WO1995002724A1 - Detergent compositions containing percarbonate and making processes thereof - Google Patents

Detergent compositions containing percarbonate and making processes thereof Download PDF

Info

Publication number
WO1995002724A1
WO1995002724A1 PCT/US1994/007877 US9407877W WO9502724A1 WO 1995002724 A1 WO1995002724 A1 WO 1995002724A1 US 9407877 W US9407877 W US 9407877W WO 9502724 A1 WO9502724 A1 WO 9502724A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
percarbonate
composition
alkali metal
hydrophobic material
accordance
Prior art date
Application number
PCT/US1994/007877
Other languages
French (fr)
Inventor
Gerard Marcel Baillely
Paul Amaat Raymond G. France
Carole Patricia D. Wilkinson
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/055Peroxyhydrates; Peroxyacids or salts thereof
    • C01B15/10Peroxyhydrates; Peroxyacids or salts thereof containing carbon
    • C01B15/106Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite, attapulgite
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds

Abstract

A granular detergent composition comprising an alkali metal percarbonate, characterized in that percarbonate has a mean particle size of from 250 to 900 micrometers, and that said compositions comprise a hydrophobic material, selected from silica, talc, zeolite DAY and hydrotalcit, in a weight ratio of alkali metal percarbonate to hydrophobic material, of from 4:1 to 40:1, preferably 7:1 to 20:1. Both laundry detergent compositions including laundry additives and automatic dishwashing compositions are encompassed by the term 'detergent composition' herein. Making processes thereof are also described.

Description

DETERGENT COMPOSITIONS CONTAINING PERCARBONATE AND MAKING

PROCESSES THEREOF

Technical Field

The present invention relates to detergent compositions containing percarbonate bleach, and a hydrophobic material such as hydrophobic silica at narrowly defined ratios to provide optimum bleach stability.

The invention also encompasses processes to make such compositions.

Background of the Invention

The inorganic perhydrate bleach most widely used in laundry detergent compositions is sodium perborate in the form of either the monohydrate or tetrahydrate. However, an increased interest in other perhydrate salts is being observed, of which sodium percarbonate is the most readily available.

Detergent compositions containing sodium percarbonate are known in the art. Sodium percarbonate is an attractive perhydrate for use in detergent compositions because it dissolves readily in water, is weight efficient and, after giving up its available oxygen, provides a useful source of carbonate ions for detergency purposes. The inclusion of percarbonate salts in laundry detergent compositions has been restricted hitherto by the relative instability of the bleach. In particular, percarbonate salts decompose rapidly when stored in a moist and/or warm atmosphere. It is known that acceptable storage characterisitics may however be obtained through the protection of the carbonate by coating the crystalline product, or by the inclusion of stabilizing agents during its manufacture, or both. A variety of suitable coating agents have been proposed including silicates and mixtures of inorganic sulphate and carbonate salts.

In WO92/06163 are described percarbonate-containing compositions wherein the Equilibrium Relative Humidity as well as the level of heavy metal ion have to be carefully controlled to ensure percarbonate stability.

There is still, however, the need to improve storage stability of the percarbonate bleach, and to achieve this in all types of detergent compositions, including compositions made by the various making processes currently available.

The Applicants have however unexpectedly discovered that when a hydrophobic material selected from silica, talcs or waxes is used into the detergent compositions, in certain ratios to percarbonate particles of a determined size, and particularly when said hydrophobic material such as silica is used as dusting agent onto said percarbonate particles prior to their incorporation into the composition, the storage stability of the percarbonate is remarkably improved, in all types of compositions, including dishwashing compositions adapted for use in automatic dishwashing.

The use of silica as flow aid for detergent granules is known in the art, although the art usually does not distinguish between the different types of silica most advantageous for this purpose; in many cases, the use of precipitated silicas which are mainly hydrophilic, are described.

JP 61 069897, laid open 10th April, 1986 states that aluminosilcate, silicon dioxide, bentonite and clay having an average particle diameter of not more than 10 micrometers can be used as a surface modifier at a level of from 0;5% to 35%; Percarbonate is merely mentioned among the bleach ingredients.

Summary of the Invention

The present invention relates to a granular detergent composition comprising an alkali metal percarbonate, characterized in that percarbonate has a mean particle size of from 250 to 900 micrometers, and that said compositions comprise a hydrophobic material selected from silica, talc, Zeolite DAY and hydrotalcit, in a weight ratio of alkali metal percarbonate to hydrophobic material of from 4:1 to 40:1, preferably 7:1 to 20:1

Both laundry detergent compositions including laundry additives and automatic dishwashing compositions are encompassed by the term "detergent composition" herein. Making processes thereof are also described.

Detailed Description of the Invention

Percarbonate

The ■ laundry detergent or automatic dishwashing compositions herein typically contain from 1% to 40%, preferably from 3% to 30% by weight, most preferably from 5% to 25% by weight of an alkali metal percarbonate bleach in the form of particles having a mean size from 250 to 900 micrometers, preferably 500 to 700 micrometers. Laundry additives typically contain from 20% to 80% of said percarbonate particles.

