EP1507844B1 - Utilisation, d'un copolymere amphotere dans une composition lavante de la vaisselle en machine - Google Patents

Utilisation, d'un copolymere amphotere dans une composition lavante de la vaisselle en machine Download PDF

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Publication number
EP1507844B1
EP1507844B1 EP03755203A EP03755203A EP1507844B1 EP 1507844 B1 EP1507844 B1 EP 1507844B1 EP 03755203 A EP03755203 A EP 03755203A EP 03755203 A EP03755203 A EP 03755203A EP 1507844 B1 EP1507844 B1 EP 1507844B1
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EP
European Patent Office
Prior art keywords
water
soluble
use according
washing
amphoteric copolymer
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.)
Expired - Lifetime
Application number
EP03755203A
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German (de)
English (en)
French (fr)
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EP1507844A1 (fr
Inventor
Eric Aubay
Garry Embleton
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.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/08—Silicates
    • 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
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds

Definitions

  • the subject of the present invention is the use, in a "two-in-one" or “three-in-one” washing and rinsing composition of machine crockery, of an amphoteric water-soluble or water-dispersible copolymer as an anti-redeposition agent for soiling (" repellent agent "). It also relates, as a new industrial product, a solid preformulation, especially in the form of granules, comprising said amphoteric copolymer adsorbed and / or absorbed on a water-soluble solid inorganic support, and the use, in a composition "two in one "or” three in one "washing and rinsing machine dishware, said preformulation as a soil repellent agent agent (" soil repellent agent ").
  • compositions for the treatment of hard surfaces water-soluble or water-dispersible amphoteric copolymers derived from at least one cationic monomer of the family of diallyldimethylammonium chloride (DADMAC for diallyldimethylammonium chloride), at least one anionic monomer (acrylic acid in particular) and optionally at least one nonionic monomer, to give the treated surface hydrophilization properties.
  • DMDMAC diallyldimethylammonium chloride
  • anionic monomer acrylic acid in particular
  • nonionic monomer optionally at least one nonionic monomer
  • compositions confer, in particular, on the treated surfaces anti-flow, anti-fogging, anti-stain or anti-stick remanent properties; anti-stick or anti-stain properties means that the treated surface retains these properties over time, including after subsequent contact with water, whether it is rainwater, distribution system water or rinse water with or without rinse aid. This is to avoid essentially stains or traces of water and limestone.
  • the ion X - is advantageously chosen from halide ions (chloride, ...) sulfate, hydrosulphate, phosphate, citrate, formate and acetate.
  • the copolymer according to the invention advantageously has a molecular weight of at least 1,000, advantageously at least 10,000; it can go preferentially from 50,000 to 500,000.
  • GPC gel permeation chromatography
  • the copolymer is preferably random.
  • the monomer (a) has the following structure:
  • a particularly preferred monomer is that of the above formula wherein X - represents CI - , referred to as DADMAC.
  • the monomers (b) are advantageously water-soluble monoethylenic unsaturated C 3 -C 8 carboxylic, sulphonic, sulfuric, phosphonic or phosphoric acids, their anhydrides and their water-soluble salts.
  • carboxylic acids such as acrylic acid, methacrylic acid, ⁇ -ethacrylic acid, ⁇ , ⁇ -dimethylacrylic acid, methylenemalonic acid and vinylacetic acid. allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacrylate alanine, N-acryloyl-hydroxy-glycine. and the alkali metal and ammonium salts thereof.
  • carboxylic acids such as acrylic acid, methacrylic acid, ⁇ -ethacrylic acid, ⁇ , ⁇ -dimethylacrylic acid, methylenemalonic acid and vinylacetic acid. allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-
  • acrylamide vinyl alcohol
  • C 1 -C 4 alkyl esters of acrylic acid and methacrylic acid C 1 -C 4 hydroxyalkyl esters of acrylic acid and methacrylic acid, especially acrylate and methacrylate of ethylene glycol and propylene glycol
  • polyalkoxylated esters of acrylic acid and of methacrylic acid especially the polyethylene glycol and polypropylene glycol esters.
