CA2187311A1 - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- CA2187311A1 CA2187311A1 CA002187311A CA2187311A CA2187311A1 CA 2187311 A1 CA2187311 A1 CA 2187311A1 CA 002187311 A CA002187311 A CA 002187311A CA 2187311 A CA2187311 A CA 2187311A CA 2187311 A1 CA2187311 A1 CA 2187311A1
- Authority
- CA
- Canada
- Prior art keywords
- detergent composition
- composition
- antioxidant
- surfactant
- ethoxylated
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2058—Dihydric alcohols aromatic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2034—Monohydric alcohols aromatic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
A particulate detergent composition containing more than 5 wt.% of C8-20 primary alcohol sulphate and/or at least 8 wt.% of an ethoxylated C8-20 alcohol nonionic surfactant and/or more than 15 wt.% of total non-soap organic surfactant, and a builder system containing alkali metal aluminosilicate, also comprises from 0.01 to 5 wt.% of an antioxidant, preferably a sterically hindered phenol, more preferably butylated hydroxytoluene or butylated hydroxyanisole. The composition exhibits improved stability of the surfactant system on bulk storage and handling.
Description
2 8 1 ~ I lI!~ . . 709 _ DETER~T~T COMPOSITIONS
T~ r, FIT1'T,n The present invention relates to particulate detergent compositions containing high levels of high performance organic surfactants, and especially to compositions Cgnti~inin~
primary alcohol sulphate or ethoxylated alcohol nonionic 10 surfactants or both. The compositions exhibit improved stability owing to the presence of low levels of antioxidants.
EP 283 252B and EP 320 219B (Procter & Gamble) disclose particulate detergent compositions in which an antioxidant is incorporated within bleach activator granules, in order to improve bleach activator stability.
Various particulate detergent compositions C~nt~inin~
antioxidants are also disclosed in JP 50 066 502A/JP 77 003 730B, JP 50 151 g05A/JP 78 028 163B
and JP 57 128 798A/ JP 84 012 720B (Lion) and in JP 73 008 324B (Daiichi Kogyo Seijaku KK). The benefit is reduced odour and discoloration on storage.
It has now been discovered that in particulate detergent compositions containing high surfactant levels and 30 high performance surfactants, especially those containing primary alcohol sulphate and/or ethoxylated nonionic surfactant, improved stability of the surfactant system may be achieved by incorporating antioxidants, especially sterically hindered phenols. The increased safety margin thus achieved 35 facilitates factory handling and bulk storage of these high-active products, thereby providing increased manufacturing f lexibility .
wo 96/06151 2 1 8 7 3 1 1 . ~11~ . ~
ON OF TTT~ INVENTION
The present invention accordingly provides a particulate deter~ent composition comprisiny (i) an organic surfactant system comprising anionic and/or nonionic non-soap surfactants, the composition containing more than 5 wt~ of C~_20 primary alcohol sulphate andlor at least 8 wt% of an ethoxylated C~ 2~
alcohol nonionic surfactant and/or more than 15 wt% of total non-soap organic sutfactant, (ii~ a detergency builder system comprising alkali metal aluminosilicate, (iii) from 0. 01 to 5 wt% of an antioxidant, (iv) optionally other detergent ingredients to 100 wt96, 20 all percentages being based on the total composition.
DETATT ~n D~scRTpTIoN OF TF~ T~VENTION
The sllrfact~nt svstem 5 The composition of the invention contains a high level or non-soap organic surfactant, preferably 15 wt96 or above, preferably from 15 to 25 wt%. However, as indicated below, certain compositions containing total surfactant levels below 0 15 wt96 are also within the scope of the invention.
The surfactants may be chosen from anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof. ~Many suitable detergent-35 active compounds are available and are fully described in theliterature, for example, in ~Surface-Active Agents and Detergents~, Volumes I and II, by Schwartz, Perry and Berch.
-wo 96/06151 - 3 - . ~1~ _,v.
Anionic surfactants are well-known to those skille~ in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of Ca-C1s; primary and secondary alkylsulphates, 5 particularly C8-C1s primary alkyl sulphates; alkyl ether sulphates; olef in sulphonates; alkyl xylene sulphonates;
dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Sodium salts are generally preferred.
Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especiallY the C8-C20 aliphatic alcohols ethoxylated with an average of from l to 20 moles of ethylene oxide per mole of alcohol, and more especially the C1o-Cls primary and secondary aliphatic alcohols ethoxylated with an average of from l to l0 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, lactobionamides, and polyhydroxyamides (glucamide).
