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WO1996037596A1 - Agents detergents pour lave-vaisselle renfermant des agents anti-corrosion de l'argent - Google Patents

Agents detergents pour lave-vaisselle renfermant des agents anti-corrosion de l'argent Download PDF

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Publication number
WO1996037596A1
WO1996037596A1 PCT/EP1996/002045 EP9602045W WO9637596A1 WO 1996037596 A1 WO1996037596 A1 WO 1996037596A1 EP 9602045 W EP9602045 W EP 9602045W WO 9637596 A1 WO9637596 A1 WO 9637596A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
weight
agent
cystine
agents
Prior art date
Application number
PCT/EP1996/002045
Other languages
German (de)
English (en)
Inventor
Jürgen Härer
Helmut Blum
Thomas Holderbaum
Peter Jeschke
Christian Nitsch
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1996037596A1 publication Critical patent/WO1996037596A1/fr

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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
    • C11D3/26—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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion 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
    • C11D3/20—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3436—Organic compounds containing sulfur containing disulfide groups
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof

Definitions

  • the present invention relates to agents for machine cleaning of dishes which contain cystine as a silver corrosion inhibitor.
  • peroxygen compounds such as sodium perborate or sodium percarbonate were used, which serve to remove bleachable stains, such as, for example, tea stains / tea deposits, coffee residues, dyes from vegetables, lipstick residues and the like.
  • the silver surfaces are generally more sensitive to the changed recipe parameters of the new generation of active chlorine-free cleaners with lowered pH values and activated oxygen bleaching.
  • the problem of tarnishing silver surfaces in the field of automatic dishwashing has therefore increased particularly with the introduction of dishwasher detergents containing active oxygen instead of active chlorine.
  • alkaline dishwashing detergents which contain benzotriazoles as a corrosion inhibitor for silver.
  • machine-applicable dishwashing detergents are described, which, among other things, are used as oxidizing agents. May contain perborate with an organic bleach activator. As a preventive agent, additives are used also recommended by benzotriazole and iron (III) chloride.
  • European patent specifications EP 135226 and EP 135 227 describe weakly alkaline machine dishwashing detergents containing peroxy compounds and activators, which, among other things, act as silver protection agents. May contain benzotriazoles and fatty acids.
  • the international applications PCT / EP94 / 01386 and PCT / EP94 / 01387 disclose the use of inorganic or organic redox compounds as silver corrosion inhibitors in machine dishwashing detergents.
  • the international application W094 / 19445 describes the use of certain manganese (III) and manganese (IV) complexes as silver corrosion protection agents in automatic dishwashing detergents.
  • Patent application EP-A-634478 discloses the use of isocyanuric acid as a silver corrosion inhibitor in machine dishwashing detergents.
  • International application WO94 / 07981 also discloses the use of cysteine and isocyanuric acid as silver protection agents.
  • the present invention relates to an agent for machine cleaning of dishes, containing 15 to 60% by weight, preferably 30 to 50% by weight of a builder component, 5 to 25% by weight, preferably 10 to 15% by weight of one Oxygen-based bleaching agents, in each case based on the total agent, and silver corrosion protection agents, cystine being present as the silver corrosion protection agent.
  • Cystine is preferably present in an amount of 0.005 to 3% by weight, particularly preferably 0.05 to 1% by weight and in particular 0.1 to 0.5% by weight, based on the total agent.
  • Isocyanuric acid which is then used in amounts of 0.01 to 5% by weight, preferably 0.1 to 2% by weight and in particular 0.3 to 1% by weight, is suitable as an additional silver protection agent which synergistically reinforces the silver protection effect.
  • % based on the total automatic dishwashing detergent, is included.
  • the weight ratio of cystine to isocyanuric acid is preferably between 1:10 and 2: 1, particularly preferably between 1:10 and 1: 2, and in particular between 1: 8 and 1: 3.
  • Cystine and isocyanuric acid interact synergistically with regard to the silver corrosion protection effect.
  • the silver corrosion-preventing effect according to the invention can be observed within a wide range of formulations for automatic dishwashing detergents, e.g. in the presence of builder systems consisting predominantly of citrate, or those based on citrate and polycarboxylate, or also in the presence of phosphate builders.
  • the alkali carrier system can also be varied widely, e.g. Soda / bicarbonate, disilicate or soda / disilicate.
  • the dishwashing detergents according to the invention are not exclusively, but preferably lower alkali dishwashing detergents of the newer generation.
  • the problem of silver corrosion is particularly evident in these.
  • Low-alkaline agents in the sense of the invention are agents whose 5% by weight aqueous solution has a pH of 8.0 to 11.5, preferably 9.0 to 10.5, at 20 ° C.
  • builder components especially water-soluble builder components, e.g. B. polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts.
  • B. polymeric alkali metal phosphates which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples include: tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • the amounts of phosphate are in the range of up to about 60% by weight, based on the total agent; for ecological reasons, however, the agents according to the invention are preferably free of such phosphates.
  • Other possible builder components are e.g. B. organic polymers of native or synthetic origin, especially polycarboxylates, which act in particular in hard water systems as co-builders. For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these poly- mer acids.
  • Commercial products include Sokal, n ( R ) CP 5 and PA 30 from BASF, Alcosperse ( R ) 175 or 177 from Alco, LMW ( R ) 45 N and SP02 N from Norsohaas.
