EP0238956A2 - Glass-cleaning agent - Google Patents

Glass-cleaning agent Download PDF

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Publication number
EP0238956A2
EP0238956A2 EP87103730A EP87103730A EP0238956A2 EP 0238956 A2 EP0238956 A2 EP 0238956A2 EP 87103730 A EP87103730 A EP 87103730A EP 87103730 A EP87103730 A EP 87103730A EP 0238956 A2 EP0238956 A2 EP 0238956A2
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EP
European Patent Office
Prior art keywords
weight
gew
component
und
mpas
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EP87103730A
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German (de)
French (fr)
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EP0238956A3 (en
Inventor
Heinz-Dieter Soldanski
Marlis Kalibe
Bernd-Dieter Holdt
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0238956A2 publication Critical patent/EP0238956A2/en
Publication of EP0238956A3 publication Critical patent/EP0238956A3/en
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • 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
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • C11D3/43—Solvents

Definitions

  • the object of the present invention was therefore to develop an agent with better properties overall.
  • the agent according to the invention has an exceptionally high cleaning ability even on heavily oil and grease soiled windows, such as motor vehicle windscreens. It can be easily applied to the panes without fear of running down or dripping. Despite its pasty consistency, the product can be easily distributed over a large area. After drying, the back polish the stands easily and almost dust-free, and the result is completely clear streak-free and residue-free surfaces.
  • the agents preferably contain only gasoline as the organic solvent, in particular those qualities which have boiling ranges between 120 and 250 ° C., preferably between 140 and 180 ° C. For reasons of smell, dearomatized gasoline types and synthetic isoparaffins are preferred.
  • solvents from the group of alcohols, ketones and glycol ethers can also be used in the agents; however, their share always makes up less than half of the gasoline share.
  • the boiling point of these solvents is between 55 and 250 ° C.
  • solvents are acetone, isopropanol and ethylene glycol monobutyl ether.
  • the amount of gasoline in the compositions is 2 to 30% by weight, preferably 3 to 20% by weight and in particular 4 to 12% by weight.
  • the other organic solvents mentioned can contain 0 to 10, preferably 0 to 5% by weight.
  • the calcium carbonate used in the agents as an abrasive component is microcrystalline natural or, preferably, synthetic calcium carbonate. Fine-particle material with a weight average grain size between 0.2 and 10 ⁇ m is suitable. 98% by weight of the calcium carbonate should have grain sizes below 300 ⁇ m, preferably below 200 ⁇ m and in particular below 100 ⁇ m.
  • the share of Calcium carbonate in the compositions is 5 to 40% by weight, preferably 10 to 30% by weight and in particular 15 to 25% by weight.
  • Low viscosity silicone oils for example polydimethylsiloxanes, with viscosities of 20 to 1000 mPas, preferably 30 to 500 mPas and in particular 50 to 150 mPas at 20 ° C. are suitable for the agents according to the invention.
  • Their proportion of the agents is 0.2 to 2.5% by weight, preferably 0.3 to 1.8% by weight and in particular 0.7 to 1.3% by weight.
  • Suitable anionic emulsifiers are conventional anionic, but preferably nonionic, emulsifiers which lead to oil-in-water emulsions.
  • the alkali metal, ammonium, amine and alkaline earth metal salts of long-chain alkyl sulfates, sulfonates and phosphoric acid partial esters are suitable as anionic emulsifiers.
  • Particularly suitable are the salts of sulfuric acid semiesters or phosphoric acid partial esters of linear alcohols or oxo alcohols each having 12 to 18 carbon atoms or the polyglycomonoalkyl ethers having 12 to 18 carbon atoms in the alkyl group and the olefin sulfonates, ester sulfonates and alkanesulfonates containing 12 to 20 carbon atoms, the alkylbenzenesulfonates with 6 to 16 carbon atoms in the alkyl groups, the sulfonates of the polyglycol monoalkyl ethers with 12 to 18 carbon atoms in the alkyl groups and the salts of the fatty acids with 12 to 18 carbon atoms.
  • anionic emulsifiers fatty acid amine salts, in particular salts of alkanolamines or alkanolalkylamines having 2 to 7 carbon atoms, are preferably used.
  • Suitable nonionic emulsifiers include, for example, the sorbitan esters of higher fatty acids and the alkyleneoxy adducts with higher linear mono- and polyhydric alcohols, alkylphenols, long-chain carboxylic acids, carboxamides and hydroxy fatty acids with 10 to 24 carbon atoms and on fatty acid glycerol or sorbitan esters.
  • the adducts of 5 to 40 mol of ethylene oxide with long-chain, in particular primary alcohols with 12 to 18 carbon atoms and with fatty acid sorbitan esters are preferably used as nonionic emulsifiers.
  • the adducts of 5 to 20 mol EO of fatty acid sorbitan esters are particularly preferred.
  • the proportion of emulsifiers in the total emulsion is generally 0.05 to 2% by weight, preferably 0.1 to 0.8% by weight and in particular 0.15 to 0.4% by weight, regardless of whether a single emulsifier or a mixture of several emulsifiers is used.
  • the polyacrylic acid contained in the agents serves on the one hand as a consistency agent, but on the other hand also as a suspending agent and is responsible for the fact that the agents can be polished easily and without residue after drying.
  • Polyacrylic acids with average molecular weights between 0.8 ⁇ 106 and 5 ⁇ 106, preferably 1 ⁇ 106 to 4 ⁇ 106, are suitable.
  • the polymer is preferably used in the acidic form in the preparation of the compositions, but is generally present in the finished compositions in a partially neutralized form.
  • the proportion of polyacrylic acid in the compositions is 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight and in particular 0.4 to 0.8% by weight.
  • the task of the alkalizing agents is to give the finished glass cleaning agent, in interaction with the acids contained, a neutral to slightly alkaline pH, preferably between 7.5 and 9.5.
  • Alkali metal salts, ammonia and alkanolamines and alkanolalkylamines having 2 to 7 carbon atoms, for example, are suitable.
  • the amount of Alkalizing agents depend primarily on the amount of polyacrylic acid contained in the agents. Usually no more than 2% by weight, preferably between 0.05 and 1% by weight, of alkalizing agents is used.
  • the agents according to the invention can contain up to 3% by weight, preferably not more than 1% by weight, of conventional auxiliaries and additives.
  • auxiliaries and additives examples are perfume, preservatives, salts and dyes.
  • a particularly preferred composition of the glass cleaning agent has the following composition: 4 - 12% by weight of de-aromatized gasoline and / or isoparaffin with boiling ranges from 140 to 180 ° C, 15-25% by weight of microcrystalline calcium carbonate with a particle size of 98% by weight below 100 ⁇ m, 0.7 - 1.3% by weight silicone oil with a viscosity of 50 to 150 mPas, 0.15-0.4% by weight adduct of fatty acid sorbitan ester and 5 to 20 moles of ethylene oxide, 0.4-0.8% by weight polyacrylic acid with average molecular weight between 1 ⁇ 106 and 4 ⁇ 106, 0.05-1% by weight alkali hydroxide and ad 100 wt .-% water.
  • the procedure is generally such that water, emulsifier and, if appropriate, other auxiliaries are initially introduced and then the polyacrylic acid is added with vigorous stirring. After swelling of the polyacrylic acid, the desired pH is adjusted with alkalizing agent and the calcium carbonate is then stirred in. Finally, a mixture of organic solvents, silicone oil and optionally perfume is emulsified into the aqueous phase.
  • the preparation of the agent can also be varied in such a way that the polyacrylic acid solution is first strongly alkalized before the calcium carbonate is stirred in and only then adjusted to the desired pH by adding acid. The viscosity can be determined with a Brookfield viscometer using the spindle 6 at 20 revolutions per minute.
  • the finished paste-like agent can be filled in cans, tubes or dispensers made of different materials.
  • the agent is used in such a way that the product is preferably spread over a large area on the surface to be cleaned, with the aid of a damp cloth or damp sponge.
  • the applied agent is allowed to dry and then the remaining residues are removed, for example by rubbing with a cloth, a fleece or with paper.
  • the agents are equally suitable for cleaning surfaces made of glass, shiny ceramics or enamel. However, the advantages of the agents have a particularly clear effect when cleaning windows or mirrors.
  • the resulting dispersion was mixed with a mixture of 23 kg isoparaffin (boiling range 155 to 173 ° C), 4.6 kg silicone oil (Baysilon M 100) and 0.23 kg perfume oil, resulting in a stable paste-like emulsion. It had a pH of 8.1 and a viscosity of 20,000 mPas at 20 ° C (measured with a Brookfield viscometer, spindle 6, at 20 revolutions per minute).
  • the percentage composition of the mass was:
  • the product was packed in aluminum tubes for sale.
  • a detergent exhibited similarly good cleaning properties and, with an otherwise identical structure, contained a ground natural calcium carbonate with an average particle size of 2.8 ⁇ m (99.9% by weight below 10 ⁇ m).

