HU214049B - Detergent preparatives with reduced foaming containing alkyl-sulphate and n-(polyhydroxi-alkyl)-fatty acid amide as surface active agent - Google Patents

Abstract

An alkyl sulphate-based, controlled sudsing liquid or solid laundry detergent compsn. Useful for cleaning fabrics in automatic washing machines comprises: (a) at least 1 wt. % of polyhydroxy fatty acid amide cpd. of formula R2-C-(O)-N(R1)-Z (I) (c) pref. a suds suppressing amt. of a suds suppressor. In (I), R1 = H, 1-4 hydrocarbyl, 2-hydroxyethyl and/or 2-hydroxypropyl; R2 = 5-31C hydrocarbyl; Z = polyhydroxyhydrocarbyl having linear hydrocarbyl chain with at least 3-OH gps. directly connected to the chain or its alkoxylated deriv. The compsn. has a wt. ratio of (a):(b) of 1:10 to 10:1. Also claimed is a detersive particle comprising 5-90 % of cpd. (I) and 10-90% of an alkylsulphate surfactant and 1-30 wt. % of a solubilising agent. The compsn. pref. comprises at least 3% of cpd. (I) and at least 3% alkylsulphate in a wt. ratio of 6:1 to 1:6 (esp. 1.25:1 to 1:4). The compsn. further comprises 1-30% of an auxiliary surfactant component selected from alkyl benzene sulphonate surfactants, alkyl ester sulphonate surfactants, alkyl ethoxylate surfactants, alkyl polyglycoside surfactants, paraffin sulphonate surfactants and/or alkyl phenol alkoxylate surfactants. The suds suppressor is selected from silicone suds suppressors, hydrocarbon suds suppressors and/or monostearyl phosphate suds suppressors (esp. at least 0.5 wt. % of a monocarboxylate fatty acid or its salt).

Description

The present invention relates to detergent compositions comprising alkyl sulfate surfactants. More particularly, the present invention relates to detergent compositions comprising a mixture of alkyl sulfates and certain polyhydroxy fatty acid amide surfactants.

The ability of detergent compositions to provide a good general cleaning effect to remove the wide variety of soils and stains from a wide variety of materials that may be present in a typical detergent dose is critical to the evaluation of such detergents. Mixtures of linear alkyl benzene sulfonates ("LAS") and alkyl sulfate ("AS") surfactants in granular detergents have been used effectively for general cleaning under both cold and warm aqueous washing conditions. LAS surfactants are often used because they have excellent cleaning properties on grease and oil stains. A combination of LAS and AS is desirable, as it combines the excellent lipid and oil cleansing effect of LAS (with a good cleaning effect on a wide range of stain types) with the excellent performance of AS surfactants to remove particulate dirt.

While AS surfactants can be readily produced from renewable resources, it would be desirable to provide a detergent composition having a similar or superior cleaning performance, but in which LAS is partially or completely replaced by a natural, renewable, non-petroleum based raw material. can be easily produced.

It would also be desirable to effectively blend certain AS surfactants into high-performance liquid detergents in order to benefit from their good general cleaning performance, in particular the excellent ability to clean particulate dirt. While shorter alkyl chain alkyl sulfate surfactants can easily be incorporated into delicate detergents (fine fabric detergent), one of ordinary skill in the art will have difficulty in mixing C14 and longer chain alkyl sulfate surfactants into liquid detergents. These longer chain surfactants are those which are generally advantageous for laundry and other textile cleaning applications.

In addition, for granular detergents, it would be desirable to increase the solubility and solubility of alkyl sulfate surfactants in aqueous solutions, particularly C | | |. Alkyl sulfates having ₄ or more carbon atoms.

The present invention provides detergents that contain alkyl sulfates and may contain or eliminate LAS surfactants in reduced concentrations and exhibit excellent overall cleaning performance, including grease and oil stains. According to the present invention is directed to detergent compositions that can be in granular form, and those which are in liquid form and are C] ₄ alkyl and higher alkyl sulfate surfactants contain. The incorporation of polyhydroxy fatty acid amides in granular detergent formulations may increase the solubility and dissolution of alkyl sulfate surfactants in aqueous solutions.

The present invention also provides novel detergent granules for the preparation of surfactant, alkyl sulfate and polyhydroxy fatty acid surfactants in granular form, wherein the detergent particles comprise two surfactants and a third component for further enhancing solubility in aqueous solutions. These detergent granules are advantageous because they provide the polyhydroxy fatty acid amide in an improved non-adhesive form to granular detergent formulations without the need to resort to the use of a substantial amount of an inert and therefore uneconomical component. Polyhydroxy fatty acid amides generally exhibit adhesive or tack properties which are undesirable in granular formulations. Furthermore, these detergent granules are more soluble in aqueous solutions, particularly in automatic washers.

Numerous polyhydroxy fatty acid amides have been reported in the literature. Α-acyl-, -N-methylglucamides are described, for example, in J.W. Goodby, M.A. Marcus, E. Chin and P.L. Finn: "The Thermotropic Liquid-Crystalline Properties of Somé Straight Chain Carbohydrate Amphiphiles", Liquid Crystals, 3, No.ll, 1569-1581 (1988); and A. Muller-Fahmow, V. Zabee, M. Steifa and R. Hilgenfeld, "Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-Methylglucamide," J. Chem. Soc. Chem. Commun., 1573-1574 (1986). N-alkyl polyhydroxyamide surfactants are of recent interest in biochemical applications, for example in the dissociation of biological membranes. See, for example, "N-DGluco-N-methyl-alkanamide Compounds, New Class of Non-Tonic Detergents, Fór Membrane Biochemistry," Biochem. J. 207, 363-366 (1982), by J.E.K. Hildreth.

The use of N-alkyl glucamides in detergent formulations has also been reported. U.S. Patent No. 2,965,576 relates to detergent compositions containing anionic surfactants and certain amide surfactants, such as N-methylglucamide, which are incorporated at low temperature as a foaming agent. These compounds contain an N-acyl group of a C 10-14 straight chain fatty acid. The formulations may also contain additional ingredients such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. Usually they also indicate; It is also contemplated that additional components providing beneficial properties to the compositions may be incorporated into the compositions, such as fluorescent dyes, bleaching agents, perfumes, and the like.

U.S. Patent 2,703,798 relates to aqueous detergent compositions comprising a condensation reaction product of an N-alkylglucamine and an aliphatic ester of a fatty acid. According to the description, the product of this reaction can be used in aqueous detergent compositions without further purification. It is also known to prepare the sulfuric acid ester of acylated glucamine as disclosed in U.S. Patent No. 2,717,894.

PCT International Application WO-83/04412 relates to amphiphilic compounds which are polyhydroxy

HU 214 049 Β

-aliphatic groups and as described herein can be used for various purposes such as surfactants in cosmetics, pharmaceuticals, shampoos, lotions and ointments, as emulsifiers and dispersants in pharmaceuticals, and in biochemistry for the preparation of membranes, whole cells or other liposomes for solubilization. The application describes compounds of the formulas R'CON / R / CH ₂ R "and R" CON / R / R 'in which R is hydrogen or an organic group, R' is an aliphatic hydrocarbon group having at least three carbon atoms and R 'is an aldose group. .

European Patent 0 285 768 relates to N-polyhydroxyalkyl fatty acid amides as thickeners in aqueous detergent systems. These include amides of the formula R 1 C / O / N / X / R 2 wherein R 1 is C 1-17 (preferably 7-17) alkyl, R _{2 is} hydrogen, C 1-18 (preferably 1-6) alkyl or alkylene oxide and X

C4-C7 polyhydroxyalkyl; for example, N-methyl coconut fatty acid glucamide. The thickening properties of amides are said to be particularly useful in liquid surfactant systems containing paraffin sulfonates, but aqueous surfactant systems may also contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonates, sulfobutyric aliphatic alcohols, and nonionic surfactants such as aliphatic alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, polypropylene oxide poly (ethylene oxide) mixed polymers, and the like. By way of example, shampoo compositions containing non-ionic surfactant are referred to as paraffin sulfonate (N-methyl coconut fatty acid glucamide). In addition to their thickening properties, N-polyhydroxyalkyl fatty acid amides are described as having a very good tolerance to the skin.

U.S. Patent No. 2,982,737 relates to detergent bars comprising urea, sodium lauryl sulfate anionic surfactant and an N-alkylglucamide nonionic surfactant, which may be N-methyl-N-sorbityl lauramide or N-methyl, N-sorbityl myristamide.

Other glucamide surfactants are disclosed, for example, from DE 2226872 patent specification, containing one or more surfactants and builder salts selected from polymeric phosphates, sequestering agents, and washing alkalis, improved to a RIC / O / N / R ₂ / CH ₂ / By adding N-acyl polyhydroxyalkylamine of the formula CHOH / _n -CH ₂ OH, wherein R 1 is C 1 -C 3 alkyl, R _{2 is C} 10 -C 22 alkyl and n = 3 or 4. The N-acyl poly hydroxyalkylamine as a soil suspending agent is added.

U.S. Patent No. 3,654,166 relates to detergent compositions containing at least one anionic, zwitterionic, or nonionic surfactant and a N-acyl-N- R ₁ N / Z / C / O / R ₂ fabric softener. alkyl polyhydroxyalkyl compound, wherein R] 10 to 22 carbon atoms, R ₂ 7-21 carbon atoms, R] and _R2 contain a total of 23-39 carbon atoms and Z is a polyhydroxy alkyl, which can be a

-CH ₂ / CHOH / _m -CH ₂ OH, wherein m = 3 or 4.

U.S. Pat. No. 4,021,539 relates to cosmetic skin care compositions containing N-polyhydroxyalkylamines. Such compounds include the compounds of formula R 1 N / R / CH / CHOH / _m R ₂ wherein R 1 is hydrogen, lower alkyl, hydroxy lower alkyl or aminoalkyl and heterocyclic aminoalkyl. , R is the same as R 1 except hydrogen, and R _{2 is} -CH ₂ OH or -COOH.

French Patent No. 1,360,018 relates to solutions of formaldehyde which are stabilized against polymerization by the addition of amides of the formula RC / O / N / Rj / G, wherein R is at least C7 carboxylic acid, R is hydrogen or lower alkyl and G is at least the 5-carbon glycityl.

German Patent No. 1,261,861 relates to glucamine derivatives of the formula N / R / R 1 / R ₂ , which may be used as wetting and dispersing agents, wherein R is a sugar group of glucamine, R 10 -C 20 alkyl and R _{2 is C} 1 -C 5 acyl.

British Patent No. 745,036 relates to heterocyclic amides and their carboxylic acid esters, which are described herein as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, fabric softeners, and the like. The compounds correspond to the formula N / R / R 1 / C / O / R ₂ in which R is an anhydrated hexane-pentol group or a carboxylic ester group thereof, R 1 a monovalent hydrocarbon group; and -C / O / R _{2 is} an acyl group of a C 2 -C 25 carboxylic acid.

U.S. Patent No. 3,312,627 relates to solid toilet rods which are substantially free of anionic detergents and alkaline builders, but contain lithium soaps of certain fatty acids, contain a nonionic surfactant such as certain propylene oxide / ethylenediamine; propylene oxide / propylene glycol / ethylene oxide condensates or polymerized ethylene glycol, and further comprising a nonionic foaming component, which may be a polyhydroxyamide of formula RC / O / NR 1 / R ² , wherein RC / O / 10-14 C ¹ and R ¹ and R ² are each hydrogen or C 1 -C 6 alkyl, in addition the alkyl groups contain a total of 2 to 7 carbon atoms and a total of 2 to 6 hydroxy substituents. Substantially similar disclosure is found in U.S. Patent 3,312,626.

In one aspect, the present invention relates to low-foaming detergent compositions which may be used for washing textiles in an automatic washing machine, optionally containing conventional detergent additives and further comprising:

EN 214 049 Β (a) at least 3% by weight of polyhydroxy fatty acid amide of formula (I):

R ¹ is hydrogen, C 1-4 alkyl,

2-hydroxyethyl or 2-hydroxypropyl,

R ² is C 7 -C 19 alkyl or alkenyl and

Z is a polyhydroxy hydrocarbon group or a mixture thereof obtained from a reducing sugar by a reductive amination reaction;

(b) at least 3% by weight of a C10-C24 alkyl sulfate or a C10-C20 hydroxyalkyl sulfate surfactant, and (c) optionally at least 0.01% by weight of silicone antifoam, hydrocarbon antifoam, monocarboxylic fatty acid an antifoam agent and an antifoam agent selected from the group consisting of antifoam and a weight ratio of components (a) and (b) (1: 4) to (4: 1).

The detergent of the present invention may be liquid or solid.

One preferred composition comprises at least 5% by weight of granules having 5 to 90% by weight of polyhydroxy fatty acid amide, 10 to 90% by weight of alkyl sulfate surfactant and 1 to 30% by weight of solubilizer, preferably surfactant anionic sulfonate, of at least 0.5 ethoxylation. surfactant, cyclic polyhydroxy fatty acid amide, alkyl polyglycoside, polyethylene glycol or poly (acrylic acid) polymer.

Alkyl sulphate surfactants

The compositions of the invention at least 3 parts by weight ⁰ / », preferably 3-50% by weight, more preferably

5 to 30% by weight of a ⁰ % alkyl sulfate surfactant.

Alkyl sulfate surfactants are well known in the art. The alkyl sulfate surfactants used in the compositions of the present invention are water-soluble salts or acids of the formula ROSO3M, wherein R10 is a hydrocarbon radical of 10 or more carbon atoms, preferably of 10 to 24 carbon atoms, preferably of 10 to 20 carbon atoms. more preferably C14-C18 alkyl or hydroxyalkyl; and M is a hydrogen atom or a cation such as an alkali metal cation such as sodium, potassium or lithium or ammonium or substituted ammonium such as methyl, dimethyl or trimethylammonium or quaternary ammonium cation such as tetramethylammonium or dimethyl quaternary ammonium cations derived from alkyl amines such as ethylamine, diethylamine, triethylamine or mixtures thereof, and the like. In the detergent compositions used for washing, alkyl groups having 14 carbon atoms and longer are generally preferred.

When used for washing (particularly in automatic washers), C12-C16 alkyl chains, especially C14-C16 alkyl chains, are preferred at lower wash temperatures (e.g., below 50 ° C) and C16-C18 alkyl chains are preferred at higher wash temperatures (e.g., above 50 ° C).

Polyhydroxy fatty acid amide surfactants

The compositions of the invention at least 3 parts by weight ⁰ / », typically 3-5 wt ⁰ /», preferably 3-30 wt ⁰ / »described below polyhydroxy fatty acid amide.

The polyhydroxy fatty acid amides used in the process of the present invention are compounds of formula I; wherein ^R] is hydrogen, C1-4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl group, preferably C1-4 alkyl, more preferably C1-2 alkyl, most preferably methyl; R ² , preferably straight-chained C 7 -C 19 alkyl or alkenyl, more preferably straight-chained C 9 -C 17 alkyl or alkenyl, most preferably straight-chained C 11 -C 17 alkyl or alkenyl, and Z polyhydroxy hydrocarbon, straight a hydrocarbon chain and at least three hydroxy groups directly linked to the chain or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z is derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. The raw materials used are high dextrose starch syrup, high fructose starch syrup and high maltose starch syrup, as well as the sugars listed above individually. These starch syrups can add a mixture of sugar components to Z. It should be noted, however, that this is by no means intended to exclude other appropriate raw materials. Preferably Z is -CH ₂ - / CHOH / _n -CH ₂ OH, -CH / CH ₂ OH / - / CHOH / -CH ₂ OH, -CH ₂ - / CHOH / ₂ / CHOR 7 / CHOH / -CH. ₂ OH, wherein n = 3-5 is an integer and R 'is hydrogen or a cyclic or aliphatic monosaccharide or an alkoxylated derivative thereof. Most preferred are glycityls in which n = 4, especially -CH ₂ -CHOH / ₄ -CH ₂ OH.

In the formula (I), R ¹ can be, for example, N-methyl, N-ethyl, Ν-isopropyl, Ν-butyl, N- (2-hydroxyethyl) or N- (2-hydroxypropyl). -group.

Examples of R ² -CO-N < 1 &gt; include coconut amide, stearic acid amide, oleic amide, lauric acid amide, myristic acid amide, capric acid amide, palmitic acid amide, tallow fatty acid amide, and the like.

Z can be 1-deoxyglycityl, 2-deoxyphthytityl, 1-deoxy-maltityl, 1-deoxy-galactityl, 1-deoxy-mannityl, 1-deoxy-maltotriothityl, group etc.

Methods for preparing polyhydroxy fatty acid amides are known in the art. These compounds can generally be prepared by reacting an alkylamine with a reducing sugar in a reductive amination reaction to obtain the corresponding N-alkylpolyhydroxyamine and then reacting the N-alkylpolyhydroxyamine with an aliphatic ester or triglyceride / amidation step to form the N-alkyl-N-polyhydroxy fatty acid amide product. Processes for preparing compositions containing polyhydroxy fatty acid amides are described, for example, in British Patent No. 809,060 and in U.S. Patent No. 2,965,576,2,703,798 and

HU 214 049 Β

U.S. Patent No. 985,424.

In one process for the preparation of N-alkyl or N-hydroxyalkyl-N- (deoxyglycityl) fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl group is Ν-methyl , N-ethyl, N-propyl, N-butyl, N-hydroxyethyl or N-hydroxypropyl, the product is prepared by aliphatic N-alkyl or N-hydroxyalkyl glucamine. with an ester such as an aliphatic methyl ester, ethyl ester or triglyceride, a catalyst such as trilithium phosphate, trisodium phosphate, tricalcium phosphate, tetrasodium pyrophosphate, pentkalium tripolyphosphate, lithium hydroxide, lithium hydroxide, -hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tricalcium citrate, sodium silicates, potassium silicates, sodium , potassium aluminum silicates or mixtures thereof detect the presence. The amount of catalyst is preferably 0.5-50 mol%, more preferably 2.0-10 mol%, per molar basis of N-alkyl or N-hydroxyalkylglucamine. The reaction is preferably carried out at a temperature of 138-170 ° C, usually for 20-90 minutes. When triglycerides are used as the source of aliphatic esters in the reaction mixture, the reaction may be advantageously carried out by adding 1-10% by weight of the phase mixture, such as saturated fatty alcohol polyethoxylate, alkyl polyglycoside, linear glucamide surfactant or mixtures thereof. .

