DK164706B - GRANULAR DETERGENT COMPOSITION - 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

in

DK 164706 B

The invention relates to granular detergent compositions with reduced phosphate levels and with excellent purification effect, whiteness retention and stain removal functions, as well as improved bleaching stability and fabric protecting properties.

5

The function of phosphate detergent builders as adjuvants for organic, water-soluble, synthetic detergents and their value in improving the overall effect of such detergents is well known. In recent years, the use of high content of phosphate builders, such as tripolyphosphates, however, have been subjected to critical studies due to the suspicion that soluble phosphate compounds enhance the eutrophication or aging process of streams, lakes and the like. Therefore, there is a need for compound detergent compositions having reduced phosphate content, but which is comparable to a traditional tripolyphosphate-based composition for overall purification efficiency.

The mechanism by which detergent builders effect an improved purification effect of water-soluble organic detergent compounds is not exactly known, but appears to depend on a combination of factors such as water softening effect, suspension of dirt and antigen deposition, swelling and peptization of clay and pH adjustment. However, the present theory does not allow for a prediction of which compounds will serve as effective detergent builders.

Sodium aluminum silicates, commonly known as zeolites, have been proposed to be used as substitutes for phosphate builders, being able to soften the water by removing calcium ions (see, e.g., BE-A-814,874 and BE-A-813,581). . However, zeolites are unable to duplicate the entire range of builder functions exhibited by phosphates.

One way to enhance the overall detergent effect of low phosphate formulations is to use bleaching aids such as inorganic or organic peroxy bleaches and organic bleach activators. Although careful balancing of builder and bleach types and contents may provide some improvement in performance, such formulations remain fundamentally weak in three areas, for it

DK 164706B

2, in the case of bleaching stability, secondly in terms of dust damage properties, and thirdly in the removal of grease and particulate dirt, especially at low washing temperatures.

In EP-A-70,079, it has been proposed to improve the bleaching effect of aluminum silk in cat-built compositions by the addition of a nine trilotriacetic acid compound. The combined content of aluminum silicate and nitrilotriacetic acid is stated to be critical and corresponds to a relatively high total content of the final product. At high concentrations, both aluminum silicates and nitrilotriacetates present significant treatment problems, aluminum silicates causing dispersion stability and pumping properties, while nitrilotriacetates present thermal stability problems. Furthermore, high content of aluminum silicates can have a detrimental effect on the appearance of the substance. On the other hand, bleaching, purging and fabric damage properties will once again be adversely affected if the content of aluminum silicate and nine trilotriacetate is reduced to a more acceptable level.

20

It has now been found that bleaching, purifying and fabric damage properties can be greatly improved, even with a relatively low total level of aluminum silicate and nine trilotriacetate, by the addition of a tripolyphosphate builder in certain amounts having a critical maximum limit for pyrophosphate content. Furthermore, it has further been found that certain bleach precursors of organic chain length peroxic acids in combination with a low phosphate builder system provide a purification effect at least equivalent to a fully phosphate-built formulation over the entire range of washing temperatures, with particularly excellent effect on the fat and batch. Cool the dirt at low washing temperatures.

This is achieved with the granular detergent composition of the invention comprising, by weight, from 5% to 60% organic surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof, and from 5 to 30% of all potassium carbonate. which composition is peculiar in that it further comprises:

DK 164706 B

3 (a) from 6% to 18% by weight of a water-insoluble aluminum ilate cation exchange material, (b) from 1% to 8% of an alkali metal salt of nitrilotriacetic acid, 5 (c) from 6% to 14% phosphate builder wherein the phosphate builder is selected from sodium and potassium tripolyphosphates, less than 12% of which are pyrophosphate, 10 (d) from 5% to 35% of inorganic or organic peroxy bleach, (e) from 0% to 10% of organic peroxyacid bleaching precursors, and (f) an agent for heavy metal capture, 15 wherein the percentages of (a) + 2 (b) range from 13 to 27%.

Thus, the composition of the invention contains a specified detergent builder system and a bleach agent system. Also, the composition comprises an organic soap or synthetic surfactant detergent material as well as an alkali metal carbonate. Particularly preferred compositions also contain specific proportions of polycarboxylate polymers and all potassium metal silicate, which serve to provide improved detergent properties and appearance.

The builder system comprises three essential components, a water-insoluble aluminum silicate cation exchange material, an alkali metal salt of 30 nitrilotriacetic acid and a phosphate builder.

The aluminum silicate cation exchange material comprises from 6% to 18%, preferably from 7% to 16%, and especially from 8% to 17%, based on the weight of the detergent composition. The aluminum silicate may have a crystalline or amorphous character, and the preferred materials have a unit cell formula I:

Mz [(A102) z (SiO2) y] χΗ20 (I)

DK 164706 B

4 where M represents a calcium exchange! in g cation, z and y are at least 6; The molar ratio of z to y is from 1.0 to 0.5, and x is at least 5, preferably from 7.5 to 275, more preferably from 10 to 254. The aluminum silica materials are in hydrated form and are 5 is preferably crystalline and contains from ca. 10% to 28%, more preferably from 18% to 22% water.