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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)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Das pastenförmige Mittel hat folgende Zusammensetzung:

  • a) 2 - 30  Gew.-% Benzin mit Siedebereich zwischen 120 und 25o °C
  • b) 0 - 10  Gew.-% organischem Lösungsmittel aus der Gruppe Alkohole, Ketone und Glykolether mit Siedepunkten zwischen 55 und 250 °C, wobei dessen Anteil weniger als die Hälfte des Benzinanteils ausmacht,
  • c) 5 - 40  Gew.-% mikrokristallinem Calciumcarbonat, dessen Teilchen zu mehr als 98 Gew.-% kleiner als 300 µm sind,
  • d) 0,2- 2,5  Gew.-% Silikonöl mit einer Viskosität von 20 - 1000 mPas,
  • e) 0,05- 2  Gew.-% nichtionischem und/oder anionischem Emulgator für O/W-Emulsionen,
  • f) 0,1--3  Gew.-% Polyacrylsäure, die ein mittleres Molekulargewicht zwischen 0,8 × 10⁶ und 5 × 10⁶ aufweist,
  • g) 0 - 2  Gew.-% Alkali aus der Gruppe alkalisch reagierende Alkalimetallsalze, Ammoniak und Alkanolamine,
  • h) 0 - 3  Gew.-% weiteren üblichen Hilfsstoffen und
  • i) ad 100  Gew.-% Wasser
The paste-like composition has the following composition:
  • a) 2 - 30 wt .-% gasoline with boiling range between 120 and 25o ° C.
  • b) 0-10% by weight of organic solvent from the group consisting of alcohols, ketones and glycol ethers with boiling points between 55 and 250 ° C., the proportion of which is less than half the proportion of petrol,
  • c) 5-40% by weight of microcrystalline calcium carbonate, the particles of which are more than 98% by weight smaller than 300 µm,
  • d) 0.2-2.5% by weight silicone oil with a viscosity of 20-1000 mPas,
  • e) 0.05-2% by weight of nonionic and / or anionic emulsifier for O / W emulsions,
  • f) 0.1-3% by weight of polyacrylic acid, which has an average molecular weight between 0.8 × 10⁶ and 5 × 10⁶,
  • g) 0-2% by weight of alkali from the group of alkali metal salts, ammonia and alkanolamines,
  • h) 0-3% by weight of other customary auxiliaries and
  • i) ad 100 wt .-% water

Es zeichnet sich durch außergewöhnlich hohes Reinigungsver­mögen und geringe Rückstandsbildung aus läßt sich bequem und sauber handhaben. It is characterized by exceptionally high cleaning power and low residue formation, can be handled comfortably and cleanly.