  • the level of monomers (c) is advantageously between 0 and 50%, preferably 0 to 30 mol%.
  • the most preferred copolymers are DADMAC / acrylic acid copolymers whose molar ratio is between 15/85 and less than 50/50, preferably between 25/75 and 45/55.
  • the "two-in-one" or “three-in-one” washing and rinsing composition according to the invention comprises at least one copolymer as described above at a content of between 0.01% and 10%, preferably between 0.02% and % and 0.5% by weight relative to the total weight of the composition.
  • composition according to the invention generally comprises at least one surfactant.
  • This is advantageously nonionic and / or anionic and / or amphoteric; preferably it is a nonionic surfactant.
  • alkylene oxide condensates especially of ethylene oxide and optionally of propylene with alcohols, polyols, alkylphenols, fatty acid esters, amides of fatty acids and fatty amines; amine oxides, sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, especially sucrose monopalmitate; long-chain tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and polyoxypropylene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly (ethylene oxide) and amides of fatty acids modified so as to confer a hydrophobic character (for example, mono- and diethanolamides of fatty acids containing from 10 to 18 carbon atoms ).
  • alkylene oxide condensates especially of ethylene oxide and optionally of propylene with alcohols, polyols, alkylphenols, fatty acid esters, amide
  • amphoteric surfactants mention may be made of sodium alkyl iminopropionates or iminodipropionates, such as Mirataine H2C HA and Mirataine JC HA from Rhodia.
  • the surfactants may be present in an amount of 0.1 to 20%, preferably 0.2 to 10% by weight.
  • the copolymer weight ratio of general formula (I) / surfactant is between 1/2 and 1/100, advantageously 1/5 and 1/50.
  • a washing and rinsing composition "3 in 1" differs from a washing and rinsing "2 in 1" in particular by a higher concentration of organic builders and sodium tripolyphosphate.
  • the "two-in-one" or “three-in-one” washing and rinsing composition may be in the form of a liquid, a gel, a compacted powder or no ; in a preferential manner, it is in the form of a monolayer or multilayer tablet.
  • a particularly advantageous embodiment consists in the use, according to the invention, of said amphoteric water-soluble or water-dispersible copolymers in the form of a solid preformulation, in particular in the form of granules, comprising said amphoteric copolymer adsorbed and / or absorbed on an inorganic support water-soluble solid.
  • a second subject of the invention consists, as a new industrial product, in a dry solid preformulation intended for a "two-in-one" or "three-in-one” washing and rinsing composition for an automatic dishwashing machine, said preformulation consisting essentially of a solution or dispersion of said amphoteric copolymer adsorbed and / or absorbed on a particulate solid support into at least one water-soluble inorganic material.
  • water-soluble inorganic carriers there may be mentioned sulphates, tripolyphosphates, carbonates, bicarbonates, sesquicarbonates of alkali metals, preferably sodium.
  • said support is sodium tripolyphosphate, preferably in anhydride form obtained by atomization.
  • the weight ratio, expressed as dry, amphoteric copolymer / inorganic support is from 5/95 to 50/50, preferably from 10/90 to 30/70.
  • said preformulation is in the form of cogranules having a median diameter of 250 to 1000 ⁇ m (measurement by sieve size).
  • Said preformulation may be obtained by granulation of the support material in particulate form with the aid of an aqueous solution or dispersion of amphoteric copolymer, said solution or dispersion having a solids content of 10 to 40%, preferably from 15 to 35%.
  • the support material in particulate form may have a median diameter of 150 to 700 ⁇ m.
  • the granulation operation can be carried out in a known manner using a granulation apparatus such as drum, plate, fluidized bed, etc. If necessary the cogranules obtained are dried, in fluidized bed in particular, to improve their flowability.
  • Said preformulation may further contain other components, including nonionic surfactants and organic cobuilders already mentioned above.
