FI85382B - MJUKGOERANDE OCH ANTISTATISK NON-JONISK TVAETTMEDELSKOMPOSITION. - Google Patents

Description

1 85382

This invention relates to an aqueous liquid detergent composition for washing and softening soiled garments which can be added to the washing cycle of an automatic washing machine.

Compositions that can be used to treat textiles to improve their softness and feel are known in the art.

When fabric softeners are used in household laundry, they are typically added to the rinse water during a rinse cycle lasting only 2-5 minutes. The consumer must therefore monitor the washing operation or take other precautions so that the fabric softener is added at the appropriate time. This forces the consumer to return to the washing machine just before or at the start of the rinsing cycle of the washing operation, which is obviously inconvenient for the consumer. In addition, special care must be taken to use an appropriate amount of textile softener to avoid overdosing, which may make clothing water-repellent when a greasy film precipitates on the surface of the textiles, and to make the textiles slightly yellowed.

As a solution to the above problems, it has been known to use textile softeners which are compatible with ordinary laundry detergents, so that the softeners can be combined with the detergents in one and the same package for use during the washing cycle of the laundry operation. Examples of such textile softener compositions added to a wash cycle are disclosed in U.S. Patents 3,351,438, 3,660,286 and 3,703,480 and several 2,85,382 others. These fabric softening compositions added to the wash cycle usually contain a cationic quaternary ammonium compound as a softener and in addition ingredients that make the softener compounds suitable for combination with conventional laundry detergents.

It is also known that cationic softeners added to the wash cycle either as an ingredient in the detergent-softener composition or as a fabric softener in the wash cycle interfere with the brightening effect as well as the cleaning efficiency of the detergent. As a result, attempts have been made to prevent some of this interfering effect in detergent-softener compositions by using nonionic surfactants, higher brightener concentrations, carboxymethylcellulose, anti-yellowing agents, sealants, etc. But little improvement has been achieved in the wash cycle. of softening compositions using a large number of detergents, most of them anionic.

Several disclosures of detergent compositions containing cationic plasticizers, such as a quaternary ammonium compound as a plasticizer and nonionic surfactants, are known in the art. Representatives of this technique include U.S. Patents 4,264,457, 4,239,659, 4,259,217, 4,222,905, 3,951,879, 3,360,470, 3,351,483, 3,644,203, etc. In addition, U.S. Patents 3,537,993, 3 In particular, 583,912, 3,983,079, 4,203,872 and 4,264,479 disclose combinations comprising a nonionic surfactant, a cationic textile softener and another ionic surfactant or modifier such as zwitterionic surfactants. substances, amphoteric surfactants, etc.

Although many of these prior art recipes provide satisfactory washing and / or softening under a variety of conditions, they still suffer from the disadvantage that they do not provide sufficient softening - compared to, for example, softeners added to the rinse cycle.

U.S. Patent 3,920,565 discloses a liquid fabric softener composition added to a rinse cycle containing 2-15% cationic fabric softener and 0.5-4.0% alkali metal salt of a 16-22 carbon fatty acid (soap) and optionally Up to 2% non-ionic emulsifier, and the remainder water. Di-higher-alkyl-dimethyl-ammonium chlorides are the preferred cationic compounds, although mono-higher-alkyl-quaternary compounds are also mentioned.

Mono-higher alkyl quaternary ammonium compounds, such as stearyltrimethylammonium chloride, which are relatively soluble in water, are generally considered in the art to be less effective emollients than di-higher alkyl cationic quaternary emollients (see, e.g., U.S. Patent No. 4 23). 965), and therefore their use, for example, with anionic detergents such as fatty acid soaps, with which they are able to form emollient complexes, has been proposed as softeners for the rinse cycle.

However, as mentioned above, for some time it has been considered highly desirable for convenience to use a fabric softening mixture at the same time as the detergent in the washing cycle of the washing machine.

U.S. Patent No. 4,852,382 discloses laundry detergent compositions which may be in liquid form and which consist of certain nonionic surfactants and certain cationic surfactants such as mono-higher alkyl quaternary ammonium compounds such as from tallow alkyl litrimethylammonium halide in a weight ratio of nonionic: cationic from 5: 1 to about 1: 1. This patent advises that the amount of anion-forming substances should be kept to a minimum and preferably avoided altogether, but in all cases anionic substances having a dissociation constant of less than 1 x 10 such as sodium C,., Q, alkylbenzenesulfonate, should only be up to 10% by weight based on the cationic surfactant.

U.S. Patent 4,239,659 discloses combined nonionic / cationic surfactant-detergent compositions having a nonionic / cationic weight ratio of about 1: 1 to 40: 1 and wherein the nonionic surfactant is from the class of a hydrophilic-lipophyll balance (HLB) of about 5 to about 17, and the cationic surfactant is from the class of mono-higher alkyl-quaternary ammonium compounds having from about 20 to about 30 carbon atoms in the higher alkyl. This patent generally states that other additive components may be included in the art up to stabilized concentrations and states that they are about 0-40%. An extensive list of additive components includes semipolar nonionic, anionic, zwitterionic, and ampholytic surfactants, builders, dyes, fillers, enzymes, bleaches, and many others. There is no example or notification of anionic surfactants; however, it is stated that the co-surfactants must be compatible with nonionic and cationic compounds and may be any of the anionic compounds disclosed in U.S. Patent 4,259,217.

This latter patent discloses a mixture of nonionic surfactants having an HLB of about 5 to about 17 and a cationic surfactant and mono-higher alkyl 5,8382 li-quaternary anunonium compounds in which the nonionic / cationic weight ratio is 5.1: 1 to about 100: 1. According to this patent, detergent compositions may contain up to 50%, preferably from about 1% to about 15% of anionic surfactants and / or zwitterionic surfactants. Anionic surfactants include e.g. straight chain alkyl benzene sulfonates and alkyl ether sulfates. Example XV of this patent, column 40, discloses a high performance liquid laundry detergent composition having the following formula:

Ingredient Weight% 3 moles of ethylene oxide ethoxylated 2-alpha alcohol sodium sulfate 5.0

Ethoxylated alcohol containing an average of 6.5 moles of ethylene oxide 20.0

Coconut alkyl trimethylammonium chloride 3.5

Glycine 8.0

Sodium toluene sulphonate 10.0

Water and minor ingredients up to 100%.

The following high performance liquid composition is shown in Example XVII (column 41):

Ingredient Weight% ____ C 1 -C 4 fatty alcohol condensate with an average of 7 moles of ethylene oxide 28.5

The triethanolamine salt of a straight-chain alkylbenzenesulfonic acid having an average of 11.9 carbon atoms in the alkyl chain 20.0

C 1-6 alkyl dihydroxyoxyethylmethylammonium chloride 1,5-f-Ethanol 10.0

Diethylenetriamine-pentamethylphosphonic acid 0.3

Citric acid 0.2 6 ·: <5 362

Ingredient 9% w / w mixture of dimethyl polysiloxane and acrogel silica emulsified in a strongly ethoxylated fatty acid (commercially available from Dow Corning under the trademark DB31) 0.3

Saturated fatty acid having 16 to 22 carbon atoms in the alkyl chain 0.75

Proteolytic enzyme 0.4 Minor amounts of additives and water up to 100%.

U.S. Patent 4,264,457 discloses a liquid laundry detergent and fabric softener composition comprising about 3-35% by weight of a nonionic surfactant, 3-30% by weight of a mono-higher alkyl quaternary ammonium compound as a cationic surfactant. as an agent and a mixture of anionic surfactants such as (a) C4-C10 alcohol sulfates and (b) C12-C22 alcohol-ethoxylated ether sulfates or carboxylates. The molar ratio of total amounts of cationic surfactant / anionic surfactant can range from 0.8: 1 to 10: 1. According to this patent, the choice of these two specific anionic surfactants and their relative amounts are essential to obtain maximum detergent, softness and antistatic properties of the detergent, and other known anionic surfactants are excluded from the mixture.

An improved composition has now been found, characterized in that it contains: A) about 10 to 50% by weight of a liquid nonionic detergent selected from the group consisting of compounds of formulas I and II: RO (CH 2 CH 2 O) n H (I) li 7 8 5 382 wherein R is a primary or secondary alkyl chain having from about 8 to 22 carbon atoms and n averaging about 5 to 20; R 1 -O- (CH 2 CH 2 O) m H (II) wherein R 1 is a primary or secondary alkyl chain having about 4 to 12 carbon atoms and m averaging about 5 to 20; B) about 1-20% by weight of a mono-higher alkyl quaternary ammonium compound of formula III or IV: * r2 r3S + 'N X- (III) r3 ^ r3

N S

/ 9 N,

Rz (CH2CH2O) XH + X- (IV), / \

R · 3 (CH2CH2O) yH

wherein R 1 is a long chain aliphatic radical of about 10 to 22 carbon atoms, each of R 1 in formula III and R 1 in formula IV independently represents lower alkyl or hydroxy (lower alkyl), X is a water-soluble salt-forming anion, and x and y are each positive numbers of at least 1, and the sum of x + y is 2-15; C) about 1-20% by weight of a sulfosuccinamate detergent compound of the formula 8 85382 O R4 \ / h9c - c - n I \ _ (V) ZO3-S-CHCOOZ R5 wherein Z is a monovalent salt-forming cation, R4 is hydrogen, lower alkyl, carboxy (lower alkyl) or 1,2-dicarboxy (lower alkyl), and R 1 is an open chain hydrocarbon having from 10 to 22 carbon atoms; D) up to about 10% by weight of an anionic surfactant; selected from the group consisting of straight-chain higher alkyl aromatic sulfonates, poly-lower alkoxy-higher alkanol sulfates, olefin sulfonates and paraffin sulfonates; E) up to about 3% by weight of optical brightener; F) up to about 15% ethoxylated amine; G) up to about 5% alkaline; H) up to about 3% enzymes; I) up to about 3% soil release agent; and J) an aqueous solvent carrier, wherein the ratio of B): C) is from about 3: 1 to 1: 3.

In addition, this softening and antistatic effect is achieved without sacrificing, and in many cases even significantly improving, the bleaching and washing performance.

li 9 8S382

Although an excellent softening and antistatic advantage is obtained with liquid nonionic detergent compositions based on a complex of a cationic textile softener and a straight-chain alkyl benzene sulfonate, further improvements in overall cleaning performance are desired. It is also desired that it be possible to form a complex between a mono-higher alkyl quaternary fabric softener and many more commercially available anionic detergents than just straight-chain alkyl aromatic sulfonate anionic compounds.

With further studies, it has now been found that both of these objects can be achieved quite easily by adding one additional surfactant to the composition, which is a sulfosuccinamate compound. The addition of the sulfosuccinamate compound clearly enhances the detergency of the nonionic / cationic mixture with or without the additional benefits of other anionic surfactants such as straight chain alkyl benzene sulfonate.

The present invention is based on precisely this finding.

It is therefore an object of the present invention to improve the softening, bleaching antistatic effect in detergent compositions containing a quaternary ammonium compound as a softener and non-ionic detergent compounds, thereby clearly improving the overall cleaning performance.

It is another object of this invention to formulate stable, liquid detergent-softener compositions using mono-higher alkyl quaternary arammonium compounds as cationic softeners and nonionic compounds and sulfosuccinate surfactants as predominant surfactant surfactants. with enzymes, soil release agents and other detergent additives.

ίο 85382

It is a further object of the invention to provide a laundry detergent softener composition for use in a wash cycle which is capable of effectively cleaning a wide variety of dirt stains such as clay grades, oil, grease, etc., and softening both natural and synthetic fibers and textiles.

These and other objects of the invention will become apparent from the following description and are provided by a laundry detergent composition capable of washing soiled garments in an aqueous washing liquid, the composition containing a nonionic compound and a sulfosuccinamate surfactant as the main surfactants, mono-higher -alkyl quaternary ammonium compound as a cationic fabric softener and optionally an anionic surfactant. In a preferred embodiment, the composition is in the form of an aqueous liquid and the detergent composition comprises at least one colorant and / or bleach, in particular dyes, sealants and optical brighteners and mixtures thereof and other optional detergent additives, in particular enzymes and soil release agents.

In other useful embodiments, the composition may be formulated to contain only or substantially an anhydrous liquid carrier or a mixture of water and an organic solvent. In yet another embodiment, the composition may be formulated as a paste or a highly viscous liquid.

The nonionic surfactants contemplated can usually be any of the nonionic surfactants known to be useful detergents for washing soiled textiles.

Suitable nonionic surfactants are commercially available and are derived from the condensation of an alkylene oxide or equivalent reactant and a hydrophobic containing reactive hydrogen. Hydrophobic organic compounds may be aliphatic, aromatic or heterocyclic, although the first two classes of compounds are preferred. Preferred hydrophobic types are higher aliphatic alcohols and alkyl phenols, although others may be used, such as carboxylic acids, carboxamides, mercaptans, sulfonamides, etc. classes. The hydrophobic moiety should normally contain at least about 6 carbon atoms, and preferably at least about 8 carbon atoms, and may contain as many as about 50 carbon atoms and above, but the preferred amount is between about 8-22 carbon atoms, especially 10-18 carbon atoms with aliphatic alcohols and 12 carbon atoms. With alkylphenols higher than -20 carbon atoms. The amount of alkylene oxide varies considerably depending on the hydrophobic, but the general guideline and rule is that at least about 3 moles of alkylene oxide per mole of hydrophobic compound should be used up to 200 moles, preferably about 3-50 moles still preferably 5-20 moles of alkylene oxide per mole of hydrophobic, the desired washing performance and compatibility with other components would be achieved.

Preferred nonionic surfactants can be represented by the formula j R0 (CH2CH2O) nH (I) wherein R is a primary or secondary alkyl chain containing from about 8 to 22 carbon atoms and n is on average 5-50, lumen 5-20, especially 6-13; and R 1 - (O 2 - O- (CH 2 CH 2 O) m H (II) - wherein R 1 is a primary or secondary alkyl chain having 4 to 12 carbon atoms and m is on average 5 to 50, preferably 5 to 20, especially 6 to 13.

Preferred alcohols from which the compounds of formula I are prepared are lauryl, myristyl, cetyl, stearyl and oleyl alcohols and mixtures thereof. Particularly preferred values for R are and C 1-5 alkyl 12 85 382 and mixtures thereof are particularly preferred.

The preferred values of R 'in formula II are cg ~ C · ^' and Cg and Cg, such as octyl, iso-ok-style and nonyl, are particularly preferred.

A typical example of a non-ionic compound of formula I is lauryl alcohol condensed with 5 or 7 or 11 moles of ethylene oxide. A typical example of a nonionic compound of formula II is isooctylphenol or nonylphenol condensed with 3-8 moles of ethylene oxide.

Other nonionic compounds that can be used include polyoxyalkylene esters of organic acids such as higher fatty acids, rosin acids, tall oil acids, acids derived from petroleum oxidation products, and the like. These esters usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 3 to about 30 moles of ethylene oxide or equivalent.

Other nonionic surfactants include alkylene oxide condensates with higher fatty acid amides and amines. The fatty acid group usually contains from about 8 to about 22 carbon atoms and is condensed with from about 3 to about 30 moles of ethylene oxide in the preferred embodiment. The corresponding carboxamides and sulfonamides can also be used as suitable equivalents.

Although ethylene oxide is taken up, for example, as an alkylene oxide group in nonionic surfactants, the use of: nonionic surfactants prepared with propylene oxide, preferably ethylene oxide and. with a mixture of propylene oxide is within the scope of the invention.

“* For example, surfactants sold as a well-known Plurafac series such as Plurafac B-26, which is a reaction product of a mixture of a higher straight chain alcohol and ethylene and propylene oxides and contains a mixed chain of ethylene and propylene oxide ending in a hydroxyl group.

li 13 8 5 382

Preferred poly-lower alkoxylated higher alkanols generally have a number of lower alkoxy of 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40% to 60% thereof, and the nonionic detergent preferably contains at least 50% of the lower alkoxy. % of this preferred poly-lower-alkoxy-higher alkanol. Higher molecular weight alkanols and several other non-ionic detergents and surfactants normally in solid form may contribute to the gelation of liquid detergent formulations and are therefore preferably avoided or limited in their respective liquid compositions, although they may be used in smaller amounts. and may more preferably be more strongly present in viscous or pasta recipes. In both preferred and less preferred non-ionic detergents, the alkyl groups are preferably straight-chain, but a smaller amount of some branching is tolerated, such as the straight-chain terminal carbon at the next carbon atom or two carbon atoms away from it and the ethoxy chain branched off; alkyl is not more than three carbons in length. Normally, the relative number of carbon atoms in such a branched configuration is lower, rarely more than 20% of the total number of alkyl carbon atoms. Similarly, although straight chain alkyls terminally attached to ethylene oxide chains are preferred and are considered to provide the best combination of detergency, naturally degradable and non-gelling properties, there may be middle or secondary attachments to the ethylene oxide in the chain. Usually it is only a smaller fraction of these alkyls, usually less than 50%, but for example in the case of h Tegritols it may be a larger fraction. Also, when propylene oxide is present in the lower alkylene oxide chain, it is usually less than 20% of them and preferably less than 10% of them, although higher percentages may be used, as in some Plurafac products.

14 85382

The amount of the nonionic compound is usually at least the minimum amount which, when added to the wash water, provides a suitable cleaning effect. Generally, amounts ranging from about 1% to about 50%, more preferably from about 10% to about 40%, and particularly preferably from about 12% to about 35% by weight of the composition may be used.

The other main ingredient in the recipes in question is a cationic emollient. Softeners are used to make clothes or textiles soft, and the terms "softener" and "softener" refer to handling, hand, touch, and feel; this is the touch impression given by the fabrics or textiles on the hand or body and has aesthetic and commercial significance. The cationic fabric softeners used in this invention are mono-higher alkyl-quaternary ammonium compounds and can be represented by the following formula: "r2 r31 +

N X III

3 '\ 3

Lr r _. . ·. wherein R is a long chain aliphatic radical having 16- * to 3 22 carbon atoms and the three R groups are independently lower alkyl or hydroxyalkyl radicals and X is a water-soluble salt-forming anion such as a halide, for example chloride, bromide, iodide; sulfate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or a similar inorganic or organic solubilizing radical. Carbon chain of an aliphatic radical having 10 to 22 carbon atoms, especially 12 to 20, preferably 12 to 18 carbon atoms ·· - may be straight or branched, and saturated or unsaturated.

λ. Lower alkyl radicals have 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, especially methyl, and may contain: i .: a hydroxy radical. Carbon chains are preferably obtained from long chain fatty acids such as those derived from tallow or soybean oil. The terms "soybean" and "tallow", etc., as used herein, refer to the source from which the long chain fatty alkyl chains are derived. Quaternary am- tt can be used.

is 8 5 382 mixtures of multiium compound plasticizers. The preferred anunonium salt is mono-higher alkyl-trimethylammonium chloride in which the alkyl group is derived from tallow, hardened tallow or stearic acid. Specific examples of quaternary ammonium plasticizers of formula III suitable for use in the composition of this invention include e.g. the following: tallow trimethylammonium chloride, hardened tallow trimethylammonium chloride, trimethylstearylammonium chloride, triethylstearylammonium chloride, trimethylcetylammonium chloride, soya trimethylammonium chloride, stearyldimethylacetyl chloride -diisopropylmethylammonium chloride, their corresponding sulfate, methosulfate, ethosulfate, bromide and hydroxide salts, etc.

Another useful class of commercially available quaternary ammonium plasticizers are ethoxylated compounds of formula IV

! R3 +! 2 '; R -n- (ch2ch20) xh X (IV)

(CH2CH20) yH

2 3 ·· where X, R and R are the same as defined in the context of formula III and x and y are each positive numbers of at least 1 and the sum of x + y is 2-15,

One particularly preferred compound of formula IV is 3 2

Sold by Armak under the trademark Ethoquad 18/12 (R = CH 2 -, R = C 18 -alkyl, x + y = 12).

-I. The amount of monoalkyl quaternary cationic fabric softener may usually be from about 1% to about 20%, predominantly from about 4% to about 16%, and particularly preferably from about 5% to about 10% by weight of the composition.

The weight ratio of nonionic surfactant to cationic fabric softener may be from about 1: 1 to 15: 1, preferably from about 1.5: 1 to 10: 1, particularly preferably from about 2: 1 to 8: 1.

16 ö 5 3 8 2

The sulfosuccinamate surfactant is the third major active ingredient in the present compositions of the invention. These compounds are characterized by having a 10-22 carbon open chain hydrocarbon substituent attached to a nitrogen atom at the carbonamide group (-CON 2) at one carboxy terminus of the succinamate moiety and a sulfonyl group (-SO 2 -) attached to one of the carbon atoms alpha or beta position relative to the carbonamide group.

Examples of the sulfosuccinamate compound are disodium N-octadeyl sulfosuccinamate (available under the trademark Alkasurf SS-TA from Alkaril Chemicals or under the trademark ASTROMID 18 from Alco Chemical Corp.), disodium N-oleyl sulfosuccinamate (available from Alkaril Chemicals from Alkaril Chemicals) ; tetrasodium N- (1,2-dicarboxyethyl) -N-octadecyl sulfosuccinamate available under the trademark ASTROMID 22, Alco Chemical Corp., or under the trademark Monawet SNO-35, Mona Industries, Inc.).

More generally, however, suitable sulfosuccinamate compounds can be represented by the following general formula V: 0 R 4 "/ CHO-C-N (V): I \ 5

Z-03-S-CH-C00Z

wherein Z is a monovalent salt-forming cation such as an alkali metal, ammonium and amine, R is hydrogen, lower alkyl, carboxy (lower alkyl), or 1,2-dicarboxy (lower alkyl), and is an open chain hydrocarbon having 10-22 carbon atoms, -i. Of the alkali metals, sodium and potassium or lithium are preferred and sodium is especially preferred.

The cation forming the monovalent amine salt may be, for example: a mono-, di- or tri-lower alkanolamine such as a mono-, di- or triethanolamine.

The "lower alkyl" group may have 1 to 5, preferably 1 to 3, particularly preferably 1 to 2 carbon atoms.

The open-chain hydrocarbon represented by 5 R may be saturated or unsaturated and may be a straight-chain or branched group, predominantly alkyl or alkenyl having 14 to 18, especially 16 to 18, carbon atoms such as, for example, tallow, hydrogenated tallow, fractionated tallow, oleyl , octadecyl, stearyl, etc.

When there is carboxy (lower alkyl) or 1,2-dicarboxyl (lower alkyl), such as carboxyethyl, carboxypropyl, carboxy-2-methyl-ethyl, 1,2-dicarboxyethyl, etc., the carbonyl group or groups may be in the form -COOY, wherein Y is a group Z or lower alkyl; Y is primarily Z, especially sodium.

The amount of sulfosuccinamate must be carefully selected depending on such factors as the nature and amount of the nonionic surfactant and the cationic fabric softener and especially the sulfosuccinamate itself as well as the anticipated washing conditions, type of textiles, stains, washing temperatures, water hardness, etc. best washing results when sulfosuccinamate surfactant, nonionic surfactant and mono-higher. the amounts of alkyl cationic fabric softener are each in the following ranges - by weight based on the total composition:

Wide range Preferred range a) non-ionic surfactant: V: substance 10-50 12-35 b) monoalkyl quaternary substance 1-10 2-6 c) sulfosuccinamate surfactant: - active substance 1-10 2-6

Within the above limits, the weight ratios a): b), a): c) and b): c) are also important, although here too the optimal values may vary with different compounds and different washing conditions. In most cases, however, the ratios a): b) and a): c) are between about 15: 1-1: 1, preferably 10: 1-1.5: 1, particularly preferably 8: 1-2: 1.

18 85382

The weight ratio b): c) should usually be between about 3: 1-1: 3, preferably about 2: 1-1: 2, particularly preferably about 1.3: 1-1: 2. The weight ratio a): b) + c) is about 10: 1-1: 1, mainly 6: 1-1.5: 1.

According to a preferred embodiment of the invention, for example, when the nonionic substance is a 2'-alcohol alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of alcohol (such as Shell Oil Co. product Neodol 25-7), about 15-25% by weight. % of the total composition, the monoalkyl quaternary fabric softener is thalitrimethylammonium chloride and the sulfosuccinamate is tetrasodium N- (1,2-dicarboxyethyl) -N-octadecyl sulfosuccinate (e.g. Monawet SNO-35) are the preferred ratios nonionic / quaternary and quaternary / sulfosuccinamate between about 12: 1-4: 1 and about 1: 1-1: 2, respectively, under typical washing conditions, e.g., 49 ° C, 0.2% product concentration, hardness 100 ppm ions , with a very wide range of textile and dirt types.

An optional but most preferred additional component in the detergent composition of the invention is an anionic surfactant. As disclosed in the above-mentioned FI patent application no. 854032, the softening and antistatic effectiveness of a nonionic surfactant and a mono-higher alkyl quaternary ammonium softener are clearly improved when a straight-chain alkyl aromatic sulfonate detergent is used, primarily 1: as a molar complex with a quaternary fabric softener.

Examples of suitable anionic detergents are water-soluble salts of higher-straight-chain alkyl aromatic sulfonates containing from about 8 to 26 carbon atoms, preferably from 10 to 22 carbon atoms, in the alkyl radical, for example sodium, potassium, ammonium, alkylol ammonium salts. (The term alkyl includes the alkyl moiety of higher acyl radicals).

Preferred examples of straight-chain alkyl-N-aromatic sulfonates are those containing from 10 to 16 carbon atoms in straight-chain alkyl radicals, for example, straight-chain alkylbenzene sulfonates, higher straight-chain alkyl-toluene sulfonates, higher phenol I! 19 85382 Sodium, potassium and ammonium salts of sulphonates and higher straight-chain alkyl naphthalene sulphonates. Straight-chain higher alkyl benzenesulfonates such as C 10 -C 16 alkyl and especially C 1 -C 14 alkyl, for example (n-dodecyl) alkyl benzenesulfonates are particularly preferred anionic surfactants.

In addition to straight-chain alkyl aromatic sulfonates, another preferred class of anlonic surfactants which enhance overall detergency, especially antistatic activity and softening, in the detergent compositions of the invention comprises alkyl ether sulfates of the formula R 2 O ) -SO 2 M with higher alkyl having 8 to 20 carbon atoms, especially 10 to 18 carbon atoms., M is a solubilizing salt-forming cation such as alkali metal ion, alkaline earth metal ion, ammonium ion, ammonium ion , substituted with 1 to 3 lower alkyl or mono-, di- and trialkanolamines having 2 to 3 carbon atoms in the alkanol group or groups, and p is a number from 2 to 8, predominantly 2 to 6 (especially 1/5 to 1/3) or 1/2 of the number of carbon atoms in R. The preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company and is marketed under the name Neodol - · 25-3S. The substance, the sodium salt, is usually sold as a product containing 60% of the active ingredient in an aqueous solvent medium. Although Neodol 25-3S is a sodium salt, potassium salt and other suitable soluble salts of triethyleneoxy-higher alcohol (12 to 15 carbon atoms) sulfate and other such compounds disclosed herein, which have already been ... referenced and which will be described below, used either in whole or in part to replace sodium salts. As in many cases of the substances of the compositions in question, mixtures thereof can also be used.

Examples of higher alcohol polyethylene oxysulfates that can be used as an anionic detergent or a partial substitute for the liquid detergents in question include: mixed C12-4 normal or primary alkyl triethylene oxysulfate, sodium salt; myristyl triethylene oxysulphate, potassium salt; n-Decyl diethylene oxysulfate, diethanolamine salt; lauryl diethylene oxysulfate, ammonium salt; palmityl tetraethylene oxysulfate, sodium salt; mixed C1-normal-primary-alkyl-mixed tri- and tetraethylene oxysulfate, sodium salt; stearylpentaethylene oxysulfate, trimethylamine salt; and mixed C 1-8 normal primary alkyl triethylene oxysulfate, potassium salt. Smaller amounts of branched chain and center alkoxylated detergents, such as those described above, but modified by ethoxylation to a central carbon atom, e.g., four carbons at the end of the chain, can also be used and the number of higher alkyl carbon atoms is the same. Likewise, coupling to normal alkyl can occur on a secondary carbon at a distance of one or two carbon atoms from the end of the chain. In either case, as indicated above, only smaller relative amounts should be present, as in the normal case of 10 or 20%.

As is the case with the preferred nonionic detergents, these poly-lower alkoxy-higher alkanol sulfates are readily degradable in nature and have better detergency when the fatty alkyl is terminally linked to the poly-lower oxyalkylene chain terminally linked to the sulfate. In this case as well, as in the case of non-ionic detergents, a smaller amount, for example not more than 10% branching and, in the middle, is tolerated. It is generally preferred that the alkyl in an anionic alkoxylate detergent, such as a nonionic detergent, be a mixture of different chain lengths, such as 11, 12, 13, 14 and 15 carbon atoms or chains containing 12 and 13 carbon atoms, rather than all of the same chain length. However, the invention can be applied to liquid detergents containing pure nonionic and anionic components.

Ethylene oxide is, of course, the preferred lower alkylene oxide in an anionic alkoxylate detergent as it is in a nonionic detergent and its proportion in polyethoxylated higher alkanol sulfate is predominantly 2-5 moles of ethylene 21 8 5 3 8 2 mole per oxide group and in the preferred compositions, 2 to 4 moles, of which three moles are most preferred, especially when the higher alkanol has 12 to 13 carbon atoms or 11 or 12 to 15 carbon atoms. To maintain the desired hydrophilic-lipophilic balance when the number of carbon atoms in the alkyl chain is less than 10-18 at the end of the carbon number range, the ethylene oxide content in the detergent can be reduced to about two moles per mole, while the higher alkanol contains 16-18 carbon atoms at the larger end. add to 4 or 5 and in some cases as high as 8 or 9. Likewise, the salt-forming cation can be exchanged for best solubility. It may be any suitable solubilizing metal or radical, but it is most often an alkali metal, for example sodium, or ammonium. If lower alkylamine or alkanolamine groups are used, the alkyls and alkanols usually contain 1 to 4 carbon atoms, and the amines and alkanolamines may be mono-, di- or trisubstituted, such as monoethanolamine, diisopropanolamine and trimethylamine.

Poly-lower alkoxy-higher-alkanol sulfates and straight-chain--. non-alkyl aromatic sulfonates are considered to be the best complementary detergents in such compositions, but other anionic detergents may be used with or in place of such compounds. In particular, alpha-olefin sulfonates, paraffin sulfonates and higher alcohol sulfates can be used. Olefin sulfonate salts usually contain long chain alkenyl sulfonates or long chain hydroxyalkane sulfonates (wherein OH is on the carbon atom not directly attached to the carbon atom having the -SO 2 H group). The olefin sulfonate detergent usually comprises these types of .1. to varying degrees, often in combination with long chain disulfonates or sulfate sulfonates.

These are olefin sulfonates and are described in several patents, such as U.S. Patent Nos. 2,061,618, 3,409,637, 3,332,880, 3,420,875, 3,428,654, 3,506,580 and GB Patent No. 1,129,158.

The number of carbon atoms in the olefin sulfonate is usually between 10 and 25, more usually between 10 and 20, or between 12 and 18, for example a mixture of 22 85382 predominantly C , and an average of about 16 carbon atoms.

Another class of useful anionic detergents is higher paraffin sulfonates. These may be primary or secondary paraffin sulfonates prepared by reacting long chain alpha-olefins and bisulfites, e.g. or by some other suitable base (such as in U.S. Patents 2,503,280, 2,507,088, 3,260,741, 3,372,188 and DE Patent 735,096). Paraffin sulfonates contain primarily 13 to 17 carbon atoms and are usually monosulfonates, but may be di-, tri-, or higher sulfonates if desired. Typically, di- and polysulfonates are used in admixture with the corresponding monosulfonate, for example, as a mixture of mono- and disulfonates containing up to about 30% disulfonate. Their hydrocarbon substituent is predominantly straight chain, but if desired, branched chain paraffin sulfonates can be used and, although they are not as good in terms of natural decomposition.

The paraffin sulfonate may be sulfonated at its ends or the sulfonate substituent may be attached to the carbon of the chain at position 2 or to another carbon atom, and likewise any di- or higher sulfonate used may have sulfonate groups distributed to different carbon atoms in the hydrocarbon chain.

Paraffin sulfonates and olefin sulfonates are used in the form of their alkali metal salts, for example in the form of sodium and potassium, ammonium or mono-, di- and tri-lower alkanolamine salts: or mixtures thereof. Triethanolamine is the preferred alkanol salt-forming cation. Straight-chain alkylbenzenesulfonates and alkyl ether sulfates are considered to be particularly preferred anionic surfactants.

li 23 85382 These anionic surfactants are capable of reacting with a mono-higher alkyl quaternary compound, thus enhancing the softening and antistatic effect, and in addition have the effect of providing a number of optional detergent additives, which will be described in more detail. behind, especially optical brighteners, to land more effectively on the surfaces of washable textiles.

Although no special rules can be applied to each combination of ingredients and all washing conditions, it has been found as a general rule that of the two preferred classes of anionic surfactants, straight-chain alkyl benzene sulfonates are usually somewhat more effective than alkyl ether sulfonates the addition of any anionic surfactant often causes only a slight improvement in the cleansing effect compared to the same composition without anionic surfactant. Of course, mixtures of two or more anionic surfactants can be used.

Since the anionic surfactant is expected to form a complex with the cationic softener, which provides an enhanced softening / antistatic effect without interference, or slightly improving the cleaning effect of the nonionic agent or the effect of the brightener in the detergent composition, the cationic / anionic ratio is particularly important. either component could adversely affect overall performance. Therefore, cationic / anionic ratios of about 1.3: 1-1: 1.5, preferably 1.2: 1-1: 1.2, particularly preferably 1.1: 1-1: 1.1, and most preferably about 1: 1 provide an improved softening effect and antistatic effect, as well as improved whiteness and perhaps cleansing.

The total amount of cationic / anionic plasticizer mixture in the detergent composition is usually between about 2-20%, preferably 5-15% by weight based on the total composition. The total amount of cationic plasticizer and anionic surfactant is usually between about 20-100%, preferably 30-80% by weight, based on the nonionic surfactant. In the amounts and ratios indicated above, the cationic / anionic plasticizer mixture is compatible with the sulfosuccinate amate and optical brightener, etc. of the nonionic surfactant.

The solvent carrier for the liquid detergent composition in question is aqueous and may be water only or may be predominantly water to which co-solvents have been added for some specific ingredients. Due to the easy availability of water and the minimal cost, it is considered best to use water as the main solvent. However, other solvents may be used, usually up to 20% and preferably up to 15% of the total concentration. Such a co-solvent is usually either a lower alkanol or a lower diol or a polyol, for example ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, etc. Ether polyols such as diethylene glycol and those known as Cellosolve may also be used.

In addition to the complementary solvent, it is usually preferred to add a hydrotropic agent to the recipe to make the compatibility of all active ingredients as good as possible and to make the liquid recipe more homogeneous and stable. Examples of suitable hydrotropes include alkali metal aryl sulfonates such as sodium benzene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate and the like potassium salts. The hydrotrope may be used in an amount of about 15%, preferably 10% by weight of the total mixture, for example 1-8% or 2-6%. Although aqueous carriers are best. . anhydrous liquid carriers such as the above-mentioned organic co-solvents can also be used as the sole or main carrier, i.e. non-aqueous liquid carriers may comprise about 50-100% by weight of the liquid carrier and the remainder, if necessary, is water and / or hydrotropic material. Mixtures of two or more organic solvents may also be used.

: ·: In addition, the following detergent compositions consisting of three main components can be formulated: non-ionic surfactant, mono-higher-alkyl-quaternary ammonium compound

II

65382 and sulfosuccinamate detergent plus optional anionic surfactant and any detergent additives, in the form of highly viscous compositions such as gels, pastes, etc., using, for example, well known and conventional thickeners with a liquid carrier, for example cellulose ethers, methylhydroxyethylcellulose, hydroxypropylcellulose, etc., xanthan gum, clay minerals, etc. Alternatively, the compositions may also be prepared directly as pastes or high viscosity liquids by simply mixing the various ingredients without a liquid carrier or only in small amounts, for example up to about 20% by weight. mainly water or water / organic solvent.

The water used to formulate the liquid or pasty detergents in question may come from the starting materials themselves, such as solutions or suspensions of the various detergent salts, or may be added. When added, it is preferred to use deionized water, or water with a low degree of hardness, for example less than 50 ppm hardness as salts such as calcium carbonate, primarily less than 10 ppm CaCO 2 · But although it is disadvantageous to use hard water, it may still be done and obtained. good products from waters as hard as 200 ppm, but usually the use of such water is avoided if possible.

Various selected suitable additives may also be included in the liquid detergent composition to provide the desired additional properties that are either functional or aesthetic in nature. Thus: enzymes can be added to the recipe; for example proteases, amylases, lipases, etc., and mixtures thereof; bleach; bleach activating and stabilizing agents; stain suspending or anti-settling agents, for example polyvinyl alcohol, sodium carboxymethylcellulose, hydroxypropylmethylcellulose; dirt removers, for example, Polymer QCJ from Alkaril Chemicals for removing engine oil stains, etc .; dyes, sealants 26 85382 substances, pigments, optical brighteners, for example brighteners for cotton, amide and polyester fibers; preservatives, for example methyl paracept or sodium benzoate; ultraviolet absorbers, pH modifiers, for example amines, pH buffers; opalescent agents, for example behenic acid, polystyrene suspensions, etc .; bactericides, for example hexachlorophene; and perfumes. The additives are, of course, selected to be compatible with the main ingredient of the detergent composition.

Of the additives mentioned, perhaps the most important in terms of functional effect are optical brighteners, because the modern hostess expects washed clothes not only to be clean and white, but also to look bright. Optical brighteners are substantive over washed textiles (such substantivity may be selective) and are sometimes relatively poorly soluble. As a result, it is important that they remain dissolved in the liquid detergent composition and, more importantly, they must be immediately dispersed in the wash water so as to avoid a washing result with clearly visible brighter spots rather than a clear appearance throughout. The choice of brightener, so that the best results are obtained, can be easily ascertained by an expert. It has been found that relatively small amounts of brighteners should be used so that solubility limits are not exceeded. In the category of these substances, it has also been found that certain brighteners dissolve particularly easily and are therefore suitable for addition to these products. Fortunately, these preferred brighteners are brighteners for both cotton and amide polyester fibers, making them suitable for use in laundry containing a variety of materials and synthetic materials.

Commercial brighteners used in this system include Tinopal UNPC, Tinopal CBS (Ciba-Geigy), Arctic White CC (Hilton V,. Davis) and the following Phorwhites products from Verona: BKL, BUP, BBC solution, BRV solution, DCR fluid, DCBVF, EV-nest.e, DBS fluids and ANR.

27 8 5 382

Other types of optical brighteners which give an excellent bleaching effect are those components which have a sulfonate moiety. The preferred class of brighteners for use in this invention is 2- (4-styrylphenyl) -2H-naphthol / 1,2-d7-triazoles, 4,4'-bis- (1,2,3-triazol-2-yl) -stilbenes, 4,4'-bis- (styryl) -bisphenyls and γ-aminocoumarins. Specific examples of brighteners are 4-methyl-7-diethylaminocoumarin, 1,2-bis (benzimidazol-2-yl) ethylene and 1,3-diphenylfrazolines, as well as 2,5-bis- (benzoxazole) 2-yl) -thiophene, 2-Styryl-naphth- [1,2-d] oxazole and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] -triazole.

The content of the optical brightener in the liquid composition is usually about 0.2% to about 3.0% and mainly 0.25 to 2.7%. Such concentrations are soluble in the liquid detergents described and clearly brighten the washed garments.

As mentioned above, the presence of an anionic surfactant may improve the uniform deposition of the optical brightener on the Textile.

Another optional additive is organic detergent builders except nitrilotriacetates and sequestrants. Representatives of detergent builders and sequestering or chelating agents include sodium citrate, potassium gluconate, polyacrylic acids, ethylenediaminetetraacetic acid and its alkali metal, alkaline earth metal, amine, alkanolamine and ammonium salts, etc. It is generally preferred to be preferred. , avoid inorganic builders, especially phosphate builders. But where they are not prohibited due to environmental conditions, lower: * · ’· amounts of inorganic phosphate enhancers may be added to the compositions.

Concentrations of other additives are preferably kept below 5% by weight of the product, preferably below 3%. The use of such compounds in excess of the indicated proportions can often significantly alter the properties of the liquid detergent, e.g. stability, and should therefore be avoided.

28 85382

Although the detergent-softener composition of this invention is a stable, clear single phase liquid, a suitable opacifying agent may be added to give the recipe a creamy appearance.

Another optional but highly preferred ingredient in the detergent compositions in question is an ethoxylated fatty amine, such as the Ethomeen series of compounds from Armak Company, and the Varonic series of compounds from Ashland Chemicals. These compounds can be represented by the general formula ^ <ch2ch2O) xh

R -N I

"V (CH2CH20) yH

7 wherein R is a fatty alkyl group having from about 10 to 22, preferably from 12 to 18 carbon atoms and the sum of x + y is from about 2 to about 15. The R 1 group may be saturated or unsaturated and may be derived, for example, from coconut fatty acid, oleic acid, soya fatty acid, tallow fatty acid, stearic acid or mixtures of these acids.

Ethoxylated amines, in turn, help improve purification, softening, and antistatic properties. Suitable amounts of ethoxylated amine are usually at most 15%, in particular at most about 10%, for example 1-10% or 1-8, especially 2-8% by weight of the total liquid composition.

-V: A small amount of alkaline substance or a mixture of such substances is often added to the compositions in question to promote the solubility of the detergents and optical brighteners present in liquid detergents. Suitable time substances include mono-, di- and trialkanolamines, alkylamines, ammonium hydroxide and alkali metal hydroxides. Of these, alkanolamines are preferred, especially trialkanolamines and, especially triethanolamine. The pH of the final liquid detergent containing such a base is usually neutral or slightly basic. Suitable pH ranges are 7-10, preferably about 7.5-9.5, but since reading the pH of a liquid detergent using a glass electrode and a comparison of li 29 85382 calomel electrodes may be inaccurate due to the fact that the detergent system is often almost anhydrous, it is better found out by measuring the pH of a 1% solution of a liquid detergent in water. This pH is also normally about 7-10, mainly 7.5-9.5. In wash water, the pH is usually in this range, or could be slightly more acidic, such as 0.5 to 1 pH unit, due to the organic acid content of the dirty laundry. Liquid formulations have a viscosity at 25 ° C of between 40 and 120 centipoise, preferably 40 to 100 centipoise, more preferably 70 to 100 centipoise, and most preferably 80 to 95 centipoise as measured by a Brookfield viscometer at room temperature, using No. 1 rotation and 12 round-ing / min.

The liquid composition is usually added to the washing water of an automatic washing machine, either of the top or side type, and its concentration in the washing water may be about 0.05-1.5%, usually 0.1-1.2%. Depending on the type of machine and the amount of dirty textiles, the amount of liquid mixture to be added is about 1/4 to about 1 1/4 cups and the typical amount is about 1/2 cup (120 ml).

The wash water used may be fairly soft water or fairly hard and is generally used at an elevated temperature of about 38 ° C or above, such as 49 ° C to 82 ° C or above.

The composition of this invention is also useful in very hard water and at lower temperatures for washing clothes. The hardness of the water can thus vary between 0 and more than 300 ppm calculated as calcium carbonate and the washing temperatures can: ‘be 4.5 to 49 ° C or more. Washing is performed in an automatic; in a washing machine where washing is followed by rinsing and spinning or some other cycle or step of draining or squeezing the water. The detergent composition can, of course, also be used for washing the laundry by hand, in which case it can sometimes be used in full strength for certain stains on the laundry,: - or the laundry can be soaked in higher concentrations of detergent before washing.

so 8 5 382

The washing steps usually take from three minutes to one hour, depending on the textiles to be washed and the dirt detected. When the washing and spinning, draining, or squeezing steps are complete, it is considered best to dry the laundry in an automatic dryer soon after, but string drying can also be used.

The detergent-softener composition in question dissolves very easily regardless of whether the wash water is warm or cold and cleans, softens and removes static charge very effectively from laundry and other textiles without making them water repellent. It can be used in either top or front-loading washing machines and can be adjusted to a suitable degree of foaming if desired. The product is a pleasantly clear, stable liquid that retains its potency and consistent quality for a very long shelf life. In tests comparing its effectiveness when used with other commercial liquid laundry detergents, it received very favorable grades.

This product can be prepared simply by mixing the various ingredients together at room temperature and ensuring its dissolution in an aqueous medium by stirring.

The order in which the ingredients are added and the temperature of incorporation may be varied without adversely affecting the development of this invention; a single-phase, clear liquid product according to the invention. to form. Formulations or pastes having a higher viscosity can likewise be prepared by conventional techniques.

The liquid detergent-softener composition of the present invention has several advantageous properties over both physical properties and performance when used. In terms of physical properties, liquid compositions are pourable and flow freely; - from the container, both freshly prepared and stored for a long time.

They have a high degree of stability when stored at normal room temperature of about 21 ° C for several months li 3 li 8 5382 without any noticeable precipitation. As a result, they can be used by the consumer conventionally by adding very small doses to the washing solution, and the detergent and fabric softener are included in the standard composition in each dose. Although suitable additives can be added to make the final product translucent or opaque, as desired, the single phase solution of the main ingredients ensures that an effective washing and softening force is obtained with each dose and the product is stable and homogeneous. The composition may be packaged in any suitable container or packaging material such as metal, plastic or glass.

The following specific examples illustrate several different embodiments of this invention. It is to be understood, however, that these examples are provided for illustrative purposes only, and the present invention is not to be construed as limiting them in any way.

To test the detergency of detergent compositions, several different formulations were prepared and used in standard test methods with several different types of dirt and different types of textiles, and with different concentrations and doses of active ingredients. All wash tests were performed under the same conditions (unless otherwise indicated) in identical washing machines (Terg-O tometer): 49 ° C, 100 ppm Ca ++, 64.5 L of wash water, 0.2% concentration (1/2 cup). The test fabrics were nylon, cotton and polyester (Dacron) / cotton blend (65/35). Test stains were sekatah-ra (TF), Test Fabrics Co., Piscataway Clay (PC) and oil stain (on cotton) (EMPA), Test Fabrics Co. The cleaning performance is measured as reflectance readings (Rd) as a measure of whiteness and these readings are correlated to give a total soil removal value (SR), where Rd values for different soiled textiles are each multiplied by a factor assigned to each artificially soiled fabric to reflect the correlation: between cleaning ability and practical laundry detergent tests. By comparing the SR values of any two compositions, the total cleaning performance (SRI) of the two compositions can be estimated.

32 85382

Example 1

The following compositions were prepared: 33 8 5382

(N rH CN LO CO 'J' CN CN

rH CN ·· »rH 00 LO 00

H "rH

(OF

ra

• P

ro O i — I

t l i— (I I I - I o rH CN ro 00 n + o E ta CN · Γ * ι Γ ~ - ta „-p c cn

O -H

O rH CN CN rH ΟΊ l'- E

rH CN * · * “s v ta r-t rH σι LO 'T en (0 + iH tn ¢ 3> CN O £ ro Ώ - Ή LO ro ro ~ + j

(TirHCOlO - '^' -H t0 -P

CN r-HLOCOiH r-t -ro ta • · rH rH ΓΝ O ta ta

• H + CN .C -P E

O en fa * i -5 t-H CTt CN 00 ta fH X.

COrHinro '' 'I ta x cn r ~ oocNin ca> o ·> i r-π σι> en

rH I rH tn * O

to Ή 4H

P T3 rH

rH ΓΟ Γ -H O

I e p 55 t "· rH 00 l CO LO rH Qjtnoi CN I — I rH CTl C -P rH · Ρ I I i — 1 * PO ^ * —i

P 3 E rH

i i e p e ω aa in m -h ch o t3. LO rH I 00 I - '' p Eta r-1 tN CO LO ro Oj rH E + j

H- i — t I -H ta X

O CN I / O I O

JjT -P rH * (H f

Vf P O · —e rH J2

"P Pr I I — I>, T

P O co m m cnq>>, · -.

rH in ITl I I rH I * · - * r — jc -P ‘H

3 CN rH rH LO ULOCUrH

ra + I o S> 1 cj cn · * ia -ri>,

M <u -n p HJ

e ta -p ei) • H 4-1 I -rl h rr (N cn ta tn -h en LT rH ·· *. *. *, -H rH ^ HS 3 SS 5 5 8 + "5 5 .. ö S * § 3 in ro ro -H - »-H Ό ·

ro rH I * T I - '' -p Q C Γ O

____ CN oomro Ai W Q CN G

+ rH ta | H. e ** M

CN I '- E rH

-S 3 i tn C -h C 2 0)

rH ro n- · Η Ό (1) I -H

CN rH O 'I I * · * * Ot-HCEP

cn σ cn m cn · ρ 3 4-> rH CN CO G Ai P -H tn

I I rH δ O: ¾ P P

e -H: -P'O

s s e cn co 0 Φ 0) ta

rH rH I I I I ~ -H rH 4J PO

cn co o; I> 1 ca -P e

- I O -H -P> (D Q

CN W tl) 2 EH S

\ \ UI ilO - \ \\ - rH cn ro p I I I rH (N ro 1 P p d m cn

f- O O 0) ftH WH H f "o O

I m 2 ^ Sy Λ SL? ^ 03 I era Z

::: mi tn ta o CL o &. o e m j tn

(N EH> 2 ···· 0 CN H

v M tn · et · ex to +) - ha ip> b «, o tn rH xj mas LiS '»' ϊί s in § 8 1 inside * 58 isg <2 5-mijW-pW4jw <2 <Ä 34 8 5382

With respect to the above table, it should be noted that wash test 11 is a repetition of wash test 1 using the freshly prepared sample composition.

The following observations and conclusions can be drawn from the results reported in Table 1:

The addition of the quaternary compound alone (washing tests No. 2 and 7) to the non-ionic (washing test No. 1) has a very significant negative effect on the washing performance.

The addition of succinamate surfactant alone (Washing Tests Nos. 3 and 6) significantly improves the washing performance, but of course does not appear to soften at all, which is the effect of the quaternary compound.

The addition of the quaternary compound to the succinate in a ratio of 1.7: 1 (washing test No. 8) represents a clear improvement compared to the addition of the quaternary compound alone (washing tests No. 2 and 7), but is still clearly worse than the comparison (washing test No. 1). .

A total addition of 8% by weight of quaternary to succinate gives the best cleaning result when the ratio of quaternary / succinate is 1: 1.7 (washing test No. 9) and slightly better than the ratio of 1: 1 (washing test No. 4), while a ratio of 1: 3 (wash test 12) gives approximately the same purity result as succinate amate (wash tests Nos. 3 and 6) at both 4% and 8% concentrations. A ratio of 1: 3 at a concentration of 8% by weight (wash test No. 12) is worse than a ratio of 1: 1 (wash test No. 10) at a total content of 4%.

Thus, under the conditions of this experiment, the preferred ratios of quaternary compound to succinate are from about 1: 1 to about 1: 2, and ratios of about 1: 2 to about 1: 3 provide further improvements in cleaning performance (e.g., bleaching) as well as improved softening / softening. antistatic result.

li 35 85382

Example 2

Washing Tests Nos. 1 to 12 of Example 1 are repeated all but with the addition of an anionic surfactant: straight-chain dodecyl benzene sulfonate (Na salt) (LDBS), in the amounts shown in Table 1. The results are also shown in Table 2. To facilitate comparison, Table 2 also shows the SR values (total values) and SRI vs., wash test No. 1, from Example 1.

Table 2

Wash- Weight% Weight% LDBS SR (total) SRI vs. Wash test 1 tin No. with LDBS SNO without LDBS without _ _ _ _ with LDBS_ with LDBS 1 4 - 207.3 204.8 2 41 213.3 185.7 +6.0 -19.1 344 212.8 213.3 +5.5 +8.5 4 41 4 219.2 219.2 +11.9 +14 4,5 (29% non-ionic) δ - 211.4 206.5 +4.2 +1.8 6 8 8 214.4 213.4 +7.1 + -8.8 7 81 208.7 191, 7 +1.3 -13.1 8 51 3 220.5 195.8 +13.1 -8.9 9 31 5 218.7 221.3 +11.4 +16.6 10 21 2 218.2 214 .7 +10.9 +9.9 11 4 210.7 208.0 +3.4 +3.2 12 21 6 218.1 213.2 +10.8 +8.4 ^ The weight ratio quaternary / LDBS is 1 1

The following observations can be made and conclusions drawn from the results reported in Table 2.

Washing test No. 2 and washing test No. 7 correspond to the compositions 1, which are the main content in FI patent application 854032, i.e. mixtures of a nonionic surfactant with 1: 1 mixtures of a cationic fabric softener and an anionic surfactant (without sulfosuccinamate).

36 85382

Washing Tests Nos. 3, 4, 6, 8, 9, 10 and 12 are in accordance with this invention. As can be seen, quaternary / succinate ratios ranging from 1.7: 1 (wash test No. 8) to 1: 3 (wash test No. 12) give a clearly better cleaning result compared to either quaternary alone (wash tests No. 2). and 7) or succinate alone (washing tests Nos. 3 and 6).

In addition, the presence of an anionic surfactant in these formulations is a further advantage to enhance the antistatic and emollient effect of the mono-higher alkyl quaternary ammonium compound, and in the preferred composition containing an optical brightener, the anionic further aids in the precipitation of the brightener on textiles. At the same time, it is also apparent that in some formulations, the combination of succinate and anionic surfactant clearly enhances the overall cleaning performance, e.g., compare the total SR in wash test 8, Example 2, with wash test No. 8 in Example 1.

In Examples 1 and 2, it should be noted that when using 1/2 cup of 21% and 29% Neodol 25-7, it corresponds to 25 g per wash and 35 g per wash, respectively; 4% and 8% Arquad T-50 correspond to 5 g / wash and 10 g / wash, respectively; 4% and 8% Monawet SNO correspond to 5 g / wash and 10 g / wash, respectively.

Example 3 - If Example 1 or Example 2 is repeated using the same amount of Neodol 23-6.5 (R = (C 2 H 4 O) g H, where R = a mixture of primary alcohols containing 12 and 13 carbon atoms) or Tergitol 15-S-7 or Tergitol 15-S-9 (both of which are straight-chain secondary alcohol (C 1-4) ethoxylate and, trademarks of Union Carbide Corp., the former contains 7 moles of ethylene oxide and the latter 9 moles of ethylene oxide), or any nonylphenol which is. ** ·. condensed with 5, 7 or 9 moles of ethylene oxide, isooctylphenol condensed with 9, 10, 11 or 12 moles of ethylene oxide, etc. Neodol 25-7 is obtained. similar results.

li 37 85382

If in Example 1 or Example 2 Monawet SNO-35 is replaced by the same amount some of the following: Astromid 18, Astromid 22, Alkasurf SS-OA or Alkasurf SS-ΤΑ, similar results are obtained.

Examples 1 and 2 also give similar results when using hydrogenated tallow trimethylammonium chloride stearyltrimethylammonium chloride stearyltriethylammonium chloride stearyldimethylethylammonium chloride tallow diisopropylmethylammonium chloride and the like sulfate, ethosulfate, methosulfate and hydroxide salts in place of Arquad T-50. Arquad T-50 can also be replaced, in whole or in part, by, for example, Ethoquad 18/12 or some other similar ethoxylated mono-higher alkyl quaternary compound.

In Example 2, similar results are obtained when a straight-chain dodecyl benzenesulfonate anionic surfactant is used in place of, for example, Neodol 25-3S (Shell Oil Products, formula RO 2), R = C 1 -C 3, .-mixture of primary fatty alcohols). The LDBS anionic surfactant may also be replaced, in whole or in part, by, for example, sodium sodium alpha-olefin sulfonate having 14 to 18 carbon atoms or sodium paraffin sulfonate having 13 to 17 carbon atoms or the like. potassium salts of a representative of the compounds.

Example 4

The following compositions (shown in Table 3) were tested in the same manner as in Example 1, and the results are also shown in * '(SR total value) in Table 3.