Description

Zur Reinigung von Glasflächen werden in der Literatur zahlreiche Verfahren und Mittel vorgeschlagen und auch in der Praxis werden für diesen Zweck unterschiedliche Mittel angeboten. Weite Verbreitung besitzen beispielsweise Fensterreinigungsmittel in Form verdünnter wäßriger Tensidlösungen, die auch flüchtiges Alkali und organisches Lösungsmittel enthalten können. Mit Hilfe derartiger Mittel lassen sich fettige und hydrophobe Anschmutzun­gen aber nur schwer entfernen. Eine bessere Reinigung dieser Anschmutzungen läßt sich mit Mitteln erreichen, die Polierkörper enthalten. Sie erfordern eine zweistufige Arbeitsweise, bei der zunächst die Mittel auf den Glasflächen verteilt und eingerieben werden, ehe sie beispielsweise durch Abspülen oder durch Ab­polieren nach dem Trocknen wieder entfernt werden. Als Nachteil dieser Mittel ist zu werten, daß häufig Rückstände der Polier­körper auf den Scheiben selbst oder in der Umgebung der Scheibe zurückbleiben.Numerous methods and agents are proposed in the literature for cleaning glass surfaces, and various agents are also offered for this purpose in practice. Window cleaning agents, for example, are widely used in the form of dilute aqueous surfactant solutions, which can also contain volatile alkali and organic solvents. Such means are difficult to remove greasy and hydrophobic stains. A better cleaning of these stains can be achieved with agents that contain polishing agents. They require a two-stage procedure, in which the agents are first distributed and rubbed in on the glass surfaces before they are removed again, for example by rinsing or polishing after drying. A disadvantage of these agents is that residues of the polishing bodies often remain on the disks themselves or in the vicinity of the disk.

Der vorliegenden Erfindung lag somit die Aufgabe zugrunde, ein Mittel mit insgesamt besseren Eigenschaften zu entwickeln.The object of the present invention was therefore to develop an agent with better properties overall.

Gegenstand der Erfindung ist ein Reinigungsmittel für Glas­scheiben in Form einer Paste, die bei 20 °C eine Viskosität von 10 000 bis 40 000 mPas aufweist. Das Mittel besteht aus:

  • a) 2 - 30 Gew.-% Benzin mit Siedebereich zwischen 120 und 25o °C
  • b) 0 - 10 Gew.-% organischem Lösungsmittel aus der Gruppe Alkohole, Ketone und Glykolether mit Siedepunkten zwischen 55 und 250 °C, wobei dessen Anteil weniger als die Hälfte des Benzinanteils ausmacht,
  • c) 5 - 40 Gew.-% mikrokristallinem Calciumcarbonat, dessen Teilchen zu mehr als 98 Gew.-% kleiner als 300 µm sind,
  • d) 0,2 - 2,5 Gew.-% Silikonöl mit einer Viskosität von 20 - 1000 mPas,
  • e) 0,05 - 2 Gew.-% nichtionischem und/ oder anionischem Emulgator für O/W-Emulsionen,
  • f) 0,1 - 3 Gew.-% Polyacrylsäure, die ein mittleres Molekulargewicht zwischen 0,8 × 10⁶ und 5 × 10⁶ aufweist,
  • g) 0 - 2 Gew.-% Alkali aus der Gruppe alkalisch reagierende Alkalimetallsalze, Ammoniak und Alkanolamine,
  • h) 0 - 3 Gew.-% weiteren üblichen Hilfsstoffen und
  • i) ad 100 Gew.-% Wasser.
The invention relates to a cleaning agent for glass panes in the form of a paste which has a viscosity of 10,000 to 40,000 mPas at 20 ° C. The remedy consists of:
  • a) 2 - 30 wt .-% gasoline with boiling range between 120 and 25o ° C.
  • b) 0-10% by weight of organic solvent from the group Alcohols, ketones and glycol ethers with boiling points between 55 and 250 ° C, the proportion of which is less than half that of petrol,
  • c) 5-40% by weight of microcrystalline calcium carbonate, the particles of which are more than 98% by weight smaller than 300 µm,
  • d) 0.2-2.5% by weight of silicone oil with a viscosity of 20-1000 mPas,
  • e) 0.05-2% by weight of nonionic and / or anionic emulsifier for O / W emulsions,
  • f) 0.1-3% by weight of polyacrylic acid which has an average molecular weight between 0.8 × 10⁶ and 5 × 10⁶,
  • g) 0-2% by weight of alkali from the group of alkali metal salts, ammonia and alkanolamines,
  • h) 0-3% by weight of other customary auxiliaries and
  • i) ad 100 wt .-% water.

Das erfindungsgemäße Mittel besitzt ein außergewöhnlich hohes Reinigungsvermögen selbst an stark öl- und fettverschmutzen Scheiben, wie etwa Kraftfahrzeug-Windschutzscheiben. Es läßt sich problemlos auf die Scheiben auftragen, ohne daß ein Herunterlaufen oder ein Vertropfen zu befürchten wäre. Trotz seiner pastenförmigen Konsistenz läßt sich das Mittel mühelos großflächig verteilen. Nach dem Trocknen lassen sich die Rück­ stände leicht und nahezu staubfrei abpolieren, und es resultieren völlig klare streifen- und rückstandsfreie Flächen.The agent according to the invention has an exceptionally high cleaning ability even on heavily oil and grease soiled windows, such as motor vehicle windscreens. It can be easily applied to the panes without fear of running down or dripping. Despite its pasty consistency, the product can be easily distributed over a large area. After drying, the back polish the stands easily and almost dust-free, and the result is completely clear streak-free and residue-free surfaces.

Es folgt eine Beschreibung der einzelnen Bestandteile:A description of the individual components follows:

Organische LösungsmittelOrganic solvents

Vorzugsweise enthalten die Mittel als organisches Lösungsmittel nur Benzin, insbesondere solche Qualitäten, die Siedebereiche zwischen 120 und 250 °C, vorzugsweise zwischen 140 und 180 °C, aufweisen. Aus Geruchsgründen werden entaromatisierte Benzin­typen und synthetische Isoparaffine bevorzugt.The agents preferably contain only gasoline as the organic solvent, in particular those qualities which have boiling ranges between 120 and 250 ° C., preferably between 140 and 180 ° C. For reasons of smell, dearomatized gasoline types and synthetic isoparaffins are preferred.

Neben Benzin können aber auch Lösungsmittel aus der Gruppe der Alkohole, der Ketone und der Glykolether in den Mitteln verwendet werden; ihr Anteil macht aber stets weniger als die Hälfte des Benzinanteils aus. Im allgemeinen liegt der Siedepunkt dieser Lösungsmittel zwischen 55 und 250 °C. Beispiele solcher Lösungsmittel sind Aceton, Isopropanol und Ethylenglykolmono­butylether.In addition to petrol, solvents from the group of alcohols, ketones and glycol ethers can also be used in the agents; however, their share always makes up less than half of the gasoline share. In general, the boiling point of these solvents is between 55 and 250 ° C. Examples of such solvents are acetone, isopropanol and ethylene glycol monobutyl ether.

Die Menge an Benzin beträgt in den Mitteln 2 bis 30 Gew.-%, vorzugsweise 3 bis 20 Gew.-% und insbesondere 4 bis 12 Gew.-%. An den genannten anderen organischen Lösungsmitteln können 0 bis 10, vorzugsweise 0 bis 5 Gew.-% enthalten sein.The amount of gasoline in the compositions is 2 to 30% by weight, preferably 3 to 20% by weight and in particular 4 to 12% by weight. The other organic solvents mentioned can contain 0 to 10, preferably 0 to 5% by weight.

CalciumcarbonatCalcium carbonate

Bei dem in den Mitteln als Abrasivkomponente verwendeten Calcium­carbonat handelt es sich um mikrokristallines natürliches oder, vorzugsweise, synthetisches Calciumcarbonat. Geeignet ist fein­teiliges Material, bei dem das Gewichtsmittel der Korngröße zwischen 0,2 und 10 µm liegt. Dabei sollen 98 Gew.-% des Calciumcarbonats Korngrößen unter 300 µm, vorzugsweise unter 200 µm und insbesondere unter 100 µm aufweisen. Der Anteil an Calciumcarbonat in den Mitteln beträgt 5 bis 40 Gew.-%, vor­zugsweise 10 bis 30 Gew.-% und insbesondere 15 bis 25 Gew.-%.The calcium carbonate used in the agents as an abrasive component is microcrystalline natural or, preferably, synthetic calcium carbonate. Fine-particle material with a weight average grain size between 0.2 and 10 µm is suitable. 98% by weight of the calcium carbonate should have grain sizes below 300 μm, preferably below 200 μm and in particular below 100 μm. The share of Calcium carbonate in the compositions is 5 to 40% by weight, preferably 10 to 30% by weight and in particular 15 to 25% by weight.

SiliconölSilicone oil

Für die erfindungsgemäßen Mittel eignen sich dünnflüssige Sili­conöle, beispielsweise Polydimethylsiloxane, mit Viskositäten von 20 bis 1000 mPas, vorzugsweise 30 bis 500 mPas und insbesondere 50 bis 150 mPas bei 20 °C. Ihr Anteil an den Mitteln beträgt 0,2 bis 2,5 Gew.-%, vorzugsweise 0,3 bis 1,8 Gew.-% und insbeson­dere 0,7 bis 1,3 Gew.-%.Low viscosity silicone oils, for example polydimethylsiloxanes, with viscosities of 20 to 1000 mPas, preferably 30 to 500 mPas and in particular 50 to 150 mPas at 20 ° C. are suitable for the agents according to the invention. Their proportion of the agents is 0.2 to 2.5% by weight, preferably 0.3 to 1.8% by weight and in particular 0.7 to 1.3% by weight.

EmulgatorenEmulsifiers

Als Emulgatoren eignen sich übliche anionische, vorzugsweise aber nichtionische Emulgatoren, die zu Öl-in-Wasser-Emulsionen führen. Als anionische Emulgatoren kommen die Alkali-, Ammonium-, Amin- ­und Erdalkalisalze langkettiger Alkylsulfate, Sulfonate und Phosphorsäurepartialester in Frage. Insbesondere eignen sich die Salze von Schwefelsäurehalbestern oder Phosphorsäurepartialestern der linearen Alkohole oder Oxoalkohole mit jeweils 12 bis 18 C-­Atomen oder der Polyglykomonoalkylether mit 12 bis 18 C-Atomen in der Alkylgruppe sowie die 12 bis 20 C-Atome enthaltenden Ole­finsulfonate, Estersulfonate und Alkansulfonate, die Alkylbenzol­sulfonate mit 6 bis 16 C-Atomen in den Alkylgruppen, die Sulfo­nate der Polyglykolmonoalkylether mit 12 bis 18 C-Atomen in den Alkylgruppen und die Salze der Fettsäuren mit 12 bis 18 C-­Atomen. Vorzugsweise werden von diesen anionischen Emulgatoren Fettsäureaminsalze, insbesondere Salze der Alkanol- oder Alka­nolalkylamine mit 2 bis 7 C-Atomen verwendet.Suitable anionic emulsifiers are conventional anionic, but preferably nonionic, emulsifiers which lead to oil-in-water emulsions. The alkali metal, ammonium, amine and alkaline earth metal salts of long-chain alkyl sulfates, sulfonates and phosphoric acid partial esters are suitable as anionic emulsifiers. Particularly suitable are the salts of sulfuric acid semiesters or phosphoric acid partial esters of linear alcohols or oxo alcohols each having 12 to 18 carbon atoms or the polyglycomonoalkyl ethers having 12 to 18 carbon atoms in the alkyl group and the olefin sulfonates, ester sulfonates and alkanesulfonates containing 12 to 20 carbon atoms, the alkylbenzenesulfonates with 6 to 16 carbon atoms in the alkyl groups, the sulfonates of the polyglycol monoalkyl ethers with 12 to 18 carbon atoms in the alkyl groups and the salts of the fatty acids with 12 to 18 carbon atoms. Of these anionic emulsifiers, fatty acid amine salts, in particular salts of alkanolamines or alkanolalkylamines having 2 to 7 carbon atoms, are preferably used.

Zu den geeigneten nichtionischen Emulgatoren zählen bespielsweise die Sorbitanester der höheren Fettsäuren sowie die Alkylenoxy­addukte an höhere lineare ein- und mehrwertige Alkohole, Alkyl­phenole, langkettige Carbonsäuren, Carbonsäureamide und Hydroxy­ fettsäuren mit 10 bis 24 C-Atomen sowie an Fettsäureglycerin- ­oder Sorbitanester. Vorzugsweise werden als nichtionische Emul­gatoren die Addukte von 5 bis 40 Mol Ethylenoxid an langkettige, insbesondere primäre Alkohole mit 12 bis 18 C-Atomen und an Fett­säuresorbitanester eingesetzt. Besonders bevorzugt sind die Addukte von 5 bis 20 Mol EO an Fettsäuresorbitanester.Suitable nonionic emulsifiers include, for example, the sorbitan esters of higher fatty acids and the alkyleneoxy adducts with higher linear mono- and polyhydric alcohols, alkylphenols, long-chain carboxylic acids, carboxamides and hydroxy fatty acids with 10 to 24 carbon atoms and on fatty acid glycerol or sorbitan esters. The adducts of 5 to 40 mol of ethylene oxide with long-chain, in particular primary alcohols with 12 to 18 carbon atoms and with fatty acid sorbitan esters are preferably used as nonionic emulsifiers. The adducts of 5 to 20 mol EO of fatty acid sorbitan esters are particularly preferred.

Der Anteil der Emulgatoren an der Gesamtemulsion beträgt im all­gemeinen 0,05 bis 2 Gew.-%, vorzugsweise o,1 bis 0,8 Gew.-% und insbesondere 0,15 bis 0,4 Gew.-% unabhängig davon, ob ein einzelner Emulgator oder ein Gemisch mehrerer Emulgatoren ver­wendet wird.The proportion of emulsifiers in the total emulsion is generally 0.05 to 2% by weight, preferably 0.1 to 0.8% by weight and in particular 0.15 to 0.4% by weight, regardless of whether a single emulsifier or a mixture of several emulsifiers is used.

PolyacrylsäurePolyacrylic acid

Die in den Mitteln enthaltene Polyacrylsäure dient einerseits als Konsistenzgeber, andererseits aber auch als Suspendierhilfsmittel und ist mit verantwortlich dafür, daß die Mittel nach dem Ab­trocknen leicht und rückstandsfrei zu polieren sind. Geeignet sind Polyacrylsäuren mit mittleren Molekulargewichten zwischen 0,8 × 10⁶ und 5 × 10⁶, vorzugsweise 1 × 10⁶ bis 4 × 10⁶. Das Polymere wird vorzugsweise in der sauren Form bei der Her­stellung der Mittel eingesetzt, liegt aber in den fertigen Mitteln im allgemeinen in teilneutralisierter Form vor. Der Anteil der Polyacrylsäure in den Mitteln beträgt o,1 bis 3 Gew.-%, vorzugsweise 0,3 bis 1,5 Gew.-% und insbesondere 0,4 bis 0,8 Gew.-%.The polyacrylic acid contained in the agents serves on the one hand as a consistency agent, but on the other hand also as a suspending agent and is responsible for the fact that the agents can be polished easily and without residue after drying. Polyacrylic acids with average molecular weights between 0.8 × 10⁶ and 5 × 10⁶, preferably 1 × 10⁶ to 4 × 10⁶, are suitable. The polymer is preferably used in the acidic form in the preparation of the compositions, but is generally present in the finished compositions in a partially neutralized form. The proportion of polyacrylic acid in the compositions is 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight and in particular 0.4 to 0.8% by weight.