The invention is especially applicable to compositions containing a surfactant system comprising a C8 20 primary alcohol sulphate, an ethoxylated C8 20 alcohol nonionic surfactant, or both. Preferred compositions of the invention contain more than 5 wt% of Ca 20 primary alcohol sulphate, and/or at least 8 wt~v, preferably at least l0 wt%, of ethoxylated C8 20 alcohol nonionic surfactant. If one or both of these conditions is met, the total level of non-soap organic surfactant in the compositions of the invention need not be greater than 15 wt~, but is however preferably at least l0 wt96 and is more preferably at least 12 wt~s.
One class of preferred compositions of the invention comprises compositions containing more than 5 wt~v, based on the whole product, of C8 20 primary alcohol sulphate, 35 optionally in combination with an ethoxylated C8 20 alcohol nonionic surfactant.
WO 96/06151 _ 4 _ P,~ 709 The pre~erred compositions may contain at least 8 wt%, more preferably at least 10 wt%, of ethoxylated nonionic surfactant, and advantageously the ratio of primary alcohol sulphate to ethoxylated nonionic sulphate may be less than 5 1:1. However, compositions c~nt~inlng lesser proportions of nonionic surfactant, for example, those containing additiQnal anionic surfactants, are also within the scope of ~the invent ion .
Another class of preferred compositions of the invention, also containing at least 8 wt% and more preferably at least 10 wt~ of ethoxylated nonionic surfactant, are those in which the non-soap surfactant system consists wholly or substantially wholly of nonionic surfactants.
The compositions of the invention may also contain fatty acid soap. ~owever, where the limit of at least ~5 wt96 total surfactant applies, this does not include any fatty acid soap present .
The detercencv blli lder svstem The compositions of the invention contain, as detergency 25 builder, an alkali metal aluminosilicate, either alone or in conjunction with one or more supplementary builders.
The total amount of detergency builder in the compositions may suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
An essential component of the composition of the invention is an alkali metal, preferably sodium, aluminosilicate builder. ~Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 7096 by weight (anhydrous basis), preferably from 25 to 50 wt%.
21~731 1 W0 96/~6151 - 5 ~
The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula:
0.8-1.5 Na2O. Al2O3. 0.8-6 SiO2 These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium a~uminosilicates contain 1.5-3.5 SiO2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
The zeolite may be the commercially available zeolite 4A
now widely used in laundr,v deter~ent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in ~:he compositions of the invention is maximum aluminium zeolite P ( zeolite MAP) as described and claimed in EP 384 070A (Unilever). Zeolite ~P
is defined as an alkali metal aluminosilicate of the zeolite P
type having a silicon to aluminium ratio not exceeding 1. 33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
EspeciaIly preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1. 07, more preferably about 1.00. The calcium binding capa~ity of zeolite MAP is 35 generally at least 150 mg CaO per ~ of anhydrous material.
wo 96106151 - 6 . ~1/~ v, The zeolite is advantageously used in conjunction with a supplementary builder. Supplementary organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30~ wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0 . 5 to 15 wt%, preferably from 1 to 10 wt% .
The compositions of the invention may also contain l~r^ll~r crystalline sodium silicate having the composition NaMSix02x~ YH20 wherein M denotes sodium or hydrogen, ~Eeferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
These materials are described in US 4 664 839, US 4 728 443 and US 4 820 439 (F[oechst AG). They are crystalline materials and can easily be characterised by means 30 of their X-ray diffraction patterns. Compared with amorphous silicates, they are signlficantly better binders of calcium and magnesium ions.
Preferred materials are those in which 35 x = 2, ie compounds of the foEmula NaMSi20s . YE~20.
Both natural and synthetic compounds of this formula are of interest, the synthetic material known as Na-SKS-6 being especially preferred. This material is commercially available from Hoechst AG; its preparation is described, and 5 it is defined in terms of its X-ray diffraction pattern, in the aforementioned US 4 664 839.
10 The ~ntiox~ nt The antioxidant is a material capable of retarding oxidation of the surfactant system of the composition at elevated temperatures, for example, above 100C.
The antioxidant is preferably present in an amount of from 0 . 01 to 2 wt%, more preferably from 0 . 05 to 1 wt% and more especially from 0 .1 to 0 . 5 wt% .