  • a third object of the invention consists in a method for improving the anti-redeposition properties of soils of a "two-in-one" or "three-in-one” washing and rinsing composition for machine dishwashing, by addition to said composition of an effective amount of at least one water-soluble or water-dispersible amphoteric copolymer described above or a preformulation as described above.
  • the amounts of amphoteric copolymer, as well as the nature and amounts of the other additives possibly present have already been mentioned above.
  • the sodium silicate is a cogranulate of sodium silicate hydrated SiO 2 / Na 2 O ratio ranging from 1.5 to 3.5, and sodium carbonate, the weight ratio of silicate to carbonate ranging from 5/95 to 45/55, preferably from 15/85 to 35/65, such as NABION 15 marketed by Rhodia.
  • Said “2 in 1” or “3 in 1” formulation may further comprise usual additives present in the dishwashing compositions, such as those described above and in amounts already mentioned above.
  • the washing and rinsing formulation is implemented in the dishwashing machine, by introduction into the compartment of the machine provided for this purpose. 20 g of conventional washing powder containing 0.1% or 0.2% of polymer to be tested are thus used.
  • the test is performed on 10 soda glasses regularly placed in the machine.
  • the dirt used is a mixture of salad dressing (50%), Ketchup (5%), mayonnaise (10%), milk (25%) and cream (10%).
  • Example 1 Powder or tablet formula "3 in 1"
  • the test is performed in hard water (40 ° TH), without rinsing salts or regenerating salt.
  • the tested formulation is as follows: NABION 15 (builder, co-granulated Carbonate / Sodium silicate) 25% Rhodiaphos HD7 (STPP) 52% Antarox B12 DF (non-ionic surfactant, defoamer) 0.9% Antarox B79R (nonionic surfactant) 0.9% Briquest 543-25S (phosphonates) 1.1% Perborate Monohydrate (bleaching agent) 8% TAED (bleach catalyst) 2% Rhodoline DP 226 35 (polymer builder) 2% Amylase (enzyme) 1.3% Protease (enzyme) 0.7% Polymer to test 0.2% Na 2 SO 4 5.9%
  • the formulation is in powder form or in the form of a tablet of 44 mm in diameter and 1 cm in thickness, obtained by compacting 20 g of powder under a pressure of 2 MPa.
  • a real anti-redeposition benefit of the stains and rinses brought about by the presence of 0.2% of AA / DADMAC copolymers with a molar distribution of 85/15 and 60/40, compared with the control, as well as with respect to AA / DIQUAT copolymers with a molar distribution of 60/40 and 50/50 or AA / MAPTAC with a molar distribution of 60/40.
  • Example 2 Powder or tablet "2 in 1" formula:
  • the test is performed in fresh water ( ⁇ 5 ° TH), without rinsing salt.
  • the tested formulation is as follows: NABION 15 (builder, co-granulated Carbonate / Sodium silicate) 34% Rhodiaphos HD7 (STPP) 30% Antarox B12 DF (non-ionic surfactant, defoamer) 0.8% Antarox B79R (nonionic surfactant) 0.8% Briquest 543-45AS (phosphonates) 0.8% Perborate Monohydrate (bleaching agent) 8% TAED (bleach catalyst) 2% Rhodoline DP 226 35 (polymer builder) 1.5% Amylase (enzyme) 1.3% Protease (enzyme) 0.7% Na 2 SO 4 20% Polymer to test 0.1%
  • the formulation is in powder form or in the form of a tablet of 44 mm in diameter and 1 cm in thickness, obtained by compacting 20 g of powder under a pressure of 4 MPa.
  • Example 1 The operation described in Example 1 is carried out using the formulations given in the following table: Formulation Nonionic surfactant 0.9% 0.9% Anhydrous STPP 50% 50% Sodium perborate monohydrate 8% 8% Sodium disilicate 14% * 3.48% ** Sodium carbonate 6.6% 6.6% ** Sokalan CP5 (polymer builder) 2% 2% phosphonate 1% 1% DAT 2% 2% Enzymes (protease + amylase) 2% 2% AA / DADMAC 60/40 Polymer 0.1% 0.1% Sodium sulphate qs 100 qs 100 Test result 5 9 * supplied by atomized sodium disilicate (80%) ** contributed by 12% of Nabion 15
  • Example 1 The operation described in Example 1 is carried out using the formulations given in the following table: Formulation Nonionic surfactant 1.8% 1.8% 1.8% 1.8% Anhydrous STPP 52% 52% 52% 52% Sodium perborate monohydrate 8% 8% 8% Sodium disilicate 3.48% ** 7% * 12% * 18% * Sodium carbonate 6.6% ** 6.6% 6.6% 6.6% Briquest 543-25S (phosphonates) 1.1% 1.1% 1.1% 1.1% Rhodoline DP 226 35 (polymer builder) 2% 2% 2% 2% 2% 2% 2% 2% DAT 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% Enzymes (protease + amylase) 2% 2% 2% 2% 2% 2% 2% Polymer AA / DADMAC 70/30 0.1% 0.1% 0.1% 0.1% Sodium sulphate qs 100 qs 100 qs 100 qs 100 Test result 9 8 5 3 * supplied by atomized sodium disilicate (80%