AlkalisierungsmittelAlkalizing agent

Die Alkalisierungsmittel haben die Aufgabe, dem fertigen Glas­reinigungsmittel im Zusammenspiel mit den enthaltenen Säuren einen neutralen bis schwach alkalischen pH-Wert, vorzugsweisezwischen 7,5 und 9,5 zu geben. Geeignet sind beispielsweise alkalisch reagierende Alkalimetallsalze, Ammoniak sowie Alkanol-­amine und Alkanolalkylamine mit 2 bis 7 C-Atomen. Die Menge an Alkalisierungsmitteln richtet sich in erster Linie nach der Menge der Polyacrylsäure, die in den Mitteln enthalten ist. Üblicherweise werden nicht mehr als 2 Gew.-%, vorzugsweise zwischen 0,05 und 1 Gew.-% an Alkalisierungsmitteln verwendet.The task of the alkalizing agents is to give the finished glass cleaning agent, in interaction with the acids contained, a neutral to slightly alkaline pH, preferably between 7.5 and 9.5. Alkali metal salts, ammonia and alkanolamines and alkanolalkylamines having 2 to 7 carbon atoms, for example, are suitable. The amount of Alkalizing agents depend primarily on the amount of polyacrylic acid contained in the agents. Usually no more than 2% by weight, preferably between 0.05 and 1% by weight, of alkalizing agents is used.

HilfsstoffeAuxiliaries

Weiterhin können die erfindungsgemäßen Mittel bis zu 3 Gew.-%, vorzugsweise nicht mehr als 1 Gew.-% an üblichen Hilfs- und Zu­satzstoffen enthalten. Beispiele sind Parfüm, Konservierungsmit­tel, Salze und Farbstoffe.Furthermore, the agents according to the invention can contain up to 3% by weight, preferably not more than 1% by weight, of conventional auxiliaries and additives. Examples are perfume, preservatives, salts and dyes.

Eine besonders bevorzugte Zusammensetzung des Glasreinigungs­mittels weist folgende Zusammensetzung auf:

    4 - 12 Gew.-% entaromatisiertes Benzin und/oder Isoparaffin mit Siedebereichen von 140 bis 180 °C,

    15 - 25 Gew.-% mikrokristallines Calciumcarbonat mit einer Teilchengröße, die zu 98 Gew.-% unter 100 µm liegt,
    0,7 - 1,3 Gew.-% Silikonöl mit einer Viskosität von 50 bis 150 mPas,

    0,15 - 0,4 Gew.-% Addukt aus Fettsäuresorbitanester und 5 bis 20 Mol Ethylenoxid,
    0,4 - 0,8 Gew.-% Polyacrylsäure mit mittlerem Molekulargewicht zwischen 1 × 10⁶ und 4 × 10⁶,

    0,05 - 1 Gew.-% Alkalihydroxid und

    ad 100 Gew.-% Wasser.A particularly preferred composition of the glass cleaning agent has the following composition:

4 - 12% by weight of de-aromatized gasoline and / or isoparaffin with boiling ranges from 140 to 180 ° C,

15-25% by weight of microcrystalline calcium carbonate with a particle size of 98% by weight below 100 µm,
0.7 - 1.3% by weight silicone oil with a viscosity of 50 to 150 mPas,

0.15-0.4% by weight adduct of fatty acid sorbitan ester and 5 to 20 moles of ethylene oxide,
0.4-0.8% by weight polyacrylic acid with average molecular weight between 1 × 10⁶ and 4 × 10⁶,

0.05-1% by weight alkali hydroxide and

ad 100 wt .-% water.

Bei der Herstellung der erfindungsgemäßen Mittel geht man in der Regel so vor, daß zunächst Wasser, Emulgator und gegebenenfalls weitere Hilfsstoffe vorgelegt werden und dann die Polyacrylsäure unter starkem Rühren hinzugefügt wird. Nach dem Quellen der Polyacrylsäure wird mit Alkalisierungsmittel auf den gewünschten pH-Wert eingestellt und danach das Calciumcarbonat eingerührt. Zum Schluß emulgiert man eine Mischung aus organischen Lösungs­mitteln, Silikonöl und gegebenenfalls Parfüm in die wäßrige Phase ein. Die Herstellung des Mittels kann auch in der Weise variiert werden, daß man die Polyacrylsäurelösung zunächst stark alkalisiert, ehe das Calciumcarbonat eingerührt wird und erst danach auf den gewünschten pH-Wert durch Zugabe von Säure einstellt. Die Viskosität läßt sich mit einem Brookfield-Viskosi­meter unter Verwendung der Spindel 6 bei 20 Umdrehungen pro Minute bestimmen. Das fertige pastenförmige Mittel kann in Dosen, Tuben oder Spendern aus unterschiedlichsten Materialien abgefüllt werden.In the preparation of the agents according to the invention, the procedure is generally such that water, emulsifier and, if appropriate, other auxiliaries are initially introduced and then the polyacrylic acid is added with vigorous stirring. After swelling of the polyacrylic acid, the desired pH is adjusted with alkalizing agent and the calcium carbonate is then stirred in. Finally, a mixture of organic solvents, silicone oil and optionally perfume is emulsified into the aqueous phase. The preparation of the agent can also be varied in such a way that the polyacrylic acid solution is first strongly alkalized before the calcium carbonate is stirred in and only then adjusted to the desired pH by adding acid. The viscosity can be determined with a Brookfield viscometer using the spindle 6 at 20 revolutions per minute. The finished paste-like agent can be filled in cans, tubes or dispensers made of different materials.

Die Anwendung des Mittels geschieht in der Weise, daß man das Produkt vorzugsweise mit Hilfe eines feuchten Tuches oder feuchten Schwammes großflächig auf der zu reinigenden Fläche verteilt. Man läßt das aufgetragene Mittel trocknen und entfernt dann die verbliebenen Rückstände, beispielsweise durch Abreiben mit einem Tuch, einem Vlies oder mit Papier. Die Mittel eignen sich gleichermaßen zur Reinigung von Flächen aus Glas, glänzender Keramik oder Emaille. Besonders deutlich wirken sich die Vorzüge der Mittel aber bei der Reinigung von Fenstern oder Spiegeln aus.The agent is used in such a way that the product is preferably spread over a large area on the surface to be cleaned, with the aid of a damp cloth or damp sponge. The applied agent is allowed to dry and then the remaining residues are removed, for example by rubbing with a cloth, a fleece or with paper. The agents are equally suitable for cleaning surfaces made of glass, shiny ceramics or enamel. However, the advantages of the agents have a particularly clear effect when cleaning windows or mirrors.

