DE3839016A1 - WASHING AND CLEANING AGENTS WITH SEK CONTENT. Dialkyl ether sulfates - Google Patents

Description

The present invention relates to detergents and cleaners, as the anionic surfactant component salts of sec. Dialkyl ether sulfates contains. This new surfactant compound is excellent as an exchange component for alkylbenzenesulfonates, as they with comparably good performance properties very much more favorable ecological characteristics, d. H. a better Biodegradability and lower toxicity to fish and microorganisms unfolded in the sewage. It can also be used in the mainly made from natural, renewable raw materials become.

The invention detergent and cleaning agents are solid or liquid form containing

• a) 1 to 50 wt .-% of at least one anionic or cationic surfactant,
• b) 1 to 90 wt .-% of at least one compound from the class of Builder salts and sequestrants and
• c) difference up to 100% by weight of other customary detergent and cleaner ingredients,

characterized in that component (a) is wholly or partly from a secondary dialkyl ether sulfate of general formula I. consists:

in which the symbols have the following meaning: M = Na, K, Mg, ammonium or an organic ammonium cation, R¹ = linear C₁-C₁₆-alkyl radical, R³ = linear or branched alkyl radical having 1 to 22 carbon atoms, with the proviso in that the sum of the C atoms in (R₁ + R₂) = 1 to 18 and in (R₁ + R₂ + R₃) = 8 to 22, R⁴ = hydrogen or CH₃ and n = numbers from 0 to 15.

The meaning of M in the abovementioned general formula (I) is Na, K, Mg, ammonium, alkylammonium, alkanolammonium, wherein the Alkyl and alkanol radicals of said organic ammonium ions each 1 to 4 carbon atoms may have. The sodium salts are preferred. For Liquid agents are in particular the salts of triethanolamine good usable.

In the general formula (I), R¹ is a linear alkyl group with 1 to 16 carbon atoms. So it comes for the invention Compounds as substituent R¹, the radicals methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-hendecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n- Pentadecyl and n-hexadexyl in question. Preference is given to alkyl radicals with 6 to 14 carbon atoms.  

The meaning of R 2 in the abovementioned general formula (I) is hydrogen or a linear alkyl radical having 1 to 16 carbon atoms. In addition to hydrogen, the same alkyl radicals are used for R² as for R¹ in question. The sum of the C atoms contained in R¹ and R² is 1 to 18, preferably 6 to 14. In particular, R¹ is linear alkyl radicals having 8 to 12 C atoms and R² for hydrogen.

In the above formula (I), R³ is a linear or branched, saturated alkyl radical having 1 to 22 carbon atoms. It come thus as substituent R³ the radicals methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-Hendecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl and n -docosyl and the branched-chain isomers the said alkyl radicals in question.

R³ is linear, saturated alkyl radicals having 1 to 22 carbon atoms. A preferred embodiment comprises compounds in which R³ is for linear, saturated alkyl radicals having 1 to 12 C atoms, in particular for such alkyl radicals having 1 to 4 carbon atoms, is.

In the above-mentioned general formula (I), R⁴ represents a methyl group and preferably hydrogen. The subscript n represents a number from 0 to 15, with the range from 1 to 10 being preferred for n . However, it is also possible that ethoxy radicals and propoxy radicals are incorporated side by side in any desired ratio and in any order in the molecular chain in the compounds mentioned. Such mixed ethers are also included in the general formula (I).

The not claimed here production of dialkyl ether sulfates can be carried out in such a way that epoxides of the general formula II

in which R¹ and R² have the meanings given above, with alcohol alkoxylates the general formula III

in which R³, R⁴ and n have the meanings given above, at elevated temperature in the presence of a catalyst to Hydroxyalkylpolyethylen- and Hydroxyalkylpolypropylenglykolethern of the general formula VI

implements. This reaction takes place at temperatures of 100 to 180 ° C, preferably 120 to 160 ° C. Suitable catalysts are mineral acids, such as H₂SO₄ or Lewis acids, such as BF₃ etherates, preferably Alkali metal alcoholates, such as sodium methylate. The amount of the catalyst is 0.01 to 2 wt .-% of the reaction mixture. The compounds of formula IV thus obtained are known with Sulfating agents implemented, such as chlorosulfonic acid,  Amidosulfonic acid or - preferably - with inert gases or air diluted sulfur trioxide, the temperature during the Sulfation expediently 10 to 40 ° C. The raw one Sulfation product is then converted into a basic, an excess added to neutralizing agents containing aqueous solution. This solution is then expediently for 10 min to 1 Hour heated to temperatures of 60 to 100 ° C to the full Neutralization and the hydrolysis of anhydride derivatives accelerate the sulfuric acid. The aqueous solutions of the obtained Compounds can, if necessary after neutralization of excess basic compounds, immediately further processed or else dried, in particular spray-dried. detailed Manufacturing specifications can be found in the EP application 88/110904.