One class of preferred antioxidants is constituted by the sterically hindered phenols.
Suitable antioxidants include the following:
(i) butylated hydroxytoluene (BHT), also known as 2,6-di-tert-butyl p-cresol;
(ii) butylated hydroxyanisole (BHA), also known as (1,1-dimethylethyl)-4-methoxyphenol;
(iii) tert-butylhydroquinone (TBHQ), also known as 1, 4-benzenediol.
21~731 ~
wos6/061sl - 8 - r~l,r~ 1~709 The oDtio~l m-tA1 ion se~uestr~nt Advantageously, the composition of the invention may also contain a seguestrant for transition metal ions.
Pre~erred seguestrants include aminopolycarboxylates, for example, ethylenediaminetetraacetic acid or its salts; or aminopolyphosphonates, for example, ethylenediamine tetramethylenephosphonic acid (ETDMP) or its salts (De~uest (Trade Mark) 2041 and 2047 ex Monsanto) or higher phosphonates such as diethylenetriamine pentamethylenephosphonic acid (DETPMP) and its salts (De~uest (Trade Mark) 2~60 or 2061). ~ =
Such phosphonates are conventionally incorporated into 15 detergent compositions containing peroxy bleach compounds, as bleach stabilisers; but in the context of the present invention seguestrants are advantageously present whether or not a bleach system is also present.
The oDtion~l bleach svstPm Compositions of the invention may if desired contain a bleach system. However, the invention is not concerned with 2S bleach stability and is egually applicable to non-bleaching f ormulations .
Suitable peroxy bleach compounds include organic peroxyacids, and inorganic persalts such as the alkali metal 30 perborates, percarbonates, perphosphates, persilicates and persulphates . Preferred; nor~ni c persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. me peroxy bleach compound is suitably present in an amount of from 5 to 35 wt96, preferably from 10 to 35 25 wt~.
21 ~731 t WO 96tO6151 9 1 ~ t The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 1 to 8 wt%, 5 preferably from 2 to 5 wt96. Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. An especially preferred bleach precursor suitable for use~ in the present invention is 10 N,N,N~,N~-tetracetyl ethylenediamine (TAED).
As previously indicated, a bleach stabiliser (heavy metal se~uestrant ) may also be present . Suitable sequestrants are discussed above.
If desired, the bleach system may also include a transition metal bleach catalyst as described and claimed in EP 458 3g7A, EP 458 398A and EP 509 787A (Unilever).
Other ol~tio~l incrre~ients The compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase 25 detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%. However, compositions containing little or no sodium carbonate are also within the scope of the invention .
Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
2~:8~3 1 W096/061SI _ lo r~
--One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt~i.
Other materials that may be present in detergent 5 compositions of the invention include sodium silicate;
antiredeposition ayents such as cellulosic polymers; other soil release or antiredeposition polymers; fluorescers;
inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; detergent enzymes, 10 for example, proteases, lipases, r~ qes and amylases;
dyes; coloured speckles; perfumes~ foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.
PreD~ration ~n~ bulk densitv The invention is of especial value for compact detergent powders in which ingredients are in especially close 20 proximity, for example, compositions having bulk densities of 650 g/l or more, and especially of 750 g/l or more.
Detergent compositions of high bulk density are generally prepared either by post-tower densification of spray-dried 25 powder, or by wholly non-spray-drying~Drocesses such as mixing and granulation. In both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
Preferred processes for preparing compositions of the invention will include the step of mixing and granulating ingredients in a high-speed mixer/densifier to form a base 35 powder of high bulk density, and optionally postdosing ingredients unsuitable for such processing.
21 ~13~ l WO 96/06151 r~
The antioxidant may either ~e included in the high bulk density base powder, or postdosed. It is desirable that the antioxidant should be distributed as homogeneously as possible through the final product.
According to one preferred process, a solution or suspension of the antioxidant in nonionic surfactant or in a nonionic surfactant/fatty acid soap mixture is mixed into the base powder before the postdosing of any solid ingredients.
Alternatively, the the antioxidant may be postdosed in particulate form, either as such or in the form of granules also containing a carrier material, for example, zeolite or sodium carbonate, and optionally a binder, for example, sodium 15 silicate ,r acrylate or acrylate/maleate polymer.
20 ~XAMPT,~c:
The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated.
