EP0713524A1 - Detergent containing non-ionic cellulose ethers - Google Patents

Detergent containing non-ionic cellulose ethers

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Publication number
EP0713524A1
EP0713524A1 EP94925416A EP94925416A EP0713524A1 EP 0713524 A1 EP0713524 A1 EP 0713524A1 EP 94925416 A EP94925416 A EP 94925416A EP 94925416 A EP94925416 A EP 94925416A EP 0713524 A1 EP0713524 A1 EP 0713524A1
Authority
EP
European Patent Office
Prior art keywords
weight
cellulose ether
groups
mpas
acid
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.)
Withdrawn
Application number
EP94925416A
Other languages
German (de)
French (fr)
Inventor
Fred Schambil
Peter Krings
Eduard Smulders
Gertrud Nienhaus
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 EP0713524A1 publication Critical patent/EP0713524A1/en
Withdrawn legal-status Critical Current

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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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • the invention relates to a detergent which contains special nonionic cellulose ethers and the use of these nonionic cellulose ethers for removing grease and oil stains.
  • Ionic and nonionic cellulose ethers have long been used as graying inhibitors (dirt carriers) in detergents.
  • the preferred cellulose ethers include salts of carboxymethyl cellulose (CMC) and methyl cellulose (MC) and mixtures of these.
  • Further known as graying inhibitors are hydroxyalkylceuloses and mixed ethers, such as methylhydroxyethylcelluloses, methylhydroxypropylcelluloses and methylcarboxymethylceuloses.
  • the invention relates in a first embodiment to a detergent which contains conventional ingredients such as surfactants, builder substances and nonionic cellulose ethers, this nonionic cellulose ether being selected from the group of methylhydroxy propyl celluloses which contain a proportion of methoxyl Groups of 15 to 35 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, based on the nonionic cellulose ether. It is preferred that the agents contain methyl hydroxypropyl celluloses which contain 20 to 30% by weight of methoxyl groups and 2 to 10% by weight of hydroxypropoxyl groups, in particular 5 to 8% by weight. %, each based on the nonionic cellulose ether.
  • the nonionic cellulose ether is usually obtained in the form of a powdery to granular compound which contains sodium chloride as an impurity. It has been shown that a certain amount of sodium chloride does not have a negative effect on the improvement of fat and oil washability. However, it is preferred that the nonionic cellulose ether compound used in the agents according to the invention does not contain sodium chloride in amounts not exceeding 10% by weight. Agents which contain a nonionic cellulose ether compound with a sodium chloride content of at most 5% by weight, preferably at most 2% by weight and in particular at most 1% by weight, based in each case on the compound, are particularly advantageous.
  • the detergents contain a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains 6 to 8% by weight of water and 4 to 10% by weight of sodium chloride.
  • the content of the methoxyl groups in the methylhydroxypropyl cellulose is 25 to 30% by weight and preferably 25 to 29% by weight, the content of hydroxypropoxyl groups is 5 to 10% by weight and preferably 5.5 up to 8% by weight.
  • the detergents contain a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains water as stated above, but only 0.2 to 5% by weight, preferably up to a maximum of 2% by weight, of sodium chloride.
  • the content of the methoxyl groups and the hydroxypropoxyl groups in the methylhydroxypropyl cellulose is values as stated above.
  • a detergent which contains a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains water in amounts of 5 to 10% by weight, preferably 8% by weight, and sodium chloride in the small amounts such as stated above up to a maximum of 5% by weight and preferably up to a maximum of 2% by weight contains.
  • the content of the methoxyl groups here is only in the range from 20 to 25% by weight, preferably from 21 to 24% by weight, while the content of hydroxypropoxyl groups continues to be between 5 and 10% by weight. preferably between 6 and 8% by weight.
  • the bulk density of these compounds is generally 300 to 600 g / l.
  • the aqueous solutions of nonionic cellulose ethers must not be too viscous in order to achieve optimal fat and oil washability. It is therefore preferred that the nonionic cellulose ether compound used according to the invention at 20 ° C. in a 2% by weight aqueous solution has a viscosity between 40 and 125 mPas (Brookfield viscometer, 20 ° C., spindle 3, 4 or 5, 20 revolutions per minute), preferably between 45 and 100 mPas and in particular below 100 mPas, for example 45 to 60 mPas.
  • the preferably solid, powdery to granular detergents can have a bulk density between 300 and about 1000 g / 1 and by any known production process, for example by simple mixing of the components, spray drying, granulation, roller compaction, by extrusion or by combination are produced by several of these processes.
  • the detergents can also contain all conventional known detergent ingredients.
  • anionic and nonionic, but also cationic, zwitterionic or a photic surfactants include primarily anionic and nonionic, but also cationic, zwitterionic or a photic surfactants, inorganic and organic, in particular biodegradable, organic builder substances, inorganic alkaline and neutral salts, bleaching agents, in particular peroxy bleaching agents and bleach activators, enzymes, enzyme stabilizers, Foam inhibitors, if appropriate further ionic or nonionic graying inhibitors, for example commercially available carboxymethyl celluloses, methyl celluloses and / or polyvinylpyrrolidone, optical brighteners, colorants and fragrances and pearlescent agents.
  • anionic surfactants used are those of the sulfonate and / or sulfate type.
  • the known C9-C13-alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates are preferably used as surfactants of the sulfonate type Consideration.
  • Esters of ⁇ -sulfofatty acids or the disalts of ⁇ -sulfofatty acids are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0 , 3 to 2 moles of glycerol can be obtained.
  • Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o -C2 ⁇ ⁇ 0xoalcohols, and those of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • soaps for example saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical has a methyl or linear branching, preferably in the 2-position may be, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms, for example from coconut, palm, tallow or oleyl alcohol, and average, are preferred in particular 2 to 8 EO per mole of alcohol is preferred.
  • alkylglycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 ° C.
  • -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.
  • Another class of preferably used nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as are described, for example, in Japanese Patent Application JP 58/217598 or which are preferably described in International Patent Application WO A-90/13533 described methods can be produced.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R ⁇ CO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 is up to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known Substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • Phosphates, zeolites and layered silicates are used as inorganic builder substances.
  • the preferably used fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite NaA in detergent quality.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups, Ci2-Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measuring method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x 02 ⁇ + ⁇ * yH20, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3.
  • both .beta.- and ⁇ '-sodium disilicates Na2S ⁇ ' 2 ⁇ 5 * yH2 ⁇ preferred.
  • Further substitutes or partial substitutes for the zeolite are non-crystalline layered silicates of natural and synthetic origin, such as bentonites and smectites.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as Ci tronic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • biodegradable terpolymers for example those which are salts of acrylic acid and maleic acid and vinyl alcohol as monomers or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives.
  • biodegradable terpolymers for example those which are salts of acrylic acid and maleic acid and vinyl alcohol as monomers or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives.
  • Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the middle is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group and amino acids and / or their salts.
  • the alkali metal carbonates are partially or completely replaced by glycine or glycinate.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate.
  • the bleach activators contain bleaching agents in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N '.N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-C24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with siliconized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes.
  • the salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and Diethylene tria in pentamethylene phosphonate used in amounts of 0.1 to 1.5 wt .-%.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases and oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • the application test was carried out in a conventional household washing machine (Miele W 717) in the entrance washing process at a temperature of 40 ° C. and a load of 3.5 kg of clean household laundry and white test strips of the fabric specified below, which had already been washed three times with the respective fabrics Pre-washed and then stained with the grease and oil-containing stains also given below (aging 3 days), and a liquor of 17 l tap water with a hardness of 16 ° d.
  • the detergent dosage in Examples 1 and 2 was 96 g each. In the first example, 99 parts by weight of a commercially available color detergent were each mixed with 1 part by weight of the cellulose ethers given below.
  • the example was tested with 96 g of the same color detergent without the addition of the specified cellulose ethers (VI).
  • these tests were repeated with a commercial universal detergent with and without the addition of cellulose ether (V2).
  • the lightening of the tissue test strips was measured at 460 nm (suppression of the brightener effect).
  • Bicycle oil 12 drops of a mass of 10 g of dusty skin fat on 100 ml of oil on PES (very dirty) (III) 6 drops of this mass on PES (slightly dirty) (IV)
  • Methyl hydroxypropyl cellulose compound (MHPC1) containing 88% by weight of MHPC with a methoxyl group content of approximately 27% by weight and a hydroxypropoxyl group content of approximately 6.5% by weight on MHPC, 5% by weight sodium chloride and 7% by weight water.
  • the viscosity of a 2% by weight aqueous solution of MHPC1 at 20 ° C. was 50 mPas.
  • Methyl hydroxypropyl cellulose compound containing 91% by weight MHPC with a content of methoxyl groups of approx. 28% by weight and a content of hydroxypropoxyl groups of approx. 6% by weight, based on MHPC , 1 wt .-% sodium chloride and 8 wt .-% water.
  • the viscosity of a 2% by weight aqueous solution of MHPC2 at 20 ° C. was 50 mPas.
  • Methyl hydroxypropyl cellulose compound containing 91% by weight MHPC with a content of methoxyl groups of approx. 22% by weight and a content of hydroxypropoxyl groups of approx. 7.5% by weight on MHPC, 1% by weight sodium chloride and 8% by weight water.
  • the viscosity of a 2% by weight aqueous solution of MHPC3 at 20 ° C. was 100 mPas.
  • Methyl cellulose compound (MC) containing 88% by weight MC, 5% by weight sodium chloride and 7% by weight water.
  • the viscosity of a 2% by weight aqueous solution of MC at 20 ° C. was 40 mPas.
  • Carboxymethyl cellulose sodium salt (CMC) commercial form of offer
  • Tables 1 and 2 show the superiority of the methyl hydroxypropyl celluloses MHPC1 and MHPC2 used according to the invention over methyl celluloses and carboxymethyl celluloses both in the case of heavy and also slight contamination of the test tissue by motor oil. With the strong lipstick stains, significant advantages over MC and CMC for MHPC 1 to 3 can be seen.
  • Table 1 Engine oil
  • V1 CMC 99: 1 43.9 43.8
  • V1 MC 99: 1 67.9 70.6
  • V1 CMC 99: 1 56.4 72.3
  • V1 MC 99: 1 59.0 74.2
  • Tables 3 to 5 show the superiority of the methyl hydroxypropyl cellulose MHPCl used according to the invention over methyl celluloses and carboxymethyl celluloses both with heavy and with slight soiling of the test fabrics by motor oil and bicycle oil.
  • MHPC2 also shows if there are significant advantages for both heavy and light soiling from bicycle oil.
  • MHPC2 and MHPC3 also show advantages when slightly contaminated by motor oil. With lipstick soiling, significant advantages over MC and CMC for MHPC 1 to 3 can be seen.
  • V1 CMC 99: 1 49.5 49.4