Aluminum sealing exchange material is further characterized by a particle size diameter of from 0.1 µm to 10 µm, preferably from 0.2 µm to 4 µm. The term "particle size diameter" here refers to the average particle size diameter of a given ion exchange t erm ale, as determined by conventional analytical methods such as e.g. microscopic determination using scanning electron microscope. The aluminum silica exchange materials herein are further characterized by their ion exchange capacity for calcium ions which is at least approx. 200 mg equivalent of CaCO3 water hardness / g of aluminum silicate, calculated on anhydrous basis and generally in the range of from approx. 300 mg eq / g to approx. 352 mg eq / g. Aluminum sieve in cation exchange materials herein is further characterized by their calcium ion exchange rate, which is at least 130 mg eq. CaCOiliter / minute / gram / liter aluminum silicate (anhydrous base) and it is generally in the range of 130 mg eq. CaCO3 / liter / minute / gram / liter to 390 mg eq. CaCO 3 / liter / minute / gram / liter, based on the calcium ion hardness of calcium ion. Optimal aluminum silicates for use as builders exhibit a calcium ion exchange rate of at least 260 mg eq. CaC03 / liter / minute / gram / liter.

Aluminum silica exchange materials useful in the practice of the present invention are commercially obtainable and may be naturally occurring aluminum silicates or synthetically derived.

A process for making aluminum silica exchange material is described in the specification of U.S. Patent No. 3,985,669. Preferred synthetic crystalline aluminum silica exchange materials which are useful herein are obtainable under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In a particularly preferred embodiment, the crystalline aluminum silica exchange material is Zeolite A and has the formula:

Na2 [(A102) i2 ($ i ° 2) 12] xH2O

DK 164706 B

5 where x is from 20 to 30, in particular approx. 27. Zeolite X of formula Nagg [(A102) gg (SiO2) 106] -276 H2 O is also suitable, as well as Zeolite HS of formula Nag [(A102) g (SiO2) 6J * 7.5 H2 O.

Suitable nitrilotriacetic acid salts for use herein are trisodium and tricalcium salts of nitrilotriacetic acid. The acid itself or disodium or dipotassium salts of the acid can also be used as an additive. However, it will be appreciated that at the pH conditions typically encountered during preparation, the nitrilotriacetic acid or salt will generally be converted to a completely ionized form.

Nitrilotriacetic acid (determined in tri sodium form) is from 1% to 8%, preferably from 3% to 7% by weight of the composition. The percentage amount (b) of the nitrilotriacetic acid salt (again determined in 15 tri sodium form) and the percentage amount (a) of aluminum sieve in the cation exchange material (measured in hydrated form) is such that the sum of a + 2b is between 13 and 27, preferably between 14 and 24, more preferably between 16 and 21.

A further essential component of the compositions herein is a phosphate builder comprising from 6% to 14%, preferably from 8% to 12%. The phosphate builder is selected from sodium and potassium tripolyphosphates and hydrates thereof, but is preferably substantially anhydrous or partially hydrated (i.e., to no more than 60% of its hydration capacity). However, the phosphate builder content is determined on anhydrous basis. It is critical that the phosphate builder comprises less than 12%, preferably less than 8% of pyrophosphate bui erene. Particularly preferred is a phosphate builder system which is mixed in dry crystalline form with the rest of the detergent composition.

The detergent composition of the invention also comprises a bleaching system comprising an inorganic or organic peroxy bleaching agent, a heavy metal capture agent and in preferred compositions an organic peroxyacid bleaching precursor.

Suitable inorganic peroxygen bleaches include sodium perborate mono- and tetrahydrate, sodium percarbonate, cat sodium persil and urea hydrogen peroxide additives, and the clathrate

DK 164706 B

6 4 ^ 50 ^: 21 ^ 2: lNaCl. Suitable organic bleaches include peroxylauric acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecanedioic acid, diperoxyazelaic acid, mono- and diperoxyphthaT-acid and mono- and diperoxyisophthalic acid. For example, the agent is present in the compositions ranging from 5% to 35%, preferably from 10% to 25% by weight.

The heavy metal trapping agent is preferably a water-soluble chelating agent. Aminopoly acids with 4 or more acidic protons per

10 molecules are preferred. Suitable chelating agents include amino-carboxyl chelating agents, such as ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), dihydroxyethylethylenediamine in acetic acid (DHEEDDA), diethylenetriamine di-pentane N, N ', N'-tetraacetic acid (DCTA) and water-soluble salts thereof, as well as aminopolyphosphonate chelating agents such as ethylene diamine tetra (methylene phosphonic acid) (EDTMP), di ethylenetriamine penta (methylene phosphonic acid) (DETPMP), nitri 1 ), hexamethylenediamine tetra-methylene phosphonic acid (HMTPM) and water-soluble salts thereof. These 20 water-soluble sequestering agents are generally in the range of from 0.05% to 4%, preferably from 0.1% to 1.0% by weight.

Heavy metal capture medium may also be represented by water-soluble smectite-type clays selected from saponites, 25 hectorites, and sodium and calcium montmorillonites (sodium and calcium here represent the major inorganic cation in the clay).