Preferably, the process is carried out as follows:

a) preheating the fatty acid ester to 138-170 ° C;

b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester and stirring until a biphasic liquid / liquid mixture is obtained;

c) mixing the catalyst with the reaction mixture; and

d) stirring the reaction mixture for the required reaction time.

If the fatty acid ester is a triglyceride, then preferably 2 to 20% by weight of the prepared linear N-alkyl or N-hydroxyalkyl-N- (linear-glucosyl) fatty acid amide product is added as the phase transfer agent. This inoculates the reaction mixture and thus increases the reaction rate. A detailed experimental procedure is described in the following experimental section.

The polyhydroxy fatty acid amide materials used in the compositions of the present invention even provide the detergent formulator with the advantage that they can be made wholly or primarily from natural, renewable, non-petrochemical starting materials, and are of low toxicity to aquatic life.

It should be noted that processes for the preparation of polyhydroxy fatty acid amides of formula (I) generally also produce a certain amount of non-volatile by-products, such as ester amides and cyclic polyhydroxy fatty acid amides. The amount of these by-products will vary depending on the specific reagents and process conditions. The polyhydroxy fatty acid amide to be incorporated into the detergent compositions of the present invention is preferably formulated so that the polyhydroxy fatty acid amide composition added to the detergent contains less than 10% by weight, preferably less than 4% by weight, of cyclic polyhydroxy fatty acid amide. The preferred methods described above are advantageous in that they result in a relatively small amount of by-products, including cyclic amide by-products.

defoamers

As mentioned above, the compositions of the invention may be blended with anti-foaming or suppressing agents. The inclusion of such materials, hereinafter "antifoams", is desirable, since polyhydroxy fatty acid amide surfactants may enhance the foaming stability of detergent compositions. In particular, reducing foaming may be important if the detergent composition contains a relatively large amount of foaming surfactant in combination with polyhydroxy fatty acid amide surfactant. Foam suppression is particularly desirable for formulations intended for use in pre-filled automatic washers. These machines are typically characterized in that the wash and wash water are contained in a drum having a horizontal axis and rotating about this axis. This type of movement can result in high foaming and consequently reduced washing performance. The use of antifoam agents can be of great importance under hot water washing conditions and high surfactant concentrations.

Many different substances can be used in the compositions of the invention as an antifoam. Foam inhibitors are well known to those skilled in the art. They are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology Volume 7, pages 430-447 / John Wiley and Sons, Inc. 1979. Monocarboxylic fatty acids and their soluble salts form a particularly interesting class of antifoam agents. These materials are described in U.S. Patent No. 2,954,347. The monocarboxylic fatty acids and their salts used as antifoams typically have a hydrocarbon chain of from 10 to 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as the sodium, potassium and lithium salts, and the ammonium and alkanol ammonium salts. These materials are a preferred class of antifoam for use in detergent compositions.

Detergent compositions may also contain non-surfactant antifoams. These include, for example, high molecular weight hydrocarbons such as paraffins and halogenated paraffins, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, C 18 -C 40 aliphatic ketones (e.g., stearone), and the like. Other antifoam agents include the reaction products of N-alkylated aminotriazines, such as trihexaalkyl-melamines or di-tetraalkyldiamine chlorotriazines, which are cyanuric chloride and 2 or 3 moles of C 1 -C 24 primary or secondary amines; propylene oxide and monostearyl phosphates, such as monostearyl alcohol phosphate esters (e.g., monostearyl dialkali metal phosphate esters in which

EN 214 049 Β alkali metal (for example potassium, sodium or lithium) and monostearyl dialkali metal phosphates in which the alkali metal is for example potassium, sodium or lithium. Hydrocarbons such as paraffins and halogenated paraffins can be used in liquid form. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, with a freezing point of - (40-5) ° C and a minimum boiling point of not less than 110 ° C (at atmospheric pressure). It is also known to use waxy hydrocarbons which preferably have a melting point below 100 ° C. Hydrocarbons are a preferred class of antifoam for detergent compositions. Hydrocarbon antifoams are described, for example, in U.S. Patent No. 4,265,779. The hydrocarbons may be C 12 -C 70 aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons. The term "paraffin", used in conjunction with antifoam agents, refers to a mixture of genuine paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant antifoams is silicone antifoams. This group includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and the use of combinations of polyorganosiloxanes with silica particles, whereby the polyorganosiloxane is oxidized to silica. Silicone antifoams are well known in the art and are described, for example, in U.S. Patent No. 4,265,779.

Other silicone antifoams are described in U.S. Patent No. 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by mixing a small amount of polydimethylsiloxane liquid in the solutions.

Mixtures of silicone and silanized silica are disclosed in German Patent Application DOS 2,124,526.

Silicone defoamers and antifoams in granular detergent compositions are disclosed in U.S. Patent Nos. 3,933,672 and 4,652,392.

For example, an antifoam amount of a silicone-based antifoam for use in the compositions of the present invention is an antifoam amount of the following composition:

(i) a polydimethylsiloxane liquid having a viscosity at 25 ° C of 2 × 10 ⁵ -1.5 to 10 ^-3 cm ² / sec;

material in ii) 100 parts by weight of i) 5-50 parts of siloxane having the following composition: (CH ₃₎ SiO _3/2 units and SiO ₂ units, in addition to the (CH ₃₎ SiO _3/2 units and _SiO2 units in the molar ratio of (0 , 6: 1) - (1.2: 1); and iii) 1 to 20 parts by weight of solid silica gel per 100 parts by weight of material according to i)

Detergent formulations used in automatic washing machines should not form enough foam to spill out of the washing machine. Antifoams, when used, are preferably present in an "antifoam amount". "Antifoam amount" means that the formulator may select an amount of antifoam grains that reduces foaming sufficiently to provide a reduced foaming detergent for use in automatic washing machines. The amount of antifoaming agent depends on the detergent surfactants chosen.

Thus, for example, highly foaming surfactants need to use relatively more foaming agents than less foaming surfactants to achieve the desired foaming reduction. Generally, an amount of antifoam agent should be incorporated into a reduced foam detergent composition so that the foam formed during the washing cycle of the automatic washing machine (i.e., when the detergent is mixed in the aqueous solution at the required temperature and concentration) does not exceed 75% of the the foam should not exceed 50% of this gap volume. The gap volume is defined as the difference between the total volume of the drum and the volume of water + laundry.

When monocarboxylic fatty acids and their salts are used as antifoam agents, they are generally present in the detergent composition up to 5% by weight. Preferably 0.5 to 3% by weight of an antifoam monocarboxylic fatty acid is used. Silicone antifoams are generally used in the detergent composition in amounts of up to 2.0% by weight, although larger amounts may be used. This upper limit is practical, firstly to minimize costs, secondly because smaller amounts are also effective in providing adequate foam reduction. Preferably, 0.01 to 1% by weight, more preferably 0.25 to 0.5% by weight, of silicone antifoam is used. In the compositions of the present invention, these weight percentages apply to any silica that may be used in combination with polyorganosiloxane and any additives that may be used. Monostearyl phosphates are generally used in an amount of 0.1 to 2% by weight.

Hydrocarbon antifoams are generally used in amounts of 0.01 to 5.0% by weight, although larger amounts may be used.

The detergent compositions of the present invention may further comprise an additional surfactant which may be anionic and nonionic surfactants other than the alkyl sulfate and polyhydroxy fatty acid amides described above and other types of surfactants.

If present, the amount of these additional surfactants is at least 1% by weight, preferably 3-30% by weight of the detergent composition.

Certain types of additional surfactants, when used in the compositions of the present invention, may result in additional, surprisingly improved washing performance. These additional surfactants include alkyl ethoxylated sulfates, alkyl ethoxylates and alkyl ester sulfonates (in particular methyl ester sulfonates) and mixtures thereof. The weight ratio of polyhydroxy fatty acid amide to these additional surfactants is from 1: 10 to 10: 1, more preferably from 5: 1 to 1: 5, more preferably from 1: 4 to 4: 1.

Without limiting the invention, other additional surfactants that can be advantageously mixed with the

The formulations of the invention include paraffin sulfonates, alkylbenzene sulfonates, alkyl polyglycosides (in particular alkyl polyglucosides) and alkyl phenol alkoxylates.

Additional surfactants that may be used are described in more detail below.

Additional anionic surfactants

In the compositions of the invention, the alkyl ester sulfonate surfactants are linear esters of C8-C20 carboxylic acids (i.e., fatty acids) sulfonated with sulfur trioxide gas (1975, Journal of the American Oil Chemists Society, 52, 323-329). ]. Suitable starting materials are natural fatty acids which are derived from tallow, palm kernel and coconut oil, etc. come.

Preferred alkyl ester sulfonate surfactants, especially for washing, are alkyl ester sulfonate surfactants of formula II wherein R ^{3 is a C} 8-20 hydrocarbon group, preferably an alkyl group or a mixture thereof, R ⁴ 1-6. a hydrocarbon group, preferably an alkyl group, or a mixture thereof, and an M cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations are sodium, potassium and lithium metal cations and optionally substituted ammonium cations such as methyl, dimethyl, trimethyl and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidium ethanol, e.g. cations derived from -amine, diethanolamine and triethanolamine. Preferably R ^{3 is C} 10 -C 16 alkyl and R ^{4 is} methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates wherein R ^{3 is C} 14 -C 16 alkyl.

The alkyl alkoxylated sulfate surfactants used in the compositions of the present invention are salts or acids of the formula RO / A / _m SO 3 M wherein R is unsubstituted C 10 -C 24 alkyl or hydroxyalkyl, preferably C 12 -C 20 alkyl or hydroxy. alkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl; ??? ethoxy or propoxy; m is greater than zero, generally between 0.5 and 6, more preferably between 0.5 and 3; and M is a hydrogen atom or a cation which may be, for example, a metal cation such as sodium, potassium, lithium, calcium or magnesium, etc. or an ammonium or substituted ammonium cation. The invention includes both alkyl ethoxylated sulfates and alkyl propoxylated sulfates. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium cations, and alkanolamines such as monoethanolamine and diethanolamine. cations and mixtures thereof. Examples of such surfactants include C 12 -C 18 alkyl polyethoxylate (1,0) sulfates, C 12 -C 18 alkyl polyethoxylate (2,25) sulfates, C 12 -C 18 alkyl polyethoxylate (3) sulfates, and C 18 alkyl polyethoxylate (4,0) sulfates, wherein M is preferably sodium or potassium.

The compositions may also contain other anionic surfactants suitable for detersive purposes. These may include soaps (e.g., sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), alkylbenzene sulfonates (especially straight-chain alkylbenzene sulfonates having 9 to 20 carbon atoms), primary and secondary alkanesulfonates, C8-C24 olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonation of pyrolized products of alkaline earth metal citrates as described, for example, in British Patent 1,082,179, glycine sulfate, , alkylphenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl taurides, alkyl succinates and sulfosuccinates, monosulfate saturated and unsaturated C12-C18 monoesters), sulfosuccinate diesters (primarily saturated and unsaturated C 6 -C 14 diesters), N-acyl sarcosinates, alkyl polysaccharide sulfates such as alkyl polyglycoside sulfates (nonionic non-sulfated compounds are described below), branched-chain alkyl alkyl sulfates, carboxylates such as RO / CH ₂ CH ₂ O / kCH ₂ COOM® in which R 8 is C 22 alkyl, k = 0 to 10 and M soluble salt cation, and fatty acids esterified with isethionic acid and sodium hydroxide neutralized. Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids in or derived from tall oil. Further examples are found in Surface Active Agents and Detergents, Vol. I and II by Schwartz, Perry and Berch. U.S. Pat. No. 3,929,678, p. rows 29 to 23, column 29.

Additional nonionic detergent surfactants

Suitable nonionic detergent surfactants are generally described in U.S. Pat. No. 3,929,678, column 13, line 14 to column 16, line 6.

By way of example, but not by way of limitation, the various classes of nonionic surfactants that may be used are listed.

1. Polyethylene, polypropylene and poly (butylene oxide) condensates of alkyl phenols, polyethylene oxide condensates are generally preferred and include alkylene oxide condensation products of alkyl phenols. the alkyl group in phenol

It contains from 6 to 12 carbon atoms (in straight or branched configuration. In a preferred embodiment, the amount of ethylene oxide is 5 to 25 moles of ethylene oxide) 1 mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ™, CO-630 (manufactured by GAF Corporation); Triton ™ X-45, X-1 14, X-100 and

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X-102 (product of Rohm and Haas Company). These compounds are considered to be alkyl phenol alkoxylates, such as alkyl phenol ethoxylates.

2. Condensation products of aliphatic alcohols with 1-25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary and generally contains from 8 to 22 carbon atoms. Condensation products of alcohols having from 10 to 20 carbon atoms and from 2 to 18 mol of ethylene oxide per mole of alcohol are particularly preferred.

Commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (a condensation product of a C11-C15 straight chain alcohol with 9 moles of ethylene oxide); Tergitol ™ 24-L-6 NMW (condensation product of a C12-C14 primary alcohol with 6 moles of ethylene oxide, narrow molecular weight distribution), both from Union Carbide Corporation; Neodol ™ 45-9 (condensation product of a C14-C15 straight chain alcohol with 9 moles of ethylene oxide); Neodol ™ 23-6.5 (C 12 -C 13 straight chain alcohol condensation product with 6.5 moles ethylene oxide); Neodol ™ 45-7 (C14-C15 straight chain alcohol condensation product with 7 moles of ethylene oxide), Neodol ™ 45-4 (C14-15 straight chain alcohol condensation product with 4 moles ethylene oxide), Shell Chemical Company M ; and Kyro ™ EOB (a condensation product of C13-C15 alcohol with 9 moles of ethylene oxide) from The Procter and Gamble Company. These surfactants may be referred to as alkyl ethoxylates.

3. Condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol.

The hydrophobic moiety of these compounds preferably has a molecular weight of 1500-1800 and is water insoluble. Adding polyoxyethylene groups to this hydrophobic moiety increases the water solubility of the molecule as a whole and maintains the liquid nature of the product to the point where the polyoxyethylene content is 50% by weight of the total condensation product. -a which corresponds to a condensation of not more than 40 moles of ethylene oxide. Examples of such compounds are certain commercial Pluronic ™ surfactants sold by BASF.

4. Condensation products of ethylene oxide with products derived from the reaction of propylene oxide with ethylene diamine. The hydrophobic group of these products consists of the reaction product of ethylenediamine and excess propylene oxide, generally having a molecular weight of 2500-3000. This hydrophobic group is condensed with ethylene oxide to the extent that the condensation product contains 40 to 80% by weight of polyoxyethylene and has a molecular weight of 5,000 to 11,000. These types of nonionic surfactants are certain commercial Tetronic ™ compounds marketed by BASF.

5. Semi-polar nonionic surfactants are a special class of nonionic surfactants which are water-soluble amine oxides which may contain one C 10 -C 18 alkyl group and two C 1 -C 3 alkyl or hydroxyalkyl groups;

water-soluble phospho-oxides containing one C 10 -C 18 alkyl group and two C 1 -C 3 alkyl or hydroxyalkyl groups; or water-soluble sulfoxides containing a C 10 -C 18 alkyl group and a C 1 -C 3 alkyl or hydroxyalkyl group.

Semi-polar, nonionic detergent surfactants include the amine oxide surfactants of formula III wherein R ^{3 is} an alkyl, hydroxyalkyl or alkylphenyl group containing from 8 to 22 carbon atoms or mixtures thereof; R ^{4 is} C 2 -C 2 alkylene or hydroxyalkylene, or mixtures thereof; x = 0-3; and each R ^{5 is} C 1-3 alkyl or hydroxyalkyl or a polyethylene oxide containing 1-3 ethylene oxide groups. R ⁵ groups may be attached to each other, for example via an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants are preferably C 10 -C 18 aldimethylamine oxides or C 8 -C 12 alkoxyethyl dihydroxyethylamine oxides.

6. The alkyl polysaccharides described in U.S. Patent 4,565,647, containing a hydrophobic group having from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and a polysaccharide group having from 1.3 to 10, preferably from 1 to 10 carbon atoms. , 3 to 3, most preferably 1.3 to 2.7 saccharide units.

Any C 5 -C 6 reducing saccharide can be used, for example, glucose, galactose, and glucosyl groups can be substituted by galactosyl groups. (Optionally, the hydrophobic moiety is attached to the 2-, 3-, 4-, etc. positions such as glucose or galactose, unlike the glucoside and galactoside.) The linkages between the saccharides may be, for example, one of the positions of the additional saccharide units and the preceding saccharide. units in positions 2, 3, 4 and / or 6.

Optionally, but less conveniently, a polyalkylene oxide chain may be attached to the hydrophobic group and the polysaccharide group. The preferred alkylene oxide is ethylene oxide.

Typical hydrophobic groups are alkyl groups, branched or unbranched and containing from 8 to 18 carbon atoms, preferably from 10 to 16 carbon atoms. The alkyl group is preferably straight chain. The alkyl group may contain up to 3 hydroxy groups and / or the polyalkylene oxide chain may contain up to 10, preferably less than 5, alkylene oxide groups. Suitable alkyl polysaccharides include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-tetra-, - penta- and -hexaglycosides, -galactosides, -lactosides, -glucoses, -fructosides, -fuctoses and / or -galactoses. Suitable mixtures are coconut alkyl, di, tri, tetra and pentaglycosides and tallow alkyl tetra, penta- and hexaglycosides.

Preferred alkyl polyglycosides have the general formula (IV) wherein R ^{2 is} alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, the alkyl groups being 10-18,

Preferably having from 12 to 14 carbon atoms; n = 2 or 3, preferably 2; t = 0 to 10, preferably 0; and χ = 1.3-10, preferably 1.3-3, most preferably 1.3-2.7. The glycosyl moiety is preferably derived from glucose. For the preparation of these compounds, the alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form the glycoside (linkage at the 1-position). Further glycosyl units may be linked between their 1-position and the 2-, 3-, 4- and / or 6-positions of the previous glycosyl units, preferably in particular between their 2-position.

7. A fatty acid amide surfactant of formula (V) wherein R ^{6 is} an alkyl group having 7 to 21 carbon atoms, preferably 9 to 17 carbon atoms; and the two R ⁷ groups are hydrogen, (C 1 -C 4) alkyl, (C 1 -C 4) hydroxyalkyl, or - (C ₂ H ₄ O) .H in which x is 1-3. Preferred amides are C8-20 ammonia, monoethanolamides, diethanolamides and isopropanolamides.

Cationic surfactants

The detergent compositions of the present invention may also contain cationic detergent surfactants as additional surfactants. Cationic surfactants include ammonium surfactants such as alkyldimethylammonium halides and surfactants of formula VI wherein R ^{2 is} alkyl or alkylbenzyl having from 8 to 18 carbon atoms; each R ³ is -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH (CH 2 OH) -, -CH 2 CH 2 CH 2 -, or mixtures thereof; each R ⁴ is C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, or benzyl, joined by the two R ⁴ groups, -CH ₂ CHOH-CHOHCOR ⁶ CHOH-CH ₂ OH, wherein R ^{6 is} a hexose or hexose polymer having a molecular weight less than 1000 and hydrogen when y is other than 0; R ^{5 is the} same as R ⁴ or alkyl, and the total number of carbon atoms in R ² and R ⁵ is not more than 18; each y is from 0 to 10 and the sum of y is from 0 to 15; and any compatible anion.

Other cationic surfactants useful in the compositions of the present invention are described in U.S. Patent 4,228,044.

Other auxiliary surfactants

Ampholytic surfactants can be incorporated into the detergent compositions of the present invention. These surfactants are generally characterized as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic group is straight or branched. One of the aliphatic substituents contains at least 8 carbon atoms, usually from 8 to 18 carbon atoms, and at least one contains an anionic, water-soluble group such as a carboxy, sulfonate or sulfate group. [Cf. U.S. Patent No. 3,929,678, Col. 19, lines 18-35, for examples of ampholytic surfactants].

Zwitterionic surfactants may also be incorporated into the detergent compositions of the present invention. These surfactants are generally characterized as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds, cf. U.S. Pat. No. 3,929,678, Col. 19, line 38 to column 22, line 48. Here are examples of zwitterionic surfactants].

Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

In another aspect, the invention provides detergent compositions wherein the ratio of alkyl sulfate to polyhydroxy fatty acid amide is critically adjusted to achieve improved washing performance. In this regard, the detergent composition according to the invention has the following composition:

(a) at least 3% by weight of a polyhydroxy fatty acid amide of formula (I) wherein R ^{1 is} methyl; R ² 9-17 alkyl or alkenyl, preferably C11-17 alkyl or alkenyl; and Z is a glycityl group or an alkoxylated derivative thereof from a reducing sugar; and

b) at least 3% by weight of alkyl sulfate surfactant; in addition, the weight ratio of components b) to a) (1.25: 1: 4).

The above weight ratio is preferably (1.25: 1.0) to (1.0: 1.25).

Surprisingly, a very good overall washing performance is achieved, particularly with respect to the washing of greasy and oily soils with these compounds, with a wide variety of washing conditions, particularly with respect to the relatively high weight ratio of polyhydroxy fatty acid amide to alkyl sulfate.

In another aspect, the invention provides a liquid detergent composition having the following composition:

(a) at least 3% by weight of a polyhydroxy fatty acid amide derivative of formula (I) wherein R ^{1 is} hydrogen, C 1 -C 4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl; R ^{2 is C} 7 -C 19 alkyl or alkenyl; and Z is a polyhydroxy hydrocarbon group derived from reductive amination of a reducing sugar,

b) at least 3% by weight of alkyl sulfate surfactant having 14 or more carbon atoms;

c) a liquid carrier;

in addition, the weight ratio of polyhydroxy fatty acid amide to alkyl sulfate surfactant having 14 or more carbon atoms (1: 3) to (3: 1). The incorporation of alkyl sulfate surfactants having 14 carbon atoms and longer in liquid detergent formulations is known to have difficulties. This is due, at least in part, to the highly crystalline nature of these surfactants. This is uncomfortable because alkyl sulfate surfactants with 14 carbon atoms and longer are highly preferred detergent surfactants, even in detergents that are intended to be used at a wash temperature of less than 50 ° C, and which generally contain 12 carbon atoms. surfactant.

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However, when polyhydroxy fatty acid amides are used in formulations, alkyl sulfate surfactants with 14 carbon atoms and longer can be more easily incorporated into liquid detergent formulations.

Such compositions preferably contain from 3 to 30% by weight of polyhydroxy fatty acid amide and from 3 to 30% by weight of the above alkyl sulfate. The liquid compositions of the invention may also contain alkyl sulfate surfactants having an alkyl chain of less than 14 carbon atoms.

In another aspect, the invention provides detergent granules for use in granular detergent compositions. These detergent granules contain an intimate mixture of the following components:

(a) 5 to 50% by weight of a polyhydroxy fatty acid amide of formula (I) wherein R ^{1 is} hydrogen, C 1-4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof; R ^{2 is C} 7 -C 19 alkyl or alkenyl; and Z is a polyhydroxy hydrocarbon group as defined above with a straight hydrocarbon chain, and

b) 50-95% by weight of alkyl sulfate surfactant; in addition, the weight ratio of components a) and b) is from 4: 1 to 1: 4. In mixtures containing C12-C14 alkyl sulfate surfactants, the weight ratio of alkyl sulfate to polyhydroxy fatty acid amide is preferably 4: 1, for C14-C16 alkyl sulfates it is 3: 1 and for C16-C18 alkyl sulfates. 1: 1.

The deterrent particles may further comprise a solubility enhancer which increases the solubility of the particles in the aqueous solution. Examples of such solubilizers are anionic sulfonate surfactants, ethoxylated surfactants having a degree of ethoxylation of at least 0.5, cyclic polyhydroxy fatty acid amides, alkyl polyglycosides, polyethylene glycol polymers, polyacrylic acid polymers and mixtures thereof. Preferred solubilizers are alkyl ethoxylates, alkyl ethoxylated sulfates, alkyl ester sulfonates, cyclic polyhydroxy fatty acid amides, alkyl polyglycosides, or polyethylene glycol or polyacrylic acid polymers, or mixtures thereof. Other substances which increase the solubility or solubility of the alkyl sulfate polyhydroxy fatty acid amide particles can also be used.

The amount of dissolution aids for the detergent particles can vary from 1% by weight and preferably not more than 30% by weight. By "intimate mixture" of alkyl sulfate, polyhydroxy fatty acid amide and optionally additional solubilizer, it is understood that the components are well mixed before or at the same time as the deterrent particles are prepared, although the particles themselves need not be completely homogeneous. Methods for preparing granules from intimate mixtures of detergent components are well known in the art, such as the use of high-energy or high-shear mixers. The process for the preparation of the detergent particles is described in the Examples. The particle size may be varied as desired by the manufacturer. In granular formulations, the deterrent particles should generally be sized in the same manner as the other particles in the formulation. The particles are generally 100-1000 µm in diameter.

The detergent granules may also contain other components for detergent, construction or aesthetic or other purposes.

The detergent granules may be used alone and may be incorporated in granular detergents containing other detergent components. Such detergent compositions generally contain at least 5% by weight of detergent granules.

Hangers

The detergent compositions of the present invention may contain inorganic or organic builders for controlling mineral hardness.

The amount of builder will largely depend on the end use of the composition and the desired physical form. Liquid compositions generally contain at least 1% by weight, more typically 5-50%, preferably 5-30% by weight, of detergent builder. Granular compositions generally contain at least 1% by weight, more typically 10-80%, preferably 15-50% by weight, of detergent builder. However, smaller or larger amounts of builders cannot be ruled out.

Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanol ammonium salts of polyphosphates (such as tripolyphosphates, pyrophosphates and glass-like polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including hydrates) and aluminum silicates. Borate builders as well as builders containing borate builders (collectively referred to as "borate builders") may also be used for detergent storage or under washing conditions. Preferably, non-borate builders are used in the compositions of the invention intended to be used under washing conditions below 50 ° C, especially below 40 ° C.

Silicate builder materials are alkali metal silicates, particularly those having a SiO ₂ : Na ₂ O molar ratio (1.6: 1) to (3.2: 1); and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839. However, other silicates, such as magnesium silicates, which give the granular compositions a crunchy appearance, serve as stabilizers for oxygen bleaches, and can also be used as a component of antifoam systems.

Carbonate builders include alkali metal and alkaline earth metal carbonates, such as sodium carbonate and sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate as disclosed in German Patent Application No. 2,321,001.

Aluminum silicate builders are particularly useful in the detergent compositions of the present invention. Aluminum-silicate builder materials are of great importance for most currently

EN 214,049 in high performance granular detergent formulations and may also be important constituents of liquid buoyancy in liquid detergent formulations. Aluminum silicate builders correspond to Experimental Formula (VII) wherein M is sodium, potassium, ammonium or substituted ammonium; z 0.5-2; and y = 1. This material has a magnesium ion exchange capacity of anhydrous aluminosilicate, 1 g of at least 50 milligram equivalents of CaCO ₃ hardness.

Preferred aluminum silicates are zeolite builders of formula VIII wherein z and y are at least 6 integers, z and y have a molar ratio of 1.0-0.5 and x 15-264.

Aluminum silicate ion exchange agents for use in the compositions of the invention are commercially available. These aluminum silicates may be crystalline or amorphous in structure and may be naturally occurring or synthetic aluminum silicates. U.S. Pat. No. 3,985,669 discloses a process for the preparation of aluminum silicate ion exchange materials. Preferred synthetic crystalline aluminum silicate ion exchange materials are available under the designations Zeolite A, Zeolite P (B) and Zeolite X. In a particularly preferred form, the crystalline aluminosilicate ion exchange material is of the formula IX, x 20-30, in particular 27. This material is known as Zeolite A. The aluminum silicate preferably has a particle size of 0.1 to 10 µm in diameter.

Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, wherein the degree of polymerization is 6-21; and salts of phytic acid.

Phosphonate impurity floating salts include, for example, water-soluble salts of ethane-1-hydroxy-1,1-diphosphonate, especially sodium and potassium salts, water-soluble salts of methylene diphosphonic acid such as trisodium and tricalcium salts, and water-substituted diphosphonic acid salts thereof such as trisodium and tricalcium ethylidene, isopropylidene, benzylmethylidene and halogenated methylidene phosphonates. Phosphonate builder salts of the type mentioned above are described in U.S. Patent Nos. 3,159,581,321,230,030.3,422,021, 3,400,148, and 3,422,137.

Organic detergent builder materials suitable for the purposes of the present invention include, without limitation, a large number of polycarboxylate derivatives. As used herein, the term "polycarboxylate" refers to several compounds, preferably containing at least three carboxylate groups.

The polycarboxylate builders may generally be added in acid form, but may also be in the form of a neutralized salt. When used in salt form, the preferred salts are the alkali metal salts such as sodium, potassium and lithium, in particular sodium salts; or ammonium or substituted ammonium salts such as alkanolammonium.

Polycarboxylate builders include different classes of usable materials.

An important class of polycarboxylate builders is the ether polycarboxylates. Many ether polycarboxylates have been described for use as detergent builders. Useful ether polycarboxylates are, for example, the oxydisuccinate described in U.S. Patent Nos. 3,123,287 and 3,635,830.

A specific type of ether polycarboxylate as a builder for use in the compositions of the present invention is a compound of Formula X wherein A is hydrogen or hydroxy; B is hydrogen or -O-CH (COOX) -CH 2 (COOX); and X is hydrogen or a salt-forming cation. For example, when A and B are hydrogen in the formula (X), the compound is oxybisuccinic acid and its water-soluble salts. When A is hydroxy and B is hydrogen, the compound is tartrate monobasic acid (TMS) and its water soluble salts. When A is hydrogen and -O-CH (COOX) -CH2 (COOX), the compound is tartrate dibasic acid (TDS) and its water soluble salts. Mixtures of these builders are particularly preferred. In particular, mixtures of TMS and TDS (97: 3) to (20:80) by weight are preferred. These builder materials are described in U.S. Patent 4,663,071.

Suitable ether polycarboxylates include cyclic compounds, in particular alicyclic compounds, such as those described in U.S. Patent Nos. 3,923,679.3835,163.4,158,635.4,120,874 and 4,102,903.

Other useful detergent builders include ether hydroxypolycarboxylates of formula XI wherein M is hydrogen or a cation, the salt thus obtained is a water soluble, preferably the cation is an alkali metal, ammonium or substituted ammonium cation; n 2-15 (n preferably 2-10, more preferably n average 2-4); and the R groups are the same or different and are selected from the group consisting of hydrogen, C 1-4 alkyl and C 1-4 alkyl

C 1-4 substituted alkyl. Preferably R is hydrogen.

Other ether polycarboxylates are copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid.

Organic polycarboxylate builder materials include various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. The polyacetic acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

These include, as polycarboxylates, mellitic acid, succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, benzene-pentacarboxylic acid, carboxymethyl-succinic acid and their water-soluble salts.

Particularly important polycarboxylate builders for high performance liquid detergent compositions are citric acid and its soluble salts. They can also be used in granular formulations. Suitable salts include metal salts such as sodium, lithium and potassium, and ammonium and substituted ammonium salts.

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Other carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent No. 3,723,322.

3,3-Dicarboxy-4-oxa-1,6-hexanedioates and the like are also suitable in the detergent compositions of the present invention. They are disclosed in U.S. Patent 4,566,984. Useful succinic builders include C 5-20 alkyl succinic acids and their salts. Of these compounds, dodecenyl succinic acid is particularly preferred. Alkyl succinic acids typically correspond to the formula R-CH [COOH (CH2) COOH], i.e. succinic acid derivatives in which R is a hydrocarbon group such as an alkyl or alkenyl group having from 10 to 20, preferably from 12 to 16 carbon atoms; substituted with hydroxy, sulfo, sulfoxy or sulfone groups, all of which are described in the aforementioned patents.

Succinate builders are preferably used in the form of their water-soluble salts, such as their sodium, potassium, ammonium and alkanol ammonium salts.

Specific examples of succinate builders are: lauryl succinate, myristyl succinate, palmityl succinate,

2-dodecenylsuccinate (preferred), 2-pendadecenylsuccinate and the like. Of this group, lauryl succinates are the preferred builders described in European Patent Application 0 200 263.

Suitable builders include sodium and potassium carboxymethyl malonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, water-soluble polyacrylates (with a molecular weight of more than 2000). and copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates described in U.S. Patent 4,144,226. These polyacetal carboxylates can be prepared by bringing together an ester of glyoxylic acid and a polymerization initiator under polymerization conditions. The resulting polyacetal carboxylate ester is then coupled to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solutions, and then converted to the corresponding salt and added to the surfactant.

Polycarboxylate builders are also disclosed in U.S. Patent No. 3,308,067. These materials include water soluble salts of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other organic builders known in the art may also be used. For example, the long hydrocarbon monocarboxylic acids and their soluble salts may also be used. These are the substances commonly referred to as "soaps". Typically the chain length used is from 10 to 20 carbon atoms. Hydrocarbons can be saturated or unsaturated.

enzymes

The detergent compositions of the present invention may contain detergent enzymes for a variety of purposes, such as removing protein-based, carbohydrate-based or triglyceride-based stains and, for example, preventing dye transfer.

Miscible enzymes include proteases, amylases, lipases, cellulases and peroxidases, and mixtures thereof. The enzymes can be of any suitable origin, such as plant, animal, bacterial, fungal, or yeast. The choice of enzyme will depend on a number of factors such as pH and / or optimum stability, heat stability, stability to effective detergents and builders, and the like. In this regard, bacterial and fungal enzymes such as bacterial amylases and proteases and fungal celluloses are preferred.

Suitable proteases include, for example, subtilisins, which can be obtained from specific strains of B. subtilis and B. lichenforms. Another suitable protease can be produced from a Bacillus strain having a maximum activity in the pH range of 8-12, developed and marketed by NOVO Industries A / S as Esperasew. The preparation of this enzyme and similar enzymes is described in British Patent No. 1,243,784. Proteolytic enzymes for protein-based stain removal are available under the trade names ALCALASE ™ and SAVINASE ™ from Novo Industries A / S (Denmark) and MAXATASE ™ from International Bio-Synthetics, In. (Netherlands).

In the class of proteolytic enzymes, especially for liquid detergent compositions, protease A and protease B are preferred. Protease A and a process for its production are described in European Patent Application 130 756. Protease B is also a proteolytic enzyme that differs from protease A in that its amino acid sequence at position 217 replaces tyrosine with leucine.

Methods for the production of protease B are also described in the aforementioned European Patent Application 130 756.

Amylases include, for example, α-amylase produced from a specific strain of B. lichenforms and described in more detail in British Patent No. 1,296,839. Examples of starch degrading enzymes are RAPIDASE ™ (International Bio-Synthetics, Inc.) and TERMAMYL ™ (Novo Industries).

The cellulases useful in the detergent compositions of the present invention can be both bacterial and fungal. Their optimum pH is preferably 5-9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, which relates to fungal cellulases prepared from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2,075,028 and GB-A-2,095,275 and DE-OS-2 247832.

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These cellulases are, for example, a cellulase produced by Humicola insolens (Humicola grisea var. Thermoidea), in particular DSM 1800 Humicola; and cellulases produced by the fungus Bacillus N or cellulase 212 produced by the fungus of the genus Aeromonas; and cellulase extracted from the hepatopancreas of "maríné mullusc" (Dolabella Auricola Solander).

