de préparation d'agents empêchant la formation de tartre

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5807438A (en) * 1994-11-24 1998-09-15 Diversey Lever, Inc. Detergent composition and method for warewashing
US5863874A (en) * 1996-05-31 1999-01-26 Ecolab Inc. Alkyl ether amine conveyor lubricant
US5723418A (en) * 1996-05-31 1998-03-03 Ecolab Inc. Alkyl ether amine conveyor lubricants containing corrosion inhibitors
US6247478B1 (en) 1996-11-15 2001-06-19 Ecolab Inc. Cleaning method for polyethylene terephthalate containers
US6554005B1 (en) 1996-11-15 2003-04-29 Ecolab Inc. Cleaning method for polyethylene terephthalate containers
EP0851022A3 (fr) * 1996-12-23 2000-01-12 Unilever N.V. Compositions de rincage contenant des polymères antitartres
US6210600B1 (en) 1996-12-23 2001-04-03 Lever Brothers Company, Division Of Conopco, Inc. Rinse aid compositions containing scale inhibiting polymers
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ZA94158B (en) 1995-07-11
AU5860294A (en) 1994-08-15
BR9403765A (pt) 1999-06-15
GB9300983D0 (en) 1993-03-10
EP0631609A1 (fr) 1995-01-04

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