WO2020053316A1 - Agent de protection de l'argent - Google Patents

Agent de protection de l'argent Download PDF

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Publication number
WO2020053316A1
WO2020053316A1 PCT/EP2019/074292 EP2019074292W WO2020053316A1 WO 2020053316 A1 WO2020053316 A1 WO 2020053316A1 EP 2019074292 W EP2019074292 W EP 2019074292W WO 2020053316 A1 WO2020053316 A1 WO 2020053316A1
Authority
WO
WIPO (PCT)
Prior art keywords
salt
acid
silver
detergent
degradable
Prior art date
Application number
PCT/EP2019/074292
Other languages
German (de)
English (en)
Inventor
Christoph BRUDL
Josef LUKASSER
Original Assignee
Claro Products Gmbh
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 Claro Products Gmbh filed Critical Claro Products Gmbh
Priority to EP19766024.4A priority Critical patent/EP3850072B1/fr
Publication of WO2020053316A1 publication Critical patent/WO2020053316A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/36—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
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus

Definitions

  • the field of the present invention is that of silver protection agents, preferably for detergents, in particular for dishwashing detergents, for protecting silver-containing products during a washing process.
  • the silver-containing products can become discolored due to the contact of silver-containing products with sulfur-containing compounds that are present in eggs or onions, for example.
  • the silver over the silver-containing products can come into contact with bleach during a washing process, as a result of which the silver is oxidized to dark gray silver oxide.
  • EP 0 872 543 A2 discloses a detergent with a corrosion protection effect for silver, which has a metal-triazole complex and another triazole.
  • WO 1997/003177 A1 also shows a dishwashing machine dishwashing detergent in the form of a tablet, which has a bleaching agent, a bleach activator and a silver and / or copper corrosion protection agent, the silver and / or copper corrosion protection agent not being present in one layer together with the Bleach and the bleach activator is included.
  • a silver and / or copper anticorrosive agent is according to the
  • WO 1997/003177 A1 provided, inter alia, benzotriazole.
  • EP 0 906 407 B1 discloses a dishwashing detergent which contains methylglycinediacetic acid (MGDA) with a mass fraction of 10% and also works at a low pH. Ben zotriazole is also used as a silver and / or copper corrosion protection agent.
  • MGDA methylglycinediacetic acid
  • Benzotriazole is partially water-soluble, is drawn onto the surface of the silver-containing product in the course of the washing process and protects this surface from discoloration. What is disadvantageous, however, is that benzotriazole is an environmental toxin and is difficult is degradable. In this context, poorly degradable means slow to no decomposition into smaller molecules with the help of living beings or their enzymes. Benzotriazole is therefore only eliminated to a small extent in sewage treatment plants and reaches large quantities in rivers and lakes. Benzotriazole is classified with H-411 in the hazard and safety instructions of the globally harmonized system for the classification and labeling of chemicals (GHS), which means that benzotriazole is toxic for water organisms with long-term effects.
  • GRS globally harmonized system for the classification and labeling of chemicals
  • the silver protection agent is to be decomposed biologically by living beings or their enzymes and removed from the environment.
  • the present invention provides a silver protection agent that is biodegradable and environmentally friendly.
  • the silver protectant according to the present invention comprises bismuth citrate, a degradable carboxylate or a phosphonate, such as a salt of methylglycinediacetic acid (MGDA).
  • the carboxylate can be a simple molecule or a polymer.
  • the silver protection agent according to the invention protects silver-containing products from deposits and / or discoloration during a washing cycle. It can ver for cleaning
  • the silver protective agent according to the invention dissolved in water alone or together with constituents of detergents, for example in dishwashing detergents or in machine dishwashing detergents, who used the.
  • GB 2 311 535 A discloses detergents for reducing deposits which contain an aminotricarboxylic acid, for example MGDA. Among others, the described
  • Detergents also contain crystal growth inhibitors, for example hydroxyethane diphosphonic acid.
  • GB 2 297 096 A discloses a composition for dishwashing detergents with reduced tarnishing of silver and good washing performance, comprising an oxygen bleach and a water-soluble bismuth compound.
  • MGDA is not mentioned as a possible component.
  • the degradable carboxylate is a salt of polyepoxysuccinic acid (PESA), preferably an alkali salt of polyepoxysuccinic acid, in particular the disodium salt of polyepoxysuccinic acid.
  • PESA polyepoxysuccinic acid
  • the degradable carboxylate is a salt of polyepoxysuccinic acid (PESA), preferably an alkali salt of polyepoxysuccinic acid, in particular the disodium salt of polyepoxysuccinic acid.
  • PESA is used as an environmentally friendly water treatment agent in cooling water systems to inhibit the formation of deposits.
  • US 5,062,962 A and US 5,147,555 A disclose methods for controlling deposit formation in aqueous systems. Although the corrosion protection effect of metallic surfaces of heat exchangers is shown using PESA, neither a detergent nor a silver protection is described in US Pat. No. 5,062,962 or US Pat. No. 5,147,555 A.
  • the US 4,654,159 A discloses PESA and the production of PESA as ether hydroxypolycarboxylate from epoxy succinic acid, the use as an ingredient in detergents for the substitution of phosphorus and nitrogen-containing ingredients is shown.
  • the use of PESA as a silver protective agent or the combination of PESA with bismuth citrate or MGDA are not shown in US 4,654,159 A.
  • the degradable car boxylate is a salt of iminodisuccinic acid (IDS), preferably an alkali salt of iminodisuccinic acid, in particular the tetranate rium salt of iminodisuccinic acid.
  • IDS is a complexing agent and biodegradable.
  • WO 2009/040544 A1 describes a detergent which can comprise, for example, a salt from MGDA and a salt from IDS as a building material, and which can also have bismuth for the anticorrosive action, but there is no indication of the use of bismuth.
  • MGDA and IDS are elements of a list of components that can be considered as an ingredient and bismuth is an element of a further list of components that are suitable as corrosion inhibitors.
  • the degradable carboxylate is a salt of polyaspartic acid (PASP). Advantages of the PASP are the good water solubility and the good degradability.
  • the degradable carboxylate is a polymer or copolymer of itaconic acid.
  • the phosphonate is a salt of hydroxyethane diphosphonic acid (HEDP), a salt of phosphonobutane tricarboxylic acid (PBTC), a salt of aminotrimethylenephosphonic acid (ATMP) or a salt of diethylenetriaminepentamethylenephosphonic acid (DTPMP).
  • HEDP hydroxyethane diphosphonic acid
  • PBTC phosphonobutane tricarboxylic acid
  • ATMP aminotrimethylenephosphonic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • the salt of methylglycinediacetic acid is an alkali salt of methylglycinediacetic acid, in particular the trisodium salt of methylglycinediacetic acid.
  • the present invention contemplates, instead of the salt of methylglycinediacetic acid, the use of a combination of a salt of polyepoxysuccinic acid, preferably an alkali salt of polyepoxysuccinic acid, in particular the disodium salt of polyepoxysuccinic acid, and an alkali salt of iminodisuccinic acid, in particular the tetranate salt Iminodisuccinic acid.
  • this combination also protects silver-containing products during a washing process.
  • the present invention relates to a detergent which comprises silver protection, the silver protection comprising bismuth citrate, a degradable carboxylate or a phosphonate, and a salt of methylglycinediacetic acid.
