WO1995002674A1 - Procede permettant d'eviter la formation de taches d'eau lors du nettoyage industriel - Google Patents

Procede permettant d'eviter la formation de taches d'eau lors du nettoyage industriel Download PDF

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Publication number
WO1995002674A1
WO1995002674A1 PCT/EP1994/002211 EP9402211W WO9502674A1 WO 1995002674 A1 WO1995002674 A1 WO 1995002674A1 EP 9402211 W EP9402211 W EP 9402211W WO 9502674 A1 WO9502674 A1 WO 9502674A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
weight
acid
rinsing
hardness
Prior art date
Application number
PCT/EP1994/002211
Other languages
German (de)
English (en)
Inventor
Thomas Molz
Gaby Hecht
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 WO1995002674A1 publication Critical patent/WO1995002674A1/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
    • C11D3/37—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
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0075—Cleaning of glass
    • 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
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the invention is in the field of technical cleaning, in particular the cleaning of road and rail vehicles as well as machine cleaning etc. in factories. It relates to a process for preventing deposits, spotty drying and veils on glass, plastic, painted or metallic surfaces during rinsing processes with water that has not been completely demineralized, using cationically modified polymers of the polyacrylate type.
  • rinse aid are already known in technology, for example in automatic dishwashing. They are based on Solutions of hydroxypolycarboxylic acids containing surfactants such as citric acid or tartaric acid. However, these products primarily have the task of making it possible for the washing water to run off on the slanted dishes by reducing the surface tension. When rinsing water residues dry on horizontal surfaces or in depressions, the formation of water stains cannot be avoided with these products, especially on dark surfaces.
  • DE-A-21 61 591 describes a hydrophilizing treatment of surfaces made of glass or ceramic with 0.001 to 40% aqueous solutions of cation-active polyelectrolytes such as polymeric ethyleneimines, polymeric dimethylaminoethyl acrylate or methacrylate or their copolymers with nonionic monomers such as acrylic id, acrylonitrile or their derivatives.
  • cation-active polyelectrolytes such as polymeric ethyleneimines, polymeric dimethylaminoethyl acrylate or methacrylate or their copolymers with nonionic monomers such as acrylic id, acrylonitrile or their derivatives.
  • An application of such solutions is seen according to the task and examples in the wetting of glass, in particular in windshield washer systems of vehicles. No information is given as to whether a certain pH range is to be observed.
  • the hydrophilization is intended to prevent streaking on the vehicle windows in wet weather and thereby improve visibility.
  • DE-A-25 18 391 describes a process for preventing deposits, drying and streaks on glass, painted or metallic surfaces during rinsing operations with hard water, by treating the surfaces with solutions at temperatures between 4 and 40 ° C. which contain one or more salts of lignin sulfonic acid with monovalent cations or magnesium in concentrations of 0.02 to 0.04% by weight per degree of German hardness as well as additional surfactant and have a pH between 4 and 8.
  • Such rinse solutions have a satisfactory effect on surfaces from which the rinse water can drain off completely or can be blown off with air. However, if flushing water remains on horizontal surfaces or in depressions and dries, water stains are observed even in the presence of lignin sulfonate.
  • the invention is therefore based on the object, following an aqueous cleaning of road and rail vehicles, machines and similar technical devices, a method for preventing deposits, spotty drying and streaks on glass, plastic, painted or metallic surfaces during rinsing processes with hardness ⁇ ner-containing water and a rinse water additive for performing the method.
  • the object is achieved by using a cationically modified polymer of the polyacrylate type as an additive to the rinse water.
  • the invention relates to the
  • copolymers containing amino groups obtainable by copolymerizing, based in each case on polymer a), 15 to 90% by weight of one or more nitrogen-free monomers with an olefinic double bond and b) 10 to 85% by weight of one or more linearly polymerizable monomers containing at least one tertiary amino function, diallylamine, 2-vinylpyridine and / or 4-vinylpyridine, the amino groups of the copolymers being neutralized or quaternized with acids until a clear water-soluble preparation has been achieved are, as an additive to rinsing water after the cleaning of glass, plastic, painted or metallic surfaces with aqueous solutions,
  • esters of acrylic or methacrylic acid with Cj-C / j-monoalkanols are particularly suitable as nitrogen-free monomers.
  • Preferred monomers containing amino groups are esters of acrylic or methacrylic acid with C2-Cö monoalkanols and / or diethylamino compounds having a tertiary amine function.
  • the neutralization of the amine functions after the polymerization is preferably carried out using phosphoric acid.
  • the polymers which can be used according to the invention accordingly contain a minimum proportion of nitrogen-free monomers.
  • polymers which only contain monomers containing trialkylammonium groups.
  • Polytrimethylammonium chloride ethyl methacrylate and polytrimethylammonium ethyl ethacrylate are mentioned as examples.
  • the cationic monomers can also be copolymerized with nonionic monomers, examples of nonionic monomers being only the nitrogen-containing monomers Acrylamide and acrylonitrile can be specified.
  • the polymers of this laid-open specification are therefore modified much more cationically than those to be used according to the invention.
  • the salts of divalent cations are referred to as hardness formers.
  • These salts can be present as bicarbonates, for which the term “temporary hardness” or “carbonate hardness” is common, or they are present as "permanent hardness", for example in the form of carbonates, sulfates or chlorides.
  • the addition according to the invention to rinse water containing hardness-forming agents is suitable for degrees of hardness up to 30 ° d and is particularly effective for the German "hardness ranges 2 and 3", i.e. for 7 to 21 ° d or 1.2 to 3.8 iranol alkaline earth ions per 1. It is immaterial whether the hardness is carbonate or permanent.
  • the effective concentration range of the additive according to the invention depends on the degree of hardness of the water used.
  • polymer concentrations in the rinse water between 0.2 and 0.4% by weight are suitable, for degrees of hardness up to 30 ° d the polymer concentration can be increased to 0.4 to 0.8% by weight.
  • Polymer concentrations above 1% by weight are less preferred since the thicker polymer films caused thereby can be visually disruptive on the rinsed surfaces, for example on vehicles, particularly in wet weather.
  • the solution of the problem is added to the rinsing water only the polymer according to the invention.
  • the polymer is particularly effective when the pH of the rinse water mixed with it is between 4.5 and 6.5, preferably between 5 and 6. Depending on the degree of neutralization of the polymer solution during its manufacture, these pH values can set themselves without further measures. If desired, the If the values are too high, the pH is adjusted with acid, the pH adjustment with organic hydroxycarboxylic acids, in particular with lactic acid, citric acid and / or tartaric acid, leading to particularly positive results.
  • wetting agent in particular nonionic surfactants
  • Ethylene oxide adducts with fatty alcohols or fatty chemical fatty alcohol mixtures with 10 to 16 carbon atoms and average degrees of ethoxylation of 8 to 15 mol ethylene oxide per mol fatty alcohol and corresponding ethoxylation products from CJO to cis fatty amines are particularly preferred for this.
  • Addition products of an average of 12 moles of ethylene oxide per mole of fatty amines with mainly Cj2 and Cj4 components (coconut amine) are particularly suitable.
  • Preferred concentrations of the nonionic surfactants in the polymer-containing rinse water are between 0.005 and 0.1% by weight, in particular between 0.01 and 0.05% by weight.
  • the final rinsing is carried out at the corresponding outside or room temperature, 4 to 40 ° C. and in particular 10 to 25 ° C. having proven to be a favorable temperature interval.
  • the polymer according to the invention To facilitate handling, it is expedient to bring the polymer according to the invention to the place of use in the form of an aqueous concentrated solution and to meter it into the rinsing water in the desired concentration range.
  • the polymer content of the concentrate is set as high as possible for reasons of economy of transport, on the other hand, the upper limit of the concentration is limited by the practical requirement for the concentrate to be pumpable.
  • Polymer concentrations in the concentrate of 10 to 40% by weight have proven to be easy to handle.
  • alcohols with 2 to 4 carbon atoms in amounts of 0.01 to 20% by weight with respect to the concentrate. Isopropanol is preferred for this.
  • a concentrate according to the invention consists of 75% by weight of a 40% by weight aqueous polymer solution, 10% by weight of isopropanol, 1% by weight of wetting agent, 0.5% by weight of hydroxycarboxylic acid, the rest: VE -Water.
  • the concentrate is mixed into the rinse water in concentrations of between 0.5 and 2% by weight.
  • the invention thus relates to a further aspect
  • the production took place in a reaction vessel with stirrer, heating, cooling, reflux condenser, temperature measurement and two inlet vessels.
  • the initial solution was first prepared from water and a catalyst in the reaction vessel. Feed solutions 1 and 2 were placed in separate feed vessels. The initial solution was heated to 75 ° C. with stirring. The two feed solutions were then added in parallel within 90 minutes, the temperature rising to 85 ° C. After the feed had ended, the reaction mixture was stirred at 80 ° C. for 60 min. After cooling to less than 45 ° C., the dispersion was adjusted to a pH of about 5.5 with the neutralizing solution.
  • the reaction product was obtained in the form of a clear solution and a Brookfield viscosity of more than 5 Pa ⁇ s (spindle 4, 20 rpm); the dry residue was 40% (determined by evaporation in an oil pump vacuum at 80 ° C).
  • Example 1 Using 85% by weight of dimethylaminopropyl methacrylamide (DMAPMA) and 15% by weight of butyl acrylate (BuA), a 30% by weight aqueous preparation was neutralized with formic acid / phosphoric acid (2: 5 parts by weight) analogously to Example 1.
  • DMAPMA dimethylaminopropyl methacrylamide
  • BuA butyl acrylate
  • Example 6 Using 80% by weight of dimethylaminoethyl methacrylate (DMAEM) and 20% by weight of methyl methacrylate (MMA), a 35% by weight aqueous preparation was neutralized with formic acid analogously to Example 1.
  • DMAEM dimethylaminoethyl methacrylate
  • MMA methyl methacrylate
  • DMAEM dimethylaminoethyl methacrylate
  • MMA methyl methacrylate
  • EA ethyl acrylate
  • BuA butyl acrylate
  • Comparative solution 3 Solution of 70% by weight of a 45% by weight aqueous solution of acrylic acid polymer sodium salt (Degapas R 1105 N solution, DEGUSSA AG), 10% by weight of isopropanol, 1% by weight of coconut amine x 12 E0, 0.5% by weight lactic acid, remainder: demineralized water. Comparative solution 4
  • Rinsing water mixtures were prepared from concentrates 1 to 6 according to the invention and comparative solutions 1 to 4.
  • synthetically hard water with hardness of 20 ° d and 28 ° d was produced from demineralized water, whereby the hardness consisted of half of carbonate hardness and half of sulfate hardness and as hardening agent cations Ca (II) and Mg ( II) were used in a weight ratio of 80:20.
  • the water with a hardness of 20 ° d was mixed with a wt.%,
  • the polymer-containing rinsing water had the pH values 5.3 (20 ° d) and 5.1 (28 ° d).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé permettant d'éviter la formation de tâches d'eau lors du rinçage suivant le nettoyage de verre, de plastique, de surfaces laquées ou métalliques à l'aide d'eau contenant des durcisseurs, en utilisant des copolymères de type polyacrylate contenant des groupes amino. L'invention concerne en outre un concentré aqueux à utiliser avec le procédé.
PCT/EP1994/002211 1993-07-15 1994-07-06 Procede permettant d'eviter la formation de taches d'eau lors du nettoyage industriel WO1995002674A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934323638 DE4323638A1 (de) 1993-07-15 1993-07-15 Verhinderung von Wasserflecken bei der technischen Reinigung
DEP4323638.3 1993-07-15

