EP0249147B1 - Liquid multi-purpose cleaner - Google Patents

Liquid multi-purpose cleaner Download PDF

Info

Publication number
EP0249147B1
EP0249147B1 EP87108075A EP87108075A EP0249147B1 EP 0249147 B1 EP0249147 B1 EP 0249147B1 EP 87108075 A EP87108075 A EP 87108075A EP 87108075 A EP87108075 A EP 87108075A EP 0249147 B1 EP0249147 B1 EP 0249147B1
Authority
EP
European Patent Office
Prior art keywords
water
weight
solvents
liquid
insoluble
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87108075A
Other languages
German (de)
French (fr)
Other versions
EP0249147A1 (en
Inventor
Erich Frieser
Alexander Jainschig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0249147A1 publication Critical patent/EP0249147A1/en
Application granted granted Critical
Publication of EP0249147B1 publication Critical patent/EP0249147B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D3/43—Solvents
    • 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
    • C11D3/18—Hydrocarbons

Definitions

  • water-soluble solvents of the type of mono- and polyhydric alcohols, glycols, glycol ethers or glycol ether acetates to liquid cleaning agents are common.
  • these water-soluble solvents act as solubilizers for surfactants, but on the other hand they also offer certain advantages when cleaning surfaces that are contaminated with grease and oil.
  • European patent application 137 616 describes a liquid cleaning agent with conventional components, which contains at least 5% of a fat-removing solvent and 5 to 50% of a fatty acid or soap, the cleaning agent being a stable oil-in-water microemulsion with a pH of 6.5 and above is described.
  • a degreasing solvent is also a mixture of a non-polar solvent (terpenes, Iso-Go to CI2 paraffin oils, Ce to Ca alkylbenzenes or liquid olefins) and a polar solvent (benzyl alcohol, diethyl phthalate, dibutyl phthalate or 2- (2-butoxyethoxy ) -ethanol)) understood.
  • Cycloalkanes cyclohexane and naphtha
  • Hydrogenated naphthalenes are not among these solvents.
  • Swiss patent 160 446 relates to a process for the preparation of a cleaning paste which dissolves dirt, grease and the like and absorbs all non-water-soluble surfaces, which is characterized in that an emulsion containing carbon tetrachloride, decalin, hexalin, olive oil and water with a suspension of rice starch stirred in water until a white emulsion is formed and then as much sodium hydroxide solution and water are added as is required to obtain a white paste containing no more than 0.5% free alkali after the saponification of the olive oil.
  • a treatment agent for detaching and dispersing solidified deposits of combustion residues on machines or apparatus parts, in particular internal combustion engines which consists of an emulsifiable liquid mixture which comprises a total of 12 to 23 parts by weight of a mixture of ammonium and calcium alkylbenzenesulfonates, 50 to 70 parts by weight of hydrogenated naphthalenes and 10 to Contains 20 parts by weight of technical pyridine bases is described in DD Patent 34,996.
  • the present invention therefore relates to liquid general-purpose cleaning agents containing anionic and / or nonionic surfactants, water-soluble builders, water-soluble solvents and terpenes, which are characterized by the addition of non-polar, water-insoluble solvents based on fully or partially hydrogenated naphthalenes.
  • alkaline components can also be added to adjust the liquid cleaning agents to pH values greater than 7, preferably 8 to 10.
  • anionic surfactants used are the usual linear alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylsulfates, alpha-sulfofatty acid methyl esters, fatty alcohol ether sulfates and fatty acids in the form of their alkali metal or amine salts.
  • Preferred nonionic surfactants are ethoxylated alcohols, acids and amines with alkyl chains of 10 to 18 carbon atoms and 4 to 20 moles of ethylene oxide in the molecule and amine oxides, such as dimethylalkylamine oxides and bis (hydroxyethyl) alkylamine oxides.
  • Inorganic or organic complexing agents from the following groups can be used as water-soluble builders: Tri or pyrophosphates; Organophosphonic acids, e.g. B. aminotrimethylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid, hydroxyethane diphosphonic acid; Aminopolycarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid; Polycarboxylic acid, such as. B. copolymers of maleic anhydride with acrylic acid, with olefins or methyl vinyl ether, polyacrylic acids, polyaldehydocarboxylic acids; monomeric carboxy acids, such as. B. citric acid, gluconic acid.
  • Organophosphonic acids e.g. B. aminotrimethylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid, hydroxyethane diphosphonic acid
  • the water-soluble solvents preferably come from the group of the aliphatic C 2 -C 3 alcohols, the glycols and the glycol ethers, but can also be solubilizing compounds such as, in particular, urea or hydrotropes such as alkylbenzenesulfonates with C 1 - Cs alkyl chains.
  • Suitable terpenes are preferably the terpene hydrocarbons from the group of the monocyclic and bicyclic monoterpenes.
  • the monocyclic monoterpenes which can be used here include alpha- and beta-terpinene, D-limonene and L-limonene, dipentene, and the bicyclic monoterpenes include alpha- and beta-pinene.
  • mixtures of mono- and bicyclic terpene hydrocarbons and the so-called pine oils that is mixtures u. a. from terpenes with 60 to 80% alpha- and beta-terpineols (see Ullmann, (Volume 16, 3rd edition, "Encyclopedia of Technical Chemistry", (1965), p. 777), give the inventive synergistic cleaning effects in combination with the water-insoluble non-polar solvents.
  • the water-insoluble non-polar solvents based on fully or partially hydrogenated naphthalenes are preferably decahydronaphthalene and tetrahydronaphthalene, but hexahydronaphthalene and octahydronaphthalene are also suitable.
  • the inventive cleaning agents have advantages in the cleaning effect even with undiluted direct application on soiled surfaces.
  • Example 21 of EP 106.266 was compared in a slightly modified form with a formula with the solvent combination according to the invention.
  • the cleaning effect was checked on white PVC film soiled with black shoe polish or black mascara in the manner described above with subsequent measurement of the degree of whiteness (R value).
  • Another outstanding feature of the cleaning agent according to the invention is the absence of residues on the cleaned surfaces, which makes subsequent wiping unnecessary.

Landscapes

  • 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)
  • Detergent Compositions (AREA)

Description

Die im Haushalt und am Arbeitsplatz vorhandenen Oberflächen aus Kunststoffen, Glas, Keramik, Edelstahl werden fast ausschließlich mit flüssigen Reinigungsmitteln gereinigt. Den herkömmlichen flüssigen Allzweckreinigungsmitteln sind jedoch in ihrer fett- und schmutzlösenden Wirkung Grenzen gesetzt, da aus Gründen der Produktstabilität meist nur begrenzte Mengen an Tensiden und Komplexbildnem eingebaut werden können. Zu hohe Anteile an diesen fett- und schmutzlösenden Substanzen führen nicht nur zu lagerunstabilen Produkten, sondern auch zum Auftreten von Produktrückständen in Form von Streifen und Flecken auf den damit gereinigten Oberflächen.The surfaces made of plastics, glass, ceramics, stainless steel in the household and at the workplace are cleaned almost exclusively with liquid cleaning agents. However, the conventional liquid all-purpose cleaning agents have limits in terms of their grease and dirt-dissolving effects, since for reasons of product stability only limited amounts of surfactants and complexing agents can usually be incorporated. Excessive proportions of these grease and dirt-dissolving substances not only lead to unstable products, but also to the appearance of product residues in the form of stripes and stains on the surfaces cleaned with them.

Der Zusatz wasserlöslicher Lösungsmittel vom Typ ein- und mehrwertiger Alkohole, Glykole, Glykolether bzw. Glykoletheracetate zu flüssigen Reinigungsmitteln ist üblich. Dabei wirken diese wasserlöslichen Lösungsmittel einerseits als Lösungsvermittler für Tenside, ergeben aber andererseits auch gewisse Vorteile bei der Reinigung von fett- und ölverschmutzten Flächen.The addition of water-soluble solvents of the type of mono- and polyhydric alcohols, glycols, glycol ethers or glycol ether acetates to liquid cleaning agents is common. On the one hand, these water-soluble solvents act as solubilizers for surfactants, but on the other hand they also offer certain advantages when cleaning surfaces that are contaminated with grease and oil.

Ebenso ist der Einbau von fettlösenden und geruchsbildenden Terpenen in flüssige Allzweckreinigungsmittel bekannt. So werden beispielsweise in der europäischen Patentanmeldung 80749 flüssige Reinigungsmittel mit einem Gehalt an Tensiden, wasserlöslichen Gerüstsubstanzen, wasserlöslichen Lösungsmitteln und Terpenen und einem weiteren Gehalt an 2-(2-Butoxyethoxy)ethanol beschrieben.The incorporation of fat-dissolving and odor-forming terpenes into liquid general-purpose cleaning agents is also known. For example, European patent application 80749 describes liquid detergents containing surfactants, water-soluble builders, water-soluble solvents and terpenes and a further content of 2- (2-butoxyethoxy) ethanol.

Kombinationen von Tensiden, wasserlöslichen Gerüstsubstanzen und wasserlöslichen Lösungsmitteln mit Mono- oder Sesqui-Terpenen und polaren Lösungsmitteln mit einer Löslichkeit im Wasser von 0,2 bis 10 % Masse, vorzugsweise Benzylalkohol, sind Gegenstand der europäischen Patentanmeldung 106266 und des europäischen Patents 40882.Combinations of surfactants, water-soluble builders and water-soluble solvents with mono- or sesqui-terpenes and polar solvents with a solubility in water of 0.2 to 10% by weight, preferably benzyl alcohol, are the subject of European patent application 106266 and European patent 40882.