Suitable lipase enzymes for detergents are produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, which is described in British Patent No. 1,372,034. Suitable lipases are those which show a positive immunological cross-reaction with the lipase antibody produced by the Pseudomonas fluorescens IAM 1057 microorganism. This lipase and process for its purification are described in Japanese Patent Application No. 53-20487. This lipase is available from Amano Pharmacentical Co. Ltd., Nagoya, Japan under the trade name Lipase P, "Amano" (hereinafter "Amano-P."). Such lipases used in the present invention should have a positive immunological cross-reaction with Amano-P antibody using the standard and well-known immuno-diffusion method of Ouchterlony [ActaMed. Scan. 133: 76-79 (1950)]. These lipases and methods for their immunological cross-reaction are also described by Amano-P in U.S. Patent 4,707,291. Typical examples of lipases are Amano-P lipase, lipase from Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trademark Amano-CES) from Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum from NRRLB 3673 (available from Toyo Jozo Co. Tagata, Japan); and Chromobacter viscosum lipases (from U.S. Biochemical Corp., U.S.A.; and Disoynth Co. from the Netherlands) and lipases from Pseudomonas gladioli.

Peroxidase enzymes are supplied with oxygen sources such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. used in combination. They are used as solution bleaches to prevent the transfer of dyes or pigments from the substrates to other substrates in the washing solution during the washing operation. Peroxidases are known in the art, such as horseradish peroxidase, ligninase and halogen peroxidases such as chlorine and bromine peroxidases. Peroxidase-containing detergent compositions are described, for example, in International Patent Application WO / 89/099813.

A wide variety of enzyme materials and methods for incorporating them into synthetic detergent granules are disclosed in U.S. Patent 3,553,139. Enzymes are also discussed in U.S. Patent Nos. 4,101,457 and 4,507,219. Suitable enzyme materials and mixtures in liquid detergent compositions are disclosed in U.S. Patent No. 4,261,868.

Enzymes are generally shaken in amounts sufficient to provide up to 5 mg, more typically 0.05-3 mg, of active enzyme per Ig formulation.

For granular detergents, the enzymes are preferably coated or combined with the additives added to the enzymes to minimize dust formation and improve storage stability. Methods for doing so are well known in the art. In liquid formulations, an enzyme stabilizing system is preferably used. Enzyme stabilization methods for aqueous detergent compositions are well known in the art, for example, one method of stabilizing enzymes in aqueous solutions involves the use of free calcium ions from sources of calcium acetate, calcium formate or calcium propionate. The calcium ions may be used in combination with salts of lower carboxylic acids, preferably formates (cf. U.S. Patent No. 4,318,818). Mixtures of polyols such as glycerol and sorbitol, alkoxy alcohols, dialkyl glycol ethers, polyhydric alcohols and polyfunctional aliphatic amines (e.g., alkanolamines such as diethanolamine, triethanolamine, diisopropylamine, etc.), as well as boric acid and alkali metal have been proposed. -borates. Enzyme stabilization methods are also described in U.S. Patent Nos. 4,261,868 and 3,600,319 and European Patent Application 0 199 405. Stabilizers without boric acid and borate are preferred. Enzyme stabilization systems are also described, for example, in U.S. Patent Nos. 4,261,868,3,600,319 and 3,519,570.

Bleaching Compounds - Bleaching Agents and Bleach Activators

The detergent compositions of the present invention may contain bleaching agents or bleaching compositions comprising a bleaching agent and one or more bleach activators. If bleaching compounds are present, they will generally be present in the detergent composition in an amount of from 1 to 20%, more typically from 1 to 10% by weight. Bleaching compounds are generally compounds that may be present in non-liquid formulations, such as granular detergents. If present, the bleach activators generally comprise from 0.1 to 6% by weight of the bleaching composition, more typically from 0.5 to 10% by weight.

The bleaching agent present in the compositions of the present invention may be any bleaching agent commonly used in the cleaning of textiles for cleaning hard surfaces or for other known or known detergent cleaning purposes. Oxygen bleaches and other bleaching agents can be used in this way. For washing conditions below 50 ° C, especially below 40 ° C, compositions which do not contain borate or a substance which may form borate in situ (i.e., borate-forming agent) during detergent storage or under washing conditions are preferred. Under these conditions, it is therefore preferable to use a non-borate or non-borate-forming bleach. Detergents used at such temperatures are preferably substantially free of a

EN 214 049 Β of borate and borate former. The term "substantially free of borate and borate-forming agents" means that the formulations contain no more than 2% by weight, preferably no more than 1% by weight, of any type of borate or borate-forming material, more preferably 0%.

A class of usable bleaching agents includes percarboxylic acid bleaching agents and salts thereof. Suitable agents in this class include magnesium monoperoxyphthalate hexahydrate, magnesium salt of methachloroperbenzoic acid, 4- (nonylamino) -4-oxoperoxybutyric acid and diperoxododecanedioic acid. These bleaching agents are disclosed in U.S. Patent No. 4,483,781, U.S. Patent No. 0,133,354, and U.S. Patent No. 4,412,934. Very preferred bleaching agents are also 6- (nonylamino) -6-oxoperoperoxycaproic acid described in U.S. Patent No. 4,634,551.

Another class of bleaching agents that may be used in the detergent compositions of the present invention include halogenated bleaching agents. Examples of hypohalite bleaching agents include trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates, and N-chloro and N-bromoalkanesulfonamides. These materials are generally used in an amount of 0.5 to 10, preferably 1 to 5% by weight, in the finished product.

In addition, peroxygen bleaching agents (other than perboric compounds) may be used. Suitable peroxygen-containing bleaching agents include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.

The peroxygen-containing bleaching agents are preferably combined with bleaching activators, which leads to the in situ formation of the appropriate peroxyacid acid in the aqueous solution (i.e. during the washing operation).

Preferred bleach activators that can be incorporated into the compositions of the present invention are compounds of formula XII wherein R 1 is C 1 -C 18 alkyl, and the longest straight alkyl chain starting at the carbon atom of the carbonyl group and containing 6 to 10 carbon atoms of the carbonyl group; and leaving group L, the pKa value of which is 4-13. These bleach activators are described in U.S. Patent Nos. 4,915,854 and 4,412,934.

Other bleaching agents than oxygen bleaching agents are known and can be used in the art. One particularly interesting type of non-oxygen bleaching agent includes photoactivated bleaching agents, such as sulfonated zinc and / or aluminum phthalocyanines. These materials may be deposited on the substrate during the washing process. When irradiated with light, in the presence of oxygen, such as hanging clothes to dry in the sunlight, the sulfonated zinc phthalocyanine is activated and consequently bleaches the substrate. A preferred zinc phthalocyanine and photoactivated bleaching process is described in U.S. Patent 4,033,718. Detergent compositions are generally

Containing from 0.025 to 1.25% by weight of sulfonated zinc phthalocyanine.

Polymeric soil release agents

Any polymeric soil release agent known to those skilled in the art may be used in the practice of this invention. Polymeric dirt repellents are characterized by having both hydrophilic portions to hydrophilize the surface of hydrophobic fibers such as nylon and polyester as well as hydrophobic portions which are deposited on and remain adhered to the hydrophobic fibers during washing and rinsing and so on. they serve as "anchors" for hydrophilic portions. This makes it easier to remove stains after treatment with dirt repellents during subsequent washing operations.

Although the use of polymeric soil release agents can have a beneficial effect in any detergent formulation, particularly in formulations used for washing or other applications where grease and oil have to be removed from hydrophobic surfaces, the presence of polyhydroxy fatty acid amide in detergent formulations containing anionic surfactants can improve the performance of the type of polymeric soil release agent used. Anionic surfactants interfere with the ability of certain soil-repellents to settle and adhere to hydrophobic surfaces. These polymeric soil release agents have nonionic hydrophilic moieties or hydrophobic moieties which are anionic surfactant-interactive.

Compositions of the present invention for which the performance of a polymeric soil release agent can be improved by the use of polyhydroxy fatty acid amide are compositions comprising an anionic surfactant system, an anionic surfactant interactive soil release agent, and a polyhydroxy fatty acid amide (PFA) enhancer. wherein: (I) the anionic surfactant interaction between the soil release agent in the detergent composition and the anionic surfactant system can be demonstrated by comparing the amount of soil release grains (SRA) deposited on the hydrophobic fibers (e.g., polyester) in the aqueous solution (A). In an experiment measuring the deposition of a soil release agent in a detergent composition in an aqueous solution without the presence of other detergent components; and (B) in a "soil release agent / anionic surfactant" experiment, combining the type and amount of anionic surfactant system used in the detergent composition with an soil release agent in an aqueous solution, the same weight ratio of the soil release agent and anionic surfactant system in the detergent composition. a) the reduced deposition according to (B) indicates the anionic surfactant interaction compared to the experiment; and (II) whether the detergent composition contains an amount of a polyhydroxy fatty acid ameliorating agent can be determined by comparing the deposition of the impurities in the "impurities / anionic surfactant" experiment (B) and the impurities. deposition of the agent in the "dirt" according to (C)

EN 214 049 Β in the "anionic surfactant / polyhydroxy fatty acid amide" experiment, combining the type and amount of polyhydroxy fatty acid amide present in the detergent composition with the so called "soil release agent / anionic surfactant" experiment and the soil anionic surfactant system C, improved deposition of the soil release agent relative to Experiment (B) indicates that an amount of polyhydroxy fatty acid amide is present to enhance the effect of the soil release agent.

For purposes of the present invention, the experiments should be conducted at concentrations of the anionic surfactant in aqueous solution which are greater than the critical micelle concentration (CMC) of the anionic surfactant in aqueous solution, and preferably above 100 ppm.

The concentration of the polymeric soil release agent should be at least 15 ppm. For hydrophobic spinning we use a small piece of polyester material. Identical specimens were immersed in aqueous solutions of appropriate experiments at 35 ° C and stirred for 12 minutes, after which the sample was removed and analyzed. The amount of deposition of the polymeric soil repellant may be determined by isotopically labeling the soil repellant prior to treatment and then by radiochemical analysis according to methods well known in the art.

As an alternative to the above radiochemical method, deposition of the soil repellant can be determined in the above experiments (i.e., Experiments A, B and C) by determining the ultraviolet light absorption of the test solutions by methods well known in the art. The decrease in UV absorption in the test solution after removal of the hydrophobic fiber material corresponds to increasing deposition of dirt repellent. As is clear to one of ordinary skill in the art, UV analysis is not applicable to experimental solutions containing types and amounts of substances that cause excessive UV absorption interference, such as large amounts of surfactants containing aromatic groups (e.g., alkylbenzene sulfonates).

By "amount of polyhydroxy fatty acid amide" impurity enhancer, is meant the amount of this over-active agent that enhances the deposition of the soil release agent on hydrophobic fibers, as mentioned above, or the amount that results in improved grease / oil washing performance. fabrics which are washed in the detergent compositions of the present invention in the following washing operation.

The amount of polyhydroxy fatty acid amide required to increase deposition will vary depending upon the anionic surfactant selected, the amount of anionic surfactant selected, the specific soil release agent selected, and the particular polyhydroxy fatty acid amide selected. The compositions generally contain from 0.01% to 10% by weight, typically from 0.1% to 5% by weight, of polymeric soil release agent and from 1% to 50%, more typically from 4% to 30%, of anionic surfactant. These formulations will generally contain at least 1% by weight, preferably at least 3% by weight, of polyhydroxy fatty acid amides, although this is not necessarily intended to be limited.

Polymeric soil release agents, the performance of which is enhanced by the presence of an anionic surfactant polyhydroxy fatty acid, are those soil release agents which contain the following components: (a) one or more nonionic hydrophilic components which are substantially (i) a polyoxyethylene ) a segment having a degree of polymerization of at least 2; or (ii) an oxypropylene or polyoxypropylene segment having a degree of polymerization of 2 to 10, wherein said hydrophilic segment may not contain an oxypropylene moiety unless linked to groups adjacent to ether bonds at each end; or (iii) a mixture of oxyalkylene units containing oxyethylene and from 1 to 30 oxypropylene units, said mixture comprising a sufficient amount of oxyethylene units to provide the hydrophilic compound with sufficient hydrophilicity, to increase the hydrophilicity of the surface of a conventional synthetic polyester fiber when the soil release agent is deposited on such a surface; the hydrophilic segments preferably contain at least 250 mol% oxyethylene units and more preferably, especially for such compounds, 20-30 mol% oxypropylene units and at least 50 mol% oxyethylene units; or b) one or more hydrophobic components, such as: (i) C3-oxyalkylene terephthalate: segments in which, when the hydrophobic compounds contain oxyethylene terephthalate, the molar ratio of the oxyethylene terephthalate is 2: 1 or less for alkylene terephthalate units; (ii) C 4 -C 6 alkylene or oxy (C 4 -C 6) alkylene segments or mixtures thereof; (iii) polyvinyl ester segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2; or (iv) C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether substituents, or mixtures thereof, wherein the substituents are C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether cellulose derivatives, or mixtures thereof. and these cellulose derivatives are amphiphilic so that they have sufficient units of C 1-4 alkyl ether and / or C 4 hydroxyalkyl ether to deposit on conventional synthetic polyester fiber surfaces and retain sufficient hydroxy groups if once adhered to this conventional synthetic fiber surface to increase the hydrophilicity of the fiber surface; or a / and b / are combined.

The polyoxyethylene segments in (a) according to (a) typically have a degree of polymerization of from 2 to 200 (although higher degrees of polymerization may be used), preferably

3-150, more preferably 6-100. Suitable oxy (4-6C) alkylene hydrophobe segments include - but not necessarily - the stabilization of polymeric soil release agents chain ends, such as a MO3S _{(CH2) n OCH2 CH2} O-, where M is sodium and n = An integer of 4-6, as disclosed in U.S. Patent No. 4,721,580.

Polymeric soil release agents for use in the compositions of the invention include cellulose derivatives such as hydroxyether cellulose polymers, ethylene terephthalate or propylene terephthalate copolymer.

EN 214 049 Β with poly (ethylene oxide) or poly (propylene oxide) terephthalate and the like.

Cellulose derivatives which act as soil release agents are commercially available, such as cellulose hydroxy ethers under the tradename Methocel ^R (Dow Chem.).

Cellulosic soil release agents for use in the compositions of the present invention include C 1-4 alkyl and C 4 hydroxyalkyl celluloses such as methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, and hydroxybutylmethylcellulose. cellulose. Various cellulose derivatives useful as polymeric soil release agents are described in U.S. Patent No. 4,000,093.

Soil repellents characterized by hydrophobic polyvinyl ester segments include polyvinyl esters such as C 1-6 vinyl esters, preferably graft copolymers of polyvinyl acetate, poly (alkylene oxide) such as poly (ethylene oxide). ), the spine ojtva. These materials are known in the art and are described in European Patent Application 0 219 048. Commercially available suitable soil release agents of this type are Sokolan ™ materials such as Sokolan ™ HP-22 (BASF, Germany).

One type of preferred soil release agent is the copolymer which is a random block copolymer of ethylene terephthalate and poly (ethylene oxide) / PEO / terephthalate. More specifically, these polymers consist of repeating units of ethylene terephthalate and poly (ethylene oxide) terephthalate, the molar ratio of ethylene terephthalate units to poly (ethylene oxide) terephthalate units (25: 75) to (35: 65). in addition, the molecular weight of the polyethylene oxide in the polyethylene oxide terephthalate units is 300-2000. This polymer dirt-repellant grain has a molecular weight of 25,000-55,000. Similar polymers are disclosed in U.S. Patent Nos. 3,959,230 and 3,893,929.

Other preferred polymeric soil release agents are polyesters in which ethylene terephthalate units are repeated.

The ethylene terephthalate units contain from 10 to 15% by weight of ethylene terephthalate units with from 90 to 80% by weight of polyoxyethylene terephthalate units derived from polyoxyethylene glycol having an average molecular weight of 300-5000 and the polymer. The compound has a molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units (2: 10- (6: 1). Examples of such polymers are the commercially available Zelcon® 5126 (Dupont) and Milease® T (ICI) products. These polymers and processes for their preparation are described in U.S. Patent 4,702,857.

Another group of preferred polymeric soil release agents are sulfonated products of substantially linear ester oligomers, wherein the backbone of the ester oligomer is formed by repeating terephthaloyl and oxyalkyleneoxy units and the terminal groups are covalently attached to the backbone.

These dirt repellents are derived from allyl alcohol ethoxylate, dimethyl terephthalate, and 1,2-propylene diol, which, after sulfonation, have an average of 1-4 sulfonate groups on the oligomer. Such dirt repellents are described in detail in U.S. Patent No. 4,968,451.

Other suitable polymeric soil release agents include 1,2-propylene terephthalate polyoxyethylene terephthalate polyesters stabilized at the end of the chain with ethyl or methyl groups, oligomeric esters stabilized with anionic group at the end of the chain [ U.S. Patent No. 4,721,580], wherein the anionic chain-terminating moieties are sulfopolyethoxy groups derived from polyethylene glycol, and block polyester oligomeric compounds (U.S. Patent No. 4,702,857), which are X (OCH2CH2). They contain n-12 to 43 and X is C 1 -C 4 alkyl, preferably methyl.

Other polymeric soil release agents are those described in U.S. Patent No. 4,877,896, which are terephthalic acid esters anionically stabilized at the end of the chain, in particular with sulfoaryl groups. The terephthalate esters contain asymmetrically substituted oxy-1,2-alkyleneoxy units. Dirt-repellent polymers disclosed in the above-described 4,777,896 include polyoxyethylene hydrophilic components or repeating units of C3-oxyalkylene terephthalate (propylene terephthalate), cf. materials containing the hydrophobic components referred to in Chapter (b) (i) above. For polymeric soil repellents characterized by one or both of the above criteria, it is particularly advantageous to introduce polyhydroxy fatty acid amides in the presence of anionic surfactants.

If used, the soil release agents will generally be present in the detergent composition in an amount of 0.01 to 10.0% by weight, typically 0.1 to 5% by weight, preferably 0.2 to 3.0% by weight.

Chelating agents

The detergent compositions of the invention may optionally contain one or more iron or manganese chelating agents as adjuncts to builders. These chelating agents include aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, as defined below. Without any theoretical consideration, it is believed that the beneficial effect of these compounds is due in part to their exceptional ability to remove iron and manganese from the wash solutions to form soluble chelates.