Publications (1)

Publication Number Publication Date
WO1995002674A1 true WO1995002674A1 (fr) 1995-01-26

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/002211 WO1995002674A1 (fr) 1993-07-15 1994-07-06 Procede permettant d'eviter la formation de taches d'eau lors du nettoyage industriel

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DE (1) DE4323638A1 (fr)
WO (1) WO1995002674A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006052578A2 (fr) * 2004-11-03 2006-05-18 Johnsondiversey, Inc. Procede de nettoyage de recipients recycles
US7935666B2 (en) 2002-04-17 2011-05-03 Akzo Nobel N.V. Amine copolymers for textile and fabric protection
US8907033B2 (en) 1999-05-26 2014-12-09 Solvay Usa Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US9044413B2 (en) 1999-05-26 2015-06-02 Solvay Usa Inc. Block polymers, compositions and methods for use for foams, laundry detergents, and shower rinses and coagulants
US11028344B2 (en) 2016-08-16 2021-06-08 Diversey, Inc. Composition for aesthetic improvement of food and beverage containers and methods thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19902506A1 (de) * 1999-01-22 2000-07-27 Basf Ag Hydrophobierungsmittel für harte Oberflächen
EP1180129B1 (fr) * 1999-05-26 2007-09-26 The Procter & Gamble Company Compositions de detergent liquide contenant des activateurs polymeres bloc de mousse
US7241729B2 (en) 1999-05-26 2007-07-10 Rhodia Inc. Compositions and methods for using polymeric suds enhancers
DE10027634A1 (de) 2000-06-06 2001-12-13 Basf Ag Verwendung von kationisch modifizierten, teilchenförmigen, hydrophoben Polymeren als Zusatz zu Spül- oder Pflegemitteln für Textilien und als Zusatz zu Waschmitteln

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2024798A1 (fr) * 1968-11-02 1970-09-04 Benckiser Gmbh Joh A
DE2161591A1 (de) * 1971-12-11 1973-06-14 Stockhausen & Cie Chem Fab Hydrophilierung fester oberflaechen
DE3614336A1 (de) * 1986-04-28 1987-10-29 Henkel Kgaa Fluessige waessrige reinigungsmittel fuer harte oberflaechen
EP0308221A1 (fr) * 1987-09-18 1989-03-22 Rohm And Haas Company Composition propre à l'usage comme ou dans des agents de rinçage
EP0371378A1 (fr) * 1988-11-26 1990-06-06 Henkel Kommanditgesellschaft auf Aktien Revêtement temporaire pour cabines de peinture
WO1991009904A2 (fr) * 1990-01-03 1991-07-11 Henkel Corporation Auxiliaire de rinçage pour surfaces plastiques et peintes
EP0467472A2 (fr) * 1990-07-16 1992-01-22 Colgate-Palmolive Company Composition liquide de nettoyage pour surfaces dures avec polymères antisalissantes
EP0560519A2 (fr) * 1992-03-10 1993-09-15 Rohm And Haas Company Utilisation de polymères hydrosolubles dans des compositions de nettoyage et polymères hydrosolubles à cet effet

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2024798A1 (fr) * 1968-11-02 1970-09-04 Benckiser Gmbh Joh A
DE2161591A1 (de) * 1971-12-11 1973-06-14 Stockhausen & Cie Chem Fab Hydrophilierung fester oberflaechen
DE3614336A1 (de) * 1986-04-28 1987-10-29 Henkel Kgaa Fluessige waessrige reinigungsmittel fuer harte oberflaechen
EP0308221A1 (fr) * 1987-09-18 1989-03-22 Rohm And Haas Company Composition propre à l'usage comme ou dans des agents de rinçage
EP0371378A1 (fr) * 1988-11-26 1990-06-06 Henkel Kommanditgesellschaft auf Aktien Revêtement temporaire pour cabines de peinture
WO1991009904A2 (fr) * 1990-01-03 1991-07-11 Henkel Corporation Auxiliaire de rinçage pour surfaces plastiques et peintes
EP0467472A2 (fr) * 1990-07-16 1992-01-22 Colgate-Palmolive Company Composition liquide de nettoyage pour surfaces dures avec polymères antisalissantes
EP0560519A2 (fr) * 1992-03-10 1993-09-15 Rohm And Haas Company Utilisation de polymères hydrosolubles dans des compositions de nettoyage et polymères hydrosolubles à cet effet

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8907033B2 (en) 1999-05-26 2014-12-09 Solvay Usa Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US9044413B2 (en) 1999-05-26 2015-06-02 Solvay Usa Inc. Block polymers, compositions and methods for use for foams, laundry detergents, and shower rinses and coagulants
US7935666B2 (en) 2002-04-17 2011-05-03 Akzo Nobel N.V. Amine copolymers for textile and fabric protection
WO2006052578A2 (fr) * 2004-11-03 2006-05-18 Johnsondiversey, Inc. Procede de nettoyage de recipients recycles
WO2006052578A3 (fr) * 2004-11-03 2006-08-10 Johnson Diversey Inc Procede de nettoyage de recipients recycles
JP2008519144A (ja) * 2004-11-03 2008-06-05 ジョンソンディバーシー・インコーポレーテッド リサイクル用容器の洗浄方法
AU2005305095B2 (en) * 2004-11-03 2011-07-14 Diversey, Inc. Method of cleaning containers for recycling
KR101142601B1 (ko) * 2004-11-03 2012-05-03 디버세이, 인크 재활용을 위한 용기 세정 방법
US11028344B2 (en) 2016-08-16 2021-06-08 Diversey, Inc. Composition for aesthetic improvement of food and beverage containers and methods thereof

Also Published As

Publication number Publication date
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