EP0234334A2 - Textile washing and cleaning agent - Google Patents

Abstract

The detergent contains highly swellable sheet silicates combined with disalts of alpha-sulphonated fatty acids and/or surfactants of the classes of fatty alcohol sulphates, alkyl glycosides, fatty acid alkanolamides and/or ether amines. The textiles treated with this detergent and dried are simultaneously cleaned and softened, especially when the detergents contain no non-ionic surfactants.

Description

Granular detergent compositions containing builders, which - in addition to the usual textile detergent components, in particular based on wash-active surfactants and builder systems therefor - contain highly swellable, water-insoluble, finely divided smectite clays, have been described in numerous numbers in the literature. Reference is made, for example, to DE-AS 23 34 899, DE-OSes 32 06 265, 32 06 379, 33 11 368, 33 11 782, 33 12 774 and 33 44 099. The use of the insoluble, finely divided smectite clays, in particular corresponding montmorillonites , Hectorite and / or Saponite is said to give the textile detergent, in addition to its cleaning action, the ability to soften the washed textile, so that washing and softening can be combined in one operation. The options for softening that have so far been adjustable in practice are extremely limited. At best, hardly noticeable softening effects are achieved in the washed and dried textile. The subsequent treatment of the washed textiles in the rinsing bath or in a subsequent treatment step with the known fabric softeners based on quaternary ammonium compounds has so far been indispensable if really noticeable effects are to be achieved with regard to the fabric softening. The same also applies to the known attempts to improve the joint process of washing and softening by using combinations of the highly swellable smectite clays together with selected quaternary ammonium compounds in the textile detergents are, which usually have two long-chain alkyl radicals in addition to two short-chain alkyl radicals. In this connection, reference is made, for example, to US Pat. No. 4,141,841 and DE-OS 28 57 162.

DE-ASen 21 44 592 and 21 61 726 describe textile detergents which, in addition to the usual washing-active nonionic and / or anionic surfactant components, contain alkali metal salts of alpha-sulfonated saturated fatty acids with 14 to 20 carbon atoms. These disalts of alpha-sulfo fatty acids are either to be used alone as builders for the surfactant components used or else to be used together with conventional builder combinations, in particular based on calcium ion-binding and / or precipitating builder salts. Within the framework of this teaching it is claimed that such agents soften the textiles during washing and it is suspected that this effect is probably a result of the deposition of disalphases of the alpha-sulfonated fatty acids on the textile surface. If one tries to quantify this softening effect, it turns out that here too there is at best a very weak aviva effect, which is at the limit of perceptibility.

The present invention is based on the finding that surprisingly strong washing bath vivage effects can be obtained if the known, highly swellable, insoluble, finely divided layered silicates with an anti-aging effect in combination with disalts alpha-sulfonated fatty acids and / or in combinations. tion with certain selected surfactants are used.

• a) hochquellfähigen feinstteiligen Schichtsilikaten insbesondere auf Basis von Smectit-Tonen in Kombination mit
• b) Disalzen alpha-sulfonierter Fettsäuren und/oder
• c) ausgewählten Tensiden aus der Klasse waschaktiver Fettalkoholsulfate, waschaktiver Alkylglycoside, waschaktiver Fettsäurealkanolamide und/oder waschaktiver Alkyletheramine

The invention accordingly relates to the use of

• a) highly swellable finely divided layered silicates in particular Basis of Smectit clays in combination with
• b) disalting alpha-sulfonated fatty acids and / or
• c) selected surfactants from the class of wash-active fatty alcohol sulfates, wash-active alkyl glycosides, wash-active fatty acid alkanolamides and / or wash-active alkyl ether amines

in textile washing and cleaning agents for the development of an improved, in particular synergistically enhanced softening effect in the washed and dried textile goods with a good washing and cleaning effect for soiled textiles.

Numerous silicate materials of natural and / or synthetic origin are suitable as highly swellable, finely divided layered silicates (component a). In particular, mica-like layered silicates with a three-layer structure from the Smectite group are used. These include montmorillonite, hectorite, saponite, beidellite and comparable compounds. Bentonite is a suitable natural feed material, which is known to contain the majority of layered silicate of the montmorillonite structure. Corresponding Smectittone are available under the most varied trade names on the market. Examples are the materials which are sold under the product names "Laponite RD", "Dis-This-Extra", "Thixogel", "Softclark" or under other known trade names.

The amount of this swellable layered silicate with an anti-sag effect in the detergents according to the invention - based on the finished total dry agent - is in the range from about 3 to 25 percent by weight, in particular in the range from about 5 to 15 percent by weight.

Corresponding salts of fatty acids with 10 to 22 carbon atoms, preferably of about 12 to 18 carbon atoms, are used in particular as disalts of alpha-sulfonated fatty acids (component b). Corresponding salts with 14 to 18 carbon atoms can be particularly suitable. Corresponding salts of a fatty acid of a certain carbon number or else salts of fatty acid cuts in the specified range can be used. Particular importance can be in the range of the higher carbon numbers in the range mentioned here, in particular in the range of about 16 to 18 carbon atoms.

The corresponding alkali metal disalts and in particular the sodium disalt are particularly suitable as disalts. These fatty acid disalts are prepared in a manner known per se by sulfonating the corresponding free fatty acids or their esters, in particular the corresponding methyl ester, with subsequent ester saponification. The fatty acids themselves can be of natural and / or synthetic origin. For the production of light-colored and color-stable salts of alpha-sulfonated fatty acids, the relevant extensive knowledge of the experts applies to the sulfonation of the raw materials concerned.

The disalts of the alpha-sulfonated fatty acids are usually used in amounts of about 2 to 40 percent by weight, preferably in amounts of about 2 to 20 percent by weight, based in each case on the dry total active ingredient mixture. In an important embodiment of the invention, the disalt can simultaneously make up the essential surfactant component of the detergent mixture. In these cases, at least about 15 percent by weight, preferably at least about 20 percent by weight, of disalt should be present in the finishing detergent mixture. For the development of the synergistically enhanced anti-aging effect, however, it may be advisable to work with comparatively low amounts of disalts. The use of 1 up to 2 percent by weight of disalt bring about a substantial increase in activity, in particular the range from about 2 to 20 percent by weight of disalt comes into consideration, with amounts of about 2 to 10 percent by weight of disalt being particularly preferred.

In addition to or instead of the use of disalts according to component b, an increased anti-aging effect can also be achieved according to the invention by selecting very specific surfactant components. When these selected surfactants are used together with the swellable layered silicates (component a) and the disalts (component b), optimal results are achieved both in the direction of a high-quality washing result and in the direction of a high-quality finishing result.

• Komponente c 1: Waschaktive Fettalkoholsulfate sind die bekannten Schwefelsäureester natürlicher und/oder synthetischer Fettalkohole, vorzugsweise mit 10 bis 22, insbesondere 12 bis 20 C-Atomen. Besondere Bedeutung kann hier Fettalkoholsulfaten im Bereich von C14-C18 zukommen. C₁₆/C₁₈- Fettalkohole und insbesondere Talgalkohol beziehungsweise Talgalkoholsulfat sind in diesem Sinn wichtige Komponenten für die Erfindung.
• komponente·c 2: Waschaktive Alkylglycoside, ihre Herstellung und ihre Verwendung sind seit langer Zeit bekannt, verwiesen wird beispielsweise auf die US-PSen 3 839 318, 3 707 535 und 3 547 828, die DE-OSen 19 05 523, 19 43 689, 20 36 472 und 30 01 064. Ihre Herstellung erfolgt insbesondere durch Umsetzung von Glucose oder Oligosachariden mit Alkoholen der C-Kettenlänge von 8 bis 25 C-Atomen, insbesondere 10 bis 18 C-Atomen. Der Oligomerisationsgrad der Zuckerreste in den Alkylglycosiden kann den Zahlenwert bis zu etwa 8, vorzugsweise bis zu etwa 5 erreichen.
• Komponente c 3: Fettsäurealkanolamide sind die bekannten waschaktiven Verbindungen, die beispielsweise unter dem Handelsnamen "Comperlane" von der Anmelderin vertrieben werden. Es handelt sich hierbei um Mono- und/oder Dialkanolamide - insbesondere entsprechende Ethanolamide - von Fettsäuren des Kettenlängenbereichs von C10 bis C₂₂, insbesondere C₁₂ bis C18. Verbindungen dieser Art sind in der Praxis insbesondere als Waschkraftverstärker bekannt.
• Komponente c 4: Ebenfalls als Waschkraftverstärker bekannt sind die hier betroffenen Alkyletheramine. Es handelt sich dabei um Verbindungen, die sich beispielsweise durch Umsetzung von Sulfatestern von Fettalkoholpolyethoxylaten mit primären oder sekundären Aminen herstellen lassen. Neben einem langkettigen Alkylrest - üblicherweise C10 bis C₂₂, bevorzugt C₁₂ bis C₁₈ - enthalten sie eine Polyalkoxykette, insbesondere die Polyethoxyethergruppierung mit einem Oligomersationsgrad bis zu 5 oder 6, vorzugsweise bis zu 4, die ihrerseits wieder mit einer substituierten Aminogruppe substituiert ist.

The selected surfactants affected here are divided into the 4 classes c 1 to c 4 mentioned. The following applies in particular:

• Component c 1: wash-active fatty alcohol sulfates are the known sulfuric acid esters of natural and / or synthetic fatty alcohols, preferably with 10 to 22, in particular 12 to 20, carbon atoms. Fatty alcohol sulfates in the range of C14-C18 can be of particular importance here. C ₁₆ / C ₁₈ - fatty alcohols and especially tallow alcohol or tallow alcohol sulfate are important components for the invention in this sense.
• component · c 2: wash-active alkyl glycosides, their preparation and their use have been known for a long time, reference is made, for example, to US Pat. Nos. 3,839,318, 3,707,535 and 3,547,828, DE-OSes 19 05 523, 19 43 689 , 20 36 472 and 30 01 064. They are produced in particular by reacting glucose or oligosaccharides with alcohols with a carbon chain length of 8 to 25 carbon atoms, in particular 10 to 18 carbon atoms. The degree of oligomerization of the sugar residues in the alkyl glycosides can reach the numerical value up to about 8, preferably up to about 5.
• Component c 3: Fatty acid alkanolamides are the known washing-active compounds which are sold, for example, by the applicant under the trade name "Comperlane". These are mono- and / or dialkanolamides - in particular corresponding ethanolamides - of fatty acids in the chain length range from C10 to C ₂₂ , in particular C ₁₂ to C18. In practice, compounds of this type are known, in particular, as detergent boosters.
• Component c 4: The alkyl ether amines affected here are also known as detergent boosters. These are compounds which can be prepared, for example, by reacting sulfate esters of fatty alcohol polyethoxylates with primary or secondary amines. In addition to a long-chain alkyl radical - usually C10 to C ₂₂ , preferably C ₁₂ to C ₁₈ - they contain a polyalkoxy chain, in particular the polyethoxy ether group with a degree of oligomerization of up to 5 or 6, preferably up to 4, which in turn is substituted with a substituted amino group.

The selected surfactants (components c) are used in total in amounts of up to about 25 percent by weight, preferably in the range of about 4 to 20 percent by weight, in each case based on the total dry detergent. 5 to 15 percent by weight of these surfactants can be a particularly useful range.

In an important embodiment, the selected surfactant components are fatty alcohol sulfates (c 1), possibly in a mixture with alkyl glycosides (c 2), as the main surfactant components. In contrast, the fatty acid alkanolamides (c 3) and / or ether amines (c 4) are present in smaller amounts. For example, about 50 to 80 percent by weight of the selected surfactant components can be formed by compounds of classes c 1 and / or c 2, while the rest are washing-strengthening components of groups c 3 and / or c 4.

In addition to components a, b and / or c, the textile detergents according to the invention contain conventional constituents. The following are particularly considered:

Other common surfactants.

It is important, however, that in a preferred embodiment the known washing-active nonionic surfactant components, which are formed by polyalkoxylation of fatty alcohols and / or alkylphenols, are not used. It turns out that by using at least considerable amounts of such in detergents per se. usual nonionics, the aviva effect can be substantially impaired.

Common builder - or builder components. All known systems come into consideration here. So conventional polyphosphate builder systems - especially STP - or also be worked entirely or partially without phosphate. In the latter cases, the known crystalline synthetic aluminosilicate of the zeolite type, in particular zeolite NaA and / or NaX, is particularly suitable as a builder component. Together with this, the usual co-builders can be used, which are usually calcium complex binding and / or precipitating compounds. Reference is made in detail to the known knowledge of the person skilled in the art.

Bleaching components, especially peroxide compounds such as sodium perborate.

Washing alkalis such as water glass, soda and the like.

Additives to improve dirt-bearing capacity, for example CMC.

Enzymes, fragrances and dyes and other common additives in detergents.

The sum of components a to c essential to the invention can make up, for example, 20 to 80 percent by weight, preferably 25 to 65 percent by weight, in each case based on the total dry detergent mixture, in the detergent mixtures according to the invention. The rest is formed by the usual detergent ingredients listed above.

Example Examples 1 to 8

The fabric softener effect of various detergent formulations is tested in launderometer tests.

Test conditions in the Launderometer: 60 ° C, 16 ° d. H., fleet = 1:20, 30 min. Wash, 10 steel balls, cotton terry.

Different amounts of the active substances or combinations of active substances given in Table 1 are added to the builder combination described below, which is chosen to be the same in all experiments. Here mean:

C _16/18 disalt: sodium disalz of an alpha-sulfofatty acid mixture based on C _16/18 .

Akylglucoside: awake-active compound based on a C _12/14 alkyl residue, average degree of oligomerization 1.4.

DisThis Extra: highly swellable layered silicate

FSA: Coconut fatty acid monoethanolamide

The compositions of the tested washing powder formulations and the associated grip notes of the washed and dried textile specimens are summarized in Table 1 below. The synergistic effect enhancement is evident from the comparison of Examples 1, 2 and 6 with Examples 3 to 5, 7 and 8 according to the invention.

• Wasserglas (Portil N): 7,0;
• Natriumperborat: 22,0;
• CMC: 0,5;
• EDTA: 0,2;
• Natriumsulfat: 30,0;
• Rest: Wasser.
  

The composition of the builders used as a basic detergent powder in Examples 1 to 21 is as follows - all numerical values here and in the following tables mean percentages by weight based on the total detergent formulation:

• Water glass (Portil N): 7.0;
• Sodium perborate: 22.0;
• CMC: 0.5;
• EDTA: 0.2;
• Sodium sulfate: 30.0;
• Rest: water.
  

Examples 9 to 21

• Laponite RD: hochquellfähiges, feinteiliges Schichtsilikat
• C_16/18-Disalz: siehe die Erläuterung zu Tabelle ₁
• Alkylglucosid: siehe die Erläuterung zu Tabelle 1
• TAS: Natriumsalz des Talgalkoholsulfats
• FSA: siehe die Erläuterung zu Tabelle 1
• ABS: Alkylbenzolsulfonat
• Nio: Cocosalkoholpolyethoxylat mit 7 mol EO
• ES: alpha-Sulfofettsäuremethylester-Natriumsalz (C_16/18-Fettsäure)
• Gerüststoffkombination: siehe Erläuterung zu Tabelle 1
  

In a second series of lauderometer determinations, the use of different surfactant combinations is examined. The respective compositions of the detergent formulations examined and the gripping notes obtained are summarized in Table 2 below. The following applies:

• Laponite RD: highly swellable, finely divided layered silicate
• C _16/18 disalt: see the explanation for Table ₁
• Alkyl glucoside: see the explanation for Table 1
• TAS: sodium salt of tallow alcohol sulfate
• FSA: see the explanation for Table 1
• ABS: alkylbenzenesulfonate
• Nio: coconut alcohol polyethoxylate with 7 mol EO
• ES: Alpha-sulfofatty acid methyl ester sodium salt (C _16/18 fatty acid)
• Builders combination: see explanation of Table 1
  

The negative effect with regard to the softening effect when using non-ionic surfactant compounds customary in practice is evident from Examples 17 and 18.

Examples 22-26

Test rags made of terry towels, molton and knitwear are subjected to a 60 ° C wash 3 times in household drum machines together with the usual standard household laundry items. After each wash, the test rags are dried hanging under the conditions of a normal linen drying. The dried test rags are tactile evaluated after the 1st and 3rd wash in a test panel consisting of 5 selected people. The test subjects have the task of assigning the tactile properties of each flap to a range of grades from -6 to +6, whereby only half or full grades are assigned. The grades obtained for each rag are averaged and the differences in the mean values are checked for statistical significance. The unit of averaged grip grade and ranking is used to evaluate the individual recipes.

• Waschmittelbuilder auf Basis Zeolith NaA: 20,0;
• Wasserglas (Portil N): 7,0;
• Natriumperborat: 22,0;
• EDTA: 0,2;
• CMC: 0,5;
• Bleichaktivator (TAED): 3,0;
• CoBuilder auf Basis einer polymeren Carbonsäure (Sokalan CP5) : 4,0;
• Enzym: 0,7;
• Natriumsulfat: 10,0.

The detergent formulations used in Examples 22 to 26 are shown in Table 3 below. The builders combination used in these examples contains the following constituents (again weight percent, based on the total detergent):

• Detergent builder based on zeolite NaA: 20.0;
• Water glass (Portil N): 7.0;
• Sodium perborate: 22.0;
• EDTA: 0.2;
• CMC: 0.5;
• Bleach activator (TAED): 3.0;
• CoBuilder based on a polymeric carboxylic acid (Sokalan CP5): 4.0;
• Enzyme: 0.7;
• Sodium sulfate: 10.0.

The grades after the 1st and 3rd wash are assigned to the respective recipes in Table 3 below. The following additional information applies:

A high-quality standard detergent without additives is used in the parallel test with a grade of 0.0. A common standard detergent with the addition of wash bath leveling reaches a value of 0.22 after the 1st wash and 0.24 after the 3rd wash.

The reflectance values on soiled standard test rags achieved with the detergent recipes according to Examples 22 to 26 correspond to comparative values as can be achieved with commercially available high-quality household detergents.

Claims (9)

1. Use of a) highly swellable, finely divided sheet silicates, in particular from the class of natural and / or synthetic crystalline smectites with a strongly swellable layer structure in combination with b) disalting alpha-sulfonated fatty acids of natural and / or synthetic origin, in particular of the chain length range of C ₁₀ -C ₂₂ and / or c) selected surfactants from the class 1. Fatty alcohol sulfates 2. Alkyl glycosides 3. Fatty acid alkanolamides and / or 4. Etheramine
in textile washing and cleaning agents for the development of an improved, in particular synergistically enhanced softening effect in the washed and dried textile goods with a good washing and cleaning effect for soiled textiles. 2. Embodiment according to claim 1, characterized in that the swellable, finely divided layered silicates are used in amounts of about 3 to 25 percent by weight, preferably in amounts of about 5 to 15 percent by weight, in each case based on total detergents, in particular corresponding natural, synthetic or semi-synthetic , water-insoluble, finely divided layered silicates with smectite structure of the type of montmorillonites, hectorites and / or saponites are used. 3. Embodiment according to claims 1 and 2, characterized in that the alkali disalts alpha-sulfonated Fatty acids in amounts of about 2 to 40 percent by weight, preferably in amounts of about 2 to 30 percent by weight, based in each case on total detergents, are used, these salts being derived from corresponding fatty acids of natural and / or synthetic origin, in particular in the C number range from C ₁₄ -C ₁₈ . 4. Embodiment according to claims 1 to 3, characterized in that the selected surfactant components according to c) 1 to 4 in total in amounts of about 4 to 25 percent by weight, preferably in amounts of about 5 to 20 percent by weight - in each case based on total detergent - for use come. 5. embodiment according to claims 1 to 4, characterized in that the fatty alcohol sulfates according to c) 1 and the fatty acid alkanolamides according to c) 3 of natural and / or synthetic fatty acids in the range C ₁₀ -C ₂₂ , in particular C _{i 2} -C _i8 deduce. 6. Embodiment according to claims 1 to 5, characterized in that wash-active alkyl glycosides with 8 to 22 carbon atoms, preferably with 8 to 18 carbon atoms in the alkyl radical are used, in particular alkyl mono- and / or alkyl polyglycosides with up to 8 glycoside residues, in particular with up to 3 glycoside residues, can be used. 7. Embodiment according to claims 1 to 6, characterized in that 4 detergent-active amines are used as surfactant component c), which have an alkyl radical of natural and / or synthetic origin with 8 to 22, preferably 10 to 18 carbon atoms in connection with a polyalkylene oxide ether group have, which in turn are preferably formed from up to 6, in particular up to 4, ethylene oxide groups is and is attached to an amino group which can also be mono- or disubstituted and in particular can contain straight-chain and / or branched alkyl substituents, each having up to 10 carbon atoms. 8. Embodiment according to claims 1 to 7, characterized in that the textile detergents and cleaning agents in addition to components a), b) and c) usual detergent components such as other conventional surfactants, builders or builder systems, peroxide compounds, washing alkalis, dirt-carrying compounds, enzymes and / or contain fragrances and dyes. 9. Embodiment according to claims 1 to 8, characterized in that the textile detergents and cleaning agents are largely or completely free of conventional water-soluble synthetic nonionic organic detergent substances, in particular based on condensation products of ethylene oxide with higher fatty alcohol and / or alkylphenols.