The aminocarboxylates optionally used as chelating agents in the compositions of the present invention contain one or more, preferably at least two, subunits of the general formula (a) wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x1. 3, preferably 1. These amino carboxylates are preferably up to 16

Containing alkyl or alkenyl groups of 6 carbon atoms or less. Suitable amine carboxylates include ethylenediaminetetraacetates, N- (hydroxyethyl) ethylenediamine triacetates, nitrile diacetates, ethylenediaminetetrapropionates, triethylene tetraamine hexaacetates, diethylenetriamine pentaacetates and , their alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

Aminophosphonate chelating agents may also be used in the compositions of the present invention when at least a small amount of total phosphorus is allowed in the detergent compositions. Compounds containing one or more, preferably at least two, structural units of formula (b) wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x 1 to 3, preferably 1, can be used. These compounds are ethylenediamine tetrakis ( methylene phosphonates), nitrilotris (methylene phosphonates) and diethylene triamine pentakis (methylene phosphonates).

These aminophosphonates preferably do not contain more; such as C 6 -alkyl or alkenyl.

The alkylene groups in the substructures may be common.

Polyfunctionally substituted aromatic chelating agents may also be used in the compositions of the present invention. These substances may be compounds of the formula (XIII) wherein at least one of the substituents R is -SO3H or -COOH, their soluble salts or mixtures thereof. U.S. Patent No. 3,812,044 describes polyfunctionally substituted aromatic chelating and complexing agents. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene. Alkaline detergent compositions may contain these materials in the form of alkali metal, ammonium or substituted ammonium salts (e.g., mono or triethanolamine salts).

If used, these chelating agents will contain 0.1 to 10% by weight of the detergent compositions. More preferably, the chelating agents are present in such compositions in an amount of from 0.1 to 3.0% by weight.

rtgyago.v anti-soiling / anti-rebuilding agents

The compositions of the present invention may optionally contain water-soluble ethoxylated amines having anti-clay and anti-reuptake properties. Granular detergent compositions containing these compounds typically contain from 0.01% to 10.0% by weight of water-soluble ethoxylated amine; while liquid detergent compositions typically contain from 0.01% to 5% by weight. These compounds are preferably selected from the following groups:

1) ethoxylated monoamines of formula XIV;

2) ethoxylated diamines of formula XV, XVI or XVII;

3) ethoxylated polyamines of formula XVIII;

4) ethoxylated amine polymers of formula XIX; and

5) mixtures thereof;

in the formulas A ^{1 is} -C / = O / O-, -OC / = O / O-, -OC / = O /, or (c), (d), (e), (f), (g) or (h) or oxygen; R is hydrogen, (1-4C) alkyl or hydroxyalkyl; R ^{1 is} C 2 -C 12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or C 2 -C 2 oxyalkylene, with 2 to 20 oxyalkylene units, provided that no ON bond is formed; each R ^{2 is C} 1 -C 4 alkyl or hydroxyalkyl, 2 is a -LX group or two R ^{2 taken} together form a - (CH 2) r - or A ² - (CH 2) _S - group in which ^{2 is} -O- or -CH ² -; r = 1 or 2; s = 1 or 2; and 2 r + s = 3 or 4; X is a nonionic group, anionic group or a mixture thereof; R ^{3 is} substituted with C 3-12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl substituents; R ^{4 is a} C 1 -C 12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene group or a C 2 -C 2 oxyalkylene group having 2 to 20 oxyalkylene units, provided that neither OO nor ON bond is present. not formed; L is a hydrophilic chain containing a - [(R ⁵ O) m (CH ₂ CH ₂ O) "] - polyoxyalkylene group wherein R ^{5 is} C 3 -C 4 alkylene or hydroxyalkylene and m and n are numbers such that the - (CH ₂ CH ₂ O) _n - group represents at least 50% by weight of the above polyoxyalkylene group; and for the above monoamines, m = 0-4 and n is at least 12; for the above diamines, m = 0-3 and n is at least 6 when R ^{1 is} C 2 -C 3 alkylene, hydroxyalkylene or alkenylene and at least 3 if R ^{1 is} other than C 2 -C 3 alkylene, hydroxyalkylene or alkenylene; for the above polyamines and amine polymers, m = 0 to 10 and at least 3; p = 3-8; q = 1 or 0; t = 1 or 0, provided t = lhag = l; w = 1 or 0; x + y + z = at least 2; and y + z = at least 2. The most preferred soil release and reuptake inhibitor is ethoxylated tetraethylene pentamine. Examples of ethoxylated amines are further described in U.S. Patent 4,597,898.

Another preferred class of anti-clay / anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965. Other useful clay soiling / anti-redeposition agents are the ethoxylated amine polymers disclosed in European Patent Application 111984, the zwitterionic polymers disclosed in European Patent Application 112,592 and the amine oxides disclosed in U.S. Patent 4,548,744. U.S. Pat.

Other known clay soiling and / or reuptake inhibitors may be used in the compositions of the present invention. Another class of anti-reuptake agents is carboxymethylcellulose (CMC). These materials are well known in the art.

Polymeric dispersants

The polymeric dispersants are advantageously used in the compositions of the invention. These are the mother17

EN 214 049 Β may contribute to the control of calcium and magnesium hardness.

Suitable polymeric dispersants are polymeric polycarboxylates and polyethylene glycols, although other agents known in the art may be used.

Polymeric dispersants are generally used in the detergent composition in amounts of 0.5 to 5% by weight, more generally 1.0 to 2.0% by weight.

Polycarboxylate derivatives useful as polymeric polycarboxylate dispersants in the compositions of the present invention are polymers and copolymers comprising at least 60% by weight of a segment wherein X, Y and Z are hydrogen, methyl, carboxy, carboxymethyl, hydroxy, or hydroxymethyl; M is a salt cation; and n = 30-400. Preferably X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is hydrogen, and M is hydrogen, alkali metal, ammonium, or substituted ammonium.

Polymeric polycarboxylates of this type are prepared by polymerization or copolymerization of suitable unsaturated monomers, preferably in acid form. The unsaturated monomeric acids which when polymerized form the corresponding polymeric polycarboxylates are acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.

The presence of monomeric segments in the polymeric polycarboxylates which include carboxylate groups such as vinyl methyl ether, styrene, ethylene and the like. groups, they adequately ensure that these segments do not constitute more than 40% by weight of the formulation.

Particularly suitable polymeric polycarboxylates are derived from acrylic acid. Such acrylic acid based polymers useful in the present case are water soluble salts of polymerized acrylic acid. Such acid form polymers have an average molecular weight of 2,000 to 10,000, more preferably 4,000 to 7,000, most preferably 4,000 to 5,000.

The water-soluble salts of such acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of these polyacrylates in detergent compositions is described, for example, in U.S. Patent No. 3,308,067.

Acrylic / malein based copolymers can also be used as preferred components of dispersants / reuptake inhibitors. These materials are water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such acid-form copolymers is 2000-100,000, more preferably 5,000-75,000, most preferably 7,000-65,000. The molar ratio of acrylate and maleate segments in these copolymers is generally (30: 1) to 1: 1, more preferably (10: 10). : 1) - (2: 1). The water-soluble salts of these acrylic / maleic copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials and are described in European Patent Application 66,915.

Another polymeric material that can be used is polyethylene glycol (PEG). The polyethylene glycol dispersant may exhibit performance as well as act as an anti-clay / anti-redeposition agent. Typical molecular weights for such purposes are 500-100,000, preferably 1,000-50,000, more preferably 1500-10,000.

Elénkitőszerek

Any optical brightener or other brightener or bleach known in the art may be incorporated into the detergent compositions of the present invention.

The choice of a disintegrant for use in a detergent composition will depend on a number of factors such as the type of detergent, the nature of the other components present in the detergent composition, the temperature of the wash water, the degree of mixing, and size ratio of detergent to drum.

The choice of brightener also depends on the type of fabric being washed, for example whether the fabric is cotton, synthetic, etc. Since most detergents are used for washing different textiles, detergent compositions should contain a blend of brighteners which is effective for different textiles. Of course, it is necessary for such stimulant mixtures to be compatible with the individual components.

Commercial optical brighteners for use in the detergent compositions of the present invention may be classified into subgroups which include, but are not limited to, stilbene, pyrazoline, coumarin, carboxylic acids, methincyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-ring heterocyclic compounds; various other materials.

Such stimulants are described, for example, in "The Production and Application of Fluorescent Brightening Agents," by M. Zahradnik, published by John Wiley and Sons, New York, 1982.

The stilbene derivatives useful in the detergent compositions of the present invention are, but are not limited to, bis-triazinylaminostilbene derivatives; bis (acylamino) derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styrene derivatives of stilbene.

Certain derivatives of bis-triazinylaminostilbene which are useful in the detergent compositions of the present invention can be prepared from 4,4'-diaminostilbene-2,2'-disulfonic acid.

Coumarin derivatives useful in the compositions of the present invention include, but are not limited to, 3-position, 7-position, and 3- and 7-position substituted derivatives.

Carboxylic acid derivatives useful in the compositions of the present invention include, but are not limited to, humic acid derivatives; benzoic acid derivatives, p-phenylene bisacrylic acid derivatives; naphthalenedicarboxylic acid derivatives; derivatives of heterocyclic acids; and derivatives of cinnamic acid.

The cinnamic acid derivatives useful in the compositions of the present invention may be subdivided into further subgroups which include, but are not limited to, cinnamic acid derivatives, styryl azoles,

HU 214 049 Β

benzofitranes, styryloxadiazoles, styryltriazoles and styryl polyphenyls [cf. above Zahradnik Reference, page 77].

The styryl azoles can be further subdivided into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles described in Zahradnik Reference, p. It should be noted that the above three subgroups do not necessarily exhaust the subgroup into which the styryl azoles may be divided.

Another class of optical brighteners for use in the compositions of the present invention are dibenzothiophene-5,5-dioxide derivatives (The Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 3, pages 737-750 / John Wiley and Son, Inc., 1962). .], including 3,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5-dioxide.

Another class of optical brighteners useful in the compositions of the invention are azole derivatives of heterocyclic compounds having five ring members. These derivatives can be divided into subgroups of monoazoles and bisazoles. Examples of mono- and bisazoles are found in the Kirk-Othmer reference above.

Another class of stimulants for use in the compositions of the present invention are derivatives of the six-membered heterocyclic compounds also disclosed in the above Kirk-Othmer Reference. Examples of such compounds are stimulants derived from pyrazine and 4-aminonaphthalamide.

In addition to the aforementioned stimulants, various agents may be used as a stimulant. Such various agents are described in Zahradnik, reference 93-95. and these brighteners are 1-hydroxy-3,6,8-pyrene-trisulfonic acid, 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene, 4,5-diphenylimidazolone disulfonic acid and pyrazoline and quinoline derivatives.

Other specific examples of optical brighteners for use in the compositions of the invention are given in U.S. Patent No. 4,790,856. These enhancers include the Phorwhite ™ series (Verona). Other stimulants described herein include Tinopal UNPA, Tinopal CBS and Tinopal 5BM (Ciba-Geigy); Arctic White CC and Arctic White CWD (Hilton-Dawis, Italy); 2- (4-styrylphenyl) -2H-naphthol- [1,2d] triazoles; 4,4'-bis (1,2,3-triazol-2-yl) stilbenes; 4,4-bisztiril bisphenyls; and γ-aminocoumarin. Specific examples of these enhancers include 4-methyl-7- (diethylamino) coumarin; 1,2-bis / 2-benzimidazolyl / ethylene; 1,3-diphenylpyrazolines, 2,5-bis (2-benzoxazolyl) -thiophene; 2-styrylnaphthyl / 1,2d / oxazole; and 2- (4-stilbenyl) -2H-naphthol [1,2-d] triazole.

Other optical brighteners for use in the compositions of the invention are described in U.S. Patent 3,646,015.

Other components

Many of the other ingredients used in detergent compositions can be used in the compositions of the present invention, including other active ingredients, carriers, hydrotropic agents, processing aids, dyes or pigments, solvents for liquid compositions, and the like.

Liquid detergent compositions may contain water and other solvents as carriers. For example, low molecular weight primary and secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. Monovalent alcohols are preferred for the dissolution of the surfactant, but also polyols having from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups, such as propylene glycol, ethylene glycol, glycerol and 1,2-propanediol.

The detergent compositions of the present invention are preferably formulated such that the pH of the wash water used in aqueous washing operations is between 6.5 and 11, preferably between 7.5 and 10.5. The pH of the liquid product formulations is preferably between 7.5 and 9.5, more preferably between 7.5 and 9.0. Buffers, alkalis, acids, etc. are recommended to control pH at recommended application levels. are well known to those skilled in the art.

Stirring is recommended to enhance the washing effect. Suitable means for ensuring mixing are by hand or preferably by brushing or other means, washing in an automatic washing machine or washing in an automatic dishwasher.

Experimental part

A process for the preparation of N-methyl-1- (deoxyglycityl) laurea surfactant for use in the compositions of the present invention is described. The shape of the apparatus can be varied by one skilled in the art, but a suitable apparatus for use in the present case is a three-liter four-necked flask equipped with a motor-driven paddle stirrer and a thermometer long enough to feed into the reaction medium. The other two necks of the flask are equipped with a nitrogen inlet and a wide side branch (note: the wide side branch is important when methanol is developing very fast), with a well-functioning cooler and vacuum outlet attached. The latter is connected to a nitrogen purge gas and a vacuum gauge, then to an exhale and a siphon. The reaction mixture is heated with a 500 Watt jacket with a Variable Transformer Temperature Controller ("Variac") placed on a laboratory rack so that it can be easily raised and lowered to further control the reaction temperature.

195 g (1.0 mol) of N-methyl glucamine (Aldrich, M 4700-0) and 220.9 g (1.0 mol) of methyl laurate (Procter and Gamble CE 1270) are placed in a flask. The solid / liquid mixture was heated while stirring and introducing nitrogen to form a melt within 25 minutes. When the melt temperature reaches 145 ° C, anhydrous powdered sodium carbonate catalyst (10.5 g, 0.1 mol, J.T. Baker) is added. Nitrogen purge is completed and the exhale and nitrogen flow are adjusted to a vacuum of 16.9 kPa / 5/31 atm. The reaction temperature is then maintained at 150 ° C by adjusting the Variac and / or raising or lowering the running jacket.

EN 214 049 Β then spray the last liquid components.

The first methanol bubbles appear on the surface of the reaction mixture in% w / w. A vigorous reaction will soon follow. Methanol is redistilled until its development has subsided. The vacuum is adjusted to 33.8 kPa (1C / 31 atm). The vacuum is increased as follows: 33.8 kPa for 3 minutes, 67.6 kPa for 7 minutes and 84.5 kPa for 10 minutes. After 11 minutes from the start of the evolution of methanol, heating and stirring were stopped, with some foaming. The product is cooled and solidified.

The detergent compositions of the present invention and their preparation are illustrated by the following examples, without limiting the scope of the invention.

The subject matter of the invention is defined by the claims.

1-6. example

These examples illustrate preferred compositions containing alkyl sulfates and polyhydroxy fatty acid amides, which are suitably suitable for washing above 40 ° C at a concentration of 6000 to 8000 ppm by weight of the wash water.

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The sheet granulate 7th Second Third 25 C14-C15 alkyl sulfate 4.6 4.6 C16-C18 alkyl sulfate 2.4 2.4 2.4 12-carbon straight chain alkylbenzenesulfonate 7.6 30 C 16 -C 18 alkyl ethoxylate (11 moles) 1.1 1.1 1.1 Zeolite 22.0 24.0 21.3 Acrylate / maleate copolymer / 60,000 molar weight / 4.3 5.6 4.3 35 Water and more 9.4 9.2 10.1 Mixed and sprayed N-methyl-N- (1-deoxyglycityl) - -kókuszsavamid 7.0 40 N-methyl-N- (1-deoxyglycityl) - - oil acid amide 7.0 4.0 Sodium citrate 8.0 8.0 Sodium carbonate 17.5 17.3 17.5 Sodium silicate 45 / SiO ₂ / Na ₂ O = 1.6 / 3.5 3.0 3.5 fragrance 0.4 0.4 0.4 Silicone liquid 0.5 0.5 0.5 Various additives / filler salts, enzymes, bleach, 50 dirt repellent, polymers etc./ 19.3 26.8 19.4 700.0 700.0 700.0

1-3 above. The compositions of Examples 1 to 5 are preferably used at a concentration of 6000 ppm based on the weight of the wash water at 30-95 ° C. These formulations are prepared by suspending the components of the base granulate and spray-drying to a moisture content of 9% by weight. The remaining dry, powdered or granulated components are mixed together

ς base granules 4th 5th 6th C 12 straight chain alkylbenzenesulfonate 5.9 N-methyl-N- (1-deoxyglycityl) - -faggyúsavamid 7.1 10 C14-C15 alkyl sulfate 5.9 5.9 C16-C18 alkyl sulfate 2.5 2.5 2.5 Zeolite 20.5 14.0 20.5 Polyacrylate (4500 molecular weight) 3.9 3.9 3.9 Sodium citrate 6.0 15 N atrium carbonate 12.7 16.0 12.7 Water and more 8.1 8.2 8.7

When mixed and sprayed N-methyl-N- (1-deoxyglycyl) lauric acid 7.1

N-methyl-N- (1-deoxyglycityl) coconut amide

Miscellaneous additives (bleach, filler salts, floating salts, enzymes, etc.)

6.6

36.9 38.7

700.0 700.0

4-6. EXAMPLE 1B shows high density, high performance granular detergent compositions at a wash temperature of 30-95 ° C at a concentration of 8000 ppm by weight of wash water. The formulations are prepared by spray-drying a suspension of base granule components to a moisture content of 10-13% by weight, adding other powdered dry ingredients such as bleach, activators and other additives, and spraying liquids such as perfume, nonionic or antifoaming liquids.

7-20. example

These examples illustrate high performance granular detergent formulations containing polyhydroxy fatty acid amides, alkyl sulfates and antifoams.

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Basic granules 7. 8. 9. 10.

C14-C15 alkyl sulfate 18.7

C14-C15 alkyl ethoxy (2,25) sulfate C12-C18 alkyl sulfate straight-chain alkylbenzene sulfonate N-methyl-N- (1-deoxyglycityl) coconut acid 3.8

Zeolite A 30.1

Sodium citrate

10.1 11.3

5.6

16.9

10.1

2.4 5.6 5.6

18.8 18.8 30.1

11.3 11.3

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Basic granules 7. 8. 9. 10.

Sodium carbonate 16.9 16.9 16.9 16.9 Sodium silicate 3.1 2.5 2.5 2.5 Sodium sulfate 15.0 15.0 15.1 15.1 tallow 1.1 1.1 1.1 Various additives 3.1 3.2 2.7 4.4

Mixed and sprayed

Various additives 2.5 3.5 3.5 2.5 Anti-foaming flakes * 0.5 0.5 1.0 Residual water 5.0 5.0 5.0 5.0 100.0 100.0 700.0 700.0

* The antifoam flake contains 5% by weight of a SiO 2 / silicone oil dispersion encapsulated in a flake, which primarily contains more than 80% by weight of polyethylene glycol / "PEG", 800 Mt./ and any water soluble components.

7-10. The compositions of Example 1 are preferably used at a concentration of 1400 ppm based on the weight of the wash water at temperatures below 50 ° C.

The formulations of the Examples above were prepared by suspending the components of the base granulate and spray-drying to a residual moisture of 4-8% by weight. The remaining dry ingredients, in the form of granules or powders, are mixed with the spray-dried granules in a rotary mixing drum, and the liquid components such as nonionic surfactant and fragrance are sprayed onto the granulate.

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The sheet granulate 77th 72nd C 12 straight chain alkyl benzene sulfonate 7.6 C 14 -C 15 alkyl sulfate 3.3 tallow 3.0 Zeolite A 13.4 19.8 Polyacrylate / 4500 MB / 3.5 4.5 Polyethylene glycol / 8000 MB / 2.0 2.0 Sodium silicate / SiO ₂ / Na ₂ O = 1,6 / 2.0 2.0 N atrium carbonate 15.0 15.0 Sodium sulfate 12.0 6.0 Various additives 1.5 1.0 Mixed and sprayed The detergent granules of Example 29 are 14.3 The deterrent granules of Example 30 are 30.0 Zeolite A 5.0 5.0 Sodium citrate 5.0 Anti-foaming flakes * 0.5 0.5 Various additives 7.1 5.0 Residual water 7.8 6.2 700.0 700.0

polyethylene glycol / PEG 8000 Mt./and 10% by weight of tallow acid.

The compositions of Examples 11 and 12 are preferably used at a concentration of 1000 ppm by weight of wash water at temperatures below 50 ° C. The compositions are prepared by suspending and spray-drying the components of the base granulate to a moisture content of 7-10% by weight, and then mixing or spraying the remaining components.

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base granules 13th 14th 75th C14-C15 alkyl sulfate 4.3 6.0 C16-C18 fatty acids 2.2 2.2 Zeolite A 7.0 7.0 7.0 Polyacrylate / 4500 MB / 3.3 3.3 3.3 Polyethylene glycol / 8000 MB / 1.3 1.3 1.3 N atrium carbonate 10.7 10.7 10.7 Sodium sulfate 5.0 5.0 5.0 Sodium silicate / SiO ₂ / Na ₂ O = 2 / 5.0 5.0 5.0 Various additives 7.1 7.1 7.1 Mixed and sprayed Zeolite A 5.0 5.0 5.0 N-methyl-N- (1-deoxyglycityl) - -kókuszsavamid 6.4 6.4 Example 28 is detective particles 21.3 C 12 -C 13 alkyl sulfate 13.1 13.1 C12-18 alkyl ethoxy / 2 / sulphate 6.0 Anti-foaming flakes * 1.0 0.5 He might have gotten mixed up deterrent components 17.2 17.2 16.5 C 12 -C 13 alkyl ethoxylate / 6.5 mol / 2.0 2.0 2.0 fragrance 0.5 0.5 0.5 Water and various additives 8.2 9.4 8.4 Altogether 700.0 700.0 700.0

The antifoam flake is encapsulated in a 5% by weight SiO ₂ / silicone oil dispersion encapsulated in a flake containing more than 80% by weight polyethylene glycol / PEG 8000 Mt./ and optionally a small amount of water soluble component.

13-15. Examples 1 to 4 are concentrated granular compositions which are prepared by suspending the components of the base granulate and spray-drying to a moisture content of 5% by weight and mixing with the other dry components. The resulting mixture is dust-dried by spraying the liquid components. The product can be used at a concentration of 1000 ppm at a wash temperature of less than 30 ° C.

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Basic granulate 16. 17.

* Antifoam flakes contain 5% SiO ₂ / silicone oil dispersion encapsulated 85% by weight

C 14 -C 15 alkyl sulfate 4.6

C 16 -C 18 alkyl sulfate 2.4 2.4

HU 214 049 Β

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The sheet granulate 16th 17th C 12 straight chain alkylbenzene sulfonate youth C16-C18 alkyl ethoxylate (11 mol) 1.1 1.1 tallow 1.1 1.1 Zeolite 21.3 22.0 Acrylate / Maleate Copolymer (60,000MB) 4.3 5.6 Water and various additives 10.1 9.2 Mixed and sprayed with N-methyl-N- (1-deoxyglycityl) coconut amide 7.0 N-Methyl-N- (1-deoxyglycityl) -fatty acid amide 4.0 Sodium citrate 8.0 N atrium carbonate 17.5 17.3 Sodium silicate (1.6 ratio) 3.5 3.0 fragrance 0.4 0.4 Silicone liquid 0.5 0.5 Various additives (bleach, salt, fillers, enzymes, impurities, etc.) 18.3 25.7 100.0 100.0

The formulations of Examples 16 and 17 are preferably used at a concentration of 6000 ppm based on the weight of the wash water at 30-95 ° C. These formulations are prepared by suspending the components of the base granulate and spray-drying to a moisture content of 9% by weight. The remaining dry, powder or granular components are added to the granulate, mixed in a rotary mixing drum, and the last liquid components are sprayed onto it.

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The sheet granulate 18th 19th 20th C 12 straight chain allyl sulfonate 5.9 N-methyl-N- (1-deoxysilicylcityl) - -faggyúsavamid 7.1 C 14 -C 15 alkyl sulfate 5.9 5.9 C16-C18 alkyl sulfate 2.5 2.5 2.5 Zeolite 20.5 14.0 20.5 F agaric acid amide 1.1 1.1 Polyacrylate (4,500 MB) 3.9 3.9 3.9 Citrate 6.0 N atrium carbonate 12.7 15.6 12.7 Water and various additives 8.1 8.2 8.7

Mixed and sprayed

N-Methyl-N- (1-deoxyglycityl)-lauric acid amide 7.1

N-methyl-N- (1-deoxyglycityl) coconut amide 7.1

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base granules 18th 19th 20th fragrance 0.4 0.4 0.4 Silicone liquid 1.0 0.5 0.5 Various additives (bleach, filler, salts, builder salts, enzymes, etc.) 36.8 24.8 37.8 700.0 700.0 700.0

18-20. EXAMPLE 1B shows high density, high performance granular detergent compositions at a wash temperature of 30-95 ° C at a concentration of 8000 ppm for wash water.

The formulations are prepared by suspending the ingredients of the base granulate and spray-drying to a moisture content of 10-13% by weight, and then adding the other dry powdered ingredients such as bleach, activators and other additives, and the liquid ingredients such as perfume. spray nonionic surfactants or antifoam fluids.

Examples 21-27

The following examples illustrate high performance liquid formulations containing alkyl sulfates and polyhydroxy fatty acid amides.

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components 27th 22nd 23rd 24th C12 -C14 alkyl sulfate N-methyl-N- 12.9 12.9 9.0 11.5 - (1-deoxyglycityl) - -kókuszsavamid N-methyl-N- 8.4 8.4 - (1-Deoxyglycityl) oleic acid 8.4 6.5 Oil week 1.8 1.8 3.5 2.0 Citric acid 4.1 4.1 10.0 9.0 Dodecenyl amber tartaric acid 11.1 11.1 4.0 5.0 silicone oil 0.2 0.2 0.2 0.2

Various additives (e.g. solvents, enzymes, stimulants,

stabilizers :, buffers) 16.1 16.1 16.1 17.7 Water 45.5 45.5 48.3 48.1 700.0 700.0 700.0 700.0

21-24. The compounds of Examples 1 to 5 are preferably used at a concentration of 12,000 ppm for the wash water at 30-95 ° C.

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Components 25. 26. 27.

N-methyl-N- (1-deoxyglycityl) coconut amide 4.2 3.1 3.1

N-methyl-N- (1-deoxyglycityl) oil acid amide

HU 214 049 Β

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components 25th 26th 27th C 14 -C 15 alkyl ethoxy (2.25) sulfate 8.4 6.1 C14-C15 alkyl sulfate 4.2 3.1 C12-C18 alkyl ethoxy (2.5) sulfate 6.2 C 12 -C 14 alkyl sulfate 3.1 C 12 -C 14 alkyl ethoxylate 3.4 0.0 0.0 Dodecyltrimethylammonium chloride 0.5 0.0 0.0 Dodecenylsuccinate 5.0 Citrate 3.4 0.0 15.0 TMS / TDS / 80/20 / * 3.4 0.0 0.0 C12-C14 fatty acids 3.0 0.0 0.0 Oxydisuccinate 20.0 Ethoxylated tetraethylene pentamine 1.5 0.0 0.0 Polyacrylate / 4500 MB / 1.5 1.5 Various additives (enzymes, stimulants, dirt repellents, stabilizers etc./ 15.3 14.9 14.9 Water 52.7 51.2 51.2 100.0 100.0 100.0

* TMS / TDS = tartrate monosuccinate / tartrate disuccinate.

25-27. The compositions of Examples 1 to 4 are preferably used at a concentration of 2000 ppm for wash water at wash temperatures below 50 ° C.

21-27. The compositions of Examples 1 to 8 are prepared by mixing non-aqueous solvents, aqueous surfactant pastes or solutions, melted fatty acids, aqueous solutions of polycarboxylate builders and other salts, aqueous ethoxylated tetraethylene pentamine, buffers, lyes and the like. Adjust the pH to 8.5 using aqueous citric acid or sodium hydroxide solution. After adjusting the pH, the final ingredients such as soil release agents, enzymes, dyes and fragrances are added to the formulation and the product is blended until a single phase is obtained.

28-30. example

The following examples relate to detergent granules containing alkyl sulfates and polyhydroxy fatty acid amides which are suitable for direct addition to high performance granular detergent formulations.

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components 28th 29th 30th C12-C18 alkyl sulfate 75.0 C14-C15 alkyl sulfate 65.0 83.0 N-methyl-N- (1-deoxyglycityl) - -kókuszsavamid 18.7 21.7 12.0 Various additives 1.3 8.3 Residual water and more 5.0 5.0 5.0 100.0 100.0 100.0

28-30. The compositions of Examples 1 to 6 are prepared by mixing the molten polyhydroxy fatty acid amide with an alkyl sulfate paste at 70-100 ° C. The product is then dried to a moisture content of less than 5 wt%, finally milled and graded into particles having a diameter of 0.1 to 1 mm.

Example 31

An alternative method for preparing polyhydroxy fatty acid amides for use in the compositions of the present invention is described below. The starting reaction mixture was 84.87 g of fatty acid methyl ester (Procter and Gamble methyl ester CE 1270), 75 g of N-methyl-D-glucamine (Aldrich Chemical Company M 4700-0), 1.04 g of sodium methoxide (Aldrich). Chemical Company 16,499-2) and 68.51 g of methyl alcohol. The reactor is a standard reflux unit equipped with a drying tube, a condenser and a stir bar. In this process, N-methyl glucamine is mixed with methanol under stirring under argon and heating is begun under vigorous stirring (stirring bar, reflux). After 15-20 minutes, when the solution reaches the desired temperature, the ester and the sodium methoxide catalyst are added. From time to time, samples are taken to check the progress of the reaction, but it is noted that the solution is perfectly clear within 63.5 minutes. We find that the reaction at this point is almost complete. The reaction mixture was heated at reflux for 4 hours. Removal of methanol gave the crude product 156.16 g. The product was dried in vacuo and purified to give a total of 106.92 g of purified product. On this basis, percentage yields were not calculated, as regular sampling during the course of the reaction would render all percentage yields meaningless. The reaction can be carried out at reactant concentrations of 80% and 90% by weight in up to 6 hours, with very little by-product formation.

The following is not intended to limit the scope of the invention, but merely to illustrate further technological possibilities that the formulator may take into account in the manufacture of a plurality of detergent compositions containing polyhydroxy fatty acid amides.

It is readily appreciated that polyhydroxy fatty acid amides, by virtue of their amide bond, are subject to some instability under strongly alkaline or strongly acidic conditions. Although some degradation can be tolerated, these materials are preferably not exposed to pH values of 11, preferably above 10, or below 3 for too long. The pH of the final product (liquid) is generally from 7.0 to 9.0.

In the manufacture of polyhydroxy fatty acid amides, it is generally necessary to neutralize the base catalyst at least partially to form the amide bond. While any acid may be used for this purpose, the detergent formulator will know that it is simple and convenient to use an acid which otherwise provides a useful and necessary anion in the final detergent composition. For example, citric acid may be used for neutralization, and the citrate ion thus obtained (1 wt%) may remain within 40 wt%

EN 214 049 Β polyhydroxy fatty acid amide suspension and can be aspirated into subsequent production steps of the complete detergent manufacturing process. Similarly, the substances used, such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate / succinate, and the like, may be used.

Polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (predominantly C12-C14) are much more soluble than those derived from tallow alkyl fatty acids (predominantly C16-C18). Therefore, C12-C14 materials are somewhat easier to use in liquid formulations and are more soluble in cold water baths. C16-C18 materials are also very useful, but primarily in conditions where hot or hot wash water is used. In fact, C16-C18 materials may be better deterrent surfactants than their corresponding C12-C14. Therefore, the formulator may consider the ease of manufacture and performance when selecting the specific polyhydroxy fatty acid amide for use with a particular formulation.

It should also be noted that the solubility of polyhydroxy fatty acid amides can be increased if the fatty acid moiety contains unsaturation and / or branching sites. Therefore, polyhydroxy fatty acid amides derived from oleic acid and isostearic acid are more soluble than the corresponding n-alkyl compounds.

Similarly, disaccharides, trisaccharides, and the like. The polyhydroxy fatty acid amides produced generally have higher solubilities than the corresponding monosaccharide derived materials. This higher solubility is particularly advantageous when formulating liquid formulations. Further, polyhydroxy fatty acid amides having a polyhydroxy group derived from maltose appear to work particularly well as detergents when used in combination with conventional alkylbenzene sulfonate surfactants. Without theoretical consideration, it appears that the combination of alkylbenzene sulfonates with polyhydroxy fatty acid amides derived from higher molecular weight saccharides, such as maltose, significantly and unexpectedly reduces the surface tension in the aqueous medium, thereby increasing the effective detergent performance. (The production of polyhydroxy fatty acid amide from maltose is described below.)

Polyhydroxy fatty acid amides may be prepared not only from purified sugars, but also from hydrolyzed starches, such as corn starch, potato starch or any other suitable starch of vegetable origin, which is mono-, destb. Contains saccharide. This is mainly cost-related. Thus, it is convenient and economical to use high glucose starch syrups, high maltose starch syrups, and the like. Hydrolysed cellulose pulp, which is free of woody particles, can also be a source of raw materials for polyhydroxy fatty acid amides.

As mentioned above, higher molecular weight saccharides such as maltose, lactose and the like are used.

The polyhydroxy fatty acid amides of formula I are more soluble than the corresponding compounds derived from glucose. It also appears that the more soluble polyhydroxy fatty acid amides can, to varying degrees, help to solubilize the less soluble corresponding compounds. Thus, the formulator may, for example, choose a high glucose starch syrup as a raw material, but may choose a syrup containing a small amount (e.g. 1% or more) of maltose.

The resulting blend of polyhydroxy fatty acids generally exhibits better solubility properties over a wide range of temperatures and concentrations than polyhydroxy fatty acid amide from pure glucose, and thus, in addition to the economic benefits of using sugar blends over pure sugar reagents, the blends are derived from sugars polyhydroxy fatty acid amides can provide significant advantages in terms of performance and / or ease of preparation. However, in some cases, there may be a slight decrease in degreasing capacity (when washing dishes) when the amount of fatty acid maltamide is above 25% by weight and a slight decrease in foaming when above 33% by weight (% of maltamide-derived polyhydroxy against glucose-derived polyhydroxy fatty acid amide in the mixture). This may vary slightly depending on the chain length of the fatty acid group. If the formulator of the product chooses such a mixture for use, it will generally be preferable to have polyhydroxy fatty acid amide mixtures in which the ratio of monosaccharides (e.g. glucose) to di- and trisaccharides (e.g. 4: 1) to 99: 1 ).

The preparation of preferred non-cyclized polyhydroxy fatty acid amides from fatty acid esters and N-alkyl polyols can be carried out in alcoholic solvents at temperatures of 30-90 ° C, preferably 50-80 ° C. It has been found that it may be convenient for the formulator of the product to carry out the process in, for example, liquid detergents in 1,2-propylene glycol solvent since it is not necessary to completely remove the glycol solvent from the reaction product before using it in the final detergent composition. Similarly, for example, formulators of solid, typically granular detergent formulations may find it convenient to use ethoxylated alcohols at 30-90 ° C, such as ethoxylated (EO = 3-8) C 12-14 alcohols, e.g. ) in solvents containing ethoxylated alcohol. If these ethoxylates are used, it is preferred that they do not contain a substantial amount of non-ethoxylated alcohol and most preferably do not contain a substantial amount of monoethoxylated alcohol ("T").

Since processes for the preparation of polyhydroxy fatty acid amides are not themselves within the scope of the invention, other syntheses of polyhydroxy fatty acid amides, which are described below, may be considered by the formulator.

The industrial scale reaction sequence for the preparation of the preferred acyclic polyhydroxy fatty acid amides comprises the following steps:

Step 1: Preparation of the N-alkyl polyhydroxyamine derivative from the desired sugar or sugar mixture,

HU 214 049 Β

Forming an adduct from N-alkylamine and sugar and then hydrogenating the adduct in the presence of a catalyst;

Step 2: Preferably, said polyhydroxyamine is reacted with a fatty acid ester to form an amide bond. Many of the N-alkyl polyhydroxyamines used in Step 2 of the reaction sequence can be prepared from various methods known in the art, but the following process is convenient and uses economical sugar syrup as a raw material. It should be noted that if such a syrup is used as a raw material, in order to achieve better results, the manufacturer should select syrups which are either light in color or preferably almost colorless (water clear).

Preparation of N-alkyl polyhydroxyamine from sugar syrup of plant origin

I. Adduct training

The following standard procedure in which 420 g of a 55% solution of glucose (starch syrup, 231 glucose, 1.28 mol) having a Gardner color below 1 is reacted with 119 g of a 50% aqueous solution of methylamine ( 59.5 g, 1.92 moles of methylamine). The methylamine solution was purged with nitrogen, covered with nitrogen gas and cooled to 10 ° C or lower. The starch syrup is also flushed and covered with nitrogen at 10-20 ° C. The starch pulp is then slowly added to the methylamine solution at the temperature indicated in the table. Gardner color is measured at the indicated intervals (minutes). The results are as follows.

Table 1

Time (in minutes): Reduction temp. C 10 30 60 120 180 240 Gardner color (approximate) 0 1 1 1 1 1 1 20 1 1 1 1 1 1 30 1 1 2 2 4 5 50 4 6 10 - - -

As can be seen from the above data, the Gardner color of the adduct deteriorates as the temperature rises above 30 ° C to 50 ° C, the time until the adduct Gardner color is below 7 is only 30 minutes. The temperature should be below about 20 ° C for longer reaction times and / or retention times. The Gardner color should be less than 7 and preferably less than 4 if a good color glucamine is to be produced.

If lower temperatures are used to prepare the adduct, the time required to achieve substantially equilibrium concentration of the adduct is reduced by the use of higher amounts of amine relative to the sugar. With a 1.5: 1 molar ratio of amine to sugar, equilibrium is reached within 2 hours at a reaction temperature of 30 ° C. At a 1.2: 1 molar ratio, this period is at least 3 hours under the same conditions. In order to obtain a good color, the combination of the amine: sugar ratio, reaction temperature and reaction time is selected such that a substantially equilibrium conversion, e.g., more than 90%, preferably more than 95%, more preferably greater than 99%, is achieved with respect to the sugar. , and the color of the adduct should be below 7, preferably below 4, more preferably below 1.

Using the above procedure at temperatures below 20 ° C and with various Gardner colored starch syrups, the methylamine adduct is colored according to the following table (after equilibrium has been substantially achieved for at least 2 hours).

Table 2

Gardner color (approximate) Starch 1 1 1 1+ 0 0 0+ adduct 3 4/5 7/8 7/8 1 2 1

As can be seen from the above, the starting sugar material must be nearly colorless in order to obtain a consistently acceptable adduct. If the Gardner color of the sugar is 1, then the adduct is sometimes acceptable or not. If the Gardner color of the sugar is above 1, the adduct is not acceptable. The better the initial color of the sugar, the better the color of the adduct.

II. Hydrogenation reaction

The adduct having Gardner color of 1 or less, prepared as described above, is hydrogenated according to the following procedure.

539 g of adduct in water and 23.1 g of nickel catalyst (United Catalyst G49B) are added to a one liter autoclave. The mixture. It is purged twice at 20 ° C with hydrogen gas at 13 psig (200 psig). The hydrogen pressure is increased to 9632 kPa (1400 psi) and the temperature raised to 50 ° C. The pressure is then increased to 11008 kPa (1600 psig) and the temperature is maintained at 50-55 ° C for about 3 hours. The product is then 95% hydrogenated. The temperature is then raised to 85 ° C for 30 minutes, the reaction mixture is decanted and the catalyst is filtered off. Water and methylamine were distilled off to give 95% by weight of N-methylglucamine as a white powder.

The above procedure was repeated using 23.1 g of Raney nickel catalyst with the following changes.

The catalyst was washed three times and the reactor, including the catalyst, was purged twice with hydrogen at 1376 kPa (200 psig), then the hydrogen pressure in the reactor was raised to 11008 kPa (1600 psig) for 2 hours and the pressure was released for 1 hour. the pressure is again raised to 11008 kPa (1600 psig). The adduct is then aspirated into a reactor at 20 ° C and 200 psig, flushed with hydrogen at 1376 kPa (200 psig), and proceeded as described above. In all cases, the product obtained consists of more than 10% by weight of N-methylglucamine, less than 10 ppm Ni, calculated on glucamine, and the color of the solution is below 2 (according to Gardner).

The crude N-methylglucamine is briefly exposed to 140 ° C for a short period of time.

It is important to make a good adduct with a low sugar content (less than 5% by weight,

Preferably less than 1% by weight) and have a good color (according to Gardner below 7, preferably below 4, more preferably below 1).

In another reaction, the adduct was prepared by starting from 159 g of 50% by weight aqueous methylamine, which was purged with nitrogen gas and covered at 10-20 ° C. 330 g of a 70% by weight almost pure starch syrup is degassed with nitrogen at 50 ° C and added slowly to the methylamine solution at temperatures below 20 ° C. The solution was stirred for 30 minutes to give 95% by weight of the adduct as a very pale yellow solution.

To the 200 ml autoclave was added 190 g of adduct in water and 9 g of nickel catalyst (United Catalyst G49B) and the autoclave was purged three times with hydrogen at 20 ° C. The hydrogen pressure was increased to 200 psig (1376 kPa) and the temperature raised to 50 ° C. The pressure is then increased to 250 psig (1720 kPa) and the temperature is maintained at 50-55 ° C for about 3 hours. The product is then 95% hydrogenated. The product temperature was raised to 85 ° C for 30 minutes, then the water was removed and the residue evaporated to give 95% by weight of N-methylglucamine as a white powder.

It is also important to minimize contact between the adduct and the catalyst when the hydrogen pressure is less than 6880 kPa (1000 psig) to minimize the nickel content in the glucamine. The nickel content of N-methylglucamine in this reaction was 100 ppm, whereas in the previous reaction it was less than 10 ppm.

The following reactions are conducted with hydrogen for direct comparison of the effects of the reaction temperature.

An autoclave of 200 ml was used to perform typical operations similar to those described above for the preparation of the adduct by reaction with hydrogen at various temperatures.

For the preparation of glucamine, the adduct is prepared by 420 g of 5 glucose solution (starch syrup) (231 g, 1.28 mol glucose) (prepared from CarGrill using 99DE starch syrup, color below 1 Gardner) ) and 119 g of 50% methylamine (59.5 g, 1.92 mol of methylamine, product of Air Products).

The reaction sequence of the process is as follows:

1. To a nitrogen purged reactor was charged 119 g of a 50% solution of methylamine, covered with nitrogen and cooled to below 10 ° C.

2. The 55 wt% starch syrup is degassed and / or purged with nitrogen at 10-20 ° C to remove oxygen from the solution.

3. The starch syrup solution is slowly added to the methylamine solution and the temperature is maintained below 20 ° C.

4. When all starch syrup solutions have been added, the mixture is stirred for 1-2 hours.

The adduct is hydrogenated immediately after its preparation or stored at low temperature to prevent degradation.

Hydrogenation of the glucamine adduct is carried out as follows:

1. Into a 200 ml autoclave were added 134 g of adduct (colors below Gardner) and 5.8 g of G498 Ni catalyst.

2. The reaction mixture is purged twice with hydrogen at 200 psi at 20-30 ° C.

3. Hydrogen pressure is raised to 2752 kPa (400 psi) and temperature to 50 ° C.

4. The pressure is increased to 3440 kPa (500 psi) and reacted at 50-55 ° C for 3 hours. Remove sample 1.

5. Raise the temperature to 85 ° C for 30 minutes.

6. Decant the reaction mixture and filter the nickel catalyst. Remove sample 2.

Reaction Conditions for Constant Temperature Reactions:

1. Add 134 g adduct and 5.8 g G49B nickel to a 200 ml autoclave.

2. The reactor was purged twice with low hydrogen at 1376 kPa (200 psi).

3. Hydrogen pressure is raised to 2752 kPa (400 psi) and temperature to 50 ° C.

4. The pressure is raised to 3440 kPa (500 psi) and reacted for 3.5 hours. The temperature is indicated above.

5. Decant the reaction mixture and filter out the nickel catalyst. Sample 3 is taken at 50-55 ° C, sample 4 at 75 ° C and sample 5 at 85 ° C. (Reaction time at 85 ° C is about 45 minutes).

All experiments give similar purity N-methylglucamine (94% by weight), the Gardner color of the products is similar immediately after the reaction, but only two-stage heat treatment gives good color stability; and the 85 ° C experiment yields a border color immediately after the reaction.

Example 32

The preparation of tallow (hardened) acid amide of N-methyl maltamine for use in the compositions of the invention is carried out as follows.

Step 1

Reagents: Maltose monohydrate (Aldrich horse

0131SKW); methylamine (40% by weight in water) (Aldrich lot 03325 ™); Raney Nickel 50% w / w suspension (UAD 52-73D, Aldrich lot 12921LW).

The reagents, 250 g of maltose, 428 g of methylamine solution and 100 g of Raney nickel catalyst suspension, were placed in an internal glass tube in a 3 liter shaking autoclave with 3 x 3450 kPa (500 psig) nitrogen and 2 x 3450 kPa (500 psig). purge with hydrogen and shake under a hydrogen atmosphere at 28-50 ° C over a weekend. The crude reaction mixture was filtered twice through a glass microfiber filter and a silica gel pad. The filtrate was concentrated until a viscous material was obtained. The last traces of water are removed azeotropically by dissolving the material in methanol and removing the methanol / water mixture on a rotary evaporator and finally drying the material under high vacuum. The crude product is dissolved in boiling methanol,

Filter, cool, crystallize, filter, and dry the filter cake under vacuum at 35 ° C. This is Extraction 1. Concentrate the filtrate until a precipitate begins to form and store overnight in a refrigerator. The solid was then filtered off and dried in vacuo.

This is Extraction 2. Concentrate the filtrate to half its volume, whereupon crystallization begins, but very little precipitate is formed. A small amount of ethanol was added and the solution was left in the refrigerator over the weekend. The resulting solid was filtered off and dried in vacuo. The combined solids yield the N-methyl maltamine used in step 2 of the overall synthesis.

Step 2

Reagents: N-methyl maltamine from Step 1; hardened tallow methyl esters; sodium methoxide (25% by weight in methanol); anhydrous methanol solvent; the molar ratio of amine to ester is 1: 1, the initial catalyst level is 10 mol% (wt.% to maltamine) and this is increased to 20 mol%; the amount of solvent is 50% by weight.

In a sealed flask, a water bath was heated to 20.36 g of tallow methyl ester to its melting point and transferred to a three-necked round-bottom flask equipped with a 250 ml mechanical stirrer. The flask was heated to 70 ° C to prevent the ester from solidifying. 25.0 g of N-methyl maltamine are mixed separately with 45.36 g of methanol, and the resulting suspension is added to the tallow ester with vigorous stirring, followed by addition of 1.51 g of 25% sodium methoxide in methanol. After 4 hours, the reaction mixture did not clear, so another 10 mole% catalyst (20 mole% in total) was added to the reaction mixture, which was reacted at 68 ° C overnight to purify the mixture. The flask was then converted to distillation and the temperature raised to 110 ° C. The reaction mixture is distilled under atmospheric pressure for 60 minutes and then under high vacuum for 14 minutes, whereupon the product becomes very thick. The product was left in the flask at 110 ° C (external temperature) for 60 minutes. The product is then scraped from the flask and triturated with ethyl ether over the weekend. The ether was removed in a rotary evaporator, the product was allowed to stand overnight and then ground to a powder. The remaining N-methyl maltamine is removed from the product using silica gel. The silica gel suspension in 100% v / v methanol was poured into a separatory funnel and washed several times with 100% v / v methanol. A concentrated sample of the product (20 g in 100 mL of 100% methanol) was loaded onto silica gel and eluted several times with vacuum washing with methanol. The combined eluates were evaporated to dryness in a rotary evaporator. If the tallow ester remains, it is removed by triturating the product with ethyl acetate overnight and filtering. The filter cake was dried under vacuum overnight. The product is tallow alkyl N-methylaltamide.

Alternatively, Step 1 of the above reaction sequence is carried out using commercial starch syrup containing glucose or a mixture of glucose and generally 5% or more maltose.

The polyhydroxy fatty acid amides and mixtures thereof thus prepared can be used in any detergent composition of the invention.

Alternatively, Step 2 of the above reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. At the choice of the product manufacturer, propylene glycol or NEODOL need not be removed from the reaction product before being used in the preparation of detergent compositions. Also according to the manufacturer's wishes, the methoxide catalyst can be neutralized with citric acid to form sodium citrate and remain in the polyhydroxy fatty acid amide.

Depending on the wishes of the product manufacturer, the formulations may contain more or less different antifoaming agents. High foaming capacity is generally desirable for dishwashing, so no foaming agent is used. When washing textiles, topping machines may require some foaming reduction, and for front loading machines, some degree of foaming reduction may be beneficial. A large number of antifoaming agents are known in the art and can be routinely selected for use in the present invention. The choice of antifoaming agent or mixtures of antifoaming agents for a specific detergent composition will in fact depend not only on the presence and amount of polyhydroxy fatty acid amide used, but also on other surfactants present in the composition. However, when used with polyhydroxy fatty acid amides, various types of silicone based antifoam agents are more effective (i.e., can be used in smaller amounts) than various other types of antifoam agents. Silicone antifoam agents which are particularly useful in the present case are X2-3419 and Q2-3302 (Dow Corning).

Detergents used for washing textiles preferably contain a soil release agent. The formulator has a large number of known substances to choose from. Such soil-repellents are described, for example, in U.S. Patent Nos. 3,962,152, 4,116,885,443,838, 4,702,857, 4,721,580 and 4,877,896. Other soil release agents useful in the compositions of the invention are nonionic soil release agents. These are oligomeric esterification products of a reaction mixture that is the source of polyethoxy units having C 1-4 alkoxy end groups (e.g., CH 3 / OCH 2 CH 2/16 OH), a source of terephthaloyl units (e.g., dimethyl terephthalate), polyoxyethylene / containing a source of units such as polyethylene glycol 1500, a source of oxyisopropylene oxy units (e.g. 1,2-propylene glycol), or a source of oxyethylene oxy units (e.g. ethylene glycol), especially when the oxyethylene oxy units and the molar ratio of oxyisopropylene oxy units is at least 0.5: 1. Examples of such nonionic soil repellents are compounds of formula XX wherein R ^{1 is} lower alkyl, such as C 1-4 alkyl, especially methyl; x and y are integers from 6 to 100; m 0.75-30; n 0.25-20; and R ^{2 is a} mixture of hydrogen and methyl, so that the molar ratio of oxyethyleneoxy: oxyisopropyleneoxy is at least 0.5: 1.

HU 214 049 Β

In the following, a modem, a concentrated detergent composition, Another preferred type of soil release agent for use in the compositions of the present invention is the anionic material described in U.S. Patent 4,877,896, provided that these agents are substantially free of HOROH-type monomers, wherein R is propylene or alkyl. Thus, the soil release agents of U.S. Pat. No. 4,877,896 may include, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol, and 3-sulfonylbenzoic acid, while the additional soil release agents used herein include, for example, dimethylene terephthalate. , A reaction product of 5-sulfonylisophthalic acid sodium salt and 3-sulfonylbenzoic acid sodium salt. These agents are preferably used in granular detergents.

The product manufacturer may also find it advantageous to incorporate a non-perborate bleach, particularly in high performance granular detergents. Many peroxygen-type bleaches are commercially available for use in the compositions of the invention, but percarbonate is preferred and economical. Thus, a composition of the invention may contain a solid percarbonate bleaching agent, generally in the form of its sodium salt, in an amount of from 3 to 20% by weight, more preferably from 5 to 18% by weight, and most preferably from 8 to 15%.

Sodium percarbonate is an addition compound of the formula 2Na ₂ CO ₃ -3H ₂ O ₂ and is commercially available as a crystalline solid. Most commercially available materials contain small amounts of heavy metal complexing agents, such as ethylenediaminetetraacetate, 1-hydroxyethylidene-1,1-diphosphonic acid, or an aminophosphonate, which is mixed during production. In the present case, the percarbonate can be incorporated into the detergent composition without any particular protection, but in a preferred embodiment of the invention a stable form of the material is used. Many coatings can be used for this purpose, but the most economical is sodium silicate in which the SiO ₂ : Na ₂ O molar ratio (1.6: 1) to (2.8: 1), preferably 2.0.0: 1, when used in aqueous solution and dried to give 2-10% (usually 3-5%) solid silicate, based on the percarbonate. Magnesium silicate can also be used and a chelating agent such as the one mentioned above can also be incorporated into the coating.

The crystalline percarbonate has a particle size of 350-450 micrometers, averaging 400. If coated, the particles have a size of 400-600 micrometers.

Although the heavy metals present in the sodium carbonate used to make the percarbonate can be reduced by incorporating complexing agents into the reaction mixture, the percarbonate must be protected from heavy metal contamination present in other components of the product. It has been found that the total amount of iron, copper and manganese ions in the product should not exceed 25 ppm, preferably less than 20 ppm, in order to avoid unacceptably detrimental effects on the stability of the percarbonate.

zero.

Example 33

Components Weight%

C 14 -C 15 alkyl alcohol sulfonic acid 13

C14-C15 alkyl polyethoxy (2,25) sulfonic acid 5.60

C 12 -C 13 alkyl polyethoxylate (6.5 / 1.45)

C12-C14 fatty acid N-methylglucamide 2.50

Sodium aluminum silicate / as hydrated Zeolite A / 25.2

Crystalline Coated Silicate Diffusers') 23.3

Citric acid 10.0

Sodium carbonate to pH 9.90

Sodium polyacrylate (mt 2000-4500) 3.2

Diethylene triamine pentaacetic acid 0.45

SAVINASE ²ⁱ 0.70

6- (N -anoylamino) -6-oxoperoxycaproic acid 7.40

Sodium perborate monohydrate 2.10

Nonanoyloxybenzenesulfonic acid 5.00

0.10

') Coated silicate builders are known in the art. Such layered (coated) sodium silicate builders are described in U.S. Patent No. 4,664,859. A suitable layered silicate builder called SKS-6 is manufactured by Hoechst.

²⁾ Available from Novo Nordisk A / S (Copenhagen).

Of the granules of this type, those containing 0.0001 to 2% by weight of the active enzyme and at least 1% by weight of the above polyhydroxy fatty acid amide are most preferred, and most preferably those in which the anionic surfactant is not an alkylbenzene sulfonate surfactant.

Example 34

The following example illustrates a detergent composition of the invention comprising a perborate bleach and a bleach activator which is prepared by mixing the following components in a mixing drum.

In the example, Zeolite A refers to hydrated crystalline Zeolite A containing 20% by weight of water and having an average particle size of 1 to 10, preferably 3 to 5 micrometers of LAS straight-chained C 12.3 sodium alkylbenzene sulfonate; AS sodium (C12-C14) alkyl sulfate; nonionic designation: coconut alcohol condensed with 6.5 moles of ethylene oxide to 1 mole of alcohol, distilled of non-ethoxylated and monoethoxylated alcohols, also abbreviated as C _n AE6.5T; and DTPA represents the sodium salt of diethylenetriaminepentaacetic acid.

Part by weight a% by weight of granulate A in the final formulation

Basic granules ¹⁷ 51.97 100.00

As 9.44 18.16

HU 214 049 Β

Part by weight a% by weight of granulate A in the final formulation

LAS 2.92 5.62 Moisture 4.47 8.60 uSodium Silicate (1-6 ratios) 1.35 2.60 Sodium sulfate 6.47 12.45 Sodium Polyacrylate (4500 M.t.) 2.61 5.02 Polyethylene glycol (PEG 8000) 1.18 2.27 Non-ionic 0.46 0.89 Sodium carbonate 13.29 25.57 stimulant 0.20 0.38 Sodium aluminum silicate 9.11 17.53 DTPA 0.27 0.52 fragrance 0.20 0.38 NAPAA granules ²¹ 6.09 100.00 NAPAA 2.86 46.96 LAS 0.30 4.93 Sulphate and various additives 2.93 48.11 NOBS granules ^ 3.88 100.00 NOBS 3.15 81.19 LAS 0.12 3.09 PEG 8000 0.19 4.90 Various additives 0.421 0.82 Zeolite granules) ¹ 12.00 100.00 Sodium aluminum silicate 7.39 61.58 PEG 8000 1.50 12.47 Non-ionic 1.16 9.70 Moisture 1.66 13.83 Various additives 0.29 2.42 Blended with him Sodium SKS-6 layered silicate 15.84 Protease / 0.078 mg / g activity/ 0.52 Sodium perborate monohydrate 1.33 Citric acid 6.79 C 12 -C 14 alkyl- N-methyl glucamide 1.58

For the final preparation

Total 100.00

Notes

1 / The base granules are prepared by spray-drying a comminuted mixture of the listed components.

2 / Freshly prepared NAPAA, peroxyadipic acid mononylonyl amide, wet filter cake, typically consisting of 60% water, 2% peroxygen available oxygen (equivalent to 36% NAPAA) and the remaining 4% by weight of unreacted starting material. This wet filter cake is the crude reaction product of NAAA, adipic acid monononyl amide (monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide, wherein the reaction is stopped by adding the reaction mixture to water and then reacting the reaction mixture with distilled water and phosphate. Wash with Buffer, finally suction to obtain a wet filter cake. A portion of the wet filter cake is air-dried at room temperature to give a dried sample which typically contains 5% by weight of AVO (corresponding to 90% by weight of NAPAA) and 10% by weight of unreacted starting material. When dry, the pH of the sample is 4.5.

NAPAA granules were prepared by 51.7 parts by weight of dried NAPAA wet filter cake (containing 10% by weight of unreacted material), 11.1 parts by weight of sodium (C12.3) straight chain alkylbenzene sulfonate ( LAS) paste (45% active ingredient), 43.3 parts by weight of sodium sulfate and 30 parts by weight of water in a CUISINART mixer. The granules (containing 47% by weight of NAPAA) are dried and screened first through a No. 14 Tyler sieve and then through a No. 65 Tyler sieve, retaining any particles that do not pass through the latter. The average size of the amide peroxyacid particles (agglomerate) is 5 to 40 micrometers and the mean particle size is 10 to 20 micrometers as determined by Malvem particle size analysis.

3 / NOBS (nonanoyloxybenzenesulfonate) granules are prepared according to U.S. Patent 4,997,596.

4 / A zeolite granules are prepared that zeolite A, were mixed with PEG 8000 et.és intensive mixer was AE6,5T _Cn (Eirich RO8 energy intensive mixer). The granules have the following composition:

parts by weight

Before drying After drying

Zeolite A (with bound water) 70.00 76.99 PEG 8000 10.80 12.49 CnAE6.5T 8.40 9.72 Free water 10.80 0.80

PEG 8000 is in aqueous form, contains 50% by weight of water and has a temperature of 12.8 ° C. CnAE6.5T is in a liquid state and is kept at 32.2 ° C. The two liquids are mixed by suction through a static mixer of 12 units. The resulting binder had an outlet temperature of 23.9 ° C and a viscosity of 5 Pa (5000 cPs).

The Eirich RO8 mixer is operated intermittently. First, 34.1 kg of powdered Zeolite A is weighed into the mixer. The mixer is started by first rotating the rotor blade to the left at 75 rpm and then rotating it to the right at 1800 rpm. The binder is then pumped directly from the static mixer to the Eirich RO8 mixer, which contains Zeolite A. The binder was fed over 2 minutes. The mixer is stirred for another 1 minute so that the total mixing time is 3 minutes. The portion is then removed from the mixer and placed in a drum (fiber drum).

The batch process was repeated until 225 kg of wet product was collected. The product is then removed

HU 214 049 Β

The process for preparing granules involves various operations such as tower drying, agglomeration, mixing of dry components, etc., as will be described. The percentages refer to the finished product.

A. Shredding and blasting through the tower

Using standard procedures, the following components are minced and tower dried.

dried on a fluid bed at 116-132 ° C. During the drying process most of the free water is removed and the composition of the composition changes as above. In the batch process, the total energy consumption of the mixer is 1.31-10 ⁵ m ² / sec, 2.18-10 ² m ² / sec.

The resulting free flowing agglomerate has a mean particle size of 450-500 micrometers.

Example 35

The following describes a granular detergent suitable for relatively high concentrations, particularly in Europe, for pre-loading washers and for a wide temperature range.

Components Weight%

CHOCOLATE CP5 Crowd% 3.52% DEQUEST 20660, 0.45% TINOPAL DMS 0.28% Magnesium sulfate 0.49% Zeolite A as anhydride 7.1% CMC 0.47%

SOKOLAN CP5 / 100% active as Na salt / ¹ '3.52

DEQUEST 2066/100% as acid / ²⁷ 0.45 TINOPAL DMS ^{3 /} 0.28

MgSO ₄ 0.49

Zeolite A / anhydrous / 17.92

CMC / 100% Active / ⁴⁷ 0.47

Na ₂ CO ₃ 9.44

Citric acid 3.5

Layered Silicate SKS-6 12.9

Tallow alkyl sulfate / 100% active;

Na salt / 2.82

C14-C15 alkyl sulfate (100%) active, Na salt / 3.5

C 12 -C 15 alkyl (EO 3) sulfate 1.76

C 16 -C 18 alkyl-N-methylglucamide 4.1 DOBANOL, C 12 -C 15 alkanol ethoxylated with 3 mol of ethylene oxide 3.54

LIPOLAS / 100,000 LU / g / ^{5 /} 0.42

SAVINASE / 4.0 KNPU / ^{6 /} 1.65

Fragrance 0.53

X2-34197 / 0.22

Starch 1.08

Stearyl alcohol 0.35

Sodium percarbonate / coated / 22.3

Tetraacetyl ethylenediamine / TAED / 5.9

Zinc phthalocyanine 0.02

Water / zeolite / residue

Notes

1 / SOKOLAN sodium polyacrylate / maleate (manufactured by Hoechst).

2 / Brand name of Monsanto for pentaphosphonomethyl-diethylenetriamine.

3 / Optical brightener from Ciba-Geigy.

4 / FINNFIX available from Metasaliton.

5 / LPOLASE liposoluble enzyme from NOVO.

6 / SAVINASE protease enzyme from NOVO.

7 / X2-3419 Silicone Antifoam from Dow Corning.

B. Agglomeration of surfactants

Β1. Agglomeration of tallow alkyl sulphate sodium salt and C12-C15 alkyl EO3 / 3 sulphate sodium salt pastes

The 50% by weight active paste of tallow alkyl sulfate and the 70% by weight paste of C12-C15 alkyl-EO / 3 / sulfate are agglomerated with Zeolite A and sodium carbonate according to the following table (added to the detergent composition. after drying of the agglomerate).

Crowd%

Tallow alkyl sulfate 2.82%

C12-C15 alkyl EO (3) sulfate 1.18% Zeolite A 5.3%

Sodium carbonate 4.5%

B2. Agglomeration of C14-C15 alkyl sulfate, C12-C15 alkyl ethoxysulfate, DOBANOL C12-C15 alanyl ethoxylated with 3 moles of ethylene oxide, and C16-C18 alkyl N-methylglucosamide

The C 16 -C 18 alkylglucosamide nonionic material is synthesized by the reaction of C 3 -C 15 alkanol ethoxylated with 3 moles of ethylene oxide during the reaction of the methyl ester and N-methylglucamine. Ethanol oxylated with 3 moles of ethylene oxide having 12 to 15 carbon atoms acts as a melting point depressant, allowing the reaction to proceed without the formation of cyclic glucosamides, which is undesirable.

Thus, 20 wt.% of DOBANOL-C12-C15 alkylene-ethoxylated surfactant mixture ethoxylated with 3 moles of ethylene oxide and 80 wt.% of C16-C18 are obtained and coagglomerated with 10 wt.

Second, the above particles are co-agglomerated with a high-activity paste of 70% by weight of the sodium salt of C 14 -C 15 alkyl sulfate, C 12 -C 15 alkyl EO / 3 S sulfate, Zeolite A and more specifically sodium carbonate. This particle provides good dispersion of C16-C18 alkyl-N-methylglucosamide in cold water.

HU 214 049 Β

This granule, which is added to the detergent composition after drying the agglomerate, has the following overall composition:

Crowd%

C 16 -C 18 alkyl N-methylglucosamide 4.1% DOBANOL C 12 -C 15 alkanol ethoxylated with 3 moles of ethylene oxide 0.94%

Sodium carbonate 4.94%

Zeolite A 5.3%

Sodium (C 14 -C 15) alkyl sulfate 3.5%

Sodium (C12-C15) -alkyl EOI / 3 / sulfate 0.59%

C. Mixing Dry Additives

Mix the following components:

Wt ° / o

Percarbonate 22.3%

Tetraacetyl ethylene diamine 5.9%

Layered "silicate SKS 6" (Hoechst) 12.90%

Citric acid 3.5%

Lipolase 0.42%

100,000 LU / g

OWN 4.0 KNPU 1.65%

Zinc phthalocyanine (photo bleach) 0.02%

D. Spray on the preparation

DOBANOL C12 -C15 alkanol ethoxylated with 3 mol of ethylene oxide 2.60%

Fragrance 0.53%

E. Antifoam Input

X2-3419 Silicone Antifoam (95-97% High Molecular Weight Linear Silicone; 3-51% Hydrophobic Silica) was coagglomerated with Dow Corning, Zeolite A (2-5µm particle size), starch and stearyl alcohol binder. . The composition of the granules is as follows:

% By weight

Zeolite A 0.22%

Starch 1.08%

X2-3419 0.22%

Stearylalkol 0.35%

The detergent composition has excellent solubility, superior performance, and low foaming performance when used in European washing machines, such as AEG, using 85 g of detergent at 30 ° C, 40 ° C, 60 ° C and 90 ° C cycles.

Example 7

The fatty acid glucamide surfactant in any of the preceding examples may be replaced by an equivalent amount of maltamide surfactant or glucamide / maltamide surfactant mixtures from vegetable sugar sources. The use of ethanolamides in the formulations seems to promote the cold temperature stability of the finished products. The use of sulfobetaine (sultain) surfactants results in stronger foaming.

Where particularly high foaming compositions are required, it is preferred that the amount of fatty acids having 14 or more carbon atoms is less than 5 wt.%, More preferably less than 2 wt.%, Most preferably not present as they may inhibit foaming. Therefore, the formulator of high-foaming compositions will conveniently avoid incorporating antifoaming amounts of such fatty acids into high-foaming compositions made with polyhydroxy-fatty acid amides; and / or avoids the formation of fatty acids having 14 carbon atoms and more when storing the finished product. A simple tool for this is the use of C12 ester reagents to prepare polyhydroxy fatty acid amides. Fortunately, the use of aminooxides or sulfobetaine surfactants can eliminate the negative effects of fatty acids on foaming.

If the product manufacturer wants to add anionic optical brighteners to liquid detergents that contain relatively high concentrations (e.g., 10 wt% or more) of anionic or polyanionic substituents, such as polycarboxylate builder, then it may be useful to pre-mix polyhydroxy fatty acid amide and then add this premix to the final product.

Polyglutamic acid or polyaspartic acid dispersants are preferably used with detergents containing zeolite builder. Foam reducing agents useful in the compositions of the invention include, for example, "AE fluid" or "son" and DC-544 (Dow Corning).

One skilled in the art will appreciate that the preparation of the polyhydroxy fatty acid amides of the invention using di- and larger-molecule saccharides, such as maltose, results in the formation of polyhydroxy fatty acid amides wherein the linear Z substituent is a polyhydroxy moiety at the terminus. Such materials are perfectly suitable for use in the compositions of the invention and do not depart from the spirit and subject matter of the invention as set forth in the claims.

Claims (8)

An alkyl sulfate-based, controlled-foaming, liquid or solid detergent composition for washing fabrics in an automatic washing machine, optionally containing conventional detergent additives, characterized in that (a) at least 3% by weight of polyhydroxy fatty acid amide of formula (I) - wherein R ¹ is hydrogen, C 1 -C 4 alkyl, 2-hydroxyethyl or 2-hydroxypropyl, R ² is C 7 -C 19 alkyl or alkenyl and HU 214 049 Β Z is a polyhydroxy hydrocarbon group or a mixture thereof obtained from a reducing sugar by a reductive amination reaction; (b) at least 3% by weight of a C10-C24 alkyl sulfate or a C10-C20 hydroxyalkyl sulfate surfactant; and (c) optionally at least 0.01% by weight of silicone antifoam, hydrocarbon antifoam, monocarboxylic fatty acid an antifoam and a mixture of an antifoam selected from the group consisting of an antifoam and a weight ratio of components (a) and (b) (1: 4) to (4: 1). (Priority: September 28, 1990) Detergent composition according to claim 1, characterized in that it also contains from 1 to 30% by weight of an alkylbenzene sulfonate, an alkyl ester sulfonate, an alkyl ethoxylate, an alkyl polyglycoside, a paraffin sulfonate or an alkyl phenol alkoxylate. (Priority: September 28, 1990) Detergent composition according to claim 1, characterized in that it contains at least 0.5% by weight of monocarboxylic fatty acid or its salt, preferably monostearate, as an antifoam agent. (Priority: September 28, 1990) A detergent composition according to claim 1, characterized in that it contains a compound of formula (I): R ¹ is methyl, R ² is C ¹ -C 17 alkyl or alkenyl, and Z is -CH ₂ (CHOH) "CH ₂ OH, -CH (CH ₂ OH) (CHOH) _n -CH ₂ OH, or -CH ₂ - (CHOH) ₂ (CHOR ') (CHOH) -CH ₂ OH. wherein n is 3,4 or 5 and R 'is hydrogen or cyclic or aliphatic monosaccharide. (Priority: September 28, 1990) Composition according to claim 1, characterized in that the polyhydroxy fatty acid amide of the formula (I) comprises a group of maltose. (Priority: September 28, 1990) 6. A composition according to claim 1, characterized in that in the polyhydroxy fatty acid amide of formula (I) Z is a mixture of monosaccharides, disaccharides or optionally polysaccharides and the mixture contains at least 1% by weight of at least one disaccharide, preferably maltose. (Priority: 06/09/1991) 7. The composition of claim 1, wherein the detergent builder comprises at least 1% by weight. (Priority: September 28, 1990) 8. A composition according to claim 7, characterized in that component (a) (I) compound wherein R ¹ is methyl, R ² 9-17 alkyl or alkenyl and Z is glycityl derived from reducing sugar, preferably C11-C17-N-methylglucamide or C11-C17-N-methyl-maltamide or a mixture or alkoxylated derivative thereof, and component (b) is a C14-C18 alkyl sulfate surfactant, and (a) and ( b) weight ratio of component (1.25: 7) to (1: 4). (Priority: September 28, 1990) A detergent composition according to claim 1, characterized in that it comprises at least 5% by weight of particles comprising 5 to 90% by weight of polyhydroxy fatty acid amide, 10 to 90% by weight of alkyl sulphate surfactant and 1 to 30% by weight of solubilizer, preferably an surfactant anionic sulfonate, a surfactant with at least 0.5 ethoxylation, cyclic polyhydroxy fatty acid amide, alkyl polyglycoside, polyethylene glycol or poly (acrylic acid) polymer.