In der europäischen Patentanmeldung 137 616 wird ein flüssiges Reinigungsmittel mit üblichen Bestandteilen, das wenigstens 5 % eines fettentfemenden Lösungsmittels und 5 bis 50 % einer Fettsäure oder Seife enthält, wobei das Reinigungsmittel als stabile ÖI-in-Wasser-Mikroemulsion mit einem pH-Wert von 6,5 und darüber formuliert ist, beschrieben. Unter fettentfernendem Lösungsmittel wird auch eine Mischung aus einem nichtpolaren Lösungsmittel (Terpene, Iso-Go- bis CI2-Paraffinöle, Ce- bis Ca-AIkylbenzole oder flüssige Olefine) und einem polaren Lösungsmittel (Benzylalkohol, Diethylphthalat, Dibutylphthalat oder 2-(2-Butoxyethoxy)-ethanol)) verstanden. Als Lösungsmittel werden auch Cycloalkane (Cyclohexan und Naphtha) genannt. Hydrierte Naphthaline gehören nicht zu diesen Lösungsmitteln.European patent application 137 616 describes a liquid cleaning agent with conventional components, which contains at least 5% of a fat-removing solvent and 5 to 50% of a fatty acid or soap, the cleaning agent being a stable oil-in-water microemulsion with a pH of 6.5 and above is described. A degreasing solvent is also a mixture of a non-polar solvent (terpenes, Iso-Go to CI2 paraffin oils, Ce to Ca alkylbenzenes or liquid olefins) and a polar solvent (benzyl alcohol, diethyl phthalate, dibutyl phthalate or 2- (2-butoxyethoxy ) -ethanol)) understood. Cycloalkanes (cyclohexane and naphtha) are also mentioned as solvents. Hydrogenated naphthalenes are not among these solvents.

Die schweizerische Patentschrift 160 446 betrifft ein Verfahren zur Herstellung einer Schmutz, Fett und dergleichen auflösenden und aufsaugenden Reinigungspaste für alle nicht wasserlöslichen Flächen, das dadurch gekennzeichnet ist, daß man eine Tetrachlorkohlenstoff, Decalin, Hexalin, Olivenöl und Wasser enthaltende Emulsion mit einer Suspension von Reisstärke in Wasser bis zur Bildung einer weißen Emulsion verrührt und hierauf mit soviel Natronlauge und Wasser, wie man zur Erzielung einer nach erfolgter Verseifung des Olivenöls nicht mehr als 0,5 % freies Alkali enthaltenden weißen Paste benötigt, versetzt.Swiss patent 160 446 relates to a process for the preparation of a cleaning paste which dissolves dirt, grease and the like and absorbs all non-water-soluble surfaces, which is characterized in that an emulsion containing carbon tetrachloride, decalin, hexalin, olive oil and water with a suspension of rice starch stirred in water until a white emulsion is formed and then as much sodium hydroxide solution and water are added as is required to obtain a white paste containing no more than 0.5% free alkali after the saponification of the olive oil.

Ein Behandlungsmittel zum Ablösen und Dispergieren von verfestigten Ablagerungen von Verbrennungsrückständen auf Maschinen oder Apparateteilen, insbesondere von Brennkraftmaschinen, das aus einem emulgierbaren Flüssigkeitsgemisch besteht, welches insgesamt 12 bis 23 Gewichtsteile eines Gemisches aus Ammonium- und Calciumalkylbenzolsulfonaten, 50 bis 70 Gewichtsteile hydrierter Naphthaline und 10 bis 20 Gewichtsteile technischer Pyridinbasen enthält, wird in der DD-Patentschrift 34 996 beschrieben.A treatment agent for detaching and dispersing solidified deposits of combustion residues on machines or apparatus parts, in particular internal combustion engines, which consists of an emulsifiable liquid mixture which comprises a total of 12 to 23 parts by weight of a mixture of ammonium and calcium alkylbenzenesulfonates, 50 to 70 parts by weight of hydrogenated naphthalenes and 10 to Contains 20 parts by weight of technical pyridine bases is described in DD Patent 34,996.

Im SU Erfinderschein 1 145 027 handelt es sich im wesentlichen um ein Seifenstück, das 90 bis 95 Gewichtsteile Seife, 0,5 bis 1 Gewichtsteil Polyacrylamid, 1,5 bis 3 Gewichtsteile Decalin und 3 bis 6 Gewichtsteile Galle enthält.In SU inventor's certificate 1 145 027 it is essentially a bar of soap that contains 90 to 95 parts by weight of soap, 0.5 to 1 part by weight of polyacrylamide, 1.5 to 3 parts by weight of decalin and 3 to 6 parts by weight of bile.

Es wurde nun gefunden, daß Kombinationen von Tensiden, wasserlöslichen Gerüstsubstanzen, wasserlöslichen Lösungsmitteln und Terpenen mit bestimmten unpolaren, wasserunlöslichen Lösungsmitteln in flüssigen Reinigungsmitteln synergistische Reinigungseffekte besonders an Öl- und Fettanschmutzungen zeigen.It has now been found that combinations of surfactants, water-soluble builders, water-soluble solvents and terpenes with certain non-polar, water-insoluble solvents in liquid detergents show synergistic cleaning effects, particularly on oil and grease stains.

Die vorliegende Erfindung betrifft daher flüssige Allzweckreinigungsmittel mit einem Gehalt an anionisehen und/oder nichtionischen Tensiden, wasserlöslichen Gerüstsubstanzen, wasserlöslichen Lösungsmitteln und Terpenen, die durch einen Zusatz an unpolaren, wasserunlöslichen Lösungsmitteln auf Basis von ganz oder teilweise hydrierten Naphthalinen gekennzeichnet sind.The present invention therefore relates to liquid general-purpose cleaning agents containing anionic and / or nonionic surfactants, water-soluble builders, water-soluble solvents and terpenes, which are characterized by the addition of non-polar, water-insoluble solvents based on fully or partially hydrogenated naphthalenes.

Die erfindungsgemäßen flüssigen Allzweckreinigungsmittel weisen insbesondere folgende Zusammensetzung auf:

  • 1 bis 25, vorzugsweise 3 bis 10 Gewichtsprozent an anionischen und/oder nichtionischen Tensiden,
  • 0,1 bis 10, vorzugsweise 0,5 bis 5 Gewichtsprozent an wasserlöslichen Gerüstsubstanzen,
  • 1 bis 15, vorzugsweise 5 bis 10 Gewichtsprozent an wasserlöslichen Lösungsmitteln,
  • 0,25 bis 5,0, vorzugsweise 0,5 bis 2,5 Gewichtsprozent an unpolaren, wasserunlöslichen Lösungsmitteln auf Basis von ganz oder teilweise hydrierten Naphthalinen und
  • 0,25 bis 5,0, vorzugsweise 0,5 bis 2,5 Gewichtsprozent an Terpenen,
  • wobei die Gesamtmenge der Kombination aus vorhandenem Terpenanteil mit dem unpolaren, wasserunlöslichen Lösungsmittel 0,5 bis 10, vorzugsweise 1,0 bis 5 Gewichtsprozent beträgt.
The liquid all-purpose cleaning agents according to the invention have the following composition in particular:
  • 1 to 25, preferably 3 to 10 percent by weight of anionic and / or nonionic surfactants,
  • 0.1 to 10, preferably 0.5 to 5 percent by weight of water-soluble builders,
  • 1 to 15, preferably 5 to 10 percent by weight of water-soluble solvents,
  • 0.25 to 5.0, preferably 0.5 to 2.5 percent by weight of non-polar, water-insoluble solvents based on fully or partially hydrogenated naphthalenes and
  • 0.25 to 5.0, preferably 0.5 to 2.5 percent by weight of terpenes,
  • wherein the total amount of the combination of terpene present with the non-polar, water-insoluble solvent is 0.5 to 10, preferably 1.0 to 5 percent by weight.

Gegebenenfalls können auch noch alkalisch wirkende Bestandteile zur Einstellung der flüssigen Reinigungsmittel auf pH-Werte von größer als 7, vorzugsweise 8 bis 10 zugesetzt werden.If necessary, alkaline components can also be added to adjust the liquid cleaning agents to pH values greater than 7, preferably 8 to 10.

Als anionische Tenside werden die für diese Zwecke üblichen linearen Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylsulfate, alpha-Sulfofettsäuremethylester, Fettalkoholethersulfate und Fettsäuren in Form ihrer Alkali- oder Aminsalze eingesetzt.The anionic surfactants used are the usual linear alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylsulfates, alpha-sulfofatty acid methyl esters, fatty alcohol ether sulfates and fatty acids in the form of their alkali metal or amine salts.

Als nichtionische Tenside kommen vorzugsweise ethoxylierte Alkohole, Säuren und Amine mit Alkylketten von 10 bis 18 C-Atomen und 4 bis 20 Mol Ethylenoxid im Molekül und Aminoxide, wie Dimethylalkylaminoxide und Bis(hydroxyethyl)alkylaminoxide in Betracht.Preferred nonionic surfactants are ethoxylated alcohols, acids and amines with alkyl chains of 10 to 18 carbon atoms and 4 to 20 moles of ethylene oxide in the molecule and amine oxides, such as dimethylalkylamine oxides and bis (hydroxyethyl) alkylamine oxides.

Als wasserlösliche Gerüstsubstanzen können anorganische oder organische Komplexbildner aus folgenden Gruppen eingesetzt werden:
Tri- oder Pyrophosphate; Organophosphonsäuren, z. B. Aminotrimethylenphosphonsäure, Hexamethylendiamintetramethylenphosphonsäure, Hydroxyethandiphosphonsäure; Aminopolycarbonsäuren, wie Nitrilotriessigsäure, Ethylendiamintetraessigsäure; Polycarboxylsäure, wie z. B. Copolymere von Maleinsäureanhydrid mit Acrylsäure, mit Olefinen oder Methylvinylether, Polyacrylsäuren, Polyaldehydocarbonsäuren; monomere Carboxysäuren, wie z. B. Zitronensäure, Gluconsäure.Inorganic or organic complexing agents from the following groups can be used as water-soluble builders:
Tri or pyrophosphates; Organophosphonic acids, e.g. B. aminotrimethylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid, hydroxyethane diphosphonic acid; Aminopolycarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid; Polycarboxylic acid, such as. B. copolymers of maleic anhydride with acrylic acid, with olefins or methyl vinyl ether, polyacrylic acids, polyaldehydocarboxylic acids; monomeric carboxy acids, such as. B. citric acid, gluconic acid.

Alle Komplexbildner werden in Form ihrer Alkalisalze eingesetzt.All complexing agents are used in the form of their alkali salts.

Die wasserlöslichen Lösungsmittel stammen vorzugsweise aus der Gruppe der aliphatischen C2 - C3-Alkohole, der Glykole und der Glykolether, können aber auch lösungsvermittelnde Verbindungen sein wie insbesondere Harnstoff oder Hydrotrope wie Alkylbenzolsulfonate mit C1- Cs-Alkylketten.The water-soluble solvents preferably come from the group of the aliphatic C 2 -C 3 alcohols, the glycols and the glycol ethers, but can also be solubilizing compounds such as, in particular, urea or hydrotropes such as alkylbenzenesulfonates with C 1 - Cs alkyl chains.

Zum Einstellen des pH-Wertes eignen sich Ätzalkali, Ätznatron, Alkali-Carbonate, Ammoniak. Vorzugsweise setzt man aus Stabilitätsgründen Mono-, Di- oder Triethanolamin ein.Caustic alkali, caustic soda, alkali carbonates, ammonia are suitable for adjusting the pH. Mono-, di- or triethanolamine is preferably used for reasons of stability.

Die Einstellung eines pH-Wertes über 7 ist wegen der stärker negativen Aufladung von Schmutz und Substrat und dadurch einer verstärkten gegenwertigen elektrostatischen Abstoßung von Vorteil.Setting a pH value above 7 is advantageous because of the more negative charging of dirt and substrate and thus an increased equivalent electrostatic repulsion.

Geeignete Terpene sind vorzugsweise die Terpenkohlenwasserstoffe aus der Gruppe der monocyclischen und bicyclischen Monoterpene. Zu den verwendbaren monocyclischen Monoterpenen zählen hier alpha- und beta-Terpinen, D-Limonen und L-Limonen, Dipenten, zu den bicyclischen Monoterpenen alpha- und beta-Pinen. Aber auch Mischungen von mono- und bicyclischen Terpenkohlenwasserstoffen sowie die sogenannten Pineöle, das heißt Mischungen u. a. aus Terpenen mit 60 bis 80 % alpha- und beta-Terpineolen (siehe Ullmann,(Band 16, 3. Auflage,"Encyclopädie der techischen Chemie",(1965), S. 777), ergeben die erfindungsgemäßen synergistischen Reinigungseffekte in Kombination mit den wasserunlöslichen unpolaren Lösungsmitteln.Suitable terpenes are preferably the terpene hydrocarbons from the group of the monocyclic and bicyclic monoterpenes. The monocyclic monoterpenes which can be used here include alpha- and beta-terpinene, D-limonene and L-limonene, dipentene, and the bicyclic monoterpenes include alpha- and beta-pinene. But also mixtures of mono- and bicyclic terpene hydrocarbons and the so-called pine oils, that is mixtures u. a. from terpenes with 60 to 80% alpha- and beta-terpineols (see Ullmann, (Volume 16, 3rd edition, "Encyclopedia of Technical Chemistry", (1965), p. 777), give the inventive synergistic cleaning effects in combination with the water-insoluble non-polar solvents.

Die wasserunlöslichen unpolaren Lösungsmittel auf Basis von ganz oder teilweise hydrierten Naphthalinen sind aus kommerziellen Gründen vorzugsweise Dekahydronaphthalin und Tetrahydronaphthalin, aber auch Hexahydronaphthalin und Octahydronaphthalin kommen in Betracht.For commercial reasons, the water-insoluble non-polar solvents based on fully or partially hydrogenated naphthalenes are preferably decahydronaphthalene and tetrahydronaphthalene, but hexahydronaphthalene and octahydronaphthalene are also suitable.

Der Nachweis der synergistischen Wirkung der Kombination von wässerunlöslichen cycloaliphatischen Kohlenwasserstoffen und Terpenen geht aus den nachstehenden Beispielen hervor.The following examples demonstrate the synergistic effect of the combination of water-insoluble cycloaliphatic hydrocarbons and terpenes.

BeispieleExamples

Weiße PVC-Folie wurde mit schwarzer Schuhcreme bestrichen und dann anschließend 6 ml der Test-Reiniger mittels Kunststoffschwamm auf das Wischgerät (vgl. E. Kiewert, Seifen, Öle, Fett, Wachse 107 (1981) 35) verteilt. Nach jeweils 10 Hin- und Hergängen - also der eigentlichen Reinigung - wurde die PVC-Folie unter fließendem Wasser abgespült und luftgetrocknet. Anschließend wurde der Weißgrad der PVC-Folie ermittelt. (R = Remissionswert, gemessen mittels Farbmeßgerät LF 90 Firma Dr. Lange).White PVC film was coated with black shoe polish and then 6 ml of the test cleaner was spread onto the wiper using a plastic sponge (cf. E. Kiewert, soaps, oils, fat, waxes 107 (1981) 35). After every 10 round trips - i.e. the actual cleaning - the PVC film was rinsed under running water and air-dried. The degree of whiteness of the PVC film was then determined. (R = reflectance value, measured using an LF 90 color measuring device from Dr. Lange).

Beispiel 1example 1

Produkt 17,0% lineares Ca-CIs-Alkylbenzolsufonat, Na-Salz

  • 1,0% Addukt von 10 Mol Ethylenoxid an 1 Mol C16-C18-Fettalkohol
  • 0,4% Aminotrimethylenphosphonsäure, Na-Salz
  • 6,0% Isopropanol
  • Rest: ad 100 % Wasser; pH-Wert 10 mit Triethanolamin eingestellt.
    Figure imgb0001
    Der Synergismus der erfindungsgemäß zugesetzten Kombination ist deutlich erkennbar.
Product 17.0% linear C a -C I s alkylbenzenesulfonate, Na salt
  • 1.0% adduct of 10 moles of ethylene oxide with 1 mole of C 16 -C 18 fatty alcohol
  • 0.4% aminotrimethylenephosphonic acid, Na salt
  • 6.0% isopropanol
  • Rest: ad 100% water; pH 10 adjusted with triethanolamine.
    Figure imgb0001
    The synergism of the combination added according to the invention is clearly recognizable.