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP03755203A 2002-05-27 2003-05-26 Utilisation, d'un copolymere amphotere dans une composition lavante de la vaisselle en machine Expired - Lifetime EP1507844B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0206434A FR2839977B1 (fr) 2002-05-27 2002-05-27 Utilisation, dans une composition lavante et rincante de la vaisselle en machine, d'un copolymere amphotere comme agent anti-redeposition des salissures
FR0206434 2002-05-27
PCT/FR2003/001582 WO2003099980A1 (fr) 2002-05-27 2003-05-26 Utilisation, d'un copolymere amphotere dans une composition lavante de la vaisselle en machine

Publications (2)

Publication Number Publication Date
EP1507844A1 EP1507844A1 (fr) 2005-02-23
EP1507844B1 true EP1507844B1 (fr) 2011-05-11

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EP03755203A Expired - Lifetime EP1507844B1 (fr) 2002-05-27 2003-05-26 Utilisation, d'un copolymere amphotere dans une composition lavante de la vaisselle en machine

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US (3) US20040005990A1 (cg-RX-API-DMAC7.html)
EP (1) EP1507844B1 (cg-RX-API-DMAC7.html)
JP (1) JP4672364B2 (cg-RX-API-DMAC7.html)
CN (2) CN1656204B (cg-RX-API-DMAC7.html)
AT (1) ATE509089T1 (cg-RX-API-DMAC7.html)
AU (1) AU2003255604A1 (cg-RX-API-DMAC7.html)
BR (1) BR0304924B1 (cg-RX-API-DMAC7.html)
ES (1) ES2362181T3 (cg-RX-API-DMAC7.html)
FR (1) FR2839977B1 (cg-RX-API-DMAC7.html)
WO (1) WO2003099980A1 (cg-RX-API-DMAC7.html)

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050090994A (ko) * 2002-12-23 2005-09-14 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 세탁 첨가제로서 소수성으로 변성된 중합체
DE10342631B4 (de) * 2003-09-15 2006-04-13 Henkel Kgaa Maschinelle Geschirrspülmittel mit spezieller Polymermischung
DE10342632A1 (de) 2003-09-15 2005-04-07 Henkel Kgaa Maschinelle Geschirrspülmittel mit speziellen Polymeren
FR2863880A1 (fr) * 2003-12-23 2005-06-24 Rhodia Chimie Sa Composition cosmetique comprenant un copolymere ampholyte
DE102004015401A1 (de) * 2004-03-26 2005-10-20 Henkel Kgaa Maschinelles Geschirrspülmittel
US20060118141A1 (en) * 2004-12-08 2006-06-08 The Procter & Gamble Company Method of cleaning a washing machine or a dishwasher
US20090301519A1 (en) * 2005-07-25 2009-12-10 Rhodia Chimie Removal of dirt/make-up form unclean surfaces
JP4907199B2 (ja) * 2005-09-30 2012-03-28 花王株式会社 食器洗浄機用粉体洗浄剤組成物の製造方法
JP4633657B2 (ja) * 2005-09-30 2011-02-16 花王株式会社 自動食器洗浄機用洗浄剤組成物
JP5031309B2 (ja) * 2005-09-30 2012-09-19 花王株式会社 食器洗浄機用洗浄剤組成物
JP4841919B2 (ja) * 2005-09-30 2011-12-21 花王株式会社 食器洗浄機用洗浄剤組成物
JP4767658B2 (ja) * 2005-11-08 2011-09-07 花王株式会社 食器洗浄機用粉体洗浄剤組成物
US7310953B2 (en) * 2005-11-09 2007-12-25 Emerson Climate Technologies, Inc. Refrigeration system including thermoelectric module
DE102005060431A1 (de) * 2005-12-15 2007-06-21 Henkel Kgaa Maschinelles Geschirrspülmittel
CN100368452C (zh) * 2006-01-25 2008-02-13 四川师范大学 一种水溶性有机两性高分子絮凝剂及制备方法
JP4907327B2 (ja) * 2006-02-07 2012-03-28 花王株式会社 食器洗浄機用洗浄剤組成物
FR2898067B1 (fr) * 2006-03-03 2008-05-30 Rhodia Recherches & Tech Modification de surfaces solides par des associations de polymeres
JP4841976B2 (ja) * 2006-03-10 2011-12-21 花王株式会社 食器洗浄機用洗浄剤組成物
JP5000197B2 (ja) * 2006-05-29 2012-08-15 花王株式会社 自動食器洗浄機用洗浄剤組成物
JP4912859B2 (ja) * 2006-12-25 2012-04-11 花王株式会社 食器洗浄機用仕上げ剤組成物
JP4842119B2 (ja) * 2006-12-28 2011-12-21 花王株式会社 粉末洗剤の製造方法
DE102007019457A1 (de) * 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
JP5349783B2 (ja) * 2007-10-05 2013-11-20 花王株式会社 液体洗浄剤組成物
JP5631873B2 (ja) * 2008-06-30 2014-11-26 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 硬表面処理のための両性ポリマー
US10138587B2 (en) 2008-07-01 2018-11-27 Whirlpool Corporation Household cleaning appliance with a dispensing system operable between a single use dispensing system and a bulk dispensing system
US8286288B2 (en) 2008-07-01 2012-10-16 Whirlpool Corporation Method of indicating operational information for a bulk dispensing system
US8397544B2 (en) 2008-07-01 2013-03-19 Whirlpool Corporation Household cleaning appliance with a single water flow path for both non-bulk and bulk dispensing
US8196441B2 (en) 2008-07-01 2012-06-12 Whirlpool Corporation Household cleaning appliance with a dispensing system operable between a single use dispensing system and a bulk dispensing system
US20100000264A1 (en) 2008-07-01 2010-01-07 Whirlpool Corporation Method for converting a household cleaning appliance with a non-bulk dispensing system to a household cleaning appliance with a bulk dispensing system
FR2935390B1 (fr) * 2008-08-26 2012-07-06 Rhodia Operations Copolymere pour le traitement ou la modification de surfaces
US8852353B2 (en) * 2008-12-10 2014-10-07 Michael Oberlander Solid dishmachine detergent not requiring a separate rinse additive
WO2010107554A2 (en) * 2009-03-20 2010-09-23 Ciba Corporation Fast drying ampholytic polymers for cleaning compositions
JP5631797B2 (ja) * 2011-03-31 2014-11-26 花王株式会社 自動食器洗浄機用洗浄剤組成物
DE102011079260A1 (de) * 2011-07-15 2013-01-17 Henkel Ag & Co. Kgaa Klarspül- und Reinigungsmittel
EP2737040A1 (en) * 2011-07-27 2014-06-04 The Procter and Gamble Company Multiphase liquid detergent composition
US9068717B2 (en) * 2012-03-12 2015-06-30 L-3 Communications Corporation Backlight display using photoluminescent material tuned to improve NVIS compatibility
US9581311B2 (en) * 2012-03-12 2017-02-28 L-3 Communications Corporation Backlight display using photoluminescent material tuned to improve NVIS compatibility
WO2016014802A1 (en) 2014-07-23 2016-01-28 The Procter & Gamble Company Fabric and home care treatment compositions
EP3172300B1 (en) 2014-07-23 2018-12-26 The Procter and Gamble Company Fabric and home care treatment composition
CN106536697B (zh) * 2014-07-23 2020-06-26 宝洁公司 织物和家居护理处理组合物
JP7036508B2 (ja) * 2016-03-18 2022-03-15 スリーエム イノベイティブ プロパティズ カンパニー 金属表面をコーティングするための双性イオン性ポリマー含有組成物、方法、及び物品
EP4647482A3 (en) 2017-11-14 2025-12-31 Ecolab USA Inc. Controlled-Release Caustic Detergent Compositions (Solidos)
JP7766022B2 (ja) 2019-09-27 2025-11-07 エコラボ ユーエスエー インコーポレイティド 濃縮２ｉｎ１食器洗浄機洗剤およびすすぎ補助剤
US20230106979A1 (en) * 2020-02-28 2023-04-06 Conopco Inc., D/B/A Unilever Dishwash detergent product