The dialkyl ether sulfates can be used in amounts of from 1 to 50% by weight, preferably 2 to 25 wt .-% in conventional detergents and cleaners be used and in particular in those in which So far alkylbenzenesulfonates have been used as surfactants. On Reason of their comparable cheap cleaning ability and their good solubility properties they can in such Advantageously, the alkylbenzenesulfonates in whole or in part replace. So that the beneficial ecological properties of Dialkyl ether sulfates come to bear sufficiently, such Preferred agents in which at least 50 wt .-% of conventional Alkylbenzenesulfonates are replaced by the dialkyl ether sulfates. Particularly preferred are agents without a content of Alkylbenzenesulfonates.  

The agents containing dialkyl ether sulphates may be d. H. powdered, granular or as shaped pieces or also present in liquid or pasty form.

As constituents of component (a), the inventive Contain additional anionic or nonionic surfactants. These include, in particular, soaps, and also surfactants from the sulfonate and sulfate type and nonionic compounds, e.g. B. off the class of polyglycol ether derivatives. Surfactants with high biological Degradation rates and low toxicity in aquatic systems are preferred.

Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids having 12 to 22 carbon atoms. Particularly suitable are natural fatty acids, eg. As coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C _12-18 fatty acid soaps and 0 to 50% of oleic acid soap.

Useful surfactants of the sulfonate type are - taking into account the above-mentioned reservations - linear alkylbenzenesulfonates (C _9-13 alkyl) and olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those from C _12-18 monoolefins with terminal or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline hydrolysis of the sulfonation. Also suitable are alkanesulfonates obtainable from C _12-18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, as well as alpha-sulfo fatty acids and their esters, eg. As the alpha-sulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof. The alpha-sulfoesters and alpha-sulfofatty acid disalts are preferred.

Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as. B. coconut oil fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol or the C _10-18 oxo alcohols, sulfuric monoesters of with 1 to 6, preferably 1 to 2 moles of ethylene oxide ethoxylated aliphatic primary alcohols or ethoxylated alcohols are also well suited. Also suitable are sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides.

The additional anionic surfactants are usually in the form their sodium salts. Their share in relation to the mean is in general from 0 to 25% by weight, preferably from 3 to 20% by weight including the dialkyl ether sulfates.

Nonionic surfactants are preferably adducts from 2 to 20, preferably 3 to 15 moles of ethylene oxide to 1 mole of a Compound having substantially 10 to 20 carbon atoms from the Group of alcohols used. These include water-soluble addition products from 7 to 15 moles of ethylene oxide with primary alcohols, such as As to coconut oil or tallow fatty alcohols, to oleyl alcohol, to Oxo alcohols or to secondary alcohols having 8 to 18, preferably 12 to 20 carbon atoms. Besides these water-soluble nonionics are but also not or not completely water-soluble polyglycol ethers with 2 to 6 ethylene glycol ether radicals and the same  C chain length of interest, characterized by increased cleaning power distinguish it from greasy soiling.

Further suitable nonionic surfactants are alkyl glycosides or Alkyl polyglycosides whose alkyl group is 8 to 18, preferably 10 to 16 carbon atoms. The content of nonionic agents Surfactants or nonionic surfactant mixtures is 0 to 25 wt .-%, preferably 1 to 20 wt .-% and in particular 2 to 15 wt .-%.

As zwitterionic surfactants are those with betaine structure and the known sulfobetaines. Cationic surfactants, for example quaternary ammonium salts having a C _10-16 alkyl chain and three lower alkyl groups, preferably methyl groups, may also be included. At a weight ratio of anionic surfactant (including dialkyl ether sulfate) to cationic surfactant of from 3: 1 to 25: 1, they can increase the detergency of the compositions, especially over greasy soils.

The total content of surfactants depends on the purpose from 1 to 50 wt .-%. In solid means it is preferably 5 to 30 wt .-% and in particular 8 to 25 wt .-%. In It is usually higher and liquid than salt-free is 15 to 50 wt .-%, preferably 20 to 45 wt .-%.