  • the native polymers include, for example, oxidized starch (e.g. German patent application P 4228786.3) and polyamino acids such as polyglutamic acid or polyaspartic acid, e.g. B. from the companies Cygnus and SRCHEM.
  • oxidized starch e.g. German patent application P 4228786.3
  • polyamino acids such as polyglutamic acid or polyaspartic acid, e.g. B. from the companies Cygnus and SRCHEM.
  • Crystalline layered silicates such as the product sold by Hoechst AG under the trade name Na-SKS-6 are suitable.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as. B. mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • Preferred builder components are the salts of citric acid, in particular sodium citrate.
  • Anhydrous trisodium citrate or preferably trisodium citrate dihydrate are suitable as sodium citrate.
  • Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to citrate can also be present.
  • Sodium perborate mono- and tetrahydrate or sodium percarbonate are primarily considered as oxygen-based bleaches.
  • the use of sodium percarbonate has advantages because it has a particularly favorable effect on the corrosion behavior on glasses.
  • the oxygen-based bleach is therefore preferably a percarbonate salt, in particular sodium percarbonate.
  • So-called bleach activators are often used in amounts of up to 10% by weight, preferably 1 to 6% by weight, to activate the bleaching agents in the dishwasher.
  • Organic bleach activators are e.g.
  • PAG penentaacetylglucose
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine
  • ISA isatoic anhydride
  • TAED isatoic anhydride
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate can also be useful.
  • the dishwashing detergents according to the invention contain enzymes, Amylases, lipases and cellulases, for example proteases such as BLAP ( R ) 140 from Henkel; Optimase ( R ) -M-440, Optimase ( R ) -M-330, Opticlean ( R ) -M-375, Opticlean ( R ) -M-250 from Solvay Enzymes; Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis; Savinase ( R ) 4.0 T, 6.0 T, 8.0 T from Novo; Esperase () T from Ibis and amylases such as Termamyl ( R ) 60 T, 90 T from Novo; Amylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000, CXT 5000 or CXT 2900 from Ibis; Lipases such as Lipo
  • the agents according to the invention preferably additionally contain the alkali carriers contained in conventional machine dishwashing agents, such as. B. alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 30% by weight. , based on the total agent. The use of the highly alkaline metasilicates as alkali carriers is preferably avoided.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of essentially carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, in an amount of up to 50% by weight, preferably 10 to 40% by weight, based on the total Means, is included.
  • the ratio of carbonate and bicarbonate used varies; Usually, however, an excess of sodium hydrogen carbonate is used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.
  • surfactants in particular weakly foaming nonionic surfactants, can also be added to the agents according to the invention, which improve the detachment of fatty food residues, as wetting agents to improve the rinse aid effect, as granulating aids or as dispersing aids for better, homogeneous distribution of the aforementioned silver corrosion inhibitors in the washing liquor and on the silver top serve areas.
  • Their amount is then preferably up to 15% by weight, in particular 1 to 8% by weight, particularly preferably 2 to 8% by weight. Extremely low-foam connections are usually used.
  • Ci2-Ci8-alkylpolyethylene glycol polypropylene glycol ethers each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • a bleached quality should be used, since otherwise brown granules are formed.
  • the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers can be added.
  • a foam-suppressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers can be added.
  • Other optional additives are e.g. B. Perfume oils.
  • the cleaning agents according to the invention can optionally contain, in addition to cystine or in addition to cystine and isocyanuric acid, further silver corrosion protection agents of the prior art described above.
  • the dishwashing detergents according to the invention are preferably in the form of powder, granular or tablet-like preparations which are in themselves can be produced in a customary manner, for example by mixing, granulating, roller compacting and / or by spray drying.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is used by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 • 10-5 Pa to 1 500 • 10 * 5 Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter from 35 m to 40 mm.
  • the manufacture of machine dishwashing detergents in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 750 to 1000 g / l is characterized in that in a first process stage, the builder components are at least partially liquid Mixing components are mixed while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the further components of the dishwasher detergent, including the silver protection agents, are combined with the premix obtained in this way.
  • the agents to be used can be used both in household dishwashers and in commercial dishwashers. They are added by hand or using suitable dosing devices.
  • the application concentrations in the cleaning liquor are about 2 to 8 g / 1, preferably 2 to 5 g / 1.
  • the rinse program is generally supplemented and ended with a few intermediate rinse cycles with clear water and a rinse cycle with a common rinse aid following the cleaning cycle. After drying, not only are completely clean dishes which are an from a hygienic point of view, but above all also bright silver silver cutlery. Examples
  • compositions 5-8 cystine; compositions 9-12: isocyanuric acid; compositions 13-25: cystine + isocyanuric acid. Compositions 1-4 contain no silver corrosion inhibitor). Then the silver spoons were immersed and the solution heated to 65 ° C. The final temperature of 65 ° C was reached after about 20 minutes; the silver spoons were then left in the solution for a further 10 minutes, then removed, rinsed with water and assessed visually.
  • the tarnishing colors in the range 0 to 5 were evaluated:
  • Plurafac LF 403 fatty alcohol alkoxylate from BASF
  • Sokalan CP 5 polycarboxylate from BASF

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention a pour objet des agents détergents pour lave-vaisselle, renfermant de la cystine et de l'acide isocyanurique comme agents anti-corrosion de l'argent.
PCT/EP1996/002045 1995-05-22 1996-05-13 Agents detergents pour lave-vaisselle renfermant des agents anti-corrosion de l'argent WO1996037596A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19518693.1 1995-05-22
DE1995118693 DE19518693A1 (de) 1995-05-22 1995-05-22 Maschinelle Geschirrspülmittel mit Silberkorrosionsschutzmittel

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WO1996037596A1 true WO1996037596A1 (fr) 1996-11-28

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WO (1) WO1996037596A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0906401A1 (fr) * 1996-06-01 1999-04-07 Genencor International Inc. Nouveaux granules d'enzymes comportant une enzyme et un noyau de bisulfure organique
US6204236B1 (en) 1996-06-01 2001-03-20 Genencor International, Inc. Enzyme granulates comprising an enzyme and an organic disulfide core
US6369181B1 (en) 1997-12-29 2002-04-09 Hyundai Electronics Industries Co., Ltd. Copolymer resin, preparation thereof, and photoresist using the same
WO2002034869A1 (fr) * 2000-10-25 2002-05-02 Unilever Plc Compositions pour lave-vaisselle
WO2002034870A1 (fr) * 2000-10-25 2002-05-02 Unilever Plc Compositions pour laver la vaisselle
DE10049657C2 (de) * 2000-10-07 2003-02-27 Henkel Kgaa Maschinelles Geschirreinigungsverfahren und maschinelle Geschirrspülmittel mit verbessertem Korrosionsschutz
WO2006018107A1 (fr) * 2004-08-18 2006-02-23 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage et de nettoyage contenant des produits de rinçage et des acides amines soufres

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19649375A1 (de) 1996-11-29 1998-06-04 Henkel Kgaa Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
DE19908051A1 (de) 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5682869A (en) * 1979-12-12 1981-07-06 Seitetsu Kagaku Co Ltd Method for preventing corrosion of metal in aerosol product
SU1077337A1 (ru) * 1981-12-11 1984-12-23 Физико-химический институт АН УССР Ингибитор коррозии металлов
JPS62107092A (ja) * 1985-11-01 1987-05-18 Kurita Water Ind Ltd 酸用腐食抑制剤
WO1994026860A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produits de protection de l'argent contre la corrosion ii
WO1994026859A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produit i de protection de l'argent contre la corrosion
US5374369A (en) * 1993-10-14 1994-12-20 Lever Brothers Company, Division Of Conopco, Inc. Silver anti-tarnishing detergent composition
WO1995010588A1 (fr) * 1993-10-14 1995-04-20 Unilever N.V. Compositions detergentes contenant des agents empechant le ternissement de l'argent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5682869A (en) * 1979-12-12 1981-07-06 Seitetsu Kagaku Co Ltd Method for preventing corrosion of metal in aerosol product
SU1077337A1 (ru) * 1981-12-11 1984-12-23 Физико-химический институт АН УССР Ингибитор коррозии металлов
JPS62107092A (ja) * 1985-11-01 1987-05-18 Kurita Water Ind Ltd 酸用腐食抑制剤
WO1994026860A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produits de protection de l'argent contre la corrosion ii
WO1994026859A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produit i de protection de l'argent contre la corrosion
US5374369A (en) * 1993-10-14 1994-12-20 Lever Brothers Company, Division Of Conopco, Inc. Silver anti-tarnishing detergent composition
WO1995010588A1 (fr) * 1993-10-14 1995-04-20 Unilever N.V. Compositions detergentes contenant des agents empechant le ternissement de l'argent

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8134, Derwent World Patents Index; Class E19, AN 81-61327D, XP002012944 *
DATABASE WPI Section Ch Week 8518, Derwent World Patents Index; Class D16, AN 85-108936, XP002012942 *
DATABASE WPI Section Ch Week 8725, Derwent World Patents Index; Class E16, AN 87-174899, XP002012943 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0906401A1 (fr) * 1996-06-01 1999-04-07 Genencor International Inc. Nouveaux granules d'enzymes comportant une enzyme et un noyau de bisulfure organique
EP0906401A4 (fr) * 1996-06-01 2000-12-13 Genencor Int Nouveaux granules d'enzymes comportant une enzyme et un noyau de bisulfure organique
US6204236B1 (en) 1996-06-01 2001-03-20 Genencor International, Inc. Enzyme granulates comprising an enzyme and an organic disulfide core
US6369181B1 (en) 1997-12-29 2002-04-09 Hyundai Electronics Industries Co., Ltd. Copolymer resin, preparation thereof, and photoresist using the same
DE10049657C2 (de) * 2000-10-07 2003-02-27 Henkel Kgaa Maschinelles Geschirreinigungsverfahren und maschinelle Geschirrspülmittel mit verbessertem Korrosionsschutz
WO2002034869A1 (fr) * 2000-10-25 2002-05-02 Unilever Plc Compositions pour lave-vaisselle
WO2002034870A1 (fr) * 2000-10-25 2002-05-02 Unilever Plc Compositions pour laver la vaisselle
WO2006018107A1 (fr) * 2004-08-18 2006-02-23 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage et de nettoyage contenant des produits de rinçage et des acides amines soufres

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121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载