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3614336A1 (de) * 1986-04-28 1987-10-29 Henkel Kgaa Fluessige waessrige reinigungsmittel fuer harte oberflaechen
NZ243311A (en) * 1991-06-28 1995-02-24 Calgon Corp Composition for treatment of skin and nails which comprises an ampholyte terpolymer comprising non-ionic, cationic and anionic monomers
EP0584709B1 (de) * 1992-08-22 1998-10-21 Clariant GmbH Verwendung von wasserlöslichen Copolymeren auf Basis von Acrylamidoalkylensulfonsäure als Waschmittelzusatz
US5686024A (en) * 1995-12-18 1997-11-11 Rhone-Poulenc Surfactants & Specialties, L.P. Aqueous dispersion of a surface active polymer having enhanced performance properties
US6013617A (en) * 1996-01-19 2000-01-11 Rhone-Poulenc Chimie Q2 /Q3 alkali metal silicate/inorganic compound detergent builders
AU4412697A (en) * 1996-09-11 1998-04-02 Procter & Gamble Company, The Low foaming automatic dishwashing compositions
US5981456A (en) * 1997-07-23 1999-11-09 Lever Brothers Company Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
AU8864298A (en) * 1997-07-23 1999-02-16 Unilever Plc Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
DE19914353A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit speziellen Bleichaktivatoren
FR2796390B1 (fr) * 1999-07-15 2001-10-26 Rhodia Chimie Sa Utilisation d'un polymere amphotere pour traiter une surface dure
US6924260B2 (en) * 1999-07-15 2005-08-02 Rhodia Chimie Method of reducing and preventing soil redeposition in an automatic dishwashing machine
ATE339493T1 (de) * 2000-05-11 2006-10-15 Unilever Nv Bleichmittel und polymere enthaltende maschinengeschirrspülmittellzusammensetzungen
JP3422978B2 (ja) * 2000-08-23 2003-07-07 花王株式会社 硬質表面用洗浄剤組成物

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BR0304924A (pt) 2004-09-28
US20060270579A1 (en) 2006-11-30
FR2839977A1 (fr) 2003-11-28
AU2003255604A1 (en) 2003-12-12
US20040005990A1 (en) 2004-01-08
JP4672364B2 (ja) 2011-04-20
CN1656204B (zh) 2012-11-07
CN102936540A (zh) 2013-02-20
BR0304924B1 (pt) 2014-09-02
EP1507844A1 (fr) 2005-02-23
JP2005527686A (ja) 2005-09-15
US20070213251A1 (en) 2007-09-13
WO2003099980A1 (fr) 2003-12-04
FR2839977B1 (fr) 2005-08-12
ATE509089T1 (de) 2011-05-15
CN1656204A (zh) 2005-08-17
ES2362181T3 (es) 2011-06-29

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