EP0005850B1 - Liquid washing agent - Google Patents

Description

The present invention relates to a stable, liquid detergent with a textile-softening effect for simultaneous washing and care of delicates in the washing machine or by hand.

There has long been a need for a liquid, mild detergent containing fabric softener that gives the textiles the desired softening and antistatic properties during the washing process. Because of the known incompatibility of the usual quaternary ammonium or imidazolinium textile softeners with anionic surfactants, the use of anionic surfactants in such liquid preparations excluded. It therefore made sense to use combinations of nonionic surfactants and quaternary ammonium compounds. From GB-PS 830 864 liquid detergents are known, the nonionic surfactants and quaternary ammonium compounds which have a long-chain alkyl radical and three short-chain alkyl radicals. According to the information provided by Seifen-Ole-Fette-Wwachs (1963), 4, page 78, the washing effect of such combinations is particularly good if the ratio of the nonionic surfactant to the quaternary ammonium compound is in the ratio 4: 1 to 1: 1. A liquid detergent with a combination of a nonionic surfactant, a conventional softening quaternary ammonium compound with one or two long-chain alkyl radicals and a further quaternary ammonium compound with a methyl group, one or two long-chain alkyl groups and two or a polyglycol ether group is described in DE-OS 24 26 581 described. A liquid detergent with a combination of a nonionic surfactant of the alkyl polyglycol ether or alkylphenol polyglycol ether type and a conventional fabric softener of the difatty alkyl dimethyl ammonium halide type and a fatty acid polyglycol diester is also known from DE-OS 25 29 444.

However, these proposed solutions could not be satisfactory because these detergents cannot achieve a balance in terms of washing power, plasticizing performance and foaming behavior.

In order to avoid the disadvantages inherent in these detergents, the older German patent application P 28 17 834.9 proposes a liquid detergent with a detergent component made from two specific nonionic surfactants of the ethoxylated long-chain alcohol type and with a plasticizing component from a quaternary ammonium compound. The quaternary ammonium compound used is in particular ammonium salts with two long-chain alkyl or alkenyl and two short-chain alkyl groups, especially those compounds whose long-chain residues are derived from saturated or unsaturated tallow fatty alcohols. As is known, these are alkyl or alkenyl groups with essentially 16 and 18 carbon atoms, i.e. around palmityl, palmitoleyl, stearyl, oleyl and linoleyl residues.

In addition to satisfactory washing properties, the consumer also demands from a modern liquid detergent that it is safe to use, easy to dose and stable in storage, and that its appearance and smell meet the expectations of the consumer. In particular, high demands are placed on the perfuming of a detergent by the consumer. Not only does the cheap absorption of a detergent often depend on whether it has a pleasant fragrance, but the detergent fragrance also has the application-specific task of masking the often unpleasant smell of detergent during washing, and that which is aimed at in the case of freshly washed, moist and dried laundry Complement the washing result with a laundry smell that conveys the impression of cleanliness and freshness.

When assembling a liquid detergent based on nonionic surfactants, the proportion of which is in the range of 10-30% by weight, it has been shown that when using a conventional textile softener of the distearyldimethylammonium chloride type or the ditallow alkyldimethylammonium chloride with hardened tallow alkyl residues Because of the low water solubility of this compound, the incorporation of the required amounts is difficult and leads to mixtures which become viscous and poorly pourable, especially at low storage temperatures, and which therefore require the use of large amounts of organic solvents. The perfuming of such mixtures is problem-free, but because of their unfavorable viscosity properties it seemed necessary to switch to other fabric softeners which do not have these disadvantages.

In addition to the quaternary ammonium compounds with one or two long-chain alkyl radicals, the person skilled in the art also knows the derivatives of the unhardened tallow alcohol, which in particular contains oleyl but also palmitoleyl and linoleyl radicals in a proportion of about 45%, as useful textile plasticizers. Although the mixtures produced with this type of compound have the desired viscosity properties, which are also largely independent of the cold, the perfumed mixtures are not stable in storage, which manifests itself in a change in fragrance to an unpleasant smell and in a change in color of the liquid. The same observations were made with the corresponding imidazolinium compounds with saturated or - at least partially - unsaturated long-chain aliphatic groups.

On the basis of these findings, the expert was faced with the task of finding a textile softener which can be formulated perfectly with a detergent component based on two specific nonionic surfactants, which gives the washed waxes the expected useful properties in terms of softness, fluffiness and antistatic finish, and also that The smell of the fragrance-added product in line with the market did not change undesirably during storage.

• a) 5-18 Gew.-% eines Alky.lpolyglykoläthers der Formel
  
  in der R¹ eine geradkettige Alkylgruppe und R² zu 20-bis 75 Gew.-% - bezogen auf den dem Alkylpolyglykoläther zugrunde liegenden Alkohol - eine C_I-C_4-Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R¹ und R² 11-15 beträgt, und n einen Wert von 5-9 bedeutet, und wobei n so ausgewählt ist, daß der Äthylenoxidanteil des Alkylpolyglykoläthers etwa 50-65 Gew.-% beträgt,
• b) 5-18 Gew.-% eines Alkylpolyglykoläthers der Formel I, in der R¹ eine geradkettige Alkylgruppe und R² entweder Wasserstoff, oder zu 20-75 Gew.-% - bezogen auf den dem Alkylpolyglykoläther zugrunde liegenden Alkohol - eine C₁-C₄-Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R¹ und R² 6 - 10 beträgt und n einen Wert von 3-8 bedeutet, und wobei n so ausgewählt ist, daß der Äthylenoxidanteil des Alkylpolyglykoläthers etwa 55-70 Gew.-% beträgt, und
• c) 2,5-10, vorzugsweise 3-7 Gew.-% eines Textilweichmachers, bestehend aus Verbindungen der Formel II
  
  in der R³ geradkettige oder verzweigte Alkylreste mit im wesentlichen 14-16 Kohlenstoffatomen und X- ein Anion aus der Chlorid, Bromid, Methylsulfat, Äthylsulfat, Methan-, Äthan- oder Toluolsulfonat umfassenden Gruppe bedeutet, enthält, wobei das Mengenverhältnis von a): b) vorzugsweise 2:1 bis 1:2 beträgt.

This object was achieved according to the invention by a liquid detergent with a combination of two different nonionic surfactants and a fabric softening agent, which is characterized in that it

• a) 5-18% by weight of an alkyl polyglycol ether of the formula
  
  in which R ^{1 is} a straight-chain alkyl group and R ² is 20 to 75% by weight, based on the alcohol on which the alkyl polyglycol ether is based, a C ₁ -C ₄ -alkyl group and, moreover, hydrogen, the total number of carbon atoms in R ¹ and R ^{2 is} 11-15, and n is a value of 5-9, and where n is selected so that the ethylene oxide content of the alkyl polyglycol ether is about 50-65% by weight,
• b) 5-18% by weight of an alkyl polyglycol ether of the formula I in which R ^{1 is} a straight-chain alkyl group and R ^{2 is} either hydrogen, or 20-75% by weight, based on the alcohol on which the alkyl polyglycol ether is based, a C ₁ -C ₄ alkyl group and hydrogen mean, where the total number of carbon atoms in R ¹ and R ^{2 is} 6-10 and n is a value of 3-8, and where n is selected so that the ethylene oxide content of the alkyl polyglycol ether about 55 Is -70% by weight, and
• c) 2.5-10, preferably 3-7% by weight of a fabric softener consisting of compounds of the formula II
  
  in which R ^{3 contains} straight-chain or branched alkyl radicals with essentially 14-16 carbon atoms and X- is an anion from the group comprising chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate, the quantitative ratio of a) being: b) is preferably 2: 1 to 1: 2.

The alkyl polyglycol ethers of the formula I which are suitable according to the invention as constituent a) are derived from alcohols which are prepared by reacting linear olefins with carbon monoxide and hydrogen by the known oxo process by hydroformylation and exclusively hydrogenation. Commercially available oxo-alcohol mixtures which are suitable for the preparation of the surfactant component a) are, for example, the oxo alcohols available from Deutsche Shell Chemie Gesellschaft under the trade name "Dobanol", which have about 25% by weight of 2-alkyl branches. Other suitable oxo alcohols are available under the name "Synprol" from Imperial Chemical Industries Ltd. available alcohol mixtures with about 50-70 wt .-% 2-alkyl branches. Other suitable products based on oxo alcohols are e.g. various "Lutensol" types from BASF with approx. 30-35% by weight of branched alcohols and some "Lial" types from Liquichimica S.p.A. with about 60 wt .-% branched alcohols.

Particularly preferred as component a) are alkyl polyglycol ethers which represent ethylene oxide condensates of the aforementioned oxo alcohols with 13-15 carbon atoms with an average ethylene oxide content of approximately 55-65% by weight. Typical preferred products are, for example, "Dobanol 45-7", which consists of at least 95% C ₁₄ / C ₁₅ oxo alcohol with an average of 7 moles of ethylene oxide, and "Lutensol AO-8", which is a C ₁₃ / C ₁₅ oxo alcohol Ethoxylate with an average of 8 moles of ethylene oxide.

As component b), alkyl polyglycol ethers are preferred, the alcohol base of which is natural or synthetic primary fatty alcohols or oxo alcohols, which contain 9-12 carbon atoms and have an ethylene oxide content of approx. 60-70% by weight. Typical preferred products are, for example, the commercial product "Marlipal KF," (Chemische Werke Huls), which is a C ₁₀ / C ₁₂ fatty alcohol ethoxylate with an average of 6 moles of ethylene oxide, and the "Lutensol ON-70," which is a C ₉ / C ₁₁ -oxo represents alcohol ethoxylate with an average of 7 moles of ethylene oxide. Suitable fatty alcohols as the basis for preferred alkyl polyglycol ethers are also the commercial products "Lorol C-8 to 12" (Henkel).

The ratio of the amount of component a) used to the amount of component b) essentially determines the parameters of washing power, foaming behavior and softening effect. Optimal results are obtained when the ratio of a): b) is between about 2: 1 and 1: 2.

In general, amounts of 10 to 30% by weight, based on the total weight of the detergent, of component a) and component b) are used, an amount of 15-30% by weight being preferred.

US Pat. No. 3,691,081 describes a detergent mixture intended for industrial use, the surfactant component of which consists of a liquid mixture of longer-chain and shorter-chain primary alcohol ethoxylates. The longer-chain alcohol ethoxylates are C ₁₁ to C ₂₀ oxo alcohols with 5-10 mol of ethylene oxide, and the shorter-chain alcohols are derived from C ₆ to C ₁₀ alcohols, which also have 5-10 mol of ethylene oxide, where the main part is derived from C ₇ to C _s alcohols. From this publication, the person skilled in the art can see a liquid, biodegradable nonionic surfactant mixture which is a substitute for the known, non-degradable alkylphenol ethoxylates.

The quaternary ammonium compounds which are suitable according to the invention as component c) can be obtained by reacting 1 mol of methylamine with 2 mol of C ₁₆ / C ₁₈ epoxide, which is obtainable by epoxidation of the corresponding α-olefin, and subsequent quaternization.

Compounds of the formula II whose alkyl radicals R ³ are essentially straight-chain and have 14 and 16 carbon atoms in the ratio C ₁₄ : C ₁₆ such as 3: 7 to 7: 3 are preferably used. Such compounds are derived from an essentially C ₁₆ / C ₁₈ -α-olefin. In practice, an olefin mixture with a content of 35-45% by weight of α-C ₁₆ -olefin and 55-65% by weight of α-C ₁₆ -olefin or the epoxy produced therefrom is used in particular. The epoxide / methylamine reaction product which has been quaternized with methyl chloride or dimethyl sulfate to give compounds of the formula II has proven particularly useful as component c) of the agent according to the invention.

Similar reaction products as the quaternary ammonium compounds of formula II defined above are known from US Pat. No. 3,636,114 as textile softeners for post-washing. Quaternary ammonium compounds, the long alkyl residues of which can be interrupted by ether, amide and ester bonds, or which can have up to 2 hydroxyl groups, and the use of these compounds in powdery laundry aftertreatment agents are also known from US Pat. No. 3,591,405. However, compounds of the formula II defined above and compositions containing them are not specifically mentioned in this US Pat. From the Dutch patent application 68.08958, liquid aqueous laundry aftertreatment compositions containing the compounds of US Pat. No. 3,591,405 are also known.

In addition to the customary quaternary ammonium compounds with one or two long alkyl radicals, a large number of compounds with a completely different structure are described in the literature as textile plasticizers, e.g. Esters of sulfosuccinic acid and polyhydroxyamines (US Pat. No. 4,056,558), imidazoline oxides (US Pat. No. 3,607,765), higher tertiary aliphatic amines (DE-OS 26 46 995), alkylammonium carbamates (US Pat. Nos. 4,025,444 and 3,962,100) or certain clays (U.S. Patent 4,062,647).

The teaching of the present invention can be derived neither directly nor indirectly from the broad prior art. It is therefore highly surprising that liquid detergents which contain the quaternary ammonium compounds of the formula II as component c) in combination with the two nonionic surfactants of the formula I as components a) and b) have an optimum in terms of detergency, softening action, and foam behavior in connection with easy perfumability, good storage stability and low viscosity even at low temperatures. The agents according to the invention also have the further advantage that they have an optically appealing haze without the addition of special opacifiers, which are considered undesirable ballast in terms of washing technology and usually also have a problematic odor.

Water is preferably used as the solvent for the liquid detergents according to the invention. However, organic solvents can also be used in amounts of up to 20% by weight of the total liquid detergent. But even with much lower additions of the organic solvent, which are of the order of 5% by weight, mixtures can be produced which have perfect properties. Lower alkanols or lower diols or polyols such as, for example, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol or glycerol are particularly suitable as additional solvents. If appropriate, polyols with ether compounds such as methyl, ethyl, butyl or diethylene glycol or their acetates (for example products of the "Cellosolve" type from Union Carbide Corp.) can also be used.

Formalin is usually used as a preservative in an amount of 0.05-1% by weight.

In order to avoid discolouration of the detergents during prolonged storage, which can be caused by impurities, for example with heavy metal ions during production, complexing agents for heavy metal ions are added. Common complexing agents are Sodium, potassium or triethanolamine salts of aminopolycarboxylic acids, such as, for example, ethylenediaminetetraacetic acid or nitrilotriacetic acid. They are used in amounts of 0.1 to 1% by weight.

Examples of suitable fragrances are substances with a floral / fresh or fruity fragrance or those designated as cosmetic or creamy.

Suitable dyes are e.g. water-soluble red xanthene dyes, such as rhodamine B-extra.

• a) 10-12,5 Gew.-% eines Alkylpolyglykoläthers der Formel I, in der R¹ und R² zusammen 11-13 Kohlenstoffatome aufweisen und wobei der durchschnittliche Äthylenoxidgehalt des Alkylpolyglykoläthers 55-65 Gew.-% beträgt,
• b) 10-12,5 Gew.-% eines Alkylpolyglykoläthers der Formel 1, in det R¹ 7-10 Kohlenstoffatome aufweist, R² = H ist und wobei der durchschnittliche Äthylenoxidgehalt des Alkylpolyglykoläthers 60-70 Gew.-% beträgt.
• c) 2,5-5 Gew.-% eines quartären Ammoniumsalzes der Formel II für Bestandteil c), in der R³ einen im wesentlichen geradkettigen Alkylrest mit 14 bis 16 Kohlenstoffatomen und X- Chlorid bedeutet, wobei das Gewichtsverhältnis von C₁₄:C₁₆-Alkylresten etwa gleich 2:3 ist,
• d) Rest Wasser und organische Lösungsmittel sowie gegebenenfalls weitere übliche, in geringen Mengen anwesende Zusätze wie z.B. Farb- und Duftstoffe, Komplexierungsmittel für Schwermetallspuren sowie Konservierungsmittel.

Detergents whose composition lies within the following limits have proven particularly useful:

• a) 10-12.5% by weight of an alkylpolyglycol ether of the formula I in which R ¹ and R ² together have 11-13 carbon atoms and the average ethylene oxide content of the alkylpolyglycol ether is 55-65% by weight,
• b) 10-12.5% by weight of an alkylpolyglycol ether of the formula 1 in which R ^{1 has} 7-10 carbon atoms, R ² = H and the average ethylene oxide content of the alkylpolyglycol ether is 60-70% by weight.
• c) 2.5-5% by weight of a quaternary ammonium salt of the formula II for component c), in which R ^{3 is} an essentially straight-chain alkyl radical having 14 to 16 carbon atoms and X chloride, the weight ratio of C ₁₄ : C ₁₆ alkyl residues is approximately equal to 2: 3,
• d) remainder water and organic solvents and, if appropriate, other customary additives present in small amounts, such as colorants and fragrances, complexing agents for traces of heavy metals and preservatives.

The detergents according to the invention can be used for washing and simultaneously softening fine laundry articles made of wool, synthetic fibers such as polyester, polyacrylonitrile, polyamide and mixtures of wool and synthetic fibers. The washing and softening process can take place either in the washing machine or by hand at washing temperatures up to about 40 ° C. The application concentration of the agents is generally from 2 to 20 ml / l of washing solution, preferably from 3 to 6 ml / l. The detergents are characterized by the fact that they clean the textiles perfectly and at the same time give them a pleasant feel and anti-electrostatic properties. When washing by hand in the washbasin, they form a dense, pleasant foam, and no foaming is observed when washing in the washing machine. The foam can also be easily rinsed out.

Examples

An agent of the following composition was tested for its washing performance, its softening properties and for its foaming behavior during hand washing and in the washing machine:

example 1

The perfume oil used with a fragrance note that could be described with floral fantasy lavender with a radiantly fresh top note had the following composition (given in parts by weight):

The liquid detergent according to the invention, which contains customary additives in conventional amounts, has been found to wash fine textiles in the washing machine at up to 40 ° C. and by hand as a product with an optimal combination of properties with regard to washing power, softening effect and foaming behavior. In comparison to a detergent which contained the same amount of di (tallow alkyl) dimethyl ammonium chloride derived from unsaturated tallow alcohol residues instead of the fabric softener mixture present in the composition according to the invention, the use after previous storage at temperatures from -10 ° C. to + showed up 40 ° C for about 70 days in PVC bottles of 750 ml, that the fragrance and the appearance of the agent according to the invention as well as the washing liquors and the scent of laundry from a test panel from experienced assessors practically as good as the fragrance and appearance of the freshly made-up agent were graded. In contrast, the smell of the comparative detergent had changed so that the test subjects clearly rejected it.

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Führt man mit den Mitteln der Beispiele 2 bis 7 die gleichen Tests durch, wie sie in Beispiel 1 beschrieben sind, erhält man auch mit diesen Mitteln entsprechend günstige Resultate.

If the same tests as described in Example 1 are carried out with the means of Examples 2 to 7, correspondingly favorable results are also obtained with these means.

Claims (10)

1. A liquid detergent, characterised in that it contains

a) from 5 to 18% by weight of an alkyl polyglycol ether corresponding to the following formula

in which R¹ represents a straight-chain alkyl group and from 20 to 75% by weight of R² - based on the alcohol from which the alkyl polyglycol ether is derived - represents a C₁-C₄-alkyl group, the rest of R² being hydrogen, the total number of carbon atoms in R¹ and R² amounting to between 11 and 15, and n = 5 to 9, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between about 50 and 65% by weight,

b) from 5 to 18% by weight of an alkyl polyglycol ether corresponding to formula I in which R¹ represents a straight-chain alkyl group and R² either represents hydrogen or from 20 to 75% by weight - based on the alcohol from which the alkyl polyglycol ether is derived - of R² represents a C₁-C₄- alkyl group, the rest being hydrogen, the total number of carbon atoms in R¹ and R² amounting to between 6 and 10, and n = 3 to 8, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between about 55 and 70% by weight, and

c) from 2.5 to 10 and preferably from 3 to 7% by weight of a textile softener consisting of compounds corresponding to the following formula

in which R³ represents straight-chain or branched alkyl radicals essentially containing from 14 to 16 C-atoms and X- is an anion from the group comprising chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluene sulfonate, the quantitative ratio of a) to b) preferably amounting to between 2:1 and 1:2.

2. A liquid detergent as claimed in Claim 1, characterised in that the alkyl radicals R3 in formula II for constituent c) are substantially linear and contain 14 and 16 carbon atoms in a ratio of C₁₄:C₁₆ of from 3:7 to 7:3.

3. A liquid detergent as claimed in Claims 1 and 2, characterised in that the compounds of formula II are derived from an olefin mixture containing from 35 to 45% by weight of α-C₁₆-olefin and from 55 to 65% by weight of α-C₁₈-olefin.

4. A liquid detergent as claimed in Claims 1 to 3, characterised in that X- is the chloride or the methyl sulfate anion.

5. A liquid detergent as claimed in Claims 1 to 4, characterised in that constituent a) and constituent b) together make up from 10 to 30% by weight and preferably from 15 to 30% by weight of the detergent as a whole.

6. A liquid detergent as claimed in Claims 1 to 5, characterised in that R' and R² of constituent a) together contain from 11 to 13 carbon atoms.

7. A liquid detergent as claimed in Claims 1 to 6, characterised in that constituent a) contains from about 55 to 60% by weight of ethylene oxide.

8. A liquid detergent as claimed in Claims 1 to 7, characterised in that R' and R² of constituent b) together contain from 8 to 10 carbon atoms.

9. A liquid detergent as claimed in Claims 1 to 8, characterised in that constituent b) contains from about 55 to 65% by weight of ethylene oxide.

10. A liquid detergent as claimed in Claims 1 to 9 consisting of

a) from 10 to 12.5% by weight of an alkyl polyglycol ether of formula I in which R' and R^2. together contain 11 to 13 carbon atoms, the average ethylene oxide content of the alkyl polyglycol ether amounting to between 55 and 65% by weight,

b) from 10 to 12.5% by weight of an alkyl polyglycol ether of formula I in which R' contains from 7 to 10 carbon atoms, R² = H, the average ethylene oxide content of the alkyl polyglycol ether amounting to between 60 and 70% by weight,

c) from 2.5 to 5% by weight of a quaternary ammonium salt of formula II for constituent c) in which R³ is a substantially linear alkyl radical containing from 14 to 16 carbon atoms and X- is chloride, the ratio by weight of C₁₄:C₁₆-alkyl radicals being approximately 2:3,

d) a balance of water and organic solvents and, optionally, other standard additives in small quantities, such as for example dyes and fragrances, complexing agents for traces of heavy metals and preservatives.