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

The washing of fat and oil from textiles can be improved by the use of certain non-ionic cellulose ethers. These non-ionic cellulose ethers are methyl hydroxy propyl celluloses having a proportion of methoxyl groups of 15 to 35 wt % and hydroxypropoxyl groups of 1 to 15 wt % in relation to the non-ionic cellulose ether.

Description

"Waschmittel, enthaltend nichtionische Celluloseether" "Detergent containing nonionic cellulose ethers"
Die Erfindung betrifft ein Waschmittel, welches spezielle nichtionische Celluloseether enthält, sowie die Verwendung dieser nichtionischen Cellu¬ loseether zur Entfernung von Fett- und Ölanschmutzungen.The invention relates to a detergent which contains special nonionic cellulose ethers and the use of these nonionic cellulose ethers for removing grease and oil stains.
Es ist allgemein bekannt, daß Fette und Öle sogenannte Problemanschmutzun- gen darstellen, die nur schwer aus Textilien zu entfernen sind. Aus dem neueren Stand der Technik sind insbesondere zwei Patentanmeldungen zu nennen, die sich mit diesem Problem befassen. Es handelt sich dabei einmal um die internationale Patentanmeldung WO-A-92/13504, in der Waschmittel beschrieben werden, welche Lipase und kationische Tenside enthalten, und zum anderen um die internationale Patentanmeldung WO-A-92/06152, in der die fettlösende Eigenschaft von Gluca iden in Waschmitteln offenbart wird.It is generally known that fats and oils are so-called problem soils that are difficult to remove from textiles. From the more recent state of the art, two patent applications that deal with this problem should be mentioned in particular. The international patent application WO-A-92/13504 describes washing agents containing lipase and cationic surfactants and the international patent application WO-A-92/06152 describes the fat-dissolving properties by Gluca iden in detergents.
Ionische und nichtionische Celluloseether werden seit langer Zeit als Ver- grauungsinhibitoren (Schmutzträger) in Waschmitteln eingesetzt. Zu den bevorzugt eingesetzten Celluloseethern gehören Salze der Carboxymethyl- cellulose (CMC) und Methylcellulose (MC) sowie Mischungen aus diesen. Wei¬ terhin sind als Vergrauungsinhibitoren Hydroxyalkylce11ulosen und Misch- ether, wie Methylhydroxyethylcellulosen, Methylhydroxypropylcellulosen und Methylcarboxymethy1ce11ulosen bekannt.Ionic and nonionic cellulose ethers have long been used as graying inhibitors (dirt carriers) in detergents. The preferred cellulose ethers include salts of carboxymethyl cellulose (CMC) and methyl cellulose (MC) and mixtures of these. Further known as graying inhibitors are hydroxyalkylceuloses and mixed ethers, such as methylhydroxyethylcelluloses, methylhydroxypropylcelluloses and methylcarboxymethylceuloses.
Es wurde nun gefunden, daß die Fett- und Ölauswaschbarkeit aus Textilien in hohem Maße verbessert werden kann, wenn in den Waschmitteln bestimmte nichtionische Celluloseether eingesetzt werden.It has now been found that the fat and oil washability from textiles can be greatly improved if certain nonionic cellulose ethers are used in the detergents.
Gegenstand der Erfindung ist dementsprechend in einer ersten Ausführungs¬ form ein Waschmittel, welches übliche Inhaltsstoffe wie Tenside, Builder- substanzen und nichtionische Celluloseether enthält, wobei dieser nicht¬ ionische Celluloseether ausgewählt ist aus der Gruppe der Methylhydroxy¬ propylcellulosen, welche einen Anteil an Methoxyl-Gruppen von 15 bis 35 Gew.- und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.-%, bezogen auf den nichtionischen Celluloseether, aufweisen. Dabei ist es bevorzugt, daß die Mittel Methylhydroxypropylcellulosen ent¬ halten, welche einen Anteil an Methoxyl-Gruppen von 20 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 2 bis 10 Gew.-%, insbesondere von 5 bis 8 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, aufweisen. Der nichtionische Celluloseether wird meist in Form eines pulverförmigen bis granulären Compounds gewonnen, das als Verunreinigung Natriumchlorid enthält. Es hat sich gezeigt, daß ein Gehalt an Natriumchlorid in einem gewissen Umfang sich nicht negativ auf die Verbesserung der Fett- und Öl- auswaschbarkeit auswirkt. Es ist jedoch bevorzugt, daß das in den erfin¬ dungsgemäßen Mitteln eingesetzte nichtionische Celluloseether-Compound Natriumchlorid in Mengen nicht oberhalb von 10 Gew.-% enthält. Besonders vorteilhaft sind Mittel, welche ein nichtionisches Celluloseether-Compound mit einem Gehalt an Natriumchlorid von maximal 5 Gew.-%, vorzugsweise ma¬ ximal 2 Gew.-% und insbesondere maximal 1 Gew.-%, jeweils bezogen auf das Compound, enthalten.Accordingly, the invention relates in a first embodiment to a detergent which contains conventional ingredients such as surfactants, builder substances and nonionic cellulose ethers, this nonionic cellulose ether being selected from the group of methylhydroxy propyl celluloses which contain a proportion of methoxyl Groups of 15 to 35 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, based on the nonionic cellulose ether. It is preferred that the agents contain methyl hydroxypropyl celluloses which contain 20 to 30% by weight of methoxyl groups and 2 to 10% by weight of hydroxypropoxyl groups, in particular 5 to 8% by weight. %, each based on the nonionic cellulose ether. The nonionic cellulose ether is usually obtained in the form of a powdery to granular compound which contains sodium chloride as an impurity. It has been shown that a certain amount of sodium chloride does not have a negative effect on the improvement of fat and oil washability. However, it is preferred that the nonionic cellulose ether compound used in the agents according to the invention does not contain sodium chloride in amounts not exceeding 10% by weight. Agents which contain a nonionic cellulose ether compound with a sodium chloride content of at most 5% by weight, preferably at most 2% by weight and in particular at most 1% by weight, based in each case on the compound, are particularly advantageous.
In einer bevorzugten Ausführungsform der Erfindung enthalten die Wasch¬ mittel jedoch ein nichtionisches Celluloseether-Compound, welches außer Methylhydroxypropylcellulose 6 bis 8 Gew.-% Wasser und 4 bis 10 Gew.-% Natriumchlorid enthält. Der Gehalt der Methoxyl-Gruppen in der Methylhy- droxypropylcellulose beträgt dabei 25 bis 30 Gew.-% und vorzugsweise 25 bis 29 Gew.-%, der Gehalt an Hydroxypropoxyl-Gruppen beträgt hingegen 5 bis 10 Gew.-% und vorzugsweise 5,5 bis 8 Gew.-%.In a preferred embodiment of the invention, however, the detergents contain a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains 6 to 8% by weight of water and 4 to 10% by weight of sodium chloride. The content of the methoxyl groups in the methylhydroxypropyl cellulose is 25 to 30% by weight and preferably 25 to 29% by weight, the content of hydroxypropoxyl groups is 5 to 10% by weight and preferably 5.5 up to 8% by weight.
In einer weiteren bevorzugten Ausführungsform enthalten die Waschmittel ein nichtionisches Celluloseether-Compound, welches außer Methylhydroxy¬ propylcellulose Wasser wie oben angegeben, aber nur 0,2 bis 5 Gew.-%, vor¬ zugsweise bis maximal 2 Gew.-% Natriumchlorid enthält. Der Gehalt der Methoxyl-Gruppen und der Hydroxypropoxyl-Gruppen in der Methylhydroxypro- pylcellulose beträgt dabei Werte wie oben angegeben.In a further preferred embodiment, the detergents contain a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains water as stated above, but only 0.2 to 5% by weight, preferably up to a maximum of 2% by weight, of sodium chloride. The content of the methoxyl groups and the hydroxypropoxyl groups in the methylhydroxypropyl cellulose is values as stated above.
Ebenso ist in einer weiteren Ausführungsform der Erfindung ein Waschmittel bevorzugt, welches ein nichtionisches Celluloseether-Compound enthält, das außer Methylhydroxypropylcellulose Wasser in Mengen um 5 bis 10 Gew.-%, vorzugsweise um 8 Gew.-%, und Natriumchlorid in den geringen Mengen wie oben angegeben bis maximal 5 Gew.-% und vorzugsweise bis maximal 2 Gew.-% enthält. Der Gehalt der Methoxyl-Gruppen liegt hier aber nur im Bereich von 20 bis 25 Gew.-%, vorzugsweise von 21 bis 24 Gew.-%, während der Ge¬ halt an Hydroxypropoxyl-Gruppen weiterhin zwischen 5 und 10 Gew.-%, vor¬ zugsweise zwischen 6 und 8 Gew.-% liegt.Also preferred in a further embodiment of the invention is a detergent which contains a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains water in amounts of 5 to 10% by weight, preferably 8% by weight, and sodium chloride in the small amounts such as stated above up to a maximum of 5% by weight and preferably up to a maximum of 2% by weight contains. However, the content of the methoxyl groups here is only in the range from 20 to 25% by weight, preferably from 21 to 24% by weight, while the content of hydroxypropoxyl groups continues to be between 5 and 10% by weight. preferably between 6 and 8% by weight.
Das Schüttgewicht dieser Compounds beträgt im allgemeinen 300 bis 600 g/1.The bulk density of these compounds is generally 300 to 600 g / l.
Es hat sich auch gezeigt, daß die wäßrigen Lösungen von nichtionischen Celluloseethern nicht zu viskos sein dürfen, um eine optimale Fett- und Ölauswaschbarkeit zu erreichen. Es ist daher bevorzugt, daß das erfin¬ dungsgemäß verwendete nichtionische Celluloseether-Compound bei 20 °C in einer 2 Gew.-%igen wäßrigen Lösung eine Viskosität zwischen 40 und 125 mPas (Brookfield-Viskosimeter, 20 °C, Spindel 3, 4 oder 5, 20 Umdrehungen pro Minute), vorzugsweise zwischen 45 und 100 mPas und insbesondere unter¬ halb 100 mPas, beispielsweise 45 bis 60 mPas, aufweist.It has also been shown that the aqueous solutions of nonionic cellulose ethers must not be too viscous in order to achieve optimal fat and oil washability. It is therefore preferred that the nonionic cellulose ether compound used according to the invention at 20 ° C. in a 2% by weight aqueous solution has a viscosity between 40 and 125 mPas (Brookfield viscometer, 20 ° C., spindle 3, 4 or 5, 20 revolutions per minute), preferably between 45 and 100 mPas and in particular below 100 mPas, for example 45 to 60 mPas.
Die vorzugsweise festen, pulverförmigen bis granulären Waschmittel können ein Schüttgewicht zwischen 300 und etwa 1000 g/1 aufweisen und nach jedem beliebigen, bekannten Herstellungsverfahren, beispielsweise durch einfa¬ ches Mischen der Komponenten, Sprühtrocknung, Granulierung, Walzenkompak- tierung, durch Extrusion oder durch Kombination von mehreren dieser Ver¬ fahren hergestellt werden. Die Mittel können außerdem alle herkömmlichen bekannten Inhaltsstoffe von Waschmitteln enthalten. Hierzu zählen in erster Linie anionische und nichtionische, aber auch kationische, zwitter¬ ionische oder a photere Tenside, anorganische und organische, insbesondere biologisch abbaubare organische Buildersubstanzen, anorganische alkalische und neutrale Salze, Bleichmittel, insbesondere Peroxy-Bleichmittel und Bleichaktivatoren, Enzyme, Enzymstabilisatoren, Schauminhibitoren, gegebe¬ nenfalls weitere ionische oder nichtionische Vergrauungsinhibitoren, bei¬ spielsweise handelsübliche Carboxymethylcellulosen, Methylcellulosen und/ oder Polyvinylpyrrolidon, optische Aufheller, Färb- und Duftstoffe sowie Perlglanzmittel.The preferably solid, powdery to granular detergents can have a bulk density between 300 and about 1000 g / 1 and by any known production process, for example by simple mixing of the components, spray drying, granulation, roller compaction, by extrusion or by combination are produced by several of these processes. The detergents can also contain all conventional known detergent ingredients. These include primarily anionic and nonionic, but also cationic, zwitterionic or a photic surfactants, inorganic and organic, in particular biodegradable, organic builder substances, inorganic alkaline and neutral salts, bleaching agents, in particular peroxy bleaching agents and bleach activators, enzymes, enzyme stabilizers, Foam inhibitors, if appropriate further ionic or nonionic graying inhibitors, for example commercially available carboxymethyl celluloses, methyl celluloses and / or polyvinylpyrrolidone, optical brighteners, colorants and fragrances and pearlescent agents.
Als anionische Tenside werden meist solche vom Sulfonat- und/oder Sulfat- Typ eingesetzt. Als Tenside vom Sulfonat-Typ kommen vorzugsweise die be¬ kannten C9-Ci3-Alkylbenzolsulfonate, Olefinsulfonate und Alkansulfonate in Betracht. Geeignet sind auch Ester von α-Sulfofettsäuren bzw. die Disalze der α-Sulfofettsäuren. Weitere geeignete Aniontenside sind sulfierte Fett- säureglycerinester, welche Mono-, Di- und triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung durch ein Mono- glycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceri- den mit 0,3 bis 2 Mol Glycerin erhalten werden. Geeignete Tenside vom Sul¬ fat-Typ sind beispielsweise die Schwefelsäuremonoester aus primären Alko¬ holen natürlichen und synthetischen Ursprungs, insbesondere aus Fettalko¬ holen, z.B. aus Kokosfettalkohol, Taigfettalkohol, Oleylalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den Cιo-C2θ~0xoalkoholen, und diejenigen sekundärer Alkohole dieser Kettenlänge. Auch die Schwefelsäure¬ monoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten Alkohole, wie 2- Methyl-verzweigte Cg-Cn-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid, sind geeignet. Bevorzugte Aniontenside sind auch die Salze der Alkylsulfo- bernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäure- ester bezeichnet werden und die Monoester und/oder Diester der Sulfobern- steinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere eth¬ oxylierten Fettalkoholen darstellen. Außerdem kommen noch Seifen, bei¬ spielsweise gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure, sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Taigfettsäuren, abge¬ leitete Seifengemische. Die anionischen Tenside und Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze orga¬ nischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.Most of the anionic surfactants used are those of the sulfonate and / or sulfate type. The known C9-C13-alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates are preferably used as surfactants of the sulfonate type Consideration. Esters of α-sulfofatty acids or the disalts of α-sulfofatty acids are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0 , 3 to 2 moles of glycerol can be obtained. Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cιo -C2θ ~ 0xoalcohols, and those of secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable. Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. There are also soaps, for example saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhaf¬ terweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (E0) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2- Stellung methylverzweigt sein kann, bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkohol- resten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen bevorzugt, z.B. aus Kokos-, Palm-, Taigfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte HomologenVerteilung auf (narrow ränge ethoxylates, NRE). Außerdem können als weitere nichtionische Tenside auch Alkylglyko- side der allgemeinen Formel R0(G)x eingesetzt werden, in der R einen pri¬ mären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungs- grad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nicht¬ ionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder eth- oxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der AIkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90/13533 beschriebenen Verfahren hergestellt werden. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokos- alkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nicht¬ ionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylier- ten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (I),The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical has a methyl or linear branching, preferably in the 2-position may be, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms, for example from coconut, palm, tallow or oleyl alcohol, and average, are preferred in particular 2 to 8 EO per mole of alcohol is preferred. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition, alkylglycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 ° C. -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as are described, for example, in Japanese Patent Application JP 58/217598 or which are preferably described in International Patent Application WO A-90/13533 described methods can be produced. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
R3R3
I 2_CO-N-[Z] (I)I 2_CO-N- [Z] (I)
in der R^CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffato- men, R3 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydro- xyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfol¬ gende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.in the R ^ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 is up to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known Substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Als anorganische Buildersubstanzen werden Phosphate, Zeolithe und Schic¬ htsilikate eingesetzt. Der vorzugsweise eingesetzte feinkristalline, syn¬ thetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeo¬ lith NaA in Waschmittelqualität. Geeignet sind jedoch auch Zeolith NaX sowie Mischungen aus NaA und NaX. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtioni¬ schen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.- , bezogen auf Zeolith, an ethoxylierten Ci2-Ci8-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen, Ci2-Ci4-Fettalkoholen mit 4 bis 5 Ethylenoxid- gruppen oder ethoxylierten Isotridecanolen. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 μm (Volumenverteilung; Me߬ methode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22, insbe¬ sondere 20 bis 22 Gew.-% an gebundenem Wasser. Geeignete Substitute bzw. Teilsubstitute für Phosphate und Zeolithe sind kristalline, schichtförmige Natriumsilikate der allgemeinen Formel NaMSix02χ+ι*yH20, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kri¬ stalline Schichtsilikate sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ'-Natrium- disilikate Na2Sι'2θ5*yH2θ bevorzugt. Weitere Substitute bzw. Teilsubstitute für den Zeolith sind nicht-kristalline Schichtsilikate natürlichen und synthetischen Ursprungs wie Bentonite und Smectite.Phosphates, zeolites and layered silicates are used as inorganic builder substances. The preferably used fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups, Ci2-Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measuring method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water. Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x 02χ + ι * yH20, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3. In particular, both .beta.- and δ '-sodium disilicates Na2Sι' 2θ5 * yH2θ preferred. Further substitutes or partial substitutes for the zeolite are non-crystalline layered silicates of natural and synthetic origin, such as bentonites and smectites.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronen- säure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Ein¬ satz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Ci- tronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zucker¬ säuren und Mischungen aus diesen. Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacryl- säure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copolymere Polycarboxylate sind ins¬ besondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Insbesondere bevorzugt sind auch biologisch abbaubare Terpolymere, beispielsweise solche, die als Mo- nomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder die als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten. Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxyl¬ gruppen aufweisen, beispielsweise wie in der europäischen Patentanmeldung EP-A-0 280223 beschrieben erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Gluco- heptonsäure erhalten.Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Ci tronic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Also particularly preferred are biodegradable terpolymers, for example those which are salts of acrylic acid and maleic acid and vinyl alcohol as monomers or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives. Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
Weitere geeignete Inhaltsstoffe der Mittel sind wasserlösliche anorgani¬ sche Salze wie Bicarbonate, Carbonate, amorphe Silikate oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und amorphes Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2θ : Siθ2 von 1:1 bis 1:4,5, vorzugsweise von 1:2 bis 1:3,5, eingesetzt. Der Gehalt der Mit¬ tel an Natriumcarbonat beträgt dabei vorzugsweise bis zu 20 Gew.-%, vor¬ teilhafterweise zwischen 5 und 15 Gew.-%. Der Gehalt der Mittel an Na¬ triumsilikat beträgt im allgemeinen bis zu 10 Gew.-% und vorzugsweise zwi¬ schen 1 und 8 Gew.-%. Nach der Lehre der älteren deutschen Patentanmeldung P 43 19 578.4 können Alkalicarbonate auch durch schwefelfreie, 2 bis 11 Kohlenstoffatome und gegebenenfalls eine weitere Carboxyl- und/oder Amino- gruppe aufweisende Aminosäuren und/oder deren Salze ersetzt werden. Im Rahmen dieser Erfindung ist es dabei bevorzugt, daß ein teilweiser bis vollständiger Austausch der Alkalicarbonate durch Glycin bzw. Glycinat erfolgt. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbin¬ dungen haben das Natriumperborattetrahydrat und das Natriumperboratmono- hydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind bei¬ spielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate so¬ wie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Per- oxophthalate, Diperazelainsäure oder Diperdodecandisäure. Der Gehalt der Mittel an Bleichmitteln beträgt vorzugsweise 5 bis 25 Gew.-% und insbe¬ sondere 10 bis 20 Gew.-%, wobei vorteilhafterweise Perboratmonohydrat ein¬ gesetzt wird.Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the middle is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 1 and 8% by weight. According to the teaching of the older German patent application P 43 19 578.4, alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group and amino acids and / or their salts. In the context of this invention, it is preferred that the alkali metal carbonates are partially or completely replaced by glycine or glycinate. Among the compounds which serve as bleaching agents and supply H2O2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.
Um beim Waschen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate ein¬ gearbeitet werden. Beispiele hierfür sind mit H2O2 organische Persäuren bildende N-Acyl- bzw. 0-Acyl-Verbindungen, vorzugsweise N,N'-tetraacylier- te Diamine, ferner Carbonsäureanhydride und Ester von Polyolen wie Gluco- sepentaacetat. Der Gehalt der bleichmittelhaltigen Mittel an Bleichaktiva¬ toren liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 3 und 8 Gew.-%. Besonders bevorzugte Bleichakti¬ vatoren sind N,N,N' .N'-Tetraacetylethylendiamin und l,5-Diacetyl-2,4-di- oxo-hexahydro-1,3,5-triazin.In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations. Examples of this are N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate. The bleach activators contain bleaching agents in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N '.N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
Das Schäumvermögen der Tenside läßt sich durch Kombination geeigneter Ten- sidtypen steigern oder verringern; eine Verringerung läßt sich ebenfalls durch Zusätze nichttensidartiger Substanzen erreichen. Als Schauminhibi¬ toren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an Ci8~C24-Fettsäuren aufweisen. Geeig¬ nete nichttensidartige Schauminhibitoren sind beispielsweise Organopoly- siloxane und deren Gemische mit mikrofeiner, ggf. silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit si¬ lanierter Kieselsäure oder Bistearylethylendiamid. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Paraffinen oder Wachsen.The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-C24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with siliconized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes.
Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagie¬ renden Natriumsalze von beispielsweise l-Hydroxyethan-l,l-diphosphonat und Diethylentria inpentamethylenphosphonat in Mengen von 0,1 bis 1,5 Gew.-% verwendet.The salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and Diethylene tria in pentamethylene phosphonate used in amounts of 0.1 to 1.5 wt .-%.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus lichenifor- mis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugs¬ weise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischun¬ gen, beispielsweise aus Protease und Amylase oder Protease und Lipase oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere je¬ doch Cellulase-haltige Mischungen von besonderem Interesse. Auch Peroxid- asen und Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hü11Substanzen ein¬ gebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases and oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition.
Die Mittel können als optische Aufheller Derivate der Diaminostilbendi- sulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-l,3,5-triazinyl-6-amino)stil- ben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die an¬ stelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylamino- gruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle an¬ wesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2- sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden. As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
BeispieleExamples
Die anwendungstechnische Prüfung erfolgte in einer üblichen Haushalts¬ waschmaschine (Miele W 717) im Eingangwaschverfahren bei einer Temperatur von 40 °C und einer Beladung von 3,5 kg sauberer Haushaltswäsche und wei¬ ßen Teststreifen des unten angegebenen Gewebes, die bereits dreimal mit den jeweiligen Mitteln vorgewaschen und anschließend mit den ebenfalls un¬ ten angegebenen fett- und ölhaltigen Anschmutzungen angefleckt waren (Al¬ terung 3 Tage), und einer Flotte von 17 1 Leitungswasser mit einer Härte von 16 °d. Die Waschmitteldosierung betrug in den Beispielen 1 und 2 je¬ weils 96 g. Im ersten Beispiel wurden dazu 99 Gew.-Teile eines handelsüb¬ lichen Color-Waschmittels mit jeweils 1 Gew.-Teil der unten angegebenen Celluloseether versetzt. Zum Vergleich wurde das Beispiel mit 96 g des¬ selben Colorwaschmittels ohne Zusatz der angegebenen Celluloseether (VI) getestet. Diese Versuche wurden im zweiten Beispiel mit einem handelsüb¬ lichen Universalwaschmittel mit und ohne Zusatz von Celluloseether (V2) wiederholt. Die Aufhellung der Gewebeteststreifen (Remission in %) wurde bei 460 nm gemessen (Ausblendung des Aufheller-Effekts).The application test was carried out in a conventional household washing machine (Miele W 717) in the entrance washing process at a temperature of 40 ° C. and a load of 3.5 kg of clean household laundry and white test strips of the fabric specified below, which had already been washed three times with the respective fabrics Pre-washed and then stained with the grease and oil-containing stains also given below (aging 3 days), and a liquor of 17 l tap water with a hardness of 16 ° d. The detergent dosage in Examples 1 and 2 was 96 g each. In the first example, 99 parts by weight of a commercially available color detergent were each mixed with 1 part by weight of the cellulose ethers given below. For comparison, the example was tested with 96 g of the same color detergent without the addition of the specified cellulose ethers (VI). In the second example, these tests were repeated with a commercial universal detergent with and without the addition of cellulose ether (V2). The lightening of the tissue test strips (reflectance in%) was measured at 460 nm (suppression of the brightener effect).
Anschmutzunoen:Soiling:
Motoröl: 8 Tropfen auf Polyester (PES) (stark verschmutzt) (I) 4 Tropfen auf PES (leicht verschmutzt) (II)Motor oil: 8 drops on polyester (PES) (very dirty) (I) 4 drops on PES (slightly dirty) (II)
Fahrradöl: 12 Tropfen einer Masse von 10 g Staub-Hautfett auf 100 ml Öl auf PES (stark verschmutzt) (III) 6 Tropfen dieser Masse auf PES (leicht verschmutzt) (IV)Bicycle oil: 12 drops of a mass of 10 g of dusty skin fat on 100 ml of oil on PES (very dirty) (III) 6 drops of this mass on PES (slightly dirty) (IV)
roter Lippenstift auf PES (stark und leicht verschmutzt) (V, VI)red lipstick on PES (strong and slightly dirty) (V, VI)
Celluloseether:Cellulose ether:
Methylhydroxypropylcellulose-Compound (MHPC1), enthaltend 88 Gew.-% MHPC mit einem Gehalt an Methoxyl-Gruppen von ca. 27 Gew.-% und einem Ge¬ halt an Hydroxypropoxyl-Gruppen von ca. 6,5 Gew.-%, bezogen auf MHPC, 5 Gew.-% Natriumchlorid und 7 Gew.-% Wasser. Die Viskosität einer 2 Gew.-%igen wäßrigen Lösung von MHPC1 bei 20 °C betrug 50 mPas.Methyl hydroxypropyl cellulose compound (MHPC1), containing 88% by weight of MHPC with a methoxyl group content of approximately 27% by weight and a hydroxypropoxyl group content of approximately 6.5% by weight on MHPC, 5% by weight sodium chloride and 7% by weight water. The viscosity of a 2% by weight aqueous solution of MHPC1 at 20 ° C. was 50 mPas.
Methylhydroxypropylcellulose-Compound (MHPC2), enthaltend 91 Gew.-% MHPC mit einem Gehalt an Methoxyl-Gruppen von ca. 28 Gew.-% und einem Ge¬ halt an Hydroxypropoxyl-Gruppen von ca. 6 Gew.-%, bezogen auf MHPC, 1 Gew.-% Natriumchlorid und 8 Gew.-% Wasser. Die Viskosität einer 2 Gew.- igen wäßrigen Lösung von MHPC2 bei 20 °C betrug 50 mPas.Methyl hydroxypropyl cellulose compound (MHPC2), containing 91% by weight MHPC with a content of methoxyl groups of approx. 28% by weight and a content of hydroxypropoxyl groups of approx. 6% by weight, based on MHPC , 1 wt .-% sodium chloride and 8 wt .-% water. The viscosity of a 2% by weight aqueous solution of MHPC2 at 20 ° C. was 50 mPas.
Methylhydroxypropylcellulose-Compound (MHPC3), enthaltend 91 Gew.-% MHPC mit einem Gehalt an Methoxyl-Gruppen von ca. 22 Gew.-% und einem Ge¬ halt an Hydroxypropoxyl-Gruppen von ca. 7,5 Gew.-%, bezogen auf MHPC, 1 Gew.-% Natriumchlorid und 8 Gew.-% Wasser. Die Viskosität einer 2 Gew.-%igen wäßrigen Lösung von MHPC3 bei 20 °C betrug 100 mPas.Methyl hydroxypropyl cellulose compound (MHPC3), containing 91% by weight MHPC with a content of methoxyl groups of approx. 22% by weight and a content of hydroxypropoxyl groups of approx. 7.5% by weight on MHPC, 1% by weight sodium chloride and 8% by weight water. The viscosity of a 2% by weight aqueous solution of MHPC3 at 20 ° C. was 100 mPas.
Zum Vergleich:For comparison:
Methylcellulose-Compound (MC), enthaltend 88 Gew.-% MC, 5 Gew.-% Natrium¬ chlorid und 7 Gew.-% Wasser. Die Viskosität einer 2 Gew.-%igen wäßri¬ gen Lösung von MC bei 20 °C betrug 40 mPas.Methyl cellulose compound (MC) containing 88% by weight MC, 5% by weight sodium chloride and 7% by weight water. The viscosity of a 2% by weight aqueous solution of MC at 20 ° C. was 40 mPas.
Carboxymethylcellulose-Natriumsalz (CMC), handelsübliche AngebotsformCarboxymethyl cellulose sodium salt (CMC), commercial form of offer
Beispiel 1: ColorwaschmittelExample 1: Color detergent
Die Tabellen 1 und 2 zeigen die Überlegenheit der erfindungsgemäß einge¬ setzten Methylhydroxypropylcellulosen MHPC1 und MHPC2 gegenüber Methylcel- lulosen und Carboxymethylcellulosen sowohl bei starker als auch bei leich¬ ter Verschmutzung der Testgewebe durch Motoröl. Bei den starken Lippen- stiftanschmutzungen sind signifikante Vorteile gegenüber MC und CMC für MHPC 1 bis 3 erkennbar. Tabelle 1: MotorölTables 1 and 2 show the superiority of the methyl hydroxypropyl celluloses MHPC1 and MHPC2 used according to the invention over methyl celluloses and carboxymethyl celluloses both in the case of heavy and also slight contamination of the test tissue by motor oil. With the strong lipstick stains, significant advantages over MC and CMC for MHPC 1 to 3 can be seen. Table 1: Engine oil
Remission in % I IIRemission in% I II
Anfangswert 26,5 30,9Initial value 26.5 30.9
VI 37,2 40,2VI 37.2 40.2
V1:CMC 99:1 43,9 43,8V1: CMC 99: 1 43.9 43.8
V1:MC 99:1 67,9 70,6V1: MC 99: 1 67.9 70.6
V1:MHPC1 99:1 68,9 72,3 V1:MHPC2 99:1 70,6 72,1V1: MHPC1 99: 1 68.9 72.3 V1: MHPC2 99: 1 70.6 72.1
Tabelle 2: roter LippenstiftTable 2: red lipstick
Remission in %% Remission
V VIV VI
Anfangswert 5,0 34,6Initial value 5.0 34.6
VI 56,7 74,1VI 56.7 74.1
V1:CMC 99:1 56,4 72,3V1: CMC 99: 1 56.4 72.3
V1:MC 99:1 59,0 74,2V1: MC 99: 1 59.0 74.2
V1:MHPC1 99:1 62,9 73,8V1: MHPC1 99: 1 62.9 73.8
V1:MHPC2 99:1 65,7 73,8V1: MHPC2 99: 1 65.7 73.8
V1:MHPC3 99:1 65,4 74,0V1: MHPC3 99: 1 65.4 74.0
Beispiel 2: UniversalwaschmittelExample 2: Universal detergent
Die Tabellen 3 bis 5 zeigen die Überlegenheit der erfindungsgemäß einge¬ setzten Methylhydroxypropylcellulose MHPCl gegenüber Methylcellulosen und Carboxymethylcellulosen sowohl bei starker als auch bei leichter Ver¬ schmutzung der Testgewebe durch Motoröl und Fahrradöl. MHPC2 zeigt eben- falls signifikante Vorteile sowohl bei starker als auch bei leichter Ver¬ schmutzung durch Fahrradöl. MHPC2 und MHPC3 zeigen bei leichter Verschmut¬ zung durch Motoröl ebenfalls Vorteile. Bei den Lippenstiftanschmutzungen sind signifikante Vorteile gegenüber MC und CMC für MHPC 1 bis 3 erkenn¬ bar.Tables 3 to 5 show the superiority of the methyl hydroxypropyl cellulose MHPCl used according to the invention over methyl celluloses and carboxymethyl celluloses both with heavy and with slight soiling of the test fabrics by motor oil and bicycle oil. MHPC2 also shows if there are significant advantages for both heavy and light soiling from bicycle oil. MHPC2 and MHPC3 also show advantages when slightly contaminated by motor oil. With lipstick soiling, significant advantages over MC and CMC for MHPC 1 to 3 can be seen.
Tabelle 3: MotorölTable 3: Engine oil
Remission in % I IIRemission in% I II
Anfangswert 27,2 30,3Initial value 27.2 30.3
VI 47,6 48,3VI 47.6 48.3
V1:CMC 99:1 49,5 49,4V1: CMC 99: 1 49.5 49.4
V1:MC 99:1 50,0 49,9V1: MC 99: 1 50.0 49.9
V1:MHPC1 99:1 53,1 53,9V1: MHPC1 99: 1 53.1 53.9
V1:MHPC2 99:1 49,4 53,1V1: MHPC2 99: 1 49.4 53.1
V1:MHPC3 99:1 49,4 53,7V1: MHPC3 99: 1 49.4 53.7
Tabelle 4: FahrradölTable 4: Bicycle oil
Remission in %% Remission
III IVIII IV
Anfangswert 12,2 14,8Initial value 12.2 14.8
VI 55,9 60,5VI 55.9 60.5
VI:CMC 99:1 44,1 42,9VI: CMC 99: 1 44.1 42.9
V1:MC 99:1 63,2 64,6V1: MC 99: 1 63.2 64.6
V1:MHPC1 99:1 72,5 73,3 V1:MHPC2 99:1 70,2 70,4 Tabelle 5: roter LippenstiftV1: MHPC1 99: 1 72.5 73.3 V1: MHPC2 99: 1 70.2 70.4 Table 5: red lipstick
Remission in %% Remission
V VIV VI
Anfangswert 5,0 29,7Initial value 5.0 29.7
VI 99:1 11,8 32,0VI 99: 1 11.8 32.0
VI:CMC 99:1 9,9 42,0VI: CMC 99: 1 9.9 42.0
V1:MC 99:1 11,4 49,3V1: MC 99: 1 11.4 49.3
V1:MHPC1 99:1 12,6 63,0V1: MHPC1 99: 1 12.6 63.0
V1:MHPC2 99:1 15,1 59,0V1: MHPC2 99: 1 15.1 59.0
V1:MHPC3 99:1 15,0 57,3 V1: MHPC3 99: 1 15.0 57.3

Claims

Patentansprüche claims
1. Waschmittel, enthaltend Tenside, Buildersubstanzen und nichtionische Celluloseether, dadurch gekennzeichnet, daß der nichtionische Cellulo¬ seether ausgewählt ist aus der Gruppe der Methylhydroxypropylcellulo¬ sen, welche einen Anteil an Methoxyl-Gruppen von 15 bis 35 Gew.-% und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.- , bezogen auf den nicht¬ ionischen Celluloseether, aufweisen.1. Detergent containing surfactants, builder substances and nonionic cellulose ethers, characterized in that the nonionic cellulose ether is selected from the group of methyl hydroxypropyl celluloses, which have a proportion of methoxyl groups of 15 to 35% by weight and of hydroxypropoxyl Have groups of 1 to 15% by weight, based on the non-ionic cellulose ether.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es eine Methyl- hydroxypropylcellulose enthält, welche einen Anteil an Methoxyl-Grup¬ pen von 20 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 2 bis 10 Gew.-%, insbesondere von 5 bis 8 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, aufweist.2. Composition according to claim 1, characterized in that it contains a methyl hydroxypropyl cellulose, which has a proportion of methoxyl groups of 20 to 30 wt .-% and of hydroxypropoxyl groups of 2 to 10 wt .-%, in particular from 5 to 8% by weight, based in each case on the nonionic cellulose ether.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es den nichtionischen Celluloseether in Form eines pulverförmigen oder granu¬ lären Compounds enthält.3. Composition according to claim 1 or 2, characterized in that it contains the nonionic cellulose ether in the form of a powdery or granular compound.
4. Mittel nach Anspruch 3, dadurch gekennzeichnet, daß das nichtionische Celluloseether-Compound Natriumchlorid in Mengen nicht oberhalb 10 Gew.-% enthält.4. Composition according to claim 3, characterized in that the nonionic cellulose ether compound contains sodium chloride in amounts not above 10 wt .-%.
5. Mittel nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß das nicht¬ ionische Celluloseether-Compound Natriumchlorid in Mengen von maximal 5 Gew.-%, vorzugsweise maximal 2 Gew.-% und insbesondere maximal 1 Gew.-% enthält.5. Composition according to claim 3 or 4, characterized in that the non-ionic cellulose ether compound contains sodium chloride in amounts of at most 5% by weight, preferably at most 2% by weight and in particular at most 1% by weight.
6. Mittel nach einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, daß das nichtionische Celluloseether-Compound bei 20 °C in einer 2 Gew.- %igen wäßrigen Lösung eine Viskosität zwischen 40 und 125 mPas (Brook- field-Viskosimeter, 20 °C, Spindel 3, 4 oder 5, 20 Umdrehungen pro Minute), vorzugsweise zwischen 45 und 100 mPas und insbesondere zwischen 45 und 60 mPas aufweist. 6. Composition according to one of claims 3 to 5, characterized in that the nonionic cellulose ether compound at 20 ° C in a 2% by weight aqueous solution has a viscosity between 40 and 125 mPas (Brookfield viscometer, 20 ° C, spindle 3, 4 or 5, 20 revolutions per minute), preferably between 45 and 100 mPas and in particular between 45 and 60 mPas.
7. Verwendung eines nichtionischen Celluloseethers, ausgewählt aus der Gruppe der Methylhydroxypropylcellulosen, welche einen Anteil an Meth- oxyl-Gruppen von 15 bis 35 Gew.-% und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.-%, bezogen auf den nichtionischen Celluloseether, zur Ent¬ fernung von fett- und ölhaltigen Anschmutzungen auf Textilien.7. Use of a nonionic cellulose ether, selected from the group of methylhydroxypropyl celluloses, which have a proportion of methoxy groups of 15 to 35% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based on the nonionic cellulose ether , for the removal of greasy and oily soiling from textiles.
8. Verwendung nach Anspruch 7, dadurch gekennzeichnet, daß die Methyl- hydroxypropylcellulose einen Anteil an Methoxyl-Gruppen von 20 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 2 bis 10 Gew.-%, insbeson¬ dere von 5 bis 8 Gew.-%, jeweils bezogen auf den nichtionischen Cellu¬ loseether, aufweist.8. Use according to claim 7, characterized in that the methyl hydroxypropyl cellulose has a proportion of methoxyl groups from 20 to 30 wt .-% and of hydroxypropoxyl groups from 2 to 10 wt .-%, in particular from 5 to 8 % By weight, based in each case on the nonionic cellulose ether.
9. Verwendung nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß die Methylhydroxypropylcellulose in Form eines pulverförmigen oder granu¬ lären Compounds eingesetzt wird.9. Use according to claim 7 or 8, characterized in that the methylhydroxypropyl cellulose is used in the form of a powdery or granular compound.
10. Verwendung nach Anspruch 9, dadurch gekennzeichnet, daß das Compound Natriumchlorid in Mengen nicht oberhalb 10 Gew.-% enthält.10. Use according to claim 9, characterized in that the compound contains sodium chloride in amounts not above 10 wt .-%.
11. Verwendung nach Anspruch 9 oder 10, dadurch gekennzeichnet, daß das Compound Natriumchlorid in Mengen von maximal 5 Gew.-%, vorzugsweise maximal 2 Gew.-% und insbesondere maximal 1 Gew.-% enthält.11. Use according to claim 9 or 10, characterized in that the compound contains sodium chloride in amounts of at most 5% by weight, preferably at most 2% by weight and in particular at most 1% by weight.
12. Verwendung nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, daß das Compound bei 20 °C in einer 2 Gew.-%igen wäßrigen Lösung eine Viskosität zwischen 40 und 125 mPas, vorzugsweise zwischen 45 und 100 mPas und insbesondere zwischen 45 und 60 mPas aufweist. 12. Use according to one of claims 9 to 11, characterized in that the compound at 20 ° C in a 2 wt .-% aqueous solution has a viscosity between 40 and 125 mPas, preferably between 45 and 100 mPas and in particular between 45 and Has 60 mPas.
EP94925416A 1993-08-09 1994-07-29 Detergent containing non-ionic cellulose ethers Withdrawn EP0713524A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19934326653 DE4326653A1 (en) 1993-08-09 1993-08-09 Detergent containing non-ionic cellulose ethers
DE4326653 1993-08-09
PCT/EP1994/002527 WO1995004805A1 (en) 1993-08-09 1994-07-29 Detergent containing non-ionic cellulose ethers

Publications (1)

Publication Number Publication Date
EP0713524A1 true EP0713524A1 (en) 1996-05-29

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EP (1) EP0713524A1 (en)
DE (1) DE4326653A1 (en)
WO (1) WO1995004805A1 (en)

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Publication number Priority date Publication date Assignee Title
GB9426458D0 (en) * 1994-12-31 1995-03-01 Procter & Gamble A detergent compositions comprising cellulytic enzyme
KR19980015613A (en) * 1996-08-23 1998-05-25 문정환 Focus adjustment method of exposure apparatus
DE10351325A1 (en) 2003-02-10 2004-08-26 Henkel Kgaa Detergent or cleaning agent with water-soluble builder system and dirt-releasing cellulose derivative
ATE362511T1 (en) 2003-02-10 2007-06-15 Henkel Kgaa DETERGENT OR CLEANING AGENTS CONTAINING BLEACH WITH A WATER-SOLUBLE BUILDER SYSTEM AND A DIRT-REMOVING CELLULOSE DERIVATIVE
WO2008141858A2 (en) * 2007-04-03 2008-11-27 Henkel Ag & Co. Kgaa Detergent having active ingredients that improve the primary detergency

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Publication number Priority date Publication date Assignee Title
DE2613791A1 (en) * 1975-04-02 1976-10-21 Procter & Gamble LAUNDRY DETERGENT
SE408715B (en) * 1975-07-17 1979-07-02 Berol Kemi Ab CLEANERS CONTAINING AT LEAST ONE ACTIVE ASSOCIATION AND A CELLULOSAETER
GB1534641A (en) * 1977-05-04 1978-12-06 Unilever Ltd Detergent compositions for fabric washing
US4532067A (en) * 1984-01-11 1985-07-30 Lever Brothers Company Liquid detergent compositions containing hydroxypropyl methylcellulose

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Title
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DE4326653A1 (en) 1995-02-16

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