Although any of these smectite-type clays can be incorporated into the compositions of the invention, especially smectite-type clays with ion exchange capacity of at least 50 milliequivalents / 100 g of clay are preferred, preferably at least 70 milliequivalents / 100 g of clay (e.g. , as described in "The Chemistry and Physics of Clays", pp.264-265, Interscience (1979)). Particularly preferred materials are as follows:

Sodium montmori11 onit Brock

Vol cl ay BC Gelwhite GP

DK 164706 B

7

Thixo-Jel

Ben-A-Gel

Imvite 5 sodium hectorite

Veegum F Laponite® SP

Sodium saponite jO Barasym NAS 100

Calcium montmorillonite Soft Clark Gelwhite L 15

Li thium hectorite Barasym LTH 200 When these clays are present, they are usually added in extent 20 of from 1% to 20%, preferably from 2% to 10% by weight of the composition. The clays also impart a softening ability to the compositions.

Another suitable heavy metal trapping agent is a water-insoluble, preferably colloidal, magnesium silicate or a water-soluble magnesium salt which forms magnesium silicate in the aqueous slurry from the mixing vessel prior to spray drying. The magnesium silicate or salt is generally added to an extent ranging from 0.015% to 0.2%, preferably from 0.03% to 0.15%, more preferably from 0.05% to 0.12% of weight basis (magnesium base).

Suitable magnesium salts include magnesium sulfate, magnesium sulfate heptahydrate, magnesium chloride and magnesium chloride hexahydrate.

Preferably, the compositions of the invention also contain an organic peroxyacid bleach precursor ranging from 0.5% to 10%, preferably from 1% to 6% by weight. Suitable bleach precursors are described in UK-A-2,040,983 and include e.g. pereddic acid bleach precursors such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylhexylenediamine,

DK 164706B

8 sodium p-acetoxybenzenesulfonate, tetraacetylglycouril, pentaacetylglucose, octaacetyl1actose and methyl-o-acetoxybenzoate. Particularly preferred bleach precursors have the general formula II: 5 RC (= O) -L (II) where R represents an alkyl group containing from 6 to 12 carbon atoms, the longest linear alkyl chain extending from and including the carboxyl carbon atom , contains from 5 to 10 carbon-10 atoms, and L represents a leaving group whose conjugated acid has a pK a value in the range of 6 to 13.

The alkyl group, R, can be either linear or branched, and in preferred embodiments, it contains from 7 to 9 carbon atoms.

Preferred leaving groups L have a pKa value in the range of 7 to 11, more preferably from 8 to 10. Examples of leaving groups are compounds of the formulas: a), (CH) y 20 v ° vo <0

M

z 25 and b) £ -n-c-r CH-1 *

Y

Wherein 1 represents H, R or halogen, where R represents an alkyl group having from 1 to 4 carbon atoms, x is 0 or an integer of from 1 to 35 4, and Y is selected from SO3M, SO3M, Oyi, N + (R1) 3Q 'and N + (R1) 20 "where M represents H, alkali metal, terrestrial potassium, ammonium or substituted ammonium, and Q represents halide or methasulfate.

The preferred leaving group L has the formula (a) where Z is H, x

DK 164706 B

9 is 0 and Y represents sulfonate, carboxylate or dimethylanine oxide radical. Particularly preferred materials are sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, sodium 3,5,5-trimethylhexanoyloxybenzoate, sodium 2-ethylhexanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate and sodium octanoyloxybenzenesulfonate. is β-substituted.

The bleeding activator disclosed herein will usually be added in the form of particles comprising comminuted blend activator and binder. The binder is generally selected from nonionic surfactants such as ethoxylated tallow alcohols, polyethylene glycols, anionic surfactants, film-forming polymers, fatty acids and mixtures thereof. Particularly preferred are nonionic surfactant binders, wherein the 15 µl binder activator is mixed with the binder and extruded into a radial extruder for elongated particles as described in the EP Patent Application No. 62,523. Alternatively, the bleach activator particles can be prepared by spray drying as described in British Patent Application No. 84 22,158.

20

The detergent compositions disclosed herein contain from 5% to 60%, preferably from 8% to 30%, by weight of organic surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof. Surfactants for use herein are disclosed in US-A-4,222,905 and US-A-4,239,659.

The anionic surfactant may be one or more of the materials traditionally used in detergents. Suitable synthetic anionic surfactants are water-soluble salts of all cool benzenesulfonates, all cool sulfates, all cool polyethoxy ether sulfates, paraffin sulfonates, α-olefin sulfonates, alpha sulfocarboxylates and their esters, acyloxyalkane-1-sulfonate and 5-alkyloxyalkanesulfonate.

A particularly convenient class of anionic surfactants include water-soluble salts, especially alkali metal, ammonium and all canonium ammonium salts or organic

DK 164706 B

10 sulfuric acid reaction products having in their molecular structure an alkyl or alkaryl group containing from 8 to 22, in particular from 10 to 20 carbon atoms, and a sulphonic acid or sulfuric acid ester group. (The term "alkyl" includes the alkyl moiety in acyl groups). Examples of this group of synthetic detergents which form part of the detergent compositions of the invention are sodium and potassium alkyl sulfonates, in particular those obtained by sulfating carbon atoms in the higher alcohols (cq_q) produced by reduction of the glycerides in tallow or coconut oil, as well as sodium and potassium 10 alkyl benzene sulfonates, wherein all the cooling group contains from 9 to 15, in particular from 11 to 13 carbon atoms in an unbranched or branched configuration, e.g. of the type disclosed in the disclosures of U.S. Patent Nos. 2,220,099 and 2,477,383, as well as those prepared from all cooling benzenes obtained by alkylation with 15 unbranched chloro paraffins (using aluminum trichloride catalysis) or branched olefins (using hydrogen fluoride catalysis). Particularly valuable are linear alkyl benzenesulfonates, in which the average of the alkyl group is approx.

11.8 carbon atoms, abbreviated as g LAS and methyl branched 20 ^ 12 "^ 15alkyl sulfates.

Other anionic detergent compositions herein include sodium salts of Cjg jg alkyl alkyl glyceryl ester sulfonates, in particular the ethers of higher alcohols derived from tallow and coconut oil; 25 sodium coconut oil fatty acid monoglyceride sulphonates and sulphates, as well as the sodium or potassium salts of all cool phenol ethylene oxide ether sulphate containing from ca. 1 to approx. 10 ethylene oxide units per molecule, and wherein all the alkyl groups contain from ca. 8 to approx. 12 carbon atoms.

30

Other useful anionic detergents disclosed herein include the water-soluble salts or esters of α-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acid containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the whole unit; alkyl ether sulfates containing from 10 to 18 carbon atoms, especially from 12 to 16, in the alkyl group and from 1 to 12 moles of ethylene oxide, especially from 1 to 6, more preferably from 1 to 4; water-soluble

DK 164706B

11 salts of olefin sulfonates containing from 12 to 24 carbon atoms, preferably from 14 to 16, in particular those resulting from reaction with sulfur trioxide followed by neutralization under conditions such that all the sultones present are hydrolyzed to the corresponding hydroxyalkanesulfonates; water-soluble salts of paraffin sulfonates containing from 8 to 24 carbon atoms, in particular from 14 to 18, and / - all kyloxyalkanesulfonates containing from 1 to 3 carbon atoms in each cool group and from 8 to 20 carbon atoms in all the scaffold.

10

The alkane chains of the aforementioned non-soap, anionic surfactants may be provided from natural sources such as coconut oil or sebum, or may be synthetically produced by e.g. The Ziegler or Oxo methods. Water solubility can be achieved by using alkali metal, ammonium or all cannon ammonium cations; sodium is preferred. Suitable fatty acid soaps can be selected from ordinary alkali metal (sodium, potassium), ammonium and alkylol ammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, preferably from 10 to 22 and especially from 16 to 22 carbon atoms in the entire chain. Suitable fatty acids can be obtained from natural sources, such as e.g. from soybean oil, castor oil, sebum, whale and fish oil, fat, lard and mixtures thereof. The fatty acids can also be produced synthetically (for example, by the oxidation of petroleum or by the hydrogenation of carbon monoxide by the Fischer-Tropsch method).

Resin acids are suitable, such as rosin and the resin acids in tall oil. Naphthenic acids are also suitable. The sodium and potassium soaps can be prepared by directly saponifying the fats and oils or by neutralizing the free fatty acids produced by a separate manufacturing process. Particularly useful are the 30 sodium and potassium salts of the fatty acid mixtures derived from tallow and hydrogenated fish oil.

Mixtures of anionic surfactants are particularly useful in the invention, in particular mixtures of sulfonate and sulfate-containing surfactants in a weight ratio of 5: 1 to 1: 5, preferably from 5: 1 to 1: 1, more preferably from 5 : 1 to 1.5: 1. Particularly preferred is a mixture of an alkyl benzene sulfonate having from 9 to 15 carbon atoms, especially from 11 to 13, in the alkyl radical, the cation being an alkali metal, preferably

DK 164706 B

12 sodium, and either an all carbon sulphate having from 10 to 20 carbon atoms, preferably from 12 to 18 carbon atoms in each cooling radical, or an ethoxy sulfate having from 10 to 20 carbon atoms in each cooling radical, preferably from 10 to 20 carbon atoms. 16 carbon atoms, and an average ethoxylation degree of from 1 to 6, as well as with an all potassium metal cat in on, preferably sodium.

Nonionic surfactants useful in the present invention are ethylene oxide condensates and a hydrophobic moiety to provide a surfactant having an average hydrophilic 1-1 ipofi 1 balance (HLB) in the range of about 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5. The hydrophobic moiety may be of aliphatic or aromatic nature and the length of the polyoxyethylene group condensed by some particular hydrophobic group can be readily adapted to obtain a water-soluble compound with the desired balance between hydrophilic and hydrophobic elements.

Examples of suitable nonionic surfactants include: 1. Polyethylene oxide condensates are alkyl phenol, e.g. the condensation products from the reaction of alkyl phenol with an alkyl group containing from 6 to 12 carbon atoms in either a unbranched or branched chain configuration and ethylene oxide, wherein the ethylene oxide 25 is present in an amount equal to 3 to 30 moles of ethylene oxide per liter. moles of alkylphenol, preferably from 5 to 14 moles. The alkyl substituent in such compounds may be derived from e.g. polymerized propyl en, diisobutylene, octene and nonen. Other examples include dodecyl-phenol condensed with 9 moles of ethylene oxide per liter. moles of phenol; dinonyl-3-phenol condensed with 11 moles of ethylene oxide per ml. moles of phenol; nonyl-phenol and di-isooctylphenol condensed with 13 moles of ethylene oxide.

2. The condensation product from the reaction of primary or secondary aliphatic alcohols with from 8 to 24 carbon atoms in either unbranched or branched chain configuration and from 2 to ca. 40 moles of ethylene oxide per moles of alcohol, preferably from 2 to approx. 9 mol.

The primary alcohol preferably contains between 9 and 18 carbon atoms and is ethoxylated with between 2 and 9 moles of ethylene oxide per liter. mole of aliphatic alcohol, desirably between 3 and 8 moles. The preferred ones

DK 164706 B

13 surfactants are prepared from primary alcohols which are either unbranched (such as those derived from natural fat compounds or prepared by the Ziegler method from ethylene, e.g. myristyl, cetyl, stearyl alcohols) or partially branched, such as Lutensols, Dobanols and Neodols, which have 25% 2-methyl branching (Lutensol is a trademark of BASF, Dobanol and Neodel are trademarks of Shell) or Synperonic's, which contains approx. 50% 2-methyl branching (Synperonic is a trademark of ICI) or the primary alcohols having more than 50% branching and which are sold under the trademark Lial by Liquichimi Specific examples of nonionic surfactants falling within the scope of the invention includes Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-2.5, Dobanol 91-3, Dobanol 91-4, Dobanol 91-6, Dobanol 91-8, Dobanol 23-6, 5, Synperonic 6, Synperonic 14, 15 condensation products from the condensation between coconut alcohol and an average of between 5 and 12 moles of ethylene oxide per liter. in which the coconut alkyl part contains from 10 to 14 carbon atoms, as well as the condensation products from the condensation between tallow alcohol and an average of between 7 and 12 moles of ethylene oxide per liter. mole of alcohol, 20 wherein the tallow moiety essentially comprises between 16 and 22 carbon atoms. Secondary, unbranched alkyl ethoxylates are also suitable in the present compositions, in particular the ethoxylates of the Tergitol series having from about 9 to 15 carbon atoms in the alkyl group and up to approx. 11 ethoxy residues per molecule, especially from ca. 3 to 9.

25

The compounds formed by condensing ethylene oxide with a hydrophobic compound produced by the condensation of polypropylene oxide with polypropylene glycol. The molecular weight of the hydrophobic moiety is generally in the range of about Such synthetic non-ionic detergents are on the market under the trademark "Pluronic" derived from Wyandotte Chemicals Corporation.

Particularly preferred nonionic surfactants are the primary C C-C ^ al alcohol ethoxylates containing 3 to 8 moles of ethylene oxide per liter. moles of alcohol, in particular the primary C12 "C15 alcohol ethoxylates containing 6-8 moles of ethylene oxide per mole of alcohol.

Cationic surfactants suitable for use in

DK 164706B

14 in connection with the present invention, includes quaternary ammonium-containing surfactants and semi-polar surfactants, e.g. amine oxides.

Suitable surfactants of the amine oxide class have the general formula V: R6 R6 ~ 10 R5-N + - (CH) .- N + - R6

I 21 I

Wherein R represents an unbranched or branched alkyl or alkenyl group having 8-20 carbon atoms, each R ° independently selected from all chillers and '(Cp ^ n ^ m ^' where ^ represents a integers of from 1 to 6, j are 0 or 1, n is 2 or 3, and m is between 1 and 7 and where the total sum of (^^ O groups in a 20 molecule is not more than 7.

In a preferred embodiment, R contains from 10 to 14 carbon atoms and each R 1 is independently selected from methyl and ~ n n 2 nn 2 m 2 'where m is ^ ra * 3 3 ° 9 ^ a total sum of a ^ n 'n0' and groups in a molecule are not more than 5, preferably not more than 3. In a very preferred embodiment, j is zero, each R is methyl and R is C 12 -C 14 alkyl.

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

j: 1 R 2: tallow Cj-Cjj alkyl; palm tree tyl; oleyl; stearyl: hydroxyethyl in: 2 or 3

A specific example of this preferred class of bis-amine oxides is: N-hydrogenated Cj-Cjg tallow alkyl-Ν, Ν ', N'-tri (2-hydroxyethyl) -propylene-1,3-diamine oxide.

DK 164706 B

15

Suitable quaternary ammonium-containing surfactants for use in the present composition can be defined by the general formula VI: 5 d8 "R8" R7-N + - (CH2> i- *? + - R0 2 10> 8 R8 R Wherein R7 represents an unbranched or branched alkyl, alkenyl,

ISLAND

or alkaryl group having 8-16 carbon atoms, each R is independently selected from C 14 alkyl, C 14 alkaryl and (CnH2NO) m, where in 15 represents an integer of from 1 to 6, j is 0 or 1, n is 2 or 3 , and m is from 1 to 7, and the total sum of CnH2nO groups in a molecule is not more than 7 and where Z represents a counter-anion in a number providing electrical neutrality.