Component (b) consists of builder salts and sequestering agents, individually or mixed with each other the calcium hardness water or precipitate or disrupting heavy metal ions bind complex and thus increase the cleaning power and an undesirable Decomposition of sensitive components, such as peroxygen compounds and enzymes, prevent.  

Suitable constituents of component (b) are in particular ecological harmless builder salts, such as fine crystalline, synthetic hydrous zeolites of Tpy NaA, which have a calcium binding capacity in the range of 100 to 200 mg CaO / g (as specified in DE 22 24 837). Their particle size is usually in the Range from 1 to 10 μm. In solid or pasty means their content is generally 0 to 40, preferably 10 to 30 wt .-%, based on anhydrous substance.

As further constituents of component (b), in particular together used with the zeolites, come (co) polymers Polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid. The molecular weight the homopolymer is generally between 1000 and 100,000, that of the copolymer between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid. A special preferred acrylic acid-maleic acid copolymer has a molecular weight from 50,000 to 100,000.

Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%. Also useful are polyacetal carboxylic acids, as described, for example, in US Pat. Nos. 4,144,226 and 41 46 495 and by polymerization of esters Glycolic acid, introduction of stable terminal end groups and Saponification to the sodium or potassium salts are obtained. Suitable are also polymeric acids obtained by polymerization of Acrolein and disproportionation of the polymer to Canizzaro means strong alkalis are obtained. They are essentially  from acrylic acid units and vinyl alcohol units respectively Acrolein units built.

The content of the (co) polymeric polycarboxylic acids is based on free acid 0 to 15 wt .-%, preferably 0.5 to 10 wt .-% and in particular 1 to 5 wt .-%.

The components of component (b) further include nitrilotriacetate (NTA), preferably in the form of the sodium salt, as well as Polycarboxylic acids, such as citric acid, also preferred as the sodium salt. Furthermore, the salts of polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid, optionally also Aminoalkanpolyphosphonsäure such as aminotrimethylenephosphonic acid (ATP), ethylenediamine tetramethylene phosphonate, (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP), as well as their higher Homologues. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as hexasodium salt of EDTMP or hepta- and octa-sodium salt of DTPMP. Your share in the Means calculated on free acid is generally 0 to 3% by weight, in particular 0.1 to 1.5 wt .-%.

In cases where a phosphate content is tolerated, can Phosphates are also used, in particular pentasodium triphosphate, possibly also pyrophosphates, due to their solubility properties can be used in liquid detergents, as well as orthophosphates, which are primarily used as precipitants act for lime salts. Preferably, however, the content of phosphates, based on pentasodium triphosphate, below 30 wt .-%, in particular below 20 wt .-% are.  

The components of component (b) also include wash alkalis such as alkali metal silicates, in particular sodium silicates of Composition Na₂O: SiO₂ = 1: 1 to 1: 3.5, preferably 1: 2 to 1: 3,35. Their proportion in the agents can be 0 to 8% by weight, in particular 2 to 5 wt .-%, wherein in the presence of zeolites their proportion preferably does not substantially exceed 3% by weight.

As Waschalkali is also sodium carbonate in question, its share up to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 5 to 10 wt .-% is. The amount of sodium carbonate and Sodium silicate may contain up to 30% by weight, preferably 5 to 20% by weight. be.

To the other detergent components (component c), whose Share depending on the composition of the funds up to 80, preferably until 50 wt .-% and in particular 5 to 40 wt .-%, include graying inhibitors (Debris), bleach, bleach activators, optical brighteners, foam inhibitors, enzymes, fabric softening Fabrics, dyes, fragrances and neutral salts, Solvent and water.

As part of this component (c), the washing and cleaning agents Contain grayness inhibitors, those of the Keep fiber-loosened dirt suspended in the liquor and so on prevent graying. These are water-soluble colloids mostly organic nature suitable, such as the water-soluble Salts of polymeric carboxylic acids, glue, gelatin, salts of Ethercarbonsäuren or ether sulfonic acids of starch or Cellulose or salts of acidic sulfuric acid esters of cellulose or the strength. Also water-soluble, containing acidic groups  Polyamides are suitable for this purpose. You can continue soluble starch preparations and starch products other than those mentioned above use, such. B. degraded starch, aldehyde levels etc. Also, polyvinylpyrrolidone is useful. carboxymethylcellulose (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and their mixtures are preferably used. The proportion of compounds is generally 0.2 to 2, preferably 0.5 to 1.5% by weight.

Among those serving as bleach, in water H₂O₂ supplying Compounds have the sodium perborate tetrahydrate (NaBO₂ · H₂O₂ · 3 H₂O) and the monohydrate (NaBO₂ · H₂O₂) of particular importance. Also useful are peroxycarbonate (Na₂CO₃ · 1.5 H₂O₂), Peroxypyrophosphate, Citrated perhydrate, urea perhydrate or melamine perhydrate and H₂O₂ supplying persaure salts or peracids, such as Perbenzoates, peroxyphthalates, diperazelaic acid or diperdodecanedioic acid.

To wash at temperatures below 80 ° C, especially in Range of 40 to 60 ° C, to achieve an improved bleaching effect, Bleach activators can be incorporated into the preparations become. Examples of these are formed with H₂O₂ organic peracids N-acyl or O-acyl compounds, preferably N, N'-tetraacylated Diamines such as N, N, N ', N'-tetraacetyl-ethylenediamine, further Carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate.

The detergents can be used as optical brighteners for cotton in particular Derivatives of Diaminostilbendisulfonsäure or their alkali metal salts contain. Suitable z. B. salts of the 4,4'- Bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilben-  2,2'-disulphonic acid or compounds of similar structure, which instead of the morpholino group, a diethanolamino group, a Methylamino group or a 2-Methoxyethylaminogruppe carry. When Brightener for polyamide fibers are those of the type of 1,3-diaryl 2-pyrazolines in question, for example the compound 1- (P-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline. Farther For example, brighteners of the substituted 4,4'-distyryldiphenyl type can be used to be present; z. B. the compound 4,4'-bis- (4-chloro-3-sulfostyryl) -diphenyl. Also mixtures of the aforementioned Brightener can be used.

Suitable enzymes include those from the class of proteases, lipases and Amylases or mixtures thereof in question. Particularly suitable are Bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. The enzymes can be adsorbed to carriers and / or embedded in encasing substances to protect them against premature decomposition to protect.

Suitable foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica. Also, bis-acylamides derived from C _12-20 alkylamines and C _2-6 dicarboxylic acids are useful. Advantageously, mixtures of different foam inhibitors are used, for. As those of silicones and paraffins or waxes. Preferably, the foam inhibitors are bound to a granular, water-soluble or dispersible carrier substance.

As textile softening additives are phyllosilicates from the class of bentonites and smectites, e.g. B. those according to DE 23 34 899  and EP 2 65 529. Also suitable are synthetic finely divided Phyllosilicates with smectite-like crystal phase and reduced Swelling property of the formula

MgO (M₂O) _a (Al₂O₃) _b (SiO₂) _c (H₂O) _n

with M = sodium, optionally together with lithium, with the proviso that the molar ratio Na / Li is at least 2, a = 0.05 to 0.4, b = 0 to 0.3, c = 1.2 to 2 and n = 0.3 to 3, wherein (H₂O) _{n stands} for the bound water in the crystal phase. Also suitable are synthetic layer silicates, after suspension in water (16 ° dH, room temperature) a swelling capacity - measured as the quotient of the sediment volume (V _s) / total volume (V) after previous treatment with excess soda solution, careful washing and 20 hours after suspension in 9 parts by weight of water / one part by weight of phyllosilicate - of V _s / V less than 0.6, in particular less than 0.4, as well as synthetic phyllosilicates, which are formed in mixed crystal and thereby have structurally determining saponite and / or hectorite-like crystal phases, which are irregular in shape Arrangement interspersed with crystalline alkali metal polysilicate. Such sheet silicates are further characterized in DE 35 26 405. The content of phyllosilicates may be, for example, up to 20% by weight.

The preparation of powdery to granular agent can be in common Way, d. H. by spray drying under these conditions resistant components and then admixing the heat-sensitive components, such as bleaches, enzymes, perfumes and foam inhibitors. Other suitable methods are the granulation of the ingredients, whereby water, salt solutions, Polymer solutions and / or nonionic surfactants as Granulierflüssigkeit can be used.

Examples

As test mixtures, the following granular or liquid Detergent used. To be in the remission measurement no interference brightening with optical brightener brightener Mixtures and non-lightened test fabrics used. In In practice, the blends would be between 0.1 and 0.5% by weight conventional Contain brightener.

Table 1

It is therefore a phosphate-reduced powdery Detergent I, a phosphate-free powdered detergent II and a phosphate-free liquid detergent III. It means

AA-MA copolymer = Na salt of an acrylic acid-maleic acid copolymer, molecular weight 70,000 phosphonate = Na salt of diethylenetriaminepentamethylenephosphonic acid cellulose ethers = Mixtures of carboxymethylcellulose and hydroxyethylmethylcellulose water Total water content including the water bound to zeolite and as water of crystallization.

The anionic surfactant used in the comparative experiments (designation V) was linear C _10-13 -alkylbenzenesulfonate-Na salt (abbreviation LAS), which was replaced in the experiments according to the invention by dialkyl ether sulfates (Na salts) according to formula I. In all compounds, R² and R⁴ were H and M was Na. The remaining symbols had the meanings given in Table 2, where the numbers represent the number of C atoms in R¹ and R³ or the EO groups (n) .

Table 2

The funds were in launderometer (abbreviation LM) and in a Household machine (abbreviation WM) with horizontally arranged frontloader Drum used in the latter case, an automatic Single-lye process (without prewash) was programmed. The water hardness was 16 ° d (corresponding to 160 mg CaO per liter). The washing temperature and the detergent concentration (in g / l) are listed in the table. It was under standardized conditions Used soiled textile tabs when using the washing machine washed with 3 kg of clean linen were. The following test stains were used:

A1 Pigment / Hautfettanschmutzung on cotton and refined cotton
A2 mineral oil soiling on blended fabric of polyester fiber and refined cotton
A3 make up on blended fabric according to A2

The percentage remission (abbreviation% R) was determined photometrically. The values given in the following tables are mean values from 3 determinations within a range of 2%. A remission difference of 2% is also with the bare one Eye still recognizable and thus corresponds to one from the consumer noticeable effect.

The results show that the detergency of the dialkyl ether sulfates on the order of commercial dodecylbenzenesulfonate and even partially surpasses them.

The biodegradability test was followed Standard tests (% MBHS and BiAS in the OECD Screening Test Values for primary mining between 92 and 99%. Fish toxicity (in Milligrams of active ingredient per liter) gave LC für values of 2 mg / l to 22 mg / l and 118 mg / l with mean LC von = 7.5 g / l and LC₁₀₀ = 22 g / l. The comparative values for dodecylbenzylsulfonate are about 3 times to 5 times lower thus corresponding unfavorable. Compared to conventional nonionics, fish toxicity is reversed the factor 6 times to 8 times lower. The bacterial toxicity of all Samples tested against B. robra after oxygen deoxygenation test was above 10 000 mg AS / l (active substance per liter) and is therefore classified as very low.  

Table 3

Claims (9)

1. washing and cleaning agent of solid or liquid form, containing

• a) from 1 to 50% by weight of at least one anionic or cationic surfactant,
• b) 1 to 90 wt .-% of at least one compound from the class of builder salts and sequestering agents and
• c) difference up to 100% by weight of other customary detergent and cleaner ingredients,

characterized in that the component (a) consists wholly or partly of a secondary dialkyl ether of the general formula I. in which the symbols have the following meaning: M = Na, K, Mg, ammonium or an organic ammonium cation, R¹ = linear C₁-C₁₆ alkyl radical, R³ = linear or branched alkyl radical having 1 to 22 C atoms, with the proviso in that the sum of the C atoms in (R₁ + R₂) = 1 to 18 and in (R₁ + R₂ + R₃) = 8 to 22, R⁴ = hydrogen or CH₃ and n = numbers from 0 to 15. 2. Composition according to claim 1, characterized in that in the compounds of the formula I, the symbols have the following meaning: R² = H, R³ = C _1-12 alkyl, R⁴ = H, M = Na or triethanolamine and n = 1 until 10. 3. Composition according to claim 1 or 2, characterized in that less as 50 wt .-%, preferably 0% of component (a) Alkylbenzenesulfonates omitted. 4. Composition according to one or more of claims 1 to 3, characterized characterized in that the means 1 to 25 wt .-% of Dialkyl ether sulfates of the formula I included. 5. Composition according to one or more of claims 1 to 4, characterized characterized in that they contain additional anionic surfactants from the Class of soaps, alpha-sulfofatty acid ester salts and alpha Sulfofatty acid disalts, in proportions up to 25% by weight. 6. Composition according to one or more of claims 1 to 5, characterized characterized in that they are nonionic surfactants, in particular Ethoxylates of fatty alcohols and / or oxo alcohols with 12 to 18 C atoms and 2 to 15 ethylene oxide groups in amounts of 1 to Contain 20 wt .-%. 7. Composition according to one or more of claims 1 to 6, characterized characterized in that they contain less than 20% by weight of phosphates, based on pentasodium triphosphate. 8. Composition according to one or more of claims 1 to 7, characterized characterized in that they are fine crystalline zeolites in proportions from 10 to 30 wt .-%, based on anhydrous substance.