Beisciel 2Example 2

Produkt II 4,0 % Na-C14-C17 Alkansulfonat, Na-Salz

  • 2,0 % Addukt von 7 Mol Ethylenoxid an 1 Mol C13-C15-Oxoalkohol
  • 1,0 % Na-Seife aus Laurinsäure (C12= 93 %)
  • 3,0 % Na-Citrat
  • 3,0 % Na-Carbonat
  • 1,5 % Na-Cumolsulfonat
  • Rest: ad 100 % Wasser
Product II 4.0% Na-C 14 -C 17 alkanesulfonate, Na salt
  • 2.0% adduct of 7 moles of ethylene oxide with 1 mole of C 13 -C 15 oxo alcohol
  • 1.0% Na soap from lauric acid (C 12 = 93%)
  • 3.0% Na citrate
  • 3.0% Na carbonate
  • 1.5% Na cumene sulfonate
  • Rest: ad 100% water

Anstelle von Schuhcreme wurde die PVC-Folie diesmal mit schwarzer Wimpemtusche angeschmutzt:

Figure imgb0002
Instead of shoe polish, the PVC film was soiled this time with black mascara:
Figure imgb0002

Beispiel 3Example 3

Produkt III 5,0 % lineares C9-C13-Alkylbenzolsulfonat, Na-Salz

  • 2,0 % Addukt von 7 Mol Ethylenoxid an 1 Mol C13-C15-Oxoalkohol
  • 2,0 % K-Pyrophosphat
  • 8,0 % Isopropanol
  • Rest: Wasser
Figure imgb0003
 Product III 5.0% linear C 9 -C 13 alkylbenzenesulfonate, Na salt
  • 2.0% adduct of 7 moles of ethylene oxide with 1 mole of C 13 -C 15 oxo alcohol
  • 2.0% K pyrophosphate
  • 8.0% isopropanol
  • Rest: water
Figure imgb0003

Die erfinderischen Reinigungsmittel weisen auch bei unverdünnter direkter Anwendung auf verschmutzten Flächen Vorteile in der Reinigungswirkung auf.The inventive cleaning agents have advantages in the cleaning effect even with undiluted direct application on soiled surfaces.

Beispiel 4Example 4

Auch die Reinigungswirkung der erfindungsgemäßen Reinigungsmittel gegenüber den in der EP 106.266 genannten Formulierungen ist günstiger. Hierbei wurde das dort angeführte Beispiel 3 der Reinigungswirkung einer erfindungsgemäßen Formulierung gegenübergestellt:

Figure imgb0004
The cleaning action of the cleaning agents according to the invention compared to the formulations mentioned in EP 106,266 is also more favorable. Example 3 of the cleaning effect of a formulation according to the invention was compared here:
Figure imgb0004

Des weiteren wurde das Beispiel 21 der EP 106.266 in leicht geänderter Form vergleichsweise einer Formel mit der erfindungsgemäßen Lösungsmittelkombination gegenübergestellt.

Figure imgb0005
Furthermore, Example 21 of EP 106.266 was compared in a slightly modified form with a formula with the solvent combination according to the invention.
Figure imgb0005

Die Überprüfung der Reinigungswirkung erfolgte an mit schwarzer Schuhcreme bzw. schwarzer Wimperntusche angeschmutzer weißer PVC-Folie in der weiter oben beschriebenen Art mit anschließender Messung des Weißgrades (R-Wert).

Figure imgb0006
The cleaning effect was checked on white PVC film soiled with black shoe polish or black mascara in the manner described above with subsequent measurement of the degree of whiteness (R value).
Figure imgb0006

Herausragend bei dem erfindungsgemäßen Reinigungsmittel ist auch die Rückstandsfreiheit der gereinigten Flächen, die ein Nachwischen erübrigt.Another outstanding feature of the cleaning agent according to the invention is the absence of residues on the cleaned surfaces, which makes subsequent wiping unnecessary.

Claims (5)

1. Liquid all-purpose cleaning preparations containing anionic and/or nonionic surfactants, water-soluble builders, water-soluble solvents and terpenes, characterized in that they contain an addition of apolar, water-insoluble solvents based on completely or partially hydrogenated naphthalenes.
2. Liquid cleaning preparations as claimed in claim 1, characterized in that they contain decahydronaphthalene or tetrahydronaphthalene as the apolar water-insoluble solvent.
3. Liquid cleaning preparations as claimed in claims 1 and 2, characterized in that they contain from 0.25 to 5.0 and preferably from 0.5 to 2.5% by weight of the apolar water-insoluble solvents.
4. Liquid cleaning preparations as claimed in claims 1 and 2, characterized in that the total quantity of the combination of terpene with the apolar water-insoluble solvent is from 0.5 to 10% by weight and preferably from 1.0 to 5% by weight.
5. Liquid cleaning preparations as claimed in claims 1 and 2, characterized in that the pH value is above 7 and preferably from 8 to 10.
EP87108075A 1986-06-12 1987-06-04 Liquid multi-purpose cleaner Expired - Lifetime EP0249147B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0160186A AT385769B (en) 1986-06-12 1986-06-12 LIQUID ALL-PURPOSE CLEANER
AT1601/86 1986-06-12

Publications (2)

Publication Number Publication Date
EP0249147A1 EP0249147A1 (en) 1987-12-16
EP0249147B1 true EP0249147B1 (en) 1990-05-09

Family

ID=3516942

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87108075A Expired - Lifetime EP0249147B1 (en) 1986-06-12 1987-06-04 Liquid multi-purpose cleaner

Country Status (5)

Country Link
US (1) US4790951A (en)
EP (1) EP0249147B1 (en)
AT (1) AT385769B (en)
DE (1) DE3762631D1 (en)
ES (1) ES2015007B3 (en)

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5340407A (en) * 1988-02-08 1994-08-23 Petroferm Inc. Process of removing soldering flux and/or adhesive tape residue from a substrate
EP0354027A3 (en) * 1988-08-04 1991-02-06 Envirosolv Inc. Biodegradable, non-toxic, nonhazardous solvent composition
DE4003700A1 (en) * 1989-07-11 1991-01-24 Scheidel Georg Gmbh PREPARATION FOR REMOVING COATINGS AND ADHESIVES
US5156760A (en) * 1990-06-25 1992-10-20 Marchemco, Inc. Surface cleaning compositions
US5248343A (en) * 1990-12-07 1993-09-28 Golden Technologies Company, Inc. Method for finishing metal containers
US5271773A (en) * 1990-12-07 1993-12-21 Golden Technologies Company, Inc. Process for cleaning articles with an aqueous solution of terpene and recycle water after separation
JPH06511515A (en) * 1990-12-07 1994-12-22 ゴールデン　テクノロジーズ　カンパニー，インコーポレイテッド Metal surface finishing method using terpenes
US5496585A (en) * 1990-12-07 1996-03-05 Golden Technologies Company, Inc. Method for reducing volatile organic compound emissions
US5542983A (en) * 1990-12-07 1996-08-06 Biochem Systems Process for cleaning metal surfaces with physical emulsion of terpene and water
US5445680A (en) * 1990-12-07 1995-08-29 Golden Technologies Company, Inc. Method of decorating metal surfaces
JP2614980B2 (en) * 1991-06-14 1997-05-28 ペトロファーム インコーポレイテッド Composition and method for removing rosin soldering fluxes with terpenes and hydrocarbons
US5281354A (en) * 1991-10-24 1994-01-25 Amway Corporation Liquid cleanser composition
US5328518A (en) * 1991-12-06 1994-07-12 Golden Technologies Company, Inc. Method for separating components of liquids in industrial process
US5389156A (en) * 1991-12-10 1995-02-14 Serv-Tech, Inc. Decontamination of hydrocarbon process equipment
US5356482A (en) * 1991-12-10 1994-10-18 Serv-Tech, Inc. Process for vessel decontamination
US5425814A (en) * 1991-12-10 1995-06-20 Serv-Tech, Inc. Method for quick turnaround of hydrocarbon processing units
DE69315534T2 (en) * 1992-05-12 1998-06-18 Eastman Kodak Co ADDITIONAL FOR AN AQUEOUS PHOTOGRAPHIC STABILIZATION SOLUTION
US5525371A (en) * 1992-06-10 1996-06-11 Biochem Systems Division, A Division Of Golden Technologies Company, Inc. Method for cleaning parts soiled with oil components and separating terpenes from oil compositions with a ceramic filter
US5424010A (en) * 1993-01-06 1995-06-13 Duliba; Edward P. Light duty liquid detergent composition containing 3-methyl-3-methoxy-butanol
JPH08508523A (en) * 1993-03-30 1996-09-10 ミネソタ マイニング アンド マニュファクチャリング カンパニー Improved floor coating removal composition and method
KR960701189A (en) * 1993-03-30 1996-02-24 테릴 켄트 퀼리 CLEANING COMPOSITIONS AND METHOD OF USE
BR9406028A (en) * 1993-03-30 1995-12-26 Minnesota Mining & Mfg Composition and cleaning process
US5482563A (en) * 1993-04-06 1996-01-09 Motorola, Inc. Method for electrical assembly cleaning using a non-azeotropic solvent composition
US5510544A (en) * 1993-08-02 1996-04-23 Environmental Solvents Corporation Fluorinated terpene compounds
CN1153526A (en) * 1994-07-21 1997-07-02 美国3M公司 Concentrated cleaner compositions capable of viscosity increase upon dilution
US5462690A (en) * 1994-09-09 1995-10-31 Colgate-Palmolive Co. Liquid cleaning compositions
US5587357A (en) * 1994-09-09 1996-12-24 Colgate-Palmolive Co. Liquid cleaning compositions
GB2304111A (en) * 1995-08-04 1997-03-12 Reckitt & Colman Inc Pine oil cleaning composition
DE19638413C2 (en) * 1996-09-19 1998-09-17 J P Haas Gmbh & Co Kg Liquid detergent
US5922665A (en) * 1997-05-28 1999-07-13 Minnesota Mining And Manufacturing Company Aqueous cleaning composition including a nonionic surfactant and a very slightly water-soluble organic solvent suitable for hydrophobic soil removal
JP4516176B2 (en) * 1999-04-20 2010-08-04 関東化学株式会社 Substrate cleaning solution for electronic materials
US6849589B2 (en) 2001-10-10 2005-02-01 3M Innovative Properties Company Cleaning composition
US7229954B1 (en) * 2003-01-10 2007-06-12 Bissell Homecare, Inc. Carpet cleaning composition with citrus
TWI413155B (en) * 2005-11-22 2013-10-21 Tokyo Ohka Kogyo Co Ltd Cleaning liquid for photolithography and method of cleaning exposure equipment using the same
WO2013162926A1 (en) 2012-04-24 2013-10-31 Stepan Company Aqueous hard surface cleaners based on terpenes and fatty acid derivatives
CA3080011A1 (en) 2017-11-14 2019-05-23 Stepan Company Microemulsion flowback aids for oilfield uses

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE535335C (en) * 1926-10-27 1931-10-09 I G Farbenindustrie Akt Ges Process for the production of durable solid solutions of naphthalenesulfonic acids
BE345507A (en) * 1926-10-27
CH160446A (en) * 1931-02-11 1933-03-15 Winter Hans Process for the production of a dirt, grease and the like. Dissolving and absorbent cleaning paste.
DD34996A1 (en) * 1961-03-28 1965-01-15 Treating agents for stripping and dispersing solidified deposits and methods of treating them
US4125476A (en) * 1977-03-10 1978-11-14 Dean Ralph R Paint spray booth composition
ATE32608T1 (en) * 1980-05-27 1988-03-15 Procter & Gamble TERPEN SOLVENT MIXTURE USABLE FOR THE PREPARATION OF LIQUID CLEANING AGENT COMPOSITIONS.
US4414128A (en) * 1981-06-08 1983-11-08 The Procter & Gamble Company Liquid detergent compositions
DE3270670D1 (en) * 1981-11-12 1986-05-22 Procter & Gamble Liquid detergent compositions
SU1145027A1 (en) * 1983-01-12 1985-03-15 Химический Завод N6 Soap for washing cloth and method of obtaining same
EP0137616B1 (en) * 1983-08-11 1988-01-27 The Procter & Gamble Company Liquid detergents with solvent
US4614236A (en) * 1984-05-29 1986-09-30 Union Oil Company Of California Self-breaking foamed oil-in-water emulsion for stimulation of wells blocked by paraffinic deposits
US4597887A (en) * 1984-12-21 1986-07-01 Colgate-Palmolive Company Germicidal hard surface cleaning composition
US4612141A (en) * 1985-07-01 1986-09-16 Faurote Jr Dolph Paint removing cleaning compositions

Also Published As

Publication number Publication date
ES2015007B3 (en) 1990-08-01
US4790951A (en) 1988-12-13
ATA160186A (en) 1987-10-15
DE3762631D1 (en) 1990-06-13
AT385769B (en) 1988-05-10
EP0249147A1 (en) 1987-12-16

Similar Documents

Publication Publication Date Title
EP0249147B1 (en) Liquid multi-purpose cleaner
DE69631549T3 (en) CLEANING SOUR CLEANERS FOR HARD SURFACES
DE2819975C2 (en) Homogeneous, inherently opaque liquid cleaning agent
EP0561842B1 (en) Carpet-cleaning agent
EP0288856A2 (en) Cleaning product for hard surfaces
EP0272574A2 (en) Mixtures of liquid non-ionic surfactants
DE2600022C2 (en) Detergents and cleaning agents
DE3026090A1 (en) LIQUID DETERGENT WITH A CONTENT OF DISABLING-INHIBITING
DE69321562T3 (en) Detergent compositions with a combination of highly hydrophilic and highly hydrophobic nonionic surfactants
DE3943070A1 (en) LIQUID CLEANER FOR HARD SURFACES
EP0928829B1 (en) Cleaning of hard surfaces using rheopexic aqueous cleaning agents
DE2619668A1 (en) DETERGENT COMPOSITION
DE4210364B4 (en) Cleaning agents for hard surfaces, in particular glass
EP0197480A2 (en) Manual cleaning process of objects with hard surfaces
DE4311159A1 (en) Use of liquid concentrates for cleaning hard surfaces
EP0715647B2 (en) Liquid washing product
DE4243468A1 (en) Neutral liquid detergent (I)
WO1992015662A1 (en) Method of cleaning carpets
EP0944702B1 (en) Glass cleaning products
WO1998017774A1 (en) Method of cleaning hard surfaces using rheopectic aqueous cleaning agents
EP0900263B1 (en) Process for cleaning plastic surfaces and means for carrying out the process
DE2700640C2 (en) Detergent suitable for cold washing
DE4134973A1 (en) LIQUID CLEANING CONCENTRATE FOR HARD SURFACES
EP0095136B1 (en) Rinsing agents for use in mechanical dishwashing
DE2361448A1 (en) NEUTRAL TO WEAK ALKALINE DETERGENT DETERGENT

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE ES FR GB IT LI NL

17P Request for examination filed

Effective date: 19880509

17Q First examination report despatched

Effective date: 19890102

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB IT LI NL

REF Corresponds to:

Ref document number: 3762631

Country of ref document: DE

Date of ref document: 19900613

ET Fr: translation filed
ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910523

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19910528

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19910531

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19910601

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19910619

Year of fee payment: 5

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910630

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19910801

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19920604

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19920605

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19920630

Ref country code: CH

Effective date: 19920630

Ref country code: BE

Effective date: 19920630

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19920630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19920604

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930226

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930302

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20000301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050604