2~731 1 WO 96/061~1 - 12 ~ ~ /r.- . '^7709 es 1 to 6 High bulk density bleaching detergent compositions were 5 prepared to the following general formulation:
Coconut alcohol sulphate 5 . 52 Nonionic 7EO 7 . 50 10Nonionic 3EO 5-Zeolite MAP 34.76 Sodium soap 1. 95 Sodium carbonate :: 3.13 Sodium carboxymethylcellulose 0 . 85 15BHT see below Percarbonate, TAED etc 3 0 . 07 EDTMP (Dequest 2047) 0.42 Enzymes 1. 42 Perfume 0 . 45 20 Foam control/fluorescer granules 3.50 Water and salts to 100. O0 The composition was ~repared as follows. A high bulk density base powder was prepared-by mixing and granulating 25 surfactants, zeolite, sodium carbonate and sodium carboxymethylcellulose in a continuous high-speed mixer/densifier (Lodige (Trade Mark~ Recycler). Bleach ingredients, further sodium carbonate, enzyme granules and foam control/fluorescer granules were subsequently postdosed.
T~ r, FIT1'T,n The present invention relates to particulate detergent compositions containing high levels of high performance organic surfactants, and especially to compositions Cgnti~inin~
primary alcohol sulphate or ethoxylated alcohol nonionic 10 surfactants or both. The compositions exhibit improved stability owing to the presence of low levels of antioxidants.
EP 283 252B and EP 320 219B (Procter & Gamble) disclose particulate detergent compositions in which an antioxidant is incorporated within bleach activator granules, in order to improve bleach activator stability.
Various particulate detergent compositions C~nt~inin~
antioxidants are also disclosed in JP 50 066 502A/JP 77 003 730B, JP 50 151 g05A/JP 78 028 163B
and JP 57 128 798A/ JP 84 012 720B (Lion) and in JP 73 008 324B (Daiichi Kogyo Seijaku KK). The benefit is reduced odour and discoloration on storage.
It has now been discovered that in particulate detergent compositions containing high surfactant levels and 30 high performance surfactants, especially those containing primary alcohol sulphate and/or ethoxylated nonionic surfactant, improved stability of the surfactant system may be achieved by incorporating antioxidants, especially sterically hindered phenols. The increased safety margin thus achieved 35 facilitates factory handling and bulk storage of these high-active products, thereby providing increased manufacturing f lexibility .
wo 96/06151 2 1 8 7 3 1 1 . ~11~ . ~
ON OF TTT~ INVENTION
The present invention accordingly provides a particulate deter~ent composition comprisiny (i) an organic surfactant system comprising anionic and/or nonionic non-soap surfactants, the composition containing more than 5 wt~ of C~_20 primary alcohol sulphate andlor at least 8 wt% of an ethoxylated C~ 2~
alcohol nonionic surfactant and/or more than 15 wt% of total non-soap organic sutfactant, (ii~ a detergency builder system comprising alkali metal aluminosilicate, (iii) from 0. 01 to 5 wt% of an antioxidant, (iv) optionally other detergent ingredients to 100 wt96, 20 all percentages being based on the total composition.
DETATT ~n D~scRTpTIoN OF TF~ T~VENTION
The sllrfact~nt svstem 5 The composition of the invention contains a high level or non-soap organic surfactant, preferably 15 wt96 or above, preferably from 15 to 25 wt%. However, as indicated below, certain compositions containing total surfactant levels below 0 15 wt96 are also within the scope of the invention.
The surfactants may be chosen from anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof. ~Many suitable detergent-35 active compounds are available and are fully described in theliterature, for example, in ~Surface-Active Agents and Detergents~, Volumes I and II, by Schwartz, Perry and Berch.
-wo 96/06151 - 3 - . ~1~ _,v.
Anionic surfactants are well-known to those skille~ in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of Ca-C1s; primary and secondary alkylsulphates, 5 particularly C8-C1s primary alkyl sulphates; alkyl ether sulphates; olef in sulphonates; alkyl xylene sulphonates;
dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Sodium salts are generally preferred.
Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especiallY the C8-C20 aliphatic alcohols ethoxylated with an average of from l to 20 moles of ethylene oxide per mole of alcohol, and more especially the C1o-Cls primary and secondary aliphatic alcohols ethoxylated with an average of from l to l0 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, lactobionamides, and polyhydroxyamides (glucamide).
The invention is especially applicable to compositions containing a surfactant system comprising a C8 20 primary alcohol sulphate, an ethoxylated C8 20 alcohol nonionic surfactant, or both. Preferred compositions of the invention contain more than 5 wt% of Ca 20 primary alcohol sulphate, and/or at least 8 wt~v, preferably at least l0 wt%, of ethoxylated C8 20 alcohol nonionic surfactant. If one or both of these conditions is met, the total level of non-soap organic surfactant in the compositions of the invention need not be greater than 15 wt~, but is however preferably at least l0 wt96 and is more preferably at least 12 wt~s.
One class of preferred compositions of the invention comprises compositions containing more than 5 wt~v, based on the whole product, of C8 20 primary alcohol sulphate, 35 optionally in combination with an ethoxylated C8 20 alcohol nonionic surfactant.
WO 96/06151 _ 4 _ P,~ 709 The pre~erred compositions may contain at least 8 wt%, more preferably at least 10 wt%, of ethoxylated nonionic surfactant, and advantageously the ratio of primary alcohol sulphate to ethoxylated nonionic sulphate may be less than 5 1:1. However, compositions c~nt~inlng lesser proportions of nonionic surfactant, for example, those containing additiQnal anionic surfactants, are also within the scope of ~the invent ion .
Another class of preferred compositions of the invention, also containing at least 8 wt% and more preferably at least 10 wt~ of ethoxylated nonionic surfactant, are those in which the non-soap surfactant system consists wholly or substantially wholly of nonionic surfactants.
The compositions of the invention may also contain fatty acid soap. ~owever, where the limit of at least ~5 wt96 total surfactant applies, this does not include any fatty acid soap present .
The detercencv blli lder svstem The compositions of the invention contain, as detergency 25 builder, an alkali metal aluminosilicate, either alone or in conjunction with one or more supplementary builders.
The total amount of detergency builder in the compositions may suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
An essential component of the composition of the invention is an alkali metal, preferably sodium, aluminosilicate builder. ~Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 7096 by weight (anhydrous basis), preferably from 25 to 50 wt%.
21~731 1 W0 96/~6151 - 5 ~
The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula:
0.8-1.5 Na2O. Al2O3. 0.8-6 SiO2 These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium a~uminosilicates contain 1.5-3.5 SiO2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
The zeolite may be the commercially available zeolite 4A
now widely used in laundr,v deter~ent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in ~:he compositions of the invention is maximum aluminium zeolite P ( zeolite MAP) as described and claimed in EP 384 070A (Unilever). Zeolite ~P
is defined as an alkali metal aluminosilicate of the zeolite P
type having a silicon to aluminium ratio not exceeding 1. 33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
EspeciaIly preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1. 07, more preferably about 1.00. The calcium binding capa~ity of zeolite MAP is 35 generally at least 150 mg CaO per ~ of anhydrous material.
wo 96106151 - 6 . ~1/~ v, The zeolite is advantageously used in conjunction with a supplementary builder. Supplementary organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30~ wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0 . 5 to 15 wt%, preferably from 1 to 10 wt% .
The compositions of the invention may also contain l~r^ll~r crystalline sodium silicate having the composition NaMSix02x~ YH20 wherein M denotes sodium or hydrogen, ~Eeferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
These materials are described in US 4 664 839, US 4 728 443 and US 4 820 439 (F[oechst AG). They are crystalline materials and can easily be characterised by means 30 of their X-ray diffraction patterns. Compared with amorphous silicates, they are signlficantly better binders of calcium and magnesium ions.
Preferred materials are those in which 35 x = 2, ie compounds of the foEmula NaMSi20s . YE~20.
Both natural and synthetic compounds of this formula are of interest, the synthetic material known as Na-SKS-6 being especially preferred. This material is commercially available from Hoechst AG; its preparation is described, and 5 it is defined in terms of its X-ray diffraction pattern, in the aforementioned US 4 664 839.
10 The ~ntiox~ nt The antioxidant is a material capable of retarding oxidation of the surfactant system of the composition at elevated temperatures, for example, above 100C.
The antioxidant is preferably present in an amount of from 0 . 01 to 2 wt%, more preferably from 0 . 05 to 1 wt% and more especially from 0 .1 to 0 . 5 wt% .
One class of preferred antioxidants is constituted by the sterically hindered phenols.
Suitable antioxidants include the following:
(i) butylated hydroxytoluene (BHT), also known as 2,6-di-tert-butyl p-cresol;
(ii) butylated hydroxyanisole (BHA), also known as (1,1-dimethylethyