FI80068B - TVAETTMEDELSKOMPOSITIONER. - Google Patents

Abstract

A granular detergent composition containing about 6% to 18% aluminosilicate cation exchange material (a), about 1% to 8% nitrilotriacetate (b), about 6% to 14% phosphate builder selected from sodium and potassium tripolyphosphates with less than 12% thereof as pyrophosphate, about 5% to 35% bleaching agent, up to 10% organic peroxy acid bleach precursor, and a heavy metal scavenging agent, wherein the percentage quantities of (a) and 2(b) is from 13 to 27. The compositions display improved bleaching, cleaning and fabric damage at low aluminosilicate levels.

Description

1 80068

This invention relates to a granular detergent combination. In particular, it relates to a granular laundry detergent combination with a reduced phosphate content together with excellent cleaning properties, whiteness stability and stain removal properties, as well as improved bleaching stability and fabric care properties.

The role of the phosphate enhancing salt of a detergent as an additive in organic, water-soluble, synthetic detergents and their value in improving the overall performance of such detergents is well known. In recent years, however, the use of large amounts of phosphate-enhancing salts, such as tripolyphosphates, has been the subject of careful investigation because it is suspected that soluble phosphate species accelerate the eutrophication or aging process of water masses. Therefore, there is a need for a laundry detergent combination containing booster salts that has a lower phosphate level but has a total washing performance comparable to a conventional tripolyphosphate booster salt combination.

The exact mechanism by which the detergent builder salts affect the washing effect of water-soluble organic detergent compounds is not well known, but appears to depend on a combination of factors such as water softening effect, stain suspension and anti-reuptake effects, sludge swelling and pH swelling and pept. However, based on current theory, it is not possible to predict which compounds will act as effective detergent builder salts.

Sodium aluminosilicates, commonly known as zeolites, have been proposed for use as substitutes for phosphate-enhancing salts because of their ability to soften water by removing calcium ions (see, e.g., 2,80063 and BE-A-814,874 and BE-A-813,581). However, zeolites do not have all the potent salt effects of phosphates.

One way to enhance the overall washing performance of low phosphate preparations is to use bleaching aids such as inorganic or organic peroxy bleaches and organic bleach activators. While careful balancing of the types of booster salts and bleaches may indeed provide some improvement in performance, such formulations remain fundamentally poor in three areas, firstly in terms of bleaching stability, secondly fabric damage properties and thirdly in greasy and particulate stain removal.

EP-A-70 079 proposes to improve the bleaching effect of combinations containing aluminosilicate enhancing salts by adding a nitrile-litric acetic acid compound. The total amount of aluminosilicate and nitrile liter acetate was said to be critical 20 and corresponding to a relatively large total amount in the final product. However, high concentrations of aluminosilicate and nitrile triacetate both lead to significant processing problems, aluminosilicates cause problems with dispersion stability and pumping properties, while nitrile triacetates cause problems with thermal stability. In addition, large amounts of aluminosilicate can also adversely affect the appearance of the fabric. On the other hand, when the amounts of aluminosilicate and nitrile triacetate are reduced to a more acceptable range, bleaching, cleaning performance, and fabric damage properties are again adversely affected.

It has now been found that the bleaching, cleaning effect and damage properties of the fabric can be significantly improved, even with relatively low aluminum content.

II

3 80063 for total leachate and nitrile triacetate by adding certain amounts of tripolyphosphate enhancing salt such that the pyrophosphate content has a critical maximum limit. In addition, it has further been found that certain organic peroxyacid bleach precursors having a defined chain length are useful with a low phosphate booster salt system to provide a cleaning effect at least equal to that of a fully phosphate-based preparation over the entire wash. and at low washing temperatures relative to particulate stains is striking.

Thus, the granular detergent composition of the invention is characterized in that it comprises: (a) about 6 to about 18% by weight of a water-insoluble aluminosilicate cation exchange material, (b) about 1 to about 8% by weight of an alkali metal salt of nitrile triacetic acid, (c) about 6 to about 14% by weight of a phosphate enhancer salt, wherein the phosphate enhancer salt is selected from sodium and potassium tripolyphosphates and comprises less than about 12% by weight of pyrophosphate, (d) about 5 to about 35% by weight of an inorganic or organic peroxy bleach .25 (e) at least 0,5% by weight of organic peroxyacids

a bleach precursor of general formula II

O

K

RCL (II) 30 wherein R is an alkyl group having 6 to 12 carbon atoms and wherein the longest linear alkyl chain extending to and containing the carboxyl carbon contains 5 to 10 carbon atoms, and L is a leaving group having a conjugate acid pKa of 35 6-13, 4,80063 (f) a heavy metal rinse selected from water-soluble aminopolycarboxylates and aminopolyphosphonates having at least 4 acidic protons per molecule, or a water-insoluble smectite-type clay selected from saponites, hectares. sodium and calcium montmorillonites, and (g) about 0.5 to about 5% by weight of a polycarboxylate polymer; wherein (a) + 2 (b) constitutes from about 13% to about 27% by weight of the combination.