Beispielexample

In einem 600 l fassenden Rührkessel wurden 329 Liter Wasser, 3,4 kg einer wäßrigen Lösung eines Konservierungsmittels (Isothia­zolonderivat, 1,5 %ig) und 0,9 kg eines Emulgators (Sorbitan­monolaurat + 20 EO) vermischt und unter kräftigem Rühren langsam mit 2,3 kg einer Polyacrylsäure (mittleres Molekular­gewicht 3 × 10⁶) versetzt. Nach etwa 30 Minuten Quellzeit wurden 4,5 kg einer 10 %igen Natronlauge zugegeben und in die nun viskose Lösung 92 kg eines feinteiligen synthetischen Calcium­carbonats (mikrokristallin, mittlerer Teilchendurchmesser unter 10 µm) eingerührt. Im letzten Schritt wurde die entstandene Disper­sion mit einer Mischung aus 23 kg Isoparaffin (Siedebereich 155 bis 173 °C), 4,6 kg Silikonöl (Baysilon M 100) und 0,23 kg Par­fümöl verrührt, wobei eine stabile pastenförmige Emulsion ent­stand. Sie wies einen pH-Wert von 8,1 auf und hatte eine Visko­sität von 20 000 mPas bei 20 °C (Gemessen mit einem Brookfield-­Viskosimeter, Spindel 6, bei 20 Umdrehungen pro Minute).329 liters of water, 3.4 kg of an aqueous solution of a preservative (isothiazolone derivative, 1.5% strength) and 0.9 kg of an emulsifier (sorbitan monolaurate + 20 EO) were mixed in a 600 l stirred kettle and slowly mixed with 2 , 3 kg of a polyacrylic acid (average molecular weight 3 × 10⁶) added. After about 30 minutes of swelling time, 4.5 kg of a 10% sodium hydroxide solution were added and 92 kg of a finely divided synthetic calcium carbonate (microcrystalline, average particle diameter below 10 μm) were stirred into the now viscous solution. In the last step, the resulting dispersion was mixed with a mixture of 23 kg isoparaffin (boiling range 155 to 173 ° C), 4.6 kg silicone oil (Baysilon M 100) and 0.23 kg perfume oil, resulting in a stable paste-like emulsion. It had a pH of 8.1 and a viscosity of 20,000 mPas at 20 ° C (measured with a Brookfield viscometer, spindle 6, at 20 revolutions per minute).

Die prozentuale Zusammensetzung der Masse betrug:

Figure imgb0001
The percentage composition of the mass was:
Figure imgb0001

Für den Verkauf wurde das Mittel in Aluminiumtuben abgepackt.The product was packed in aluminum tubes for sale.

Bei der Anwendung ließ sich das Mittel mühelos mit Hilfe eines feuchten Tuches auf Glasflächen verteilen. Beim Auftrag von 2 g pro m² blieb nach dem Abtrocknen ein dünner Schleier des Putz­körpers zurück, der sich mit einem trockenen Tuch leicht voll­ständig entfernen ließ, ohne daß unangenehmer Staub entstand. Selbst ölige Anschmutzungen wurden restlos entfernt.When used, the product was effortlessly spread over glass surfaces using a damp cloth. When applying 2 g per m², a thin veil of the cleaning body remained after drying, which could easily be removed completely with a dry cloth without creating unpleasant dust. Even oily soiling was completely removed.

Ähnlich gute Reinigungseigenschaften wies ein Mittel auf, das bei ansonsten gleichem Aufbau ein gemahlenes natürliches Calcium­carbonat mit einer mittleren Teilchengröße von 2,8 µm (99,9 Gew.% unter 10 µm) enthielt.A detergent exhibited similarly good cleaning properties and, with an otherwise identical structure, contained a ground natural calcium carbonate with an average particle size of 2.8 μm (99.9% by weight below 10 μm).

Claims (9)

1. Reinigungsmittel in Pastenform mit einer Viskosität von 10 000 bis 40 000 mPas bei 20 °C, bestehend aus a) 2 - 30  Gew.-% Benzin mit Siedebereich zwischen 120 und 25o °C b) 0 - 10  Gew.-% organischem Lösungsmittel aus der Gruppe Alkohole, Ketone und Glykolether mit Siedepunkten zwischen 55 und 250 °C, wobei dessen Anteil weniger als die Hälfte des Benzinanteils ausmacht, c) 5 - 40  Gew.-% mikrokristallinem Calciumcarbonat, dessen Teilchen zu mehr als 98 Gew.-% kleiner als 300 µm sind, d) 0,2- 2,5  Gew.-% Silikonöl mit einer Viskosität von 20 - 1000 mPas, e) 0,05- 2  Gew.-% nichtionischem und/oder anionischem Emulgator für O/W-Emulsionen, f) 0,1- -3  Gew.-% Polyacrylsäure, die ein mittleres Molekulargewicht zwischen 0,8 × 10⁶ und 5 × 10⁶ aufweist, g) 0 - 2  Gew.-% Alkali aus der Gruppe alkalisch reagierende Alkalimetallsalze, Ammoniak und Alkanolamine, h) 0 - 3 Gew.-% weiteren üblichen Hilfsstoffen und i) ad 100 Gew.-% Wasser 1. Detergent in paste form with a viscosity of 10,000 to 40,000 mPas at 20 ° C, consisting of a) 2 - 30 wt .-% gasoline with boiling range between 120 and 25o ° C. b) 0-10% by weight of organic solvent from the group consisting of alcohols, ketones and glycol ethers with boiling points between 55 and 250 ° C., the proportion of which is less than half the proportion of petrol, c) 5-40% by weight of microcrystalline calcium carbonate, the particles of which are more than 98% by weight smaller than 300 µm, d) 0.2-2.5% by weight silicone oil with a viscosity of 20-1000 mPas, e) 0.05-2% by weight of nonionic and / or anionic emulsifier for O / W emulsions, f) 0.1-3% by weight of polyacrylic acid which has an average molecular weight between 0.8 × 10⁶ and 5 × 10⁶, g) 0-2% by weight of alkali from the group of alkali metal salts, ammonia and alkanolamines, h) 0-3% by weight of other customary auxiliaries and i) ad 100 wt .-% water 2. Reinigungsmittel nach Anspruch 1, bestehend aus

3 bis 20  Gew.-% der Komponente a, 0 bis 5  Gew.-% der Komponente b, 10 bis 30  Gew.-% der Komponente c, 0,3 bis 1,8  Gew.-% der Komponente d, 0,1 bis 0,8  Gew.-% der Komponente e, 0,3 bis 1,5  Gew.-% der Komponente f, 0,05 bis 1  Gew.-% der Komponente g, 0 bis 1  Gew.-% der Komponente h und ad 100  Gew.-% Wasser.2. Cleaning agent according to claim 1, consisting of

3 to 20% by weight of component a, 0 to 5% by weight of component b, 10 to 30% by weight of component c, 0.3 to 1.8% by weight of component d, 0, 1 to 0.8% by weight of component e, 0.3 to 1.5% by weight of component f, 0.05 to 1% by weight of component g, 0 to 1% by weight of the component h and ad 100 wt .-% water. 3. Reinigungsmittel nach einen der Ansprüche 1 oder 2, in dem die Komponente a) aus entaromatisiertem Benzin und/oder synthetischem Isoparaffin mit Siedebereichen von 140 bis 180 °C besteht.3. Cleaning agent according to one of claims 1 or 2, in which component a) consists of dearomatized gasoline and / or synthetic isoparaffin with boiling ranges from 140 to 180 ° C. 4. Reinigungsmittel nach einem der Ansprüche 1 bis 3, in dem die Teilchen der Komponente c) zu mehr als 98 Gew.-% kleiner als 200 µm, vorzugsweise kleiner als 100 µm sind.4. Cleaning agent according to one of claims 1 to 3, in which the particles of component c) are more than 98 wt .-% less than 200 microns, preferably less than 100 microns. 5. Reinigungsmittel nach einem der Ansprüche 1 bis 4, in dem die Komponente e) eine Viskosität von 30 bis 500 mPas, vorzugs­weise 50 bis 150 mPas aufweist.5. Cleaning agent according to one of claims 1 to 4, in which component e) has a viscosity of 30 to 500 mPas, preferably 50 to 150 mPas. 6. Reinigungsmittel nach einem der Ansprüche 1 bis 5, dessen pH-Wert zwischen 7,5 und 9,5 liegt.6. Cleaning agent according to one of claims 1 to 5, the pH of which is between 7.5 and 9.5. 7. Reinigungsmittel nach einem der Ansprüche 1 bis 6, bestehend aus a) 4 - 12  Gew.-% entaromatisiertem Benzin und/oder Isoparaffin mit Siedebereichen von 140 bis 180 °C, c) 15 - 25  Gew.-% mikrokristallinem Calciumcarbonat mit einer Teilchengröße, die zu 98 Gew.-% unter 100 µm liegt, d) 0,7- 1,3  Gew.-% Silikonöl mit einer Viskosität von 50 bis 150 mPas, e) 0,15- 0,4  Gew.-% Addukte aus Fettsäuresorbitanester und 5 bis 20 Mol Ethylenoxid, f) 0,4 - 0,8  Gew.-% Polyacrylsäure mit mittlerem Molekulargewicht zwischen 1 × 10⁶ und 4 × 10⁶, g) 0,05- 1  Gew.-% Alkalihydroxid und i) ad 100 Gew.-% Wasser. 7. Cleaning agent according to one of claims 1 to 6, consisting of a) 4 to 12% by weight of de-aromatized gasoline and / or isoparaffin with boiling ranges from 140 to 180 ° C, c) 15-25% by weight of microcrystalline calcium carbonate with a particle size of 98% by weight below 100 µm, d) 0.7-1.3% by weight of silicone oil with a viscosity of 50 to 150 mPas, e) 0.15-0.4% by weight adducts of fatty acid sorbitan ester and 5 to 20 moles of ethylene oxide, f) 0.4-0.8% by weight polyacrylic acid with average molecular weight between 1 × 10⁶ and 4 × 10⁶, g) 0.05-1% by weight alkali hydroxide and i) ad 100 wt .-% water. 8. Verwendung eines der Mittel nach Anspruch 1 bis 7 zur Reinigung von Glas- oder Keramikflächen.8. Use of one of the agents according to claim 1 to 7 for cleaning glass or ceramic surfaces. 9. Verwendung nach Anspruch 8 zur Reinigung von Fenstern oder Spiegeln.9. Use according to claim 8 for cleaning windows or mirrors.
EP87103730A 1986-03-22 1987-03-14 Glass-cleaning agent Withdrawn EP0238956A3 (en)

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