  • the detergent according to the invention is preferably degradable and is particularly suitable for cleaning silver-containing products, in particular silver cutlery, since the silver of the silver-containing products is protected from deposits and / or discoloration and / or oxidation to silver oxide.
  • the mass fraction of bismuth citrate is between 0.01% and 2.5%, preferably between 0.25% and 1%, in particular between 0.4% and 0.6% .
  • the mass fraction of the degradable carboxylate or the phosphonate, based on the total mass of the detergent is between 0.01% and 20%, preferably between 0.1% and 10%, in particular between 0.5% and 5%, lies.
  • the Mass fraction of the salt of methylglycinediacetic acid based on the total mass of the detergent between 0.01% and 35%, preferably between 5% and 15%, in particular between 7% and 15%.
  • the detergent is a machine dishwashing detergent, wherein the machine dishwashing detergent can be in the form of a tab or a powder.
  • the detergent has its full effect at low temperatures below 60 ° C.
  • the detergent according to the invention is used in a dishwasher at temperatures below 60 ° C., preferably below 55 ° C., in particular below 50 ° C.
  • dishwashing detergents GM 1 to GM 6 which comprise different silver protective agents, 6 tabs of 20 g each being pressed out of the dishwashing detergents GM 1 to GM.
  • Table 1 shows the mass fractions of the constituents of the dishwashing detergents GM 1 to GM 6.
  • the silver protection agents that are part of the dishwashing detergents GM 1 to GM 6 include benzotriazole, bismuth citrate, the sodium salt of the maleic acid-acrylic acid copolymer (MA-AA), the trisodium salt of methylglycinediacetic acid (MGDA), the disodium salt of polyepoxysuccinic acid (PESA) , the tetra sodium salt of iminodisuccinic acid (IDS) and / or a salt of polyaspartic acid (PASP).
  • the remaining constituents of the dishwashing detergents GM 1 to GM 6 are known from the prior art, so that they are not explained in more detail.
  • the silver protection agent of the dishwashing detergent GM 1 has benzotriazole and MA-AA with mass fractions of 0.3% and 4.45%.
  • the use of benzotriazole is known from the prior art.
  • the silver protective agent of the dishwashing detergent GM 2 contains bismuth citrate and MA-AA with a mass fraction of 0.5% and
  • the tabs produced from the dishwashing detergents GM 1 to GM 6 were individually placed in a dishwasher loaded with silver cutlery and each carried out 30 washing cycles in a washing program with temperatures between 45 ° C. and 65 ° C. The coating and the discoloration of the silverware was then measured and evaluated using a numerical scale.
  • the numerical scale has a sequence of numbers from 0 to 10, with 0 points representing a very high deposit and a high degree of discoloration and 10 points no significant deposit and no significant discoloration of the silver cutlery.
  • the dishwashing detergent GM 4 has a further embodiment of the silver protection agent according to the invention, which comprises bismuth citrate, MGDA and PESA with mass fractions of 0.25%, 10.0% and 10.0%. After 30 wash cycles of the wash program, the formation of deposits on the dishwashing detergent GM 4 cleaned silver cutlery with 8 points.
  • the dishwashing agent GM 4 according to the invention which comprises bismuth citrate, MGDA and PESA, a lower deposit and less discoloration of the treated silverware were found than when using the dishwashing agent GM 1, which has benzotriazole.
  • the formation of deposits on the silver cutlery when treated with the dishwasher detergent GM 5 was rated 9 points.
  • the further embodiment of the silver protection agent according to the invention used here has bismuth citrate, MGDA and IDS with mass fractions of 0.25%, 10.0% and 10.0%. Accordingly, the loading and the discoloration of the silver cutlery when using the silver protection agent of the dishwasher detergent GM 5 is significantly lower than when using the dishwasher detergent GM 1, which has benzotriazole.
  • the dishwasher detergent GM 6 has a further embodiment of the silver protection agent according to the invention, the bismuth citrate, PESA, IDS and PASP with mass fractions of 0.5%,

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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)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un agent de protection de l'argent comprenant du citrate de bismuth, un carboxylate dégradable ou un phosphonate, ainsi qu'un sel de l'acide méthylglycinediacétique. L'invention décrit en outre un détergent qui présente l'agent de protection de l'argent selon l'invention.
PCT/EP2019/074292 2018-09-12 2019-09-12 Agent de protection de l'argent WO2020053316A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19766024.4A EP3850072B1 (fr) 2018-09-12 2019-09-12 Moyen de protection d'argent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18193918.2 2018-09-12
EP18193918.2A EP3623456A1 (fr) 2018-09-12 2018-09-12 Moyen de protection d'argent

Publications (1)

Publication Number Publication Date
WO2020053316A1 true WO2020053316A1 (fr) 2020-03-19

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ID=63578990

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/074292 WO2020053316A1 (fr) 2018-09-12 2019-09-12 Agent de protection de l'argent

Country Status (2)

Country Link
EP (2) EP3623456A1 (fr)
WO (1) WO2020053316A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024088608A1 (fr) * 2022-10-27 2024-05-02 Brenntag Holding Gmbh Combinaison d'adjuvants pour compositions détergentes liquides

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB202005911D0 (en) * 2020-04-23 2020-06-10 Reckitt Benckiser Finish Bv Composition
EP4269548A1 (fr) * 2022-04-27 2023-11-01 Dalli-Werke GmbH & Co. KG Composition détergente avec agents anti-tartre

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1586067A (en) * 1976-10-28 1981-03-18 Procter & Gamble Detergent composition
US4654159A (en) 1985-06-24 1987-03-31 The Procter & Gamble Company Ether hydroxypolycarboxylate detergency builders
US5062962A (en) 1990-05-04 1991-11-05 Betz Laboratories, Inc. Methods of controlling scale formation in aqueous systems
US5147555A (en) 1990-05-04 1992-09-15 Betz Laboratories, Inc. Methods of controlling scale formation in aqueous systems
GB2297096A (en) 1995-01-20 1996-07-24 Procter & Gamble Bleaching composition.
WO1997003177A1 (fr) 1995-07-13 1997-01-30 Joh. A. Benckiser Gmbh Produit vaisselle sous forme de pastilles pour lave-vaisselle
GB2311535A (en) 1996-03-29 1997-10-01 Procter & Gamble Detergent compositions
EP0872543A2 (fr) 1997-04-17 1998-10-21 Henkel Kommanditgesellschaft auf Aktien Composition nettoyant inhibitant la corrosion
EP0906407A1 (fr) 1996-06-21 1999-04-07 Benckiser N.V. Produit de rin age pour lave-vaisselle, faiblement alcalin, contenant du mgda
WO2009040544A1 (fr) 2007-09-28 2009-04-02 Reckitt Benckiser N.V. Composition détergente

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1586067A (en) * 1976-10-28 1981-03-18 Procter & Gamble Detergent composition
US4654159A (en) 1985-06-24 1987-03-31 The Procter & Gamble Company Ether hydroxypolycarboxylate detergency builders
US5062962A (en) 1990-05-04 1991-11-05 Betz Laboratories, Inc. Methods of controlling scale formation in aqueous systems
US5147555A (en) 1990-05-04 1992-09-15 Betz Laboratories, Inc. Methods of controlling scale formation in aqueous systems
GB2297096A (en) 1995-01-20 1996-07-24 Procter & Gamble Bleaching composition.
WO1997003177A1 (fr) 1995-07-13 1997-01-30 Joh. A. Benckiser Gmbh Produit vaisselle sous forme de pastilles pour lave-vaisselle
GB2311535A (en) 1996-03-29 1997-10-01 Procter & Gamble Detergent compositions
EP0906407A1 (fr) 1996-06-21 1999-04-07 Benckiser N.V. Produit de rin age pour lave-vaisselle, faiblement alcalin, contenant du mgda
EP0872543A2 (fr) 1997-04-17 1998-10-21 Henkel Kommanditgesellschaft auf Aktien Composition nettoyant inhibitant la corrosion
WO2009040544A1 (fr) 2007-09-28 2009-04-02 Reckitt Benckiser N.V. Composition détergente

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GEMÄSS LI, X. ET AL.: "Effect of Synthesis Process Parameters of PESA on its Scaleinhibiting Performance", ADVANCED MATERIALS RESEARCH, vol. 550-553, 2012, pages 643 - 647

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024088608A1 (fr) * 2022-10-27 2024-05-02 Brenntag Holding Gmbh Combinaison d'adjuvants pour compositions détergentes liquides

Also Published As

Publication number Publication date
EP3850072A1 (fr) 2021-07-21
EP3850072B1 (fr) 2024-01-03
EP3623456A1 (fr) 2020-03-18
EP3850072C0 (fr) 2024-01-03

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