The combinations of the invention include a specific detergent booster salt system and a bleach system. In addition, these combinations generally contain an organic soap or a synthetic detergent surfactant. Highly preferred combinations include certain amounts of polycarboxylate polymers, as well as alkali metal carbonate and alkali metal silicate, designed to improve the appearance properties of the detergent and fabric.

The booster salt system comprises three essential components, a water-insoluble aluminosilicate cation exchange material, an alkali metal salt of nitrile acetic acid, and a phosphate booster salt.

The aluminosilicate cation exchange material comprises from about 6% to about 18% by weight, preferably from about 7% to about 16% by weight, and most preferably from about 8% to about 14% by weight of the detergent combination. The aluminosilicate may be crystalline or amorphous in nature, the preferred materials being of unit formula I:

Mt [(A102), (SiO2) y] · H2O (I) wherein M is a calcium exchange cation, z and y are at least 6; The molar ratio of z to y is from about 1.0 to about 0.5 and 35 x is at least 5, preferably from about 7.5 to about 276, preferably from about 10 to about 264. Aluminosilicate materials are in hydrated form and are preferably crystalline containing from about 10% to about 28%, most preferably from about 18% to about 22% water.

Aluminosilicate ion exchange materials are further characterized by a particle size diameter of about 0.1 to about 10 micrometers, preferably about 0.2 to about 4 micrometers. The term "particle size diameter" as used herein means the average particle size diameter of the ion exchange material provided herein, as determined by conventional analytical methods, such as microscopic determination using a scanning electron microscope. Aluminosilicate ion exchange materials are usually further characterized by a calcium ion exchange capacity of at least about 200 mg equivalents of CaCO 3 water content / g aluminosilicate, calculated on the anhydrous basis, and generally from about 300 mg eq./g to about 352 mg eq. / g. The aluminosilicate ion exchange materials used in the invention are further characterized by a calcium ion exchange rate of at least about 0.13 g Ca ++ / liter / minute / gram / liter aluminosilicate (on an anhydrous basis), and is generally about 0.13-0.38 grams / liter / minute / gram / liter based on calcium ion hardness. The calcium ion exchange rate of the optimal aluminum 25 silicates for the enhancer salts is at least about 0.26 grams / 4.5 l / minute / gram / 4.5 l.

Aluminum silicate ion exchange materials useful in the practice of this invention are commercially available and may be naturally occurring aluminum silicates or synthetically derived. A process for preparing aluminosilicate ion exchange materials is disclosed in U.S. Patent No. 3,985,669. Preferred synthetic crystalline aluminosilicate tion ion exchange materials useful herein are Zeolite A, Zeolite B, Zeo-35 lite X, Zeolite HS, and mixtures thereof. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula:

Na12 [((A102) 12 (SiO2) 12] - H2O5 where x is about 20 to about 30, especially about 27. Zeolite X of the formula: Nae 6 [(A102) 8 6 (SiO2) 2 0 6 · 276 H 2 O is also suitable, as is Zeolite HS of the formula Na 6 [(Al 2 O) 6 (SiO 2) 6] 7.5 H 2 O).

Suitable nitrile acetic acid salts for use herein include nitrile acetic acid tripotassium salts. The acid itself or the disodium or dipotassium salts of the acid can also be used as an additive. It is to be understood, however, that under the pH conditions typically achieved in preparation, the nitrile triacetic acid or salt is generally converted to the fully ionized form.

The nitrile triacetic acid salt (measured in the trisodium form) comprises from about 1% to about 8% by weight, preferably from about 3% to about 7% by weight of the combination. The percentage of nitrile acetic acid-20 acid salt (b) (again measured in trisodium form) and the percentage of aluminosilicate cation exchange material (a) (measured in hydrated form) are such that the sum of a + 2b is from about 13% to about 27% by weight, preferably about 14 to about 24% by weight, most preferably about 16 to 21% by weight.

The essential component of the combination of the invention is further from about 6% to about 14% by weight, preferably from about 8% to about 12% by weight of the phosphate enhancer salt. The phosphate boiling salt is selected from sodium and potassium tripolyphosphates and hydrates thereof, but is preferably substantially anhydrous or partially hydrated (i.e., not more than about 60% of its hydration capacity). However, the phosphate host host salt content is measured on an anhydrous basis. Critically, the phosphate enhancer salt comprises less than 35%, preferably less than about 8% pyrophosphates. Very preferred is a phosphate-enhanced salt system mixed in dry crystalline form with the remainder of the detergent combination.

