EP0512371A2 - Agents granulaires sans phosphate pour lavage de vaisselle en machine - Google Patents

Agents granulaires sans phosphate pour lavage de vaisselle en machine Download PDF

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Publication number
EP0512371A2
EP0512371A2 EP92107235A EP92107235A EP0512371A2 EP 0512371 A2 EP0512371 A2 EP 0512371A2 EP 92107235 A EP92107235 A EP 92107235A EP 92107235 A EP92107235 A EP 92107235A EP 0512371 A2 EP0512371 A2 EP 0512371A2
Authority
EP
European Patent Office
Prior art keywords
weight
acid
alkali
detergent according
dishwashing detergent
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.)
Granted
Application number
EP92107235A
Other languages
German (de)
English (en)
Other versions
EP0512371B1 (fr
EP0512371A3 (en
Inventor
Harald Dr. Volk
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.)
Chemolux SARL
Original Assignee
DISPO-Kommerz AG
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
Application filed by DISPO-Kommerz AG filed Critical DISPO-Kommerz AG
Publication of EP0512371A2 publication Critical patent/EP0512371A2/fr
Publication of EP0512371A3 publication Critical patent/EP0512371A3/de
Application granted granted Critical
Publication of EP0512371B1 publication Critical patent/EP0512371B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • 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
    • C11D3/02—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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