The alkali metal percarbonate bleach is usually in the form of the sodium salt. Sodium percarbonate is an addition compound having a formula corresponding to 2 a2Cθ3 3H2O2. to enhance storage stability the percarbonate bleach can be coated with e.g. a further mixed salt of an alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1, 66,799, granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:2000 to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to 1:19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which as the genral formula Na2S04.n.Na2C03 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other suitable coating materials are sodium silicate, of Siθ2:Na2θ ratio from 1.6:1 to 2.8:1, and magnesium silicate.

Commercially available carbonate/sulphate coated percarbonate bleach may include a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene I, 1- diphosphonic acid (HEDP) or an aminophosphonate, that is incorporated during the manufacturing process.

Preferred heavy metal sequestrants for incorporation as described herein above include the organic phosphonates and amino alkylene poly(alkylene phosphonates) such as the alkali metal ethane 1-hydroxy diphosphonates, the nitrilo trimethylene phsphonates, the ethylene diamine tetra methylene phosphonates and the diethylene triamine penta methylene phosphonates.

Hydrophobic material

The compositions herein further comprise as an essential ingredient a selected hydrophobic material, in a weight ratio with percarbonate of 4:1 to 40:1, preferably 7:1 to 20:1. Said material can be selected from hydrophobic silica, hydrotalcite, and zeolite DAY, and mixtures thereof.

Hydrophobic silica is the preferred material for use herein; silica is a highly dispersed amorphous silicon dioxide. It is commercially available in many forms. Most commonly silica has a tapped density of from 50 g/1 to 120 g/1. The specific surface area of the particles ranges from 25 square metres per gram to 800 square metres per gram.

The surface of silica particles can be chemically modified to change their behaviour with respect to water. For example,silica particles may be treated with organosilanes to make the particles predominantly hydrophobic. It has been found that silicas must be hydrophobised to be useful in the present invention.

In commercial practice, silica is usually prepared by one of two techniques; either by precipitation or by high temperature flame hydrolysis. Precipitated silicas generally have an agglomerate size of from 3 micrometers to 100 micrometers, whereas fumed silicas (made by flame hydrolysis) usually have primary particles which are generally spherical and have an average diameter of from 7nm to 40nm. Fumed silicas having an average primary particle size of from 7 to 25 nanometers are preferred in the present invention.

Examples of silicas which are particularly useful in the present invention include those supplied by Degussa AG, Frankfurt, Germany under the Trade Name "Aerosil". Aerosil R972 has been found to be particularly useful. This silica is a hydrophobic, fumed silica which has a specific surface area of about 110 square metres per gram and an average primary particle size of 16 nanometers. Talc is a trioctahedral mont orillonoid, and is described in e.g. "An introduction to clay colloid chemistry", van Olphen, H, page 69.

Talc has the structure : Mg3Si O^o (OH)2

Hydrotalcite has the generalised structure:

M(k+m)N(n+p) (OH)2Azy_ . xH20 :

where M is a monolvalent or divalent cation; N is a 3+ or 4+ cation; k, m, n, p are the individual mole fractions of 1+, 2+, 3+, 4+ cations respectively, so k + m + n + p = l AZy_ is any anion of charge y- and mole fraction Z; k + 2m + 3n +4p - zy = 0 and x = 1 to 100.

Hydrotalcites are described in e.g. EP-A-431 867 Specific examples of hydrotalcites have the structure :

Mg6 A12 (OH) 16 C03.4H20

Mg4 A12 (OH) 12 C12.3H20

Zn4 A12 (OH) 12 (NO3)2.xH20

Mg4 A14 (OH)y cl.35zH20 y = 16-35; z=2-5

Zeolite DAY is supplied under the trade Name "Wessalith" by

Degussa.

Zeolite DAY has the following structure :

Naz[A102) z. (Siθ2)y] .XH2O wherein z and y are at least about 6, and z is from about 10 to about 264.

In one embodiment of the present invention, the laundry detergent compositions herein also comprise a surface-active agent and a builder. Surface-active agent :

Aniόnic Surfactants

In the preferred embodiment herein, where the detergent compositions herein is a laundry detergent composition, compositions of the present invention usually contain one or more anionic surfactants as described below.

Alkyl Ester Sulfonate Surfactant

Alkyl Ester sulfonate surfactants hereof include linear esters of Cg-C20 carboxylic acids (i.e. fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society1" 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprises alkyl ester sulfonate surfactants of the structural formula:

0

3 II 4

R - CH - C - OR

Figure imgf000009_0001

3 wherein R is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R is a C^-C8 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.

Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine,

3 4 and triethanc .amine. Preferably, R is cιn~c i6 alky1' anci R is methyl, ethyl or isopropyl. Especially preferred are the

3 methyl ester sulfonates wherein R is C,.-C,g alkyl.

Alkyl Sulfate Surfactant Alkyl sulfate surfactants hereof are water soluble salts or acids or the formula ROSO3M wherein R preferably is a Cιo-c 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c10_c20 alkyl component, more preferably a C^-C^g alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quarternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) . Typically, alkyl chains of Ci2"16 are preferred for lower wash temperatures (e.g., below about 50°C) and Ci6~18 alkyl chains are preferred for higher wash temperatures (e.g., above about 50°C) .

Alkyl Alkoxylated Sulfate Surfactant

Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSθ3M wherein R is an unsubstituted CIQ~C24 alkyl or hydroxyalkyl group having a c10~c24 alkyl component, preferably a Ci2-C20 alkyl or hydroxyalkyl, more preferably C^-C^g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are Ci2~c18 alkyl polyethoxylate (1.0) sulfate, Ci2"Cι E(1.0)M) , c12~c18 alkyl polyethoxylate (2.25) sulfate, C12-C18E(2.25)M) , C12-C18 alkyl polyethoxylate (3.0) sulfate C^-CigE(3.0) , and C^-C^ alkyl polyethoxylate (4.0) sulfate Ci2-Ci8E(4.0)M) , wherein M is conveniently selected from sodium and potassium.

Other Anionic Surfactants

Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulphonates, g-C22 primary or secondary alkanesulphonates, C -C2 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, c8~c24 alkylpolyglycolethersulfates (containing up to 10 moles of ehtylene oxide) ; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated Ci2~Cιg monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below) , branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH20)kCH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al . at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference) .

When included therein, the laundry detergent compositions of the present invention typically comprise from about 1 % to about 40 %, preferably from about 3 I to about 20 I by weight of such anionic surfactants.

Nonionic Surfactants

While any nonionic surfactant may be normally employed in the present invention, two families of nonionics have been found to be particularly useful. These are nonionic surfactants based on alkoxylated (especially ethoxylated) alcohols, and those nonionic surfactants based on amidation products of fatty acid esters and N-alkyl polyhydroxy amine. The amidation products of the esters and the amines are generally referred to herein as polyhydroxy fatty acid amides. Particularly useful in the present invention are mixtures comprising two or more nonionic surfactants wherein at least one nonionic surfactant is selected from each of the groups of alkoxylated alcohols and the polyhydroxy fatty acid amides.

Suitable nonionic surfactants include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water- soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Particularly preferred for use in the present invention are nonionic surfactants such as the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.

Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing ,from 8 to 22 c rbon atoms, in either straight chain or branched configura on, with an average of up to 25 moles of ethylene oxide per more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide. Most preferred are condensation products of alcohols having an alkyl group containing from about 12 to 15 carbon atoms with an average of about 3 moles of ethylene oxide per mole of alcohol.

The nonionic surfactant system can also include a polyhydroxy fatty acid amide component.

Polyhydroxy fatty acid amides may be proc ced by reacting a fatty ac ' ester and an N-alkyl polyhydroxy amine. The preferrec mine for use in the present invention is N-(R1)- CH2 (CH20H 4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester. Most preferred is the reaction product f N-methyl glucamine with C12-C20 fatty acid methyl ester.

Methods of manufacturing polyhydroxy fatty acid amides have been described in WO 92 6073, published on 16th April, 1992. This application describes the preparation of polyhydroxy fatty acid amides in the presence of solvents. In a highly preferred embodiment of the invention N-methyl glucamine is reacted with a C12-C20 methyl ester. It also says that the formulator of granular detergent compositions may find it convenient to run the amidation reaction in the presence of solvents which comprise alkoxylated, especially ethoxylated (EO 3-8) C12-C14 alcohols (page 15, lines 22-27) . This directly yields nonionic surfactant systems which are preferred in the present invention, such as those comprising N-methyl glucamide and C12-C14 alcohols with an average of 3 ethoxylate groups per molecule.

Nonionic surfactant systems, and granular detergents made from such systems have been described in WO 92 6160, published on 16th April, 1992. This application describes (example 15) a granular detergent composition prepared by fine dispersion mixing in an Eirich RV02 mixer which comprises N-methyl glucamide (10%), nonionic surfactant (10%) .

Both of these patent applications describe nonionic surfactant systems together with suitable manufacturing processes for their synthesis, which have been found to be suitable for use in the present invention.

The polyhydroxy fatty acid amide may be present in compositions of the present invention at a level of from 0% to 50% by weight of the detergent component or composition, preferably from 5% to 40% by weight, even more preferably from 10% to 30% by weight.

Other Surfactants

The laundry detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as nonionic surfactants other than those already described herein, including the semi-polar nonionic amine oxides described below.

Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula :

[R2(0R3)y] [R4(OR3)yJ2R5N+X- wherein R2 is an alkyl or alkyl benzyl group having from about 8 tc about 18 carbon atoms in the alkyl chain, each R3 is selecte from the group consisting of -CH2CH2-,

-CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C]_- C4 alkyl, C2.-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups,

-CH2COH-CHOHCOR6CHOHCH2OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R^ is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Other cationic surfactants useful herein are also described in US Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.

When included therein, the laundry detergent compositions of the present invention typically comprise from 0 % to about 25 %, preferably form about 3 % to about 15 % by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which .the aliphatic radical can be straight- or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water- solubil: ring group e.g. carboxy, sulfonate, sulfate. See U S. Pat nt No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants. When included therein, the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 10 % by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivates of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quarternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at columns 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.

When included therein, the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 10 % by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting af alkyl groups and hydrocyalkyl groups containing form about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of form about 10 to about 18 carbon atoms and 2 moieties selected form the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula :

0 R3(OR4)xN(R5)2 Builder

The compositions herein preferably contain a builder, most preferably non-phosphate detergent builders. These can include, but are not restricted to alkali metal carbonates, bicarbonates, silicates, aluminosilicates, carboxylates and mixtures of any of the foregoing. The builder system is present in an amount of from 25% to 80% by weight of the composition, more preferably from 30% to 60% by weight.

Suitable silicates are those having an Siθ2 : Na2θ ratio in the range from 1.6 to 3.4, the so-called amorphous silicates of Siθ2 : Na2θ ratios from 2.0 to 2.8 being preferred.

Within the silicate class, highly preferred materials are crystalline layered sodium silicates of general formula

NaMSixθ2χ + l-yH20

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the general formula above has a value of 2,3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the , , and forms of Na2Si2θ5. These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is -Na2Si2θ5, NaSKS- 6. Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.

Whist a range of aluminosilicate ion exchange materials can be used, preferred sodium aluminosilicate zeolites have the unit cell formula

Naz[ (A102)2- (Si02)y] -xH20 wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula

Figure imgf000018_0001
wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.

The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, P and MAP, the latter species being described in EPA 384070. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material is a Zeolite A having the formula Na12t (A102) 12 (Si02) 12] -xH20 wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 5 microns.

Suitable carboxylate builders containing one carboxy- group include lactic acid, glycollic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686 and 2,446,687 „..nd U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing ti ae carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxytr ycarboxylate materials such as 2-oxa-l,1,3-propane tric rboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829,1, and the 1,2,2-ethane tetracarboxylates ,1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2, 3, , 5-tetrahydrofuran - cis, cis, cis- tetracarboxylates, 2, 5-tetrahydrofuran -cis- dicarboxylates, 2,2, 5, 5,-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6- hexane hexacarboxylates and carbxoymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivates disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems useful in the present invention.

In another embodiment of the invention, are provided Automatic Dishwashing Compositions :

Automatic dishwashing compositions typically contain, in addition to the percarbonate and hydrophobic material of the invention, a builder, such as described above, and a source of alkalinity, such as silicate or carbonate, those ingredients amounting to up to 70% of the formulation. Optional ingredients include polymers and enzymes.

In still another embodiment of the invention, are provided Laundry Additive Compositions : such compositions typically contain in addition to the percarbonate and hydrophobic material of the invention, a builder and a source of alkalinity. Optional Ingredients

Other ingredients which are known for use in detergent compositions may also be used as optional ingredients in the various embodiments of the present invention, such as bleach activators, other bleaching agents, polymers, enzymes, suds suppressing agents, as well as dyes, fillers, optical brighteners, pH adjusting agents, non builder alkalinity sources, enzyme stability agents, hydrotopes, perfumes.

Bleach activators

The present compositions, especially the laundry detergent compositions/additives, preferably contain from 1% to 20% by weight of the composition, preferably from 2% to 15% by weight, most preferably from 3% to 10% by weight of a peroxyacid bleach activator.

Peroxyacid bleach activators (bleach precursors) as additional bleaching components in accord with the invention can be selected from a wide range of class and are preferably those containing one or more N-or 0-acyl groups.

Suitable classes include anhydrides, esters, amides, and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789. The most preferred classes are esters such as are disclosed in GB-A-836 988, 864,798, 1 147 871 and 2 143 231 and amides such as are disclosed in GB-A-855 735 and 1 246 338.

Particularly preferred bleach activator compounds as additional bleaching components in accord with the invention are the N-,N,N'N' tetra acetylated compounds of the formula

Figure imgf000022_0001

where x can be 0 or an integer between 1 and 6.

Examples include tetra acetyl methylene diamine (TAMD) in which x=l, tetra acetyl ethylene diamine (TAED) in which x=2 and Tetraacetyl hexylene diamine (TAHD) in which x=6. These and analogous compounds are described in GB-A-907 356. The most preferred peroxyacid bleach activator as an additional bleaching component is TAED.

Another preferred class of peroxyacid bleach compounds are the amide substituted compounds of the following general formulae :

R1 - - L

Figure imgf000022_0002

wherein R is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to about 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example. tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R1 and R^ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

In addition to percarbonate, the compositions herein may also contain another bleaching system such as perborate and activator, or a preformed organic peracid or perimidic acid, such as N,N phthaloylaminoperoxy caproic acid, 2-carboxy- phtaloylaminoperoxy caproic acid, N,N phthaloylaminoperoxy valeric acid, Nonyl amide of peroxy adipic acid, 1,12 diperoxydodecanedoic acid, Peroxybenzoic acid and ring substituted peroxybenzoic acid, Monoperoxyphtalic acid (magnesium salt, hexhydrate) , Diperoxybrassylic acid.

Polymers

Also useful are various organic polymers, some of which also may function as builders to improve detergency. Included among such polymers may be mentioned sodium carooxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate) , polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.

Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other useful polymers include species known as soil release polymers, such as described in EPA 185 427 and EPA 311 342.

Enzymes

Preferred enzymatic materials include the commercially available amylases, netural and alkaline proteases, lipases, esterases, and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradnames Alcalase and Savinase by Novo Industries A/S (Denmark) • and Maxatase by International Bio- Synthetics, Inc. (The Netherlands) . Preferred amylases include, for example, -amylases obtained from a special strain of B licheniforms, described in more detail in GB- 1,296,839 (Novo) . Preferred commercially available amylases include for example, Rapidase, sold by International Bio- Synthetics Inc. and Termamyl, sold by Novo Industries A/S.

A preferred lipase enzyme is manufactured and sold by Novo Industries A/S (Denmark) under the trade name Lipolase and mentioned along with other suitable lipases in EP-A-0258068 (Novo) .

Suitable cellulases are described in e.g. WO-92/13057.

Process Details

In one process embodiment herein, the percarbonate particles are coated with the hydrophobic material herein prior to being incorporated with the remainder of the detergent ingredients to form the laundry detergent or automatic dishwashing or laundry additive compositions herein. The percarbonate particles can optionally be first coated with a water-soluble alkali metal salt, as described above; optionally too, said coated particles can further be sprayed-on with nonionic surfactant, and the hydrophobic material herein then dusted upon, to provide a final coating; This latter step can be conducted in a rotating drum, mixer, or a fluidized bed.

The liquid can be sprayed onto the percarbonate in a low shear mixer or rotating drum; the percarbonate particles are rolled within the drum/mixer in the "wet" state causing them to become sticky. Immediately afterwards, while rotating the drum, the hydrophobic material herein is slowly added to the mixer. The hydrophobic material herein coats the percarbonate and makes the particles free flowing, while protecting the percarbonate against decomposition. The invention can be practiced as a batch or continuous process. Any type of mixer may be found to be suitable for this purpose.

Still another process which is suited to the present invention is that of fluidized-bed spray. In a fluidized- bed spray process, the nonionic is sprayed into a fluidized bed of percarbonate particles. The solid particles are largely separate from one another in the fluidized bed, i.e. the fluidized state, and are therefore accessible all round to the spray drops when solution is sprayed into the bed. To obtain a fine distribution of the solution, spraying can be carried out by means of a two component nozzle. Immediately afterwards the hydrophobic material herein can be added in the fluid bed or in a rotating drum/mixer.

In a second embodiment herein, particularly suitable for making laundry detergent compositions, the hydrophobic material herein is added as part of a flow aid at a suitable time of the making process; said addition being prior or subsequent to the addition of the percarbonate to a detergent powder. The detergent powder herein may be made by many methods which are known to the man skilled in the art including dry- mixing, spray drying and various types of granulation techniques, such as encapsulation, compaction, extrusion, grinding, or combinations of these techniques.

One particularly useful method of granulation is known as agglomeration. The term agglomeration is taken herein to mean the build-up of small particles to form the granular detergent having the required particle size.

Preferably, an additional step consists in spraying some or all of the nonionic surfactant on to detergent granules in one a suitable mixer or rotating drum.

The following steps may be used in a preferred embodiment of the present invention: i) making a granular detergent powder having a bulk density of at least 650 g/1 ; ii) spraying a nonionic surfactant on to the granular detergent powder of step i) ; iii)mixing the product of step ii) with a flow aid which comprises the hydrophobic material herein, wherein the premixed powder is used at a level of from 3% to 15% by weight of the finished detergent composition.

The granular detergent powder in step i) is preferably made by agglomeration of detergent pastes, most preferably using a process of fine dispersion mixing or granulation. Even more preferably the detergent agglomerates are then dry mixed with other optional ingredients.

The process is described in more details in the Applicant's co-pending European Patent application no. 92870138.2. Step iii) above can be conducted with any suitable means, such as rotating drums or lower shear mixers, the flow aid compositions preferably of ploughshare type.

Ploughshare mixers are available from e.g. Lδdige Machinebau GmbH, Paderborn Germany, and Drain Werke GmbH, Mannheim Germany.

The flow aid contains from 0.5% to 30% of hydrophobic material preferably silica. The rest of the flow aid is typically aluminosilicate such as described above, - the crystalline species being preferred, and especially partially hydrated forms of aluminosilicates, with up to 15% hydration level, being suitable.

Examples

In these examples the following abbreviations have been used :

C45AS : Sodium C14-C15 alkyl sulfate

C35AE3S : C13-C15 alkyl ethersulfate containing an average of three ethoxy groups per mole CMC : Sodium carboxymethyl cellulose C25E3 : A Ci2-15 primary alcohol condensed with an average of 3 moles of ethylene oxide TAED : Tetraacetyl ethylene diamine

Example I

The following granular laundry detergent composition was prepared :

% by weight

Anionic surfactant agglomerate * 30 Layered silicate compacted granule (supplied by Hoechst under trade name SKS-6) 18

Percarbonate ** 25

TAED agglomerate 9

Suds suppressor agglomerate 2

Perfume encapsulate 0.2

Granular dense soda ash 8.5

Granular acrylic-maleic copolymer 3.0

Enzymes 3.5

Granular soil release polymer 0.5

*Anionic surfactant agglomerates were made from a 78% active surfactant paste which comprises C45AS/C35AE3S in the ratio of 80:20. The paste was agglomerated with a powder mixture according to the process described in EPA510746. The resulting anionic surfactant granule had a composition of 30% C45AS, 7.5% C35AE3S, 24% zeolite, 20% carbonate, 2.5% CMC, 12% acrylic-maleic co-polymer, and the balance of moisture.

** Percarbonate coated with 2.5% carbonate/sulphate with mean particle size of 500 microns.

The mixture of granular ingredients listed above was placed inside a 140 litre rotating' drum that operates at 25 rpm. While operating the drum a mixture of nonionic surfactant (C25E3) and a 20% aqueous solution of optical brightener at ratios of 14:1 were sprayed onto the granular mixture to a level of 7% by weight of the granular components. The spraying time was about 1-2 minutes. Immediately afterwards, perfume was sprayed on, at a level of 0.5% by weight of the granular components, while rotating the drum.. Then, without stopping the rotation of the drum, a flow aid was slowly added to the mixer, taking about 30 seconds. The level and type of flow aids used is given below in Table 1. Once the addition of flow aid was finished, the mixer was allowed to rotate for about 1 minute and was then stopped. The finished product was then removed from the rotating drum.

The following flow aids were prepared using Zeolite A and hydrophobic silica Aerosil R792 (Trade name) both supplied by Degussa. Mixtures were prepared in a Lδdige FM130 (Trade name) by operating at 165 rpm for 0.5 minutes.

Table 1 :

Figure imgf000029_0001

The compositions were stored at 35°C/80% Equilibrium Relative Humidity (eRH) in cartonboard boxes. The % percarbonate recovery was measured :

Storage conditions Reference Composition A Example 1

2 weeks 35°C/80% eRH 71 80

3 weeks 35°C/80% eRH 65 75

4 weeks 35°C/80% eRH 54 66

Claims

What is claimed is:
1. A granular detergent composition comprising an alkali metal percarbonate, characterized in that percarbonate has a mean particle size of from 250 to 900 micrometers, and that said compositions comprise a hydrophobic material, selected from silica, talc, zeolite DAY and hydrotalcit, in a weight ratio of alkali metal percarbonate to hydrophobic material of from 4:1 to 40:1.
2. A composition in accordance with claim 1 where said hydrophobic material is silica.
3. A composition in accordance with claim 1 wherein the weight ratio of alkali metal percarbonate to hydrophobic silica is from 7:1 to 20:1.
4. A composition in accordance with claims 2 and 3 wherein the hydrophobic silica is a fumed silica having an average primary particle size of from 7 to 25 nanometers.
5. A composition in accordance with claims 1-4 which is a laundry detergent composition containing a surface- active agent, and a builder, and has a bulk density of at least 650 g/1.
6. A ςomposition in accordance with claims 1-4, which is an automatic dishwashing composition containing a builder.
7. A composition in accordance with claims 1-4 which is a laundry detergent additive containing from 20 to 80% of the percarbonate.
8. A composition in accordance with claims 1-7 wherein the alkali metal percarbonate particles are • coated with the hydrophobic material.
9. A composition in accordance with claim 1-8 wherein the percarbonate particles are coated with a water soluble alkali metal salt, possibly further coated with nonionic surfactant, and the hydrophobic material is present at the outside layer.
10. A process for making a granular detergent composition according to claim 5 which comprises the steps of making a detergent powder, adding said alkali metal percarbonate, and adding a powdery flow aid containing the hydrophobic material.
11. A process according to claim 10 wherein the detergent powder is made by dry-mixing, spray-drying, or by a granulation process selected from encapsulation, compaction, extrusion, grinding, or a combination of these techniques.
12. A process for making a granular detergent composition according to claims 5, 6 and 7 wherein the alkali metal percarbonate particles are premixed with the hydrophobic material and the resulting particles are dry-mixed with the rest of the composition.
13. A process according to claim 12 which comprises the steps of i) spraying onto the percarbonate particles a nonionic surfactant, and ii) mixing the product of step i) with hydrophobic material.
14. A process for making a granular detergent composition according to claim 13 wherein the alkali metal percarbonate particles used in step i) have been pre- coated with a water-soluble alkali metal salt.
15. A process according to claims 9-14 wherein said hydrophobic material is silica.
PCT/US1994/007877 1993-07-14 1994-07-13 Detergent compositions containing percarbonate and making processes thereof WO1995002724A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93870139 1993-07-14
EP93870139.8 1993-07-14

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CA 2167158 CA2167158C (en) 1993-07-14 1994-07-13 Detergent compositions containing percarbonate and making processes thereof
EP19940922138 EP0708855A4 (en) 1993-07-14 1994-07-13 Detergent compositions containing percarbonate and making processes thereof
JP50470095A JPH09502743A (en) 1993-07-14 1994-07-13 Detergent compositions containing percarbonate and their preparation
US08581554 US5780410A (en) 1993-07-14 1994-07-13 Detergent compositions containing percarbonate and making processes thereof

Publications (1)

Publication Number Publication Date
WO1995002724A1 true true WO1995002724A1 (en) 1995-01-26

Family

ID=8215368

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/007877 WO1995002724A1 (en) 1993-07-14 1994-07-13 Detergent compositions containing percarbonate and making processes thereof

Country Status (5)

Country Link
EP (1) EP0708855A4 (en)
JP (1) JPH09502743A (en)
CN (1) CN1130928A (en)
CA (1) CA2167158C (en)
WO (1) WO1995002724A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5650017A (en) * 1994-07-04 1997-07-22 Lever Brothers Company, Division Of Conopco, Inc. Washing process and composition
WO1997035951A1 (en) * 1996-03-27 1997-10-02 Solvay Interox (Société Anonyme) Compositions containing sodium percarbonate
EP1111035A2 (en) * 1999-12-21 2001-06-27 Henkel Kommanditgesellschaft auf Aktien Combination of active agents for incorporation in detergent compositions
WO2004058932A1 (en) * 2002-12-20 2004-07-15 Degussa Ag Sodium percarbonate particles with improved storage stability
US7435714B2 (en) 2002-12-20 2008-10-14 Evonik Degussa Gmbh Liquid detergent and cleaning agent composition comprising a multi-coated bleach particle
US7588697B2 (en) 2003-05-07 2009-09-15 Evonik Degussa Gmbh Coated sodium percarbonate granules with improved storage stability
US7718592B2 (en) 2004-11-11 2010-05-18 Degussa, Gmbh Sodium percarbonate particles having a shell layer comprising thiosulfate

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1263258A (en) * 1918-01-03 1918-04-16 Otto Liebknecht Production of percarbonates.
US2167997A (en) * 1938-02-16 1939-08-01 Du Pont Preparation of metal percarbonates
US2625514A (en) * 1949-12-24 1953-01-13 Colgate Palmolive Peet Co Noncaking abrasive detergent compositions
US4178351A (en) * 1977-10-31 1979-12-11 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the stabilization of sodium percarbonate
US4208295A (en) * 1978-01-25 1980-06-17 Kao Soap Co., Ltd. Bleaching detergent composition
US4444674A (en) * 1980-11-06 1984-04-24 The Procter & Gamble Company Granular bleach activator compositions and detergent compositions containing them
US5149456A (en) * 1989-12-04 1992-09-22 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions comprising a hydrotalcite-like material for reducing colorant migration
US5194176A (en) * 1990-04-06 1993-03-16 Fmc Corporation Peroxygen laundry bleach

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951838A (en) * 1973-10-10 1976-04-20 E. I. Du Pont De Nemours And Company Silica sol stabilizers for improving the stability of sodium percarbonate in solid bleaches and detergents
FR2393846A1 (en) * 1977-06-09 1979-01-05 Ici Ltd Liquid detergent compsn. used as washing powder substitute - contg. nonionic polyether surfactant, active additive and dispersant
US4215990A (en) * 1978-04-14 1980-08-05 Purex Corporation Peroxygen bleaching and laundering compositions
JPS55102696A (en) * 1979-02-01 1980-08-06 Jiyonson Kk Oxygen type detergent bleaching composition
JPH045080B2 (en) * 1984-09-14 1992-01-30
JPH02283800A (en) * 1989-04-25 1990-11-21 Kao Corp Granular detergent composition
JP2850422B2 (en) * 1989-12-14 1999-01-27 三菱瓦斯化学株式会社 Secure sodium percarbonate granules
DE4221736A1 (en) * 1992-07-02 1994-01-05 Henkel Kgaa Solid detergent formulation with improved dispensing behavior

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1263258A (en) * 1918-01-03 1918-04-16 Otto Liebknecht Production of percarbonates.
US2167997A (en) * 1938-02-16 1939-08-01 Du Pont Preparation of metal percarbonates
US2625514A (en) * 1949-12-24 1953-01-13 Colgate Palmolive Peet Co Noncaking abrasive detergent compositions
US4178351A (en) * 1977-10-31 1979-12-11 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the stabilization of sodium percarbonate
US4208295A (en) * 1978-01-25 1980-06-17 Kao Soap Co., Ltd. Bleaching detergent composition
US4444674A (en) * 1980-11-06 1984-04-24 The Procter & Gamble Company Granular bleach activator compositions and detergent compositions containing them
US5149456A (en) * 1989-12-04 1992-09-22 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions comprising a hydrotalcite-like material for reducing colorant migration
US5194176A (en) * 1990-04-06 1993-03-16 Fmc Corporation Peroxygen laundry bleach

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0708855A4 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5650017A (en) * 1994-07-04 1997-07-22 Lever Brothers Company, Division Of Conopco, Inc. Washing process and composition
WO1997035951A1 (en) * 1996-03-27 1997-10-02 Solvay Interox (Société Anonyme) Compositions containing sodium percarbonate
EP1111035A2 (en) * 1999-12-21 2001-06-27 Henkel Kommanditgesellschaft auf Aktien Combination of active agents for incorporation in detergent compositions
EP1111035A3 (en) * 1999-12-21 2003-04-23 Henkel Kommanditgesellschaft auf Aktien Combination of active agents for incorporation in detergent compositions
WO2004058932A1 (en) * 2002-12-20 2004-07-15 Degussa Ag Sodium percarbonate particles with improved storage stability
US7435714B2 (en) 2002-12-20 2008-10-14 Evonik Degussa Gmbh Liquid detergent and cleaning agent composition comprising a multi-coated bleach particle
US7588697B2 (en) 2003-05-07 2009-09-15 Evonik Degussa Gmbh Coated sodium percarbonate granules with improved storage stability
US7718592B2 (en) 2004-11-11 2010-05-18 Degussa, Gmbh Sodium percarbonate particles having a shell layer comprising thiosulfate

Also Published As

Publication number Publication date Type
JPH09502743A (en) 1997-03-18 application
EP0708855A1 (en) 1996-05-01 application
CA2167158C (en) 1999-11-02 grant
CN1130928A (en) 1996-09-11 application
CA2167158A1 (en) 1995-01-26 application
EP0708855A4 (en) 1996-07-17 application

Similar Documents

Publication Publication Date Title
US4746445A (en) Process for manufacturing bentonite agglomerates
US4609473A (en) Bentonite-sulfate fabric softening particulate agglomerate, processes for manufacture and use thereof, and detergent compositions containing it
US5698504A (en) Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors
US4849125A (en) Process for preparing a phosphate-reduced granular detergent
US6133216A (en) Coated ammonium nitrile bleach activator granules
US4308151A (en) Detergent-compatible fabric softening and antistatic compositions
US6046149A (en) Detergent compositions
US5646101A (en) Machine dishwashing detergents containing an oxygen bleach and an anti-tarnishing mixture of a paraffin oil and sequestrant
US5919747A (en) Preparation of secondary alkyl sulfate particles with improved solubility
US5259981A (en) Detergent compositions
US5716923A (en) Laundry detergent containing a coated percarbonate and an acidification agent to provide delayed lowered pH
US20020013242A1 (en) Detergent-package combination
US6747000B2 (en) Process for making solid cleaning components
US5516449A (en) Detergent compositions
US6015784A (en) Secondary alkyl sulfate particles with improved solubility by compaction/coating process
US5705466A (en) High bulk density granular detergents containing a percarbonate bleach and a powdered silicate
US4136051A (en) Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation
US6716808B1 (en) Detergent compositions comprising hybrid zeolite builders containing an occluded nonsilicate
US5411673A (en) Peroxyacid bleach precursor compositions
EP0622454A1 (en) Structuring liquid nonionic surfactants prior to granulation process
WO1995012658A1 (en) LAUNDRY DETERGENTS CONTAINING A COATED PERCARBONATE AND AN ACIDIFICATION AGENT TO PROVIDE DELAYED LOWERED pH
US5747438A (en) Machine dishwashing detergent containing coated percarbonate and an acidification agent to provide delayed lowered pH
WO2000018856A1 (en) Detergent granules
US5783546A (en) Amylase-containing detergent compositions
US5821207A (en) Method for producing fine solid builder particle

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN FI JP NO US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994922138

Country of ref document: EP

ENP Entry into the national phase in:

Ref country code: CA

Ref document number: 2167158

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 2167158

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 08581554

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1994922138

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1994922138

Country of ref document: EP