The detergent combinations of the invention also include a bleaching system comprising an inorganic or organic peroxy bleach, and a precursor of a heavy metal rinse aid and an organic peroxyacid bleach.

Suitable inorganic peroxy bleaches 10 include sodium perborate, mono- and tetrahydrates, sodium percarbonate, sodium persilicate and urea-hydrogen peroxide adducts, and clathrate 4Na 2 SO 4: 2H 2 O 2: INaCl. Suitable organic bleaches include peroxy-lauric acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecanedioic acid, diperoxy-azelanoic acid, mono- and diperoxyphthalic acid and mono- and diperoxy-isophthalic acids. The bleaching agent is present in the combinations of the invention from about 5% to about 35% by weight, preferably from about 10% to about 25% by weight.

The heavy metal rinse aid is preferably a water-soluble chelating agent. Preferred are aminopoly acids having four or more acidic protons per molecule. Suitable chelating agents include amino carboxylate chelating agents such as ethylenediamine-tetraacetic acid (EDTA), hydroxyethylethylenediamine triacetic acid (HEEDTA), dihydroxyethylethylenediamine-diacetic acid (DHEEDDA), n-diethylethipodine, *, N'-tetraacetic acid (DCTA) and water-soluble salts thereof, and aminopolyphosphonate chelating agents such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriaminepipon (methylene phosphonic acid) nitro (triethylphenonic acid) (DETPMP), (DETPMP) , hexamethylenediamine tetramethylenephosphonic acid (HMTPM) and their water-soluble salts. The above water-soluble sequestrants generally comprise from about 0.05% to about 4% by weight, preferably from about 0.1% to about 1.0% by weight of the combination.

The heavy metal rinse aid may also be a water-insoluble smectite-type clay selected from saponins, hectorites and sodium and calcium montmorillonites (sodium and calcium herein represent the major inorganic cation of the clay).

Although any of the above smectite-type clays can be added to the combinations of the invention, particularly preferred smectite-type clays have an ion exchange capacity of at least 50 meq / 100 g of clay, more preferably at least 70 meq / 100 g (measured, for example, as described). in "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1979)). In particular, its preferred materials are as follows: Sodium Montmorillonite Brock

Volclay BC Gelwhite GP 20 Thixo-Jel

Ben-A-Gel Imvite

Sodium hectorite Veegum F

25 Laponite SP

Sodium saponite Barasym NAS 100 Kalslum montmorillonite Soft Clark 30 Gelwhite L

Lltium hectorlite Barasym LIH 200

When the above clays are present, they are generally added from about 1% to about 20% by weight, more preferably from about 2% to about 35% by weight of the combination. Such clays also give the combinations a fabric softening advantage.

9 80063

A water-insoluble, preferably colloidal magnesium silicate or a water-soluble magnesium salt which forms magnesium silicate in an aqueous slurry mixture before spray-drying can also be used as the heavy metal rinse aid. Magnesium silicate or salt may be added from about 0.015 to about 0.2% by weight, preferably from about 0.03 to about 0.15% by weight, most preferably from about 0.05 to about 0.12% by weight (magnesium base). Suitable magnesium salts include magnesium sulfate, magnesium sulfate heptahydrate, magnesium chloride and magnesium chloride hexahydrate.

The combinations of the invention preferably contain from about 0.5% to about 10% by weight, preferably from about 1% to about 6% by weight, of an organic peroxyacid bleach precursor of formula II. Suitable bleach precursors are described in GB-A-2040983 and include, for example, peracetic acid bleach precursors such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylhexylenediamine, sodium p-acetylbenzoxy, sodium p-acetoxybenzene -acetyl glucose, octaacetyl lactose and methyl-o-acetoxybenzoate.

In formula II, R is an alkyl group having 6 to 12 carbon atoms wherein the longest linear alkyl chain extending from and containing 25 carboxyl carbons contains 5 to 10 carbon atoms. This alkyl group R may be either linear or branched, and in preferred embodiments it contains 7-9 carbon atoms. L is a leaving group having a conjugate acid pKa of 6 to 13, preferably about 7 to about 11, and most preferably about 8 to about 10. Examples of leaving groups L are those of formula a or b:

O

(1) / (CH 2) x Y -N-C-R

1¾? ' z (a) (b) - ... I, 8008 wherein Z is H, R1 or halogen, R1 is an alkyl group having 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is SO3M, OSO 3 M, CO 2 M, N "(R 1) 3 Q- or NMR 1) 2-O ', wherein M is H, an alkali metal, an alkaline earth metal, ammonium or substituted ammonium, and Q is a halide or methosulfate.

A preferred leaving group L has the formula (a) wherein Z is H, x is 0 and Y is a sulfonate, carboxylate or dimethylamine oxide radical. Highly preferred substances are sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, sodium 3,5,5-trimethylhexanoyloxybenzoate, sodium 2-ethylhexanoyloxybenzene sulfonate and 15-sulfonate, sodium nonanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate and sodium p-substituted.

The bleach activator is normally added in particulate form comprising a finely divided bleach Akti activator and a binder. The binder is generally selected from nonionic surfactants such as ethoxylated fatty alcohols, polyethylene glycols, anionic surfactants, film-forming polymers, fatty acids and mixtures thereof. Highly preferred are nonionic surfactants, and the bleach activator is mixed with the binder 25 and compressed into long particles through a radial press, as described in EP-A-00 62 523. Alternatively, bleach activator particles can be prepared and sprayed. , as described in EP-A-01 74 132.

The detergent compositions of the invention contain from about 5% to about 60% by weight, preferably from about 8% to about 30% by weight of an organic surfactant of the anionic, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures of these. Surfactants useful herein are listed in U.S. Patent Nos. 4,222,905 and 4,239,659.

n 80068

The anionic surfactant may be one or more of the surfactants conventionally used in laundry laundry. Suitable synthetic anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, alkyl polyethoxy ether teresulfates, paraffin sulfonates, alpha-olefin sulfonates, polyol sulphonate sulfonates and alpha-sulfoxylates and their esters, alkyl glyceryl ethers, alkyl glyceryl ethers, alkyl glyceryl ethers. water-soluble salts of acyloxyalkane-1-sulfonate and beta-acyloxyalkane sulfonate.

A particularly suitable class of anionic surfactants includes water-soluble salts, especially alkali metal ammonium and alkanol ammonium salts or organic sulfur-containing reaction products having an alkyl or alkaryl group in the molecular structure containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms, and a sulfonic acid or sulfuric acid ester group. (The term "alkyl" includes the alkyl portion of acyl groups). Examples of this class of synthetic detergents which form part of the detergent combination of this invention are sodium and potassium alkyl sulfates, especially those obtained by sulfation of higher alcohols and (C8-8 carbon atoms) prepared by reduction of hydrogenated vegetable oil and coconut oil or coconut oil. and potassium alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15, especially from about 11 to about 13 carbon atoms in a straight-chain or branched-configuration, e.g., those compounds of this type described in U.S. Pat. No. 2,220,099 and U.S. Pat. 2,477,383 and those prepared from alkylbenzenes by alkylation with straight-chain chloroparaffins (using aluminum trichloride catalysis) or with straight-chain olefins (using hydrogen fluoride catalysis). Of particular value are the linear straight chain 12,80068 chain alkyl benzene sulfonates having an average of about 11.8 carbon atoms in the alkyl group, abbreviated as δ 8 LAS, and Cx 2 -C 15 methyl-branched alkyl sulfates.

5 Other anionic surfactants include sodium C10-8 alkylglyceryl ether sulfonates, in particular ethers of higher alcohols derived from hydrogenated vegetable oil and coconut oil; sodium coconut oil fatty acid monoglyceride disulfonates and 10 sulfates; and sodium or potassium salts of alkylphenol ethylene oxide ether sulfate having from about 1 to about 10 ethylene oxide units per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms.

Other useful anionic surfactants include water-soluble salts or esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; Water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkene moiety; alkyl ether sulfates containing from about 10 to about 18, especially from about 12 to 16, carbon atoms in the alkyl group, and from about 1 to 12, especially from 1 to 6, more especially from 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing about 12 to 24, preferably about 14 to 16 carbon atoms, especially those prepared by reaction with sulfur trioxide and then neutralized under conditions such that the sulfones present are hydrolyzed to the corresponding hydroxyalkane sulfonates; water-soluble salts of paraffin sulfonates containing about 8 to 24, especially 14 to 18 carbon atoms, and beta-alkyloxyalkane sulfonates containing about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane moiety.

The alkane chains of the aforementioned non-soap anionic surfactants can be derived from natural 13,80068 sources, such as coconut oil or animal fat, or can be made synthetically, such as using Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations; sodium is preferred. Suitable fatty acid soaps can be selected from conventional alkali metal (sodium, potassium), ammonium-10 and alkylammonium salts of higher fatty acids having from about 8 to 24, preferably from about 10 to 22, and especially from about 16 to about 22 carbon atoms in the alkyl chain. Suitable fatty acids can be obtained from natural sources such as soybean oil, castor oil, animal fat, whale and fish oils, fat, lard and mixtures thereof. Fatty acids can also be prepared synthetically (e.g., by oxidizing petroleum, or by hydrogenating carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable, such as rosin and tall oil rosin acids. Naphthenic acids are also suitable. Sodium and potassium soaps can be made by direct saponification of fats and oils or by neutralizing free fatty acids, which are produced in separate manufacturing processes. Sodium and potassium salts of mixtures of fatty acids derived from animal fat and hydrogenated fish oil are particularly useful.

Mixtures of anionic surfactants are particularly suitable, especially mixtures of sulfonate and sulfate surfactants in a weight ratio of about 5: 1 to about 1: 5, preferably about 5: 1 to about 1: 1, more preferably about 5: 1 to about 1.5: 1. A particularly preferred mixture of an alkylbenzenesulfonate having 9 to 15, especially 11 to 13 carbon atoms from an alkyl radical and a cation is an alkali metal, preferably sodium; and either an alkyl sulphate having 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical or any ethoxy sulphate having 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6 and having an alkali metal cation. , preferably sodium.

Non-ionic surfactants useful in this invention include ethylene oxide condensates with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic ba-5 (HLB) of about 8-17, preferably about 9. 5-13.5, more preferably about 10-12.5. The hydrophobic moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group condensed with any particular hydrophobic group may be readily adjusted to provide a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements.

Examples of suitable nonionic surfactants include the following: 1. Polyethylene oxide condensates of alkylphenol, e.g.

condensation products of alkylphenols in which the alkyl group contains 6 to 12 carbon atoms, in either a straight-chain or branched configuration, with ethylene oxide, and said ethylene oxide is present in 3 to 30, preferably 3 to 14, moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds may be derived, for example, from polymerized propylene, diisobutylene, octene and nonene. Other examples include dodecylphenol condensed with 9 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 11 moles of ethylene oxide per mole of phenol; nonylphenol and di-isooctylphenol condensed with 13 moles of ethylene oxide.

2. Condensation product of primary or secondary aliphatic alcohols having 8 to 24 carbon atoms in either a straight-chain or branched configuration with 2 to 40 moles, preferably 2 to about 9 moles of ethylene oxide per mole of alcohol. Preferably the aliphatic alcohol comprises 9-18 carbon atoms and is ethoxylated with 2-9.35, preferably 3-8 moles of ethylene oxide per mole of aliphatic alcohol. Preferred surfactants are 8006868 prepared from primary alcohols which are either linear (such as those derived from natural fats or prepared by the Ziegler process from ethylene, e.g. myristyl, cetyl, stearyl alcohols) or partially branched, such as Lutensols, Dobanols and Neodols with about 25% 2-methyl branching (Lutensol is a trade name of BASF, Dobanol and Neodol are trade names of Shell), or Synperonic, which is understood to have about 50% 2-methyl branching (Synperonic is ICI: trade name 10) or primary alcohols with more than 50% branched structure sold under the trade name Lial Liquichimica. Specific examples of nonionic surfactants that fall within the scope of the invention include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Doba-15 nol 91-2.5, Dobanol 91-3, Dobanol 91-4 , Dobanol 91-6,

Dobanol 91-8, Dobanol 23-6.5, Synperonic 6, Synperonic 14, coconut alcohol condensation products with an average of 5-12 ethylene oxide per mole of alcohol, and a coconut alkyl moiety of 10-14 carbon atoms, and animal fatty alcohol-20 in condensation products is on average 7-12 moles of ethylene oxide per mole of alcohol, and the animal fat content comprises substantially 16-22 carbon atoms. Second, linear alkyl ethoxylates are also suitable in these combinations, especially Tergitol series ethoxylates having about 9 to 15 carbon atoms in the alkyl group and up to 11, especially 3 to 9 ethoxy residues per molecule.

The compounds were formed by condensing ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic moiety generally has a molecular weight of 1500-1800. Such synthetic nonionic detergents are commercially available under the tradename "Pluronic" from Wyandotte Chemicals Corporation.

Particularly preferred nonionic surfactants for use herein are C 1 -C 5 primary alcohol ethoxylates containing 3 to 8 moles of ethylene oxide per 16 moles of alcohol, especially 2 to C 15 primary alcohols containing 6 -8 moles of ethylene oxide per mole of alcohol.

Cationic surfactants suitable for use herein include quaternary ammonium surfactants and surfactants of a semi-polar nature, for example amine oxides.

Suitable amine oxide surfactants have the general formula V: 10 R6 Γ "R6"

I I

R5-N + - (ΟΗ2) α-Ν + - R6 (V) o- L o-Jj wherein R5 is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, and each R6 is independently selected from: C 2-4 alkyl and - (CnH 2nO) .H, i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is 1-7, the total number of CnH 2nO groups in the molecule does not exceed 7.

In a preferred embodiment, R 5 has 10-14 carbon atoms and each R 6 is independently methyl or - (CnH 2nO) aH, where m is 1-3, and the total number of CnH 2nO groups in the molecule is not more than 5, preferably not more than 3.

In a highly preferred embodiment, j is 0, and each R 6 is methyl, and R 5 is C 2 -C 2 alkyl.

Another suitable class of amine oxide species is represented by bis-amine oxides having the following substituents.

j: 130 R5: fatty C1-C28-alkyl; palmityl; oleyl; stearyl R6: hydroxyethyl i: 2 or 3

A specific example of this preferred class of bis-amine oxides is: N-hydrogenated C16-C18-animal fatty alkyl-N, N ', N'-tri (2-hydroxyethyl) -propylene-1,3-diamine -oxide.

Suitable quaternary ammonium surfactants for use in this combination are determined by the following general formula VI: 17 80068 5 R8 Γ R8 “R7-N * --- (CH2) t-N + - R8 Z (VI) R8 R8 j wherein R 7 is a linear or branched alkyl, alkenyl-10 or alkaryl group having 8 to 16 carbon atoms, and each R 8 is independently selected from C 2-4 alkyl, C 1-4 alkaryl, and - (C 11 H 2 n) O; i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3, and m is 1 to 7, and the total number of CnH 2nO groups in the molecule is not more than 7, and wherein Z represents the number of opposite anions to give electrical neutrality.

In a preferred embodiment, R7 has 10-14 carbon atoms and each R8 is independently selected from methyl and (Cn H2 n O) B H, wherein m is 1-3 and the total number of Cn H2 n O groups in the molecule is not more than 5 , preferably not more than 3. In a highly preferred embodiment, j is 0, R 8 is hydroxyethyl or hydroxypropyl and R 7 is C 2 -C 2 alkyl. Particularly preferred surfactants in this class include Cx2-alkyl-trimethylammonium salts, C2-C4-alkyltrimethylammonium salts, cocoalkyltrimethylammonium salts, cocoalkyldimethyl-hydroxy-ethylammonium-ethyloxylmethylammonium-alkylammonium-propyldimethylhydroxy-piperoxy

Another group of useful cationic compounds are the diammonium salts of formula VI wherein j is 1, R 7 is C 22 -C 14 alkyl, each R 8 is methyl, hydroxyethyl or hydroxypropyl, and i is 2 or 3. In a particularly preferred surfactant of this type, R 7 is coconut-35 alkyl, R 8 is methyl and i is 3.

18 80 068

In highly preferred combinations, the enhancer salt system is supplemented, in addition to the polycarboxylate polymer, with alkali metal carbonates and alkali metal silicates.

The polycarboxylate polymers used herein are preferably selected from copolymeric polycarboxylic acids and their salts derived from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, second acrylic acid, itacenoic acid or mesaconic acid, and ethanonic acid as the first monomer. comprises at least about 10 mole percent, preferably at least about 20 mole percent polycarboxylic acid units, and has a weight average molecular weight of at least about 12,000, preferably at least about 30,000; homopoly-15 acrylates and homopolymethacrylates having a weight average molecular weight of about 1,000 to about 20,000, preferably about 1,000 to about 10,000; and mixtures thereof. The compositions are highly advantageous in terms of excellent bleaching stability, washing performance and anti-scaling performance in the low phosphorus and aluminosilicate / NTA formulations disclosed herein. Suitable blends have a copolymer: homopolymer to ratio of about 1: 2 to about 5: 1, preferably about 1: 1 to about 5: 1, more preferably about 1: 1 to 2: 1. The total amount of polycarboxy-25 tile polymer in the final product is from about 0.5% to about 5% by weight, preferably from about 2% to about 4% by weight.

The weight average molecular weights of the polymer can be determined herein by light scattering or gel permeation chromatography using Waters pPorasil 30 (RTM) GPC 60 A2 and pBondagel (RTM) in E-125, E-500 and E-1000 series, temperature controlled columns, at 40 ° C, sodium polystyrene sulfonate polymer standards from Polymer Laboratoriess Ltd, Shropshire, UK, and the polymer standards Kali-35 are brominated as their sodium salts and the eluent is 0.15 M sodium 19 80068 dihydrogen phosphate and 0.02 M tetramethyl tetramethyl 88a in 80/20 water / acetonitrile.

Alkali metal carbonate is important to achieve a suitable working solution pH for optimum washing (about pH 10 -5 to about pH 11, preferably about pH 10.4 to about pH 10.6 measured as a 1% solution). In general, the combinations of the invention contain from about 5% to about 30% by weight, preferably from about 10% to about 25% by weight of alkali metal carbonate (on an anhydrous basis). The alkali metal silicate is preferably included in the combinations of the invention from about 1% to about 4% by weight, most preferably from about 1.5% to about 2.5% by weight. At lower amounts, bleaching activity is found to be increasingly degraded; on the other hand, on the other hand, the performance of the aluminosilicate and the appearance of the fabric are adversely affected by the accumulation of aluminosilicate particles.

The combinations of the invention can be supplemented with all kinds of detergent and laundry detergent components, including antifoams, enzymes, fluorinators, photoactivators, bleach catalysts, dirt suspending agents, anti-caking agents, pigments, perfumes, fabrics.

Antifoams are represented by variants of silicone, wax, vegetable and hydrocarbon oil and phosphate ester substances. Suitable antifoam silicones include polydimethylsiloxanes having a molecular weight of about 200 to about 200,000 and a kinematic viscosity of about 20 to about 2,000,000 mm 2 / s, preferably about 3,000 to about 30,000 mm 2 / s, and mixtures of siloxanes with hydrophobic silanized (preferably trimethylated). ) with silica 30 having a particle size of about 10 to about 20 milli-microns and a specific surface area of greater than about 50 m 2 / g. Suitable waxes include microcrystalline waxes having a melting point of about 65 ° C to about 100 ° C, a molecular weight of about 400 to 1000 and a penetration value of at least 6, measured at 25 ° C according to ASTM-D-1321, and also paraffin waxes having a melting point of 0 0 6 8 theoretical waxes and natural waxes. Suitable phosphate esters include mono- and / or di-Cx6-C22 alkyl or alkenyl phosphate esters, and corresponding mono- and / or dialkyl or alkenyl ether phosphates containing up to 6 ethoxy groups per molecule.

Suitable enzymes for use herein include those mentioned in U.S. Pat. No. 3,519,570 and U.S. Pat. No. 3,533,139. Suitable fluorinating agents include Blankophor MBBH (Bayer AG) and Tinopal CBS and EMS (Ciba 10 Geigy). Photoactivators are mentioned in EP-A-570088, and highly preferred materials are zinc phthalocyanine tri- and tetrasulfonates. Suitable fabric care agents include di-C 1 -C 2 alkyl or alkenylamines and quaternary ammonium salts. Suitable bleach catalysts are disclosed in EP-A-00 72 166 and EP-A-01 24 341.

Suitable anti-re-adhesives and dirt suspending agents herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.

The combinations of the invention are preferably prepared by spray-drying an aqueous slurry containing aluminosilicate and an alkali metal silicate and an anionic surfactant when present. Nitrile triacetate can also be spray-dried or added separately to the spray-dried base granules. The tripolyphosphate boiling salt and carbonate, when present, are also mixed separately dry with spray-dried base granules. The aqueous slurry is stirred at about 45-90 ° C, and the water content of the slurry was adjusted to about 25% to about 50%. Spray drying is performed at an inlet gas inlet temperature of about 250-390 ° C, preferably about 275-350 ° C, whereby the final moisture content is adjusted to between about 8-14% by weight.

35 The abbreviations used in the following examples have the following meanings: 2i 80 063

Cx 2 LAS: sodium linear C12 benzenesulphonate TAS: sodium fatty alcohol sulphate

Cj 2 /, 4 AS: 2/14-alcohol sulphate, sodium salt 5 TAEn: hardened fatty alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol,

Cx2TMAB: 2 -alkyltriroethylammonium bromide

Dopanol 45E7: Cx4.15-primary alcohol condensed with 7 moles of ethylene oxide, TAED: tetraacetylethylenediamine PAG: Pentaacetylglucose AOBS: sodium p-acetoxybenzenesulfonate NOBS: sodium nonaoyloxybenzenesulfonate sulfonate -trimethylhexanoyloxybenzenesulfonate INOBA: sodium 3,5,5-trimethylhexanoyloxybenzenecarboxylate EHOBS: sodium 2-ethylhexanoyloxybenzenesulfonate

Silicate: sodium silicate with a SiO2: Na2O ratio of 1: 6,

Sulphate: anhydrous sodium sulphate

Carbonate: anhydrous sodium carbonate 25 CMC: sodium carboxymethylcellulose

Silicone: comprises 0.14 parts by weight of a 85:15 mixture of silanized silica and silicone granulated with 1.3 parts of sodium tripolyphosphate and 0.56 parts of 30 parts of animal fatty alcohol condensed with 25 molar proportions of ethylene oxide NTA: sodium nitrile triacetate PCI: 3: 7 maleic / acrylic acid copolymer, 35 with an average molecular weight of about 70,000, as the sodium salt 22,80068 PC2: polyacrylic acid with an average molecular weight of about 4,500, as the sodium salt phosphate: Perborate: sodium perborate tetrahydrate with the nominal formula NaBO2 · 3Η20 · Η202 Enzyme: protease EDTA: sodium ethylenediamine tetraacetate

Clarifier: Disodium 4,4'-bis (2-morpholine-4-aniline-S-triazin-6-ylamino) stilbene-2: 2'-disulfonate DETPMP: diethylenetriamine penta (methylenephosphonic acid), marketed by Monsanto, under the trade name Deguest 2060 15 EDTMP: ethylenediaminetetra (methylenephosphonic acid), marketed by Monsanto, under the trade name Dequest 2041

Clay: sodium montmorillonite

20 Examples I-VIII

Granular detergent combinations are prepared as follows. First, the base powder is prepared by mixing all components except Dobanol 45E7, bleach, bleach activator, enzyme, antifoam, phosphate and carbonate, in a mixer, as an aqueous slurry at about 55 ° C, and the slurry contains about 35% water. The slurry is then spray-dried at a gas inlet temperature of about 330 ° C to form base powder granules. The bleach activator, when present, is then mixed with TAE2 5 as a binder and compressed in the form of long particles through a radial press as described in EP-A-00 62 523. Bleach Akti-noodles, bleach, enzyme, antifoam , the phosphate and carbonate are then mixed as a dry powder base combination, and finally Dobanol 45E7 is injected into the final mixture.

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* -H rt G G rt o> itnrt-H

2 -Hrtao ^ λ:> i rt rt h h £. i — i ih ft λ ή -h tn. * mo> CP Ή M otn-HpH <rH + JpM Q) rt®UU <uOrtrt-HEH-HG-HG tsi n Σ li, an ^ ω «w 2 cowWtnx 25 80068

The above combinations are low phosphate detergent combinations with excellent bleaching stability, fabric care property and washing performance over the entire wash temperature range, and particularly excellent performance in the case of Examples I-IV over greasy and particulate soils in low washes.

Claims (1)

Granular detergent combination, characterized in that it comprises: 5 (a) about 6 to about 18% by weight of a water-insoluble aluminosilicate cation exchange material, (b) about 1 to about 8% by weight of an alkali metal salt of nitrile acetic acid, (c) about 6 - about 14% by weight of a phosphate enhancer salt, wherein the phosphate enhancer salt is selected from sodium and potassium tripolyphosphates and comprises less than about 12% by weight of pyrophosphate, (d) from about 5% to about 35% by weight of an inorganic or organic peroxy bleach, (E) at least 0.5% by weight of an organic peroxyacid bleach precursor of general formula II 0 II RCL (II) 20 wherein R is an alkyl group having 6 to 12 carbon atoms and wherein the longest linear alkyl chain extending from carboxyl oxyl carbon and contains it, contains 5 to 10 carbon atoms, and L is a leaving group having a pKa -25 of the conjugate acid of 6 to 13, (f) a heavy metal rinse selected from water-soluble aminopolycarboxylates and aminopolyphosphonates having at least 4 acidic protons per molecule, or a water-insoluble smectite-type clay selected from saponites, hectrites, and sodium and calcium montmorillonites, and (g) about 0.5 - about 5% by weight of polycarboxylate polymer; wherein (a) + 2 (b) constitutes about 13 to about 27 weight percent of the combination. Il 27 8 0 0 6 8 The granular composition of the composition, which comprises the following: 5 (a) about 6 to about 18% by weight of the aluminum silicate cationic material, (b) about 1 to about 8% by weight from alkali metal nitrile to nitrile nitrate, (c) from 6 to about 14% by weight of phosphate, from 10 to 10% by weight of sodium and potassium tripolyphosphate and from about 12% by weight of pyrophosphate, (d) from about 5 to about 35% by weight (%) 0.5% by weight of organic or organic peroxybox form, (e) 0.5% by weight of an organic peroxygen ring, 15 per cent RCL (II) 20 color R or en alkyl group with 6-12 carbon atoms, wherein the linear längsta alkyIkedjän, which extends to the carbo-xylkolen containing from och den, containing from 5-10 carbon atoms, Science L is not discharging used Grupp, vars konjugatsyra 25 being provided with a pKa of VÄRDE 6-13 ( f) ett tungmetallsköljningsmedel, som valts bland vattenlösliga aminopolykar boxylate and aminopolyphosphonate, one of the above 4 molecules per molecule, one or more olives of the smectite type, 30 ml of a single-phase saponiter, hectorite and sodium and calcium monomoronite, och (g) ca 0.5 - ca 5 vikt -% of polycarboxylate polymers; colors (a) + 2 (b) represent about 13 - about 27% by weight of 35 compositions.