Definitions

  • the invention relates to a granular phosphate-free agent for automatic dishwashing.
  • Conventional dishwashing detergents for the dishwasher essentially consist of the components alkali tripolyphosphate, alkali metasilicate and alkali carbonate.
  • organic additives such as non-foaming surfactants, polycarboxylates (homopolymers of acrylic acid or copolymers with maleic acid) chlorine releasers (e.g. sodium dichloroisocyanurate) are used.
  • DE-AS 21 49 251, DE-OS 21 62 673 and DE-OS 24 35 479 already describe phosphate-free compositions for automatic dishwashing, which include as important components polycarboxylates and polycarboxylic acids, e.g. Citric acid or tartaric acid, and some are phosphate-free.
  • dishwashing detergents which have recently been on the German market, are based on trisodium citrate combined with polycarboxylates as the most important phosphate substitute.
  • citrate became possible because its calcium binding power is much better in combination with sodium disilicate than with the more alkaline sodium metasilicate.
  • these dishwashing detergents contain nonionic non-foaming surfactants, polycarboxylates, enzymes, oxygen-based bleaches (for example sodium perborate) and bleach activators such as TAED.
  • complexing agents such as e.g. NTA or EDTA, recommended as a hardness binder.
  • the present test material shows that formulations containing these substances actually show excellent properties in the removal of tea.
  • the destruction of the tea dye complex with calcium ions is particularly important here.
  • the use of these compounds is ecologically questionable, since there is a risk of remobilization of heavy metals from the sediments of surface waters.
  • the use of larger amounts of phosphonates as complexing agents is also not advisable from an ecological point of view.
  • the present invention has for its object to provide a granular, phosphate-free dishwashing detergent for the dishwasher, the phosphate substitutes of which contribute as little as possible to water pollution.
  • the flushing performance according to DIN 44 990 should at least correspond to the IEC standard cleaner with reduced risk potential for the consumer.
  • sodium gluconate in a highly alkaline medium is known.
  • highly alkaline industrial cleaners e.g. used in bottle washing
  • polyphosphates are subject to strong hydrolysis, especially at elevated temperatures; at the same time, the complex formation constant with calcium ions drops drastically, so that the effects of phosphates are severely impaired.
  • the sodium gluconate shows very strong advantages because it is not hydrolyzed and its complex formation constant with calcium ions increases with increasing pH. At pH values below 12.5, the stability of the complex decreases, and below this, calcium salts precipitate in the temperature range of 65 ° C of interest.
  • an alkali metal gluconate in particular sodium gluconate
  • lactose derivatives such as the salts of lactobionic acid.
  • the combination according to the invention of a polycarboxylate (polyacrylate or copolymers with maleic acid), preferably copolymers with sodium disilicate (ratio SiO2: Na2O is 1.7: 1 to 2.3: 1) and sodium gluconate shows a superior effect compared to formulations based on citrate.
  • the use of layered silicates known from DE-OS 36 27 773 is also possible since, apart from the lack of water of crystallization, they have a stoichiometry corresponding to the amorphous disilicate.
  • Biodegradable polypeptides that are obtained from natural sources are also used as the polymeric sequester.
  • Such products derived from fishing waste, e.g. extracted from mussels are available under the trademark Cygnus from Cygnus Corporation, Illinois (USA).
  • sodium citrate like the complexing agent NTA already mentioned, forms a 1: 1 adduct with the calcium ions, equimolar amounts are necessary to bind the water hardness. Therefore, sodium citrate is mostly used in higher percentages. Formulations up to more than 40% by weight of citrate are not uncommon. The biodegradation of citrate in the wastewater treatment plant is extremely fast, but the biological oxygen demand is high, especially with the necessary high levels in the cleaners.
  • the dishwasher detergent according to the invention for the dishwasher manages with a fraction of sodium gluconate compared to citrate. With comparable degradability of the gluconate, which also occurs naturally, there is a significantly reduced oxygen requirement due to the lower amount used, since the wastewater pollution with organic substances is greatly reduced. The total proportion of organic substances, apart from the enzymes, is only slightly more than 14% by weight in the formulation according to the invention.
  • the inorganic substances sodium disilicate and sodium carbonate used can be regarded as ecologically harmless.
  • the cleaning effect can be very specifically improved in the combination of soda / disilicate / polycarboxylate / gluconate according to the invention with enzymes.
  • enzymes preferably amylases and proteases, but also lipases, with very good activity are to be used in the composition according to the invention.
  • the bleaching agent in the present cleaner consists of an active oxygen compound.
  • an active oxygen compound e.g. Peroxo compounds or peroxohydrates, e.g. Alkali perborate, alkali carbonate, peroxohydrate, alkali peroxosulfate, hydrogen peroxide, urea, preferably sodium perborate monohydrate.
  • an activator e.g. from the group of compounds, which split off peracetic acid under the action of hydrogen peroxide.
  • the TAED is particularly worth mentioning here.
  • Non-foaming or low-foaming surfactants are particularly advantageous in dishwashers because they suppress the foam generated by the spray arm.
  • the biodegradable surfactants of the fatty alcohol type with EO / PO chains have proven successful here.
  • biodegradable anionic surfactants which are derived from glycine have also proven to be advantageous in the agent according to the invention.
  • These polycarboxyglycinates of the general formula R- (N- (CH2) 3-CH2COONa) n-CH2COONa also contribute to the sequestration of water hardness due to their nitrogen atoms.
  • R stands for a fatty alkyl residue, such as tallow fat.
  • Preferred recipes are the subject of the dependent claims.
  • the rate of dissolution in water can be delayed, as is the case with crystalline layered silicate.
  • granular amorphous sodium disilicate shows positive behavior.
  • Additives customary for such cleaners such as e.g. Fragrances and dyes, defoamers, pouring aids, extenders and extenders are added. However, they do not contribute to the cleaning effect, but can influence consumer acceptance or improve the storage stability of the formulation.
  • Buffer substances can also be added to regulate the pH.
  • the inorganic hydrogen carbonates or sesquicarbonates are particularly worth mentioning here.
  • organic compounds e.g. Alkaline acetates, which make little contribution to cleaning performance, can serve this purpose.
  • These buffers can set the pH to a lower level so that the agent no longer has to be classified as an irritant or meets even the strictest legal requirements.
  • Example 1 is a known agent, while Examples 2-8 relate to compositions according to the invention.
  • composition according to the invention when used with the same dosage of 25 g, a much better washing result is achieved than with the IEC standard cleaner.
  • very stubborn, starchy dirt, such as oatmeal is removed very well.
  • spinach which can only be removed by sufficient dispersing and emulsifying effects of the cleaner, is removed very well.
  • the environmental impact is reduced by a much lower dosage in the dishwasher.
  • the amount used can be reduced by up to 50% compared to conventional cleaners.
EP92107235A 1991-05-02 1992-04-28 Agents granulaires sans phosphate pour lavage de vaisselle en machine Expired - Lifetime EP0512371B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4114956 1991-05-02
DE4114956A DE4114956A1 (de) 1991-05-02 1991-05-02 Granulaeres phosphatfreies mittel fuer das maschinelle geschirrspuelen

Publications (3)

Publication Number Publication Date
EP0512371A2 true EP0512371A2 (fr) 1992-11-11
EP0512371A3 EP0512371A3 (en) 1995-06-14
EP0512371B1 EP0512371B1 (fr) 1997-10-01

Family

ID=6431199

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92107235A Expired - Lifetime EP0512371B1 (fr) 1991-05-02 1992-04-28 Agents granulaires sans phosphate pour lavage de vaisselle en machine

Country Status (3)

Country Link
EP (1) EP0512371B1 (fr)
AT (1) ATE158812T1 (fr)
DE (2) DE4114956A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995012654A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Limitation de la precipitation de carbonate de calcium dans les lave-vaisselle
EP0659874A1 (fr) * 1993-12-23 1995-06-28 The Procter & Gamble Company Compositions détergents
WO1995020030A1 (fr) * 1994-01-25 1995-07-27 Unilever N.V. Co-granules et pastilles detergentes produites a l'aide desdits co-granules
WO1996008552A1 (fr) * 1994-09-13 1996-03-21 Kao Corporation Procede de lavage et composition detergente pour vetements
FR2726002A1 (fr) * 1994-10-21 1996-04-26 Rhone Poulenc Chimie Composition de builder sans zeolithes ni phostates comprenant un systeme diminuant les incrustations calciques, son utilisation dans des compositions detergentes et ces compositions detergentes
EP0812241A1 (fr) * 1995-03-01 1997-12-17 Charvid Limited Liability Company Composition de nettoyage non caustique comprenant un compose peroxygene et un silicate particulier, et procede pour preparer cette composition
EP0815192A1 (fr) * 1995-03-11 1998-01-07 The Procter & Gamble Company Composition detergente comportant un compose polycarboxylique polymere, un chelateur et une enzyme amylase
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
WO2003038028A3 (fr) * 2001-10-30 2003-10-23 Henkel Kgaa Detergent ou nettoyant dispersible sensiblement exempt de sediments
WO2006131503A2 (fr) * 2005-06-10 2006-12-14 Novozymes A/S Detergents comprenant des systemes d'adjuvant et de blanchiment enzymatiques
WO2007141635A2 (fr) * 2006-06-07 2007-12-13 Silvia Palladini Formulations détergentes ayant un impact faible sur l'environnement
JP2016538412A (ja) * 2013-11-11 2016-12-08 エコラボ ユーエスエー インコーポレイティド 強化されたスケール制御及び汚れ分散性を有する高アルカリ性物品洗浄洗剤

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2003105683A (ru) 2000-07-28 2004-08-20 Хенкель Кгаа (De) Новый амилолитический фермент из bacillus sp.а7-7(dsm12368), а также моющее и чистящее средство с этим новым амилолитическим ферментом

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3744592A1 (de) * 1987-12-31 1989-07-13 Basf Ag Wasserloesliche polymerisate enthaltende geschirrspuelmittel
JPH01198699A (ja) * 1988-02-03 1989-08-10 Kao Corp 自動食器洗浄機用洗剤
JPH03234795A (ja) * 1990-02-08 1991-10-18 Kao Corp 漂白剤組成物
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2101508C3 (de) * 1971-01-14 1979-05-17 Henkel Kgaa, 4000 Duesseldorf Geschirrspulmittel
DE3139091C2 (de) * 1980-10-11 1986-06-19 Sandoz-Patent-GmbH, 7850 Lörrach Phosphatfreie oder phosphatarme Wasch- und Reinigungsmittel
CA1334389C (fr) * 1986-03-26 1995-02-14 Ernest H. Brumbaugh Composition anti-taches pour lave-vaisselle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3744592A1 (de) * 1987-12-31 1989-07-13 Basf Ag Wasserloesliche polymerisate enthaltende geschirrspuelmittel
JPH01198699A (ja) * 1988-02-03 1989-08-10 Kao Corp 自動食器洗浄機用洗剤
JPH03234795A (ja) * 1990-02-08 1991-10-18 Kao Corp 漂白剤組成物
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8938, Derwent Publications Ltd., London, GB; AN 89-274105 & JP-A-1 198 699 (KAO) 10. August 1989 *
DATABASE WPI Week 9148, Derwent Publications Ltd., London, GB; AN 91-350051 & JP-A-3 234 795 (KAO) 18. Oktober 1991 *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995012654A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Limitation de la precipitation de carbonate de calcium dans les lave-vaisselle
EP0659874A1 (fr) * 1993-12-23 1995-06-28 The Procter & Gamble Company Compositions détergents
AU702040B2 (en) * 1994-01-25 1999-02-11 Unilever Plc Co-granules and detergent tablets formed therefrom
WO1995020030A1 (fr) * 1994-01-25 1995-07-27 Unilever N.V. Co-granules et pastilles detergentes produites a l'aide desdits co-granules
WO1996008552A1 (fr) * 1994-09-13 1996-03-21 Kao Corporation Procede de lavage et composition detergente pour vetements
CN1093169C (zh) * 1994-09-13 2002-10-23 花王株式会社 洗涤方法和衣物洗涤剂组合物
FR2726002A1 (fr) * 1994-10-21 1996-04-26 Rhone Poulenc Chimie Composition de builder sans zeolithes ni phostates comprenant un systeme diminuant les incrustations calciques, son utilisation dans des compositions detergentes et ces compositions detergentes
WO1996012784A1 (fr) * 1994-10-21 1996-05-02 Rhone-Poulenc Chimie Compositon d'adjuvant de detergence sans zeolithes ni phosphates
US6043207A (en) * 1995-03-01 2000-03-28 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound, meta/sesqui-silicate, chelate and method of making same in free-flowing, particulate form
EP0812241A4 (fr) * 1995-03-01 1999-08-18 Charvid Limited Liability Comp Composition de nettoyage non caustique comprenant un compose peroxygene et un silicate particulier, et procede pour preparer cette composition
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
EP0812241A1 (fr) * 1995-03-01 1997-12-17 Charvid Limited Liability Company Composition de nettoyage non caustique comprenant un compose peroxygene et un silicate particulier, et procede pour preparer cette composition
EP0815192A4 (fr) * 1995-03-11 1999-09-22 Procter & Gamble Composition detergente comportant un compose polycarboxylique polymere, un chelateur et une enzyme amylase
EP0815192A1 (fr) * 1995-03-11 1998-01-07 The Procter & Gamble Company Composition detergente comportant un compose polycarboxylique polymere, un chelateur et une enzyme amylase
WO2003038028A3 (fr) * 2001-10-30 2003-10-23 Henkel Kgaa Detergent ou nettoyant dispersible sensiblement exempt de sediments
WO2006131503A2 (fr) * 2005-06-10 2006-12-14 Novozymes A/S Detergents comprenant des systemes d'adjuvant et de blanchiment enzymatiques
WO2006131503A3 (fr) * 2005-06-10 2007-09-07 Novozymes As Detergents comprenant des systemes d'adjuvant et de blanchiment enzymatiques
WO2007141635A2 (fr) * 2006-06-07 2007-12-13 Silvia Palladini Formulations détergentes ayant un impact faible sur l'environnement
WO2007141635A3 (fr) * 2006-06-07 2008-09-04 Silvia Palladini Formulations détergentes ayant un impact faible sur l'environnement
JP2016538412A (ja) * 2013-11-11 2016-12-08 エコラボ ユーエスエー インコーポレイティド 強化されたスケール制御及び汚れ分散性を有する高アルカリ性物品洗浄洗剤
EP3068857A4 (fr) * 2013-11-11 2017-07-12 Ecolab USA Inc. Détergent de lavage fortement alcalin offrant un meilleur contrôle du tartre et une meilleure dispersion des salissures
JP2018159082A (ja) * 2013-11-11 2018-10-11 エコラボ ユーエスエー インコーポレイティド 強化されたスケール制御及び汚れ分散性を有する高アルカリ性物品洗浄洗剤
US10316272B2 (en) 2013-11-11 2019-06-11 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US10745651B2 (en) 2013-11-11 2020-08-18 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US11339354B2 (en) 2013-11-11 2022-05-24 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US11920109B2 (en) 2013-11-11 2024-03-05 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion

Also Published As

Publication number Publication date
EP0512371B1 (fr) 1997-10-01
DE59208935D1 (de) 1997-11-06
ATE158812T1 (de) 1997-10-15
DE4114956A1 (de) 1992-11-05
EP0512371A3 (en) 1995-06-14

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