In a preferred embodiment, R7 contains from 10 to 14 carbon atoms.

ISLAND

atoms, and each R is independently selected from methyl and (Cn ^ n ^ m ^ ') our m is from 1 to 3 and the total sum of (^ I ^ O groups in a molecule is not more than 5 , preferably not more than 3. In an 8 very preferred embodiment, j is zero, R is selected from 25 methyl, hydroxyethyl and hydroxypropyl, and R 7 is C 1 -C 2 alkyl. Particularly preferred surfactants of this class include C trimethyl ammonium salt tea, C 1-6 cool tri methyl ammonium salts, coconut oil cool trimethyl ammonium salt tea, coconut dimethylhydroxyethylammonium salts, coconut dimethyl dimethylhydroxy-propyl ammonium salts and C 1-4 alkyl dihydroxyethyl salts

Another group of useful cationic compounds are the di ammonium salts of formula VI wherein j represents I, R7 represents C] 2 14 'a ^ yl, each R ^ represents methyl, hydroxyethyl or hydroxypropyl and i is oc 2 or 3. I a particularly preferred surfactant of this type is R 8 denotes coconut alkyl, R is methyl, and i is 3.

In very preferred compositions, the builder system is supplemented with three additional components, namely polycarboxylate polymers,

DK 164706 B

16 al potassium carbonates and all potassium silicates.

Polycarboxylate polymers are preferably selected from copolymers of polycarboxylic acids and their salts derived from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid or mesaconic acid as the first monomer and the ethylene, methyl vinyl ether, acrylic acid or methacrylic acid as the second comprises at least approx. 10 mole percent, preferably at least approx. 20 mole percent of polycarboxylic acid units and having an average molecule -10 weight of at least approx. 12,000, preferably at least approx. 30000; homo-polyacrylates and homopolymethacrylates having an average molecular weight of from ca. 1,000 to approx. 20,000, preferably from ca. 1,000 to approx. 10,000; and mixtures thereof. Mixtures are highly preferred to provide good bleach stability, detergent action and anti-crusting action in connection with the low-phosphorus-containing and low-aluminum silicate / NTA formulations described herein. Suitable mixtures have a copolymer: homopolymer ratio of from approx. 1: 2 to approx. 5: 1, preferably from ca. 1: 1 to approx. 5: 1, but especially from approx. 1: 1 to 2: 1. Preferably, the total amount of polycarboxylate polymer in the final product is about 0.5% to approx. 5%, but especially from approx. 2% to approx. 4%.

The average molecular weights of the polymer can be determined by light scattering gel chromatography using Waters 25 pPorasil (RTM) GPC 60 A2 and / xBondagel (RTM) E-125, E-500 and E-1000 in series, temperature controlled columns at 40 ° C. standards of sodium polystyrene sulfate polymers obtainable from Polymer Laboratories Ltd., Shropshire, UK, which polymer standards are calibrated as their sodium salts, and the eluent is 0.15 M sodium dihydrogen phosphate and 0.02 M tetramethylammonium hydroxide at pH 7.0 in water / acetonitrile 80/20 ratio.

Alkali metal carbonate is important in providing a suitable pH in the solution used to obtain optimum detergent action 35 (from a pH of about 10 to pH 11, preferably from pH 10.4 to pH 10.6, measured in a 1% resolution). Generally, the compositions comprise from 5% to 30%, preferably from 10% to 25%, of an alkali metal carbonate (on anhydrous basis).

DK 164706 B

17

Preferably, all potassium silicate is included in the compositions of the invention in the range of from 1% to 4%, preferably from 1.5% to 2.5%. To a lesser extent, it is found that bleaching ability is becoming more and more impaired; to a greater extent, aluminum silk in the cat action and the appearance of the fabric, on the other hand, are adversely affected by the al umi n i urns in the 1 in cat parti cel aggregation.

The compositions of the invention can be supplemented with all sorts of other detergents and detergent components, including antifoaming agents, enzymes, fluorescent agents, photoactivating agents, bleaching catalysts, dirt suspending agents, antifouling agents, pigments, perfumes, fabric conditioners, and more.

Anti-foaming agents are represented by materials such as various silicone, wax, vegetable and hydrocarbon oil and phosphate esters. Suitable silicone foam control agents include polydimethylsiloxanes having a molecular weight in the range of about 200 to approx. 200,000 and a kinematic viscosity in the range of approx. 20 to o 2 approx. 2,000,000 mm / s, preferably from ca. 3,000 to approx. 30,000 mm / s and mixtures of siloxanes and hydrophobic silanized (preferably trimethylsilanated) silica having a particle size in the range of about 10 mill in μπι to approx. 20 mil / µm and a specific surface area of over approx. 50 m / g. Suitable wax types include in crocrystal 1in wax compounds having a melting point in the range of about 25 65 ° C to approx. 100 ° C, a molecular weight in the range of about 400 to 1000 and a throughput value of at least approx. 6 measured at 25 ° C (77 ° F) by ASTM-D1321, and also paraffin wax compounds, synthetic wax compounds and natural wax compounds. Suitable phosphate esters include mono- and / or di-C

Enzymes suitable for use herein include those described in the disclosures of U.S. Patent No. 3,519,570 and U.S. Patent No. 3,533,139 to McCarty and McCarty et al. issued on July 7, 1970, and January 5, 1971. Suitable fluorescent agents include Blankophor MBBH (Bayer AG) and Tinopal CBS and EMS (Ciba Geigy). Photo activators are discussed in the description of EP A no.

DK 164706 B

18 57088, very preferred materials being zinc phthalocyanine tri- and tetrasulfonates. Suitable substance conditioning agents include di-C12 -C2 alkyl or alkenyl amines and ammonium and quaternary ammonium salts. Suitable bleaching catalysts are disclosed in the specification of EP Patent Application No. 72166 and EP Patent Application No.

84 302.774.9.

Suitable agents for gene deposition and dirt suspension agents include cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose.

The compositions of the invention are preferably prepared by spray drying an aqueous slurry including aluminum silicate and, when present, all potassium metal silicate and anionic surfactants. Nine trilotriacetate can also be spray dried or added separately to the spray dried base granules. Tripolyphosphate builders and carbonates are also dry mixed separately with the spray dried base granules. The aqueous slurry is mixed at a temperature in the range of approx. 45 to 90 ° C and the water content of the slurry 20 is adjusted to from approx. 25% to approx. 50%. The spray drying is carried out at an inlet temperature of the drying gas of from 250 to 390 ° C, preferably from 275 to 350 ° C, which gives a final moisture content in the range of from approx. 8 to 14% by weight.

In the following examples, the abbreviations used have the following meanings: C ^ LAS: Linear sodium C-benzene sulphonate TAS: Sodium number of crazy carbon sulphate 30 ^ 12 / 24A ^: C12 / 24 "a ^ 0 ^ su ^ at > sodium salt TAEn: Cured tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol C C TMAB: C ^-alkyltrimethylammonium bromide

Dobanol 45E7: Primary alcohol condensed with 7 moles of ethylene oxide.

TAED: Tetraacetylethylenediamine PAG: Pentaacetylglucose A0BS: Sodium p-acetoxybenzenesulfonate NOBS: Sodium nonanoyloxybenzenesulfonate

DK 164706 B

19 INOBS: Sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate INOBA: Sodium 3,5,5-trimethylhexanoyloxybenzenecarboxylate 5 EHOBS: Sodium 2-ethylhexanoyloxybenzenesulfonate

Silicate: Sodium silicate with a ratio of

SiO 2: Na 2 O at 1: 6

Sulfate: Anhydrous Sodium Sulfate Carbonate: Anhydrous Sodium Carbonate CMC: Sodium Carboxymethyl Cellulose

Silicone:: Containing 0.14 parts by weight of a mixture of siliconized silica and silicone at a weight ratio of 85:15, granulated 15 with 1.3 parts of sodium tripolyphosphate and 0.56 parts of tallow alcohol condensed with 25 parts of ethylene oxide NTA: Sodium nitrilotriacetate PCI: Copolymer of 3: 7 maleic acid / acrylic acid 20 with an average molecular weight of approx. 70,000, as sodium salt PC2: Polyacrylic acid with an average molecular weight of approx. 4500, as sodium salt.

Phosphate: Anhydrous pentane sodium tripolyphosphate (ortho / pyro content = 3%)

Perborate: Sodium perborate tetrahydrate of the nominal formula NaBO2 * 3H20-H2O2 Enzyme: Protease 30 EDTA: Sodium ethylenediamine tetraacetate

Explanatory Agent: Disodium 4,4'-bis (2-morpholino-4-anilino-5-triazin-6-ylamino) pathway Iben-2: 2'-disulfonate DETPMP: Diethylenetriamine penta (methylene phosphonic acid) marketed by Monsanto under the trademark Dequest 2060 EDTMP: Ethylene diamine tetra (methylene phosphonic acid) marketed by Monsanto under the trademark Dequest 2041

DK 164706B

20

Clay: Sodium-montmori11 onit

Magnesium: MgSO 4 H 2 O

Examples I to VIII 5

Granular detergent compositions are prepared as follows. A basic powder composition is first prepared by mixing all the components with the exception of Dobanol 45E7, bleach, bleach activator, enzyme, antifoam, phosphate and carbonate in a mixing vessel as an aqueous slurry at a temperature of approx. 55 ° C and with a water content of approx. 35%. The slurry is then spray dried with a gas inlet temperature of approx. 330 ° C to form base powder granules. The bleach activator, when present, is then blended with TAE® as the binder and extruded in a radial elongated particle extruder as described in the specification for European Patent Application No. 62,523. Blend agent activator noodles, bleach, enzyme, antifoam, phosphate and carbonate are then dry blended with the baking soda composition and finally Dobanol 45E7 is injected into the final mixture.

20

examples

I II III IV V VI VII VIII

25 C] 2LAS 5 9 8 8 4 4 3 5 TAS -33-4 --- C12 / I4AS 5--8-414 TAE25 0.5 0.5 0.8 0.3 0.8 0.8 0, 2 - 30 TAEn -1--0.6--1

Dobanol 45E7 2 - 4 2 4 8 10 5 C12TMAB 2 3 --- 2 2 - N0BS 3 ------ - 35 IN0BS 3 ----- INOBA 5 - - -.

EH0BS --- 2 ---- TAED .1-.3- ..

DK 164706 B

21

Examples (continued!

I II III IV V VI VII VIII

5 PAG 4 AOBS ------ 1 -

Perborate 25 20 10 24 20 18 24 28 EDTMP - 0.3 0.3 - - - 1.0 - DETPMP 0.4 - - 0.5 - - 0.1 10 EDTA 0.2 0.2 0.2 0 , 1 0.3 0.1 0.2 0.3

Laughs --- 6-4--

Magnesium (ppm) - 1000 750 - - - - 800 PCI 1.5 2 2 2 1 3 2.5 2 15 PC2 0.5 1 - 0.5 1 2 0.5 2

Zeolite A * 9 8 12 6 13 8 9 14

Phosphate 10 8 9 12 7 8 9 8 Soap 1--2-332

Carbonate 8 18 10 8 5 13 6 11 20 Silicate 1.5 2 2 1 7 2 2.5 1.5 NTA 4 6 3 5 5 6 4 6

Silicone 0.2 0.2 0.3 0.2 0.2 0.4 0.5 0.2

Enzyme 0.1 0.5 0.4 0.3 0.4 0.5 0.7 1.0

Clarifier 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

Sulfate, moisture and miscellaneous ................... to 100 ..................

3q * Zeolite A with 4 A pore size

The above compositions are low phosphate detergent compositions which exhibit excellent bleach stability, fabric protection and cleansing performance over the entire range of washing temperatures 33 having particularly good effect on Examples I to IV of the grease and particulate dirt at low washing temperatures.

Claims (11)

A granular detergent composition comprising, by weight, from 5% to 60% organic surfactant selected from anionic, 5 nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof and from 5 to 30% of all potassium carbonate, characterized by It further comprises: (a) from 6 to 18% by weight of a water-insoluble 10 µmini aluminum cation exchange material, (b) from 1% to 8% of an alkali metal salt of nine triototric acid, 15 (c) from 6 % to 14% phosphate builder wherein the phosphate builder is selected from sodium and potassium tripolyphosphates, less than 12% of which is pyrophosphate, 2o (d) from 5% to 35% inorganic or organic peroxy bleach, (e) from 0% to 10% organic peroxyacid bleach precursors; and (f) a heavy metal capture agent, the percentages of (a) + 2 (b) ranging from 13 to 27%. 30 Composition according to claim 1, characterized in that the amounts of (a) + 2 (b) are from 14 to 24, preferably from 16 to 21%. Composition according to claim 1 or 2, characterized in that it comprises from 7% to 16%, preferably from 8% to 14%, of a water-insoluble aluminum silicate cation exchange material. Composition according to any one of claims 1 to 3, characterized in that the cation exchange material has the general formula I Mz [(A102) z (SiO 2) y] x h 2 O (I) 5 wherein M represents a calcium exchangeable cation , z and y are at least 6; mole ratio of z to y is in the range of 1.0 to 0.5; and x is from 10 to 264; the aluminum silicate has a calcium ion exchange capacity of at least 200 mg equivalent CaCOg / gram, an ion exchange rate of calcium ions of at least 130 mg equivalent CaCO3 / liter / minute / gram / liter, and a particle size diameter of 0.1 µm to 10 µm. zm. Composition according to any one of claims 1-4, characterized in that it comprises from 3% to 7% of the nine trilotriacetic acid salt. Composition according to any one of claims 1-5, characterized in that it comprises from 8% to 12% 20 phosphate builders, less than 8% of which is pyrophosphate. Composition according to any one of claims 1-6, characterized in that it comprises at least 0.5% organic peroxyacid bleach precursors. Composition according to claim 7, characterized in that the organic peroxyacid blend precursors have the general formula II 30 0 RCL II wherein R represents an alkyl group containing from 6 to 12 carbon atoms, the longest linear alkyl chain extending and comprises the carboxyl carbon atom, contains from 5 to 10 carbon atoms, and L represents a leaving group whose conjugated acid has a pK value in the range of 6 to 13. DK 164706 B Composition according to any one of claims 1-8, characterized in that the heavy metal trapping agent is selected from water-soluble aminopolycarboxylates and aminopolyphosphonates with at least 4 acidic protons per molecule or 5 is water-insoluble clay of the smectite type selected from saponites, hectorites and sodium and calcium montmori11 onites. Composition according to any one of claims 1-9, characterized in that it further comprises from 0.5% to about 5% of a polycarboxylate polymer. Composition according to any one of claims 1-10, characterized in that it further comprises from 0.5% to 5% of all potassium metal in a cat. 15 20 25 30 35