38 8 5382 o 0 m. — I - = r oo i — t I * l h ·> 3 · l l i · ro

CM O en (N

en m o o r- ~ i — il ^ h · I h * rr I i l- ^ ro ro (N o f— ((n en 01

O

m o io VO * —Il 'Ή I τ T I τ I I f — I ro

(NO tn (N

CT

o O Γ "m oo o r- ~ ·· m i — i ·· - h · τ I • 'r * · rr i i h r \ i ro e cn h o o en cn tr o e

Λί -H

λ; 4-) o O tn r- Momi — im 'rh «· - h · h * l · * τ I iih * ih og 3 P (N i — io en cn (0 3 tr E-ι en 0) (¾ or * m, or ~ ro fH - - II h1 II ^ 1 i — i ro <N> ho en cn tr or ~ mo oo (NH * * Ν 'II Η · I | I ^ rI ro cn »H o en cn tr o r- in oo rl rH '' 'Tl IrH Ν' cn> H o en cn tr - · Η · Η CP o • h ro ρ m> • H fH ro ro p E <CO CO (0 I ( 0 r ^ Todi 3 ro p O <n co en

l -h 2 h en ι P 2 CN H -H

: - - m h to i m -h cn to

cn O h · ro (N en H ΌΌ C

(0 G -h 2 Eqj + j-h-h O

: WfHiOrO'C -H 3 O <D E E M

OOP O ,. CD'O-HOSOO O

OJOOJOtrtOXlPXIrOPP H λ; GOHCOCQOPPCPPcn • ΗΟΡΉΌαοΐοΦοωιηα) os .. CZHE-i <, P22SSCrt:> cn 39 35382

Example 5

In each composition of Example 4, a portion of Neodol 25-7 is replaced with Ethomeen T-25, which is an ethoxylated amine, of the formula / (ch2ch2O) xh ta li-N (x + y = 15)

^ (CH2CH20) yH

available from Armak in an amount such that the ethoxylated amine is about 3-8% and about 18-13% nonionic surfactant, respectively. An improvement in cleansing, softening and antistatic can be observed. Formulations with 15% by weight of nonionic and 6% by weight of ethoxylated amine give particularly good results.

Example 6

In each of the compositions in Examples 4 and 5, the addition of an enzyme, e.g. a protease enzyme, improves up to about 1%, especially up to about 0.5%, by weight of the composition, cleaning results for some dirt stains, e.g. protease protein stains, amylase starch stains, etc. are stable in the compositions and mixtures of different enzymes can be used.

Example 7

Highly stable, homogeneous clear aqueous compositions with comparable cleaning ability are prepared from the following ingredients:

A B

Neodol 25-7 21 16

Neodol 25-3S 4

Sodium dodecyl benzene sulfonate - 4

Monawet SNO-35 4 3

Arquad T-50 4 3

Na citrate 4

Sodium xylene sulfonate 4 3

Optical brightener

Enzyme

Water qs 100 qs 100 40 85382

Example 8 This example demonstrates the importance of washing temperature to the purification result and also demonstrates that the combination of a cationic quaternary compound and a succinate detergent compound in the preferred relative amounts is effective at both low and high temperatures. In the same manner as described in Example 1, the following liquid compositions, prepared as shown in Table 4, are prepared and evaluated under the conditions described in Example 1 at wash temperatures of 49 ° C or 21 ° C. The results (SRI values) with non-ionic alone as a comparison {21% wash test No. 1) are shown in Table 4:

Table 4 12345678

Neodol 25-7 21 21 21 21 21 21 21 21

Neodol 25-3S -4444444

Mogen 471 ^ - -4 44 -44

Monawet-SNO-35 - - 44 48-

Sodium citrate ---- 44-8

Water rest SRI vs. (wash test 1 49 ° C) - +4 +3 +14 +13 +9 +10 +7 SRI vs. (wash test 1 21 ° C) - +1 -4 +10 +10 +5 0 + 4 ^ Tallow trimethylammonium chloride, from Sherex.

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Claims (12)

Aqueous liquid detergent composition for washing and softening soiled clothing, which composition can be added to the washing cycle in an automatic washing machine, characterized in that it contains: A) about 10-50% by weight of a liquid non-ionic detergent selected from a group consisting of compounds of formulas I and II: RO (CH 2 CH 2 O) n H (I) where R is a primary or secondary alkyl chain of about 8-22 carbon atoms and n Sr averages about 5-20; R 1 is O (CH 2 CH 2 °) m H (1) where R 2 is a primary or secondary alkyl chain of about 4-12 carbon atoms and m is about 5-20 on average; B) about 1-20% by weight of a mono-higher-alkyl quaternary ammonium compound of formula III or IV: "R 2 + + N X- (III), R 3 R 2 NS R 2 (CH 2 CH 2 NX "(IV), / X R3 (CH2CH2O) yH where R2 is a long chain aliphatic radical containing about 10-22 carbon atoms, of which radicals R2 of formula III and R2 of formula IV independently represent a lower alkyl or a hydroxy ( lower alkyl), X is a water-soluble, salt-forming anion, and x and y are both positive tai with at least the value of 1, and the sum x + y is 2-15; C) about 1-20% by weight of a sulfosuccinate detergent compound of the formula R4 s / HyC - C - N1 \ (V) ZO3-S-CHCOOZ R0 where Z is a monovalent salt-forming cation, R4 is hydrogen, a lower alkyl, a carboxy (lower alkyl) or 1,2-dicarboxy ( is lower open chain hydrocarbon and 10-22 carbon atoms; D) not more than about 10% by weight of an anionic surfactant; selected from a group consisting of linear-higher-alkyl-aromatic sulfonates, poly-lower alkoxy-higher-alkanol sulfonates, olefin sulfonates and paraffin sulfonates; E) not more than about 3% by weight of an optical brightener; F) not more than about 15% of an ethoxylated amine; G) not more than about 5% of an alkaline agent; H) not more than about 3% of enzymes; I) not more than about 3% of a soil release agent; and J) an aqueous solvent carrier, the ratio B): C) being between 3: 1 and 1: 3. A detergent composition according to claim 1, characterized in that in the formula (V) Z is an alkali metal, ammonium or amine, R 4 is hydrogen, methyl, ethyl, carboxymethyl, carboxyethyl, 1,2-dicarboxymethyl or 1,2-dioxide. dicarboxyethyl, and R 2 47 85382 is a saturated or unsaturated alkyl or alkenyl group which is linear or branched and has about 14-18 carbon atoms. Detergent composition according to claim 1 or 2, characterized in that the sulfosuccinamate detergent compound is disodium N-octadecylsulfosuccinamate, disodium N-oleylsulfosuccinamate or tetrasodium N- (1,2-dicarboxyethyl) -N-octadecylsulfonosulfate. Detergent composition according to any of the preceding claims, characterized in that it contains about 12-35% of a non-ionic surfactant, about 2-16% of a monoalkyl quaternary compound and about 2-16% of a sulfosuccinamate compound. Detergent composition according to any of the preceding claims, characterized in that the weight ratio of non-ionic surfactant / monoalkyl quaternary compound is between about 15: 1 - 2: 1. Composition according to claim 1, characterized in that the anionic detergent D) is present in a ratio B): D) of about 1.3: 1 to 1: 1.5. Composition according to claim 1, characterized in that it contains A) about 12-35% B) about 2-6% C) about 2-6% D) about such an amount that the ratio C): D) is about 1 , 2: 1-1: 1.2. E) 0.2-2% by weight, F) at most about 10%, G) at most about 3%, H) at most about 2%, I) at most about 2%, and J) the ester residue. * β 8 5 3 S 2 Composition according to claim 7, characterized in that A) is a compound of formula I, wherein R is a C 22 -C 15 alkyl or a mixture thereof and n is about a tai 6-13; B) is tallow trimethyl ammonium chloride; C) is disodium N-octadecylsulfosuccinamate, disodium N-oleylsulfosuccinamate or tetrasodium N- (1,2-dicarboxyethyl) -N-octadecylsulfosuccinamate, and D) is linear dodecylbenzenesulfonate. or triethoxy-C22 ~ C25-alkanol sulfate. Composition according to claim 1, characterized in that it contains A) about 15-25% of a compound of formula I, wherein R is a C20-C28 "Primer or secondary alkyl and n is about 6-13; B) about 2 -6% of a compound of formula III wherein R 2 is an aliphatic radical of 12-18 carbon atoms and each of the radicals is methyl; C) about 2-6% of a sulfosuccinamate compound of formula V, wherein r -18 carbon atoms and R 2 is hydrogen or a 1,2-dicarboxyethyl, and an aqueous liquid carrier. Composition according to claim 9, characterized in that the ratio B): C) is between about 1: 1 and about 1: 2. 11. A composition according to claim 9, further comprising D) linear-higher alkylbenzenesulfonate or polyethoxy-higher alkanol sulfate in such an amount that the ratio C): D) is about 1.1: 1 - about 1. 1.1. Composition according to claim 11, characterized in that the ratio B): C) is between about 1.5: 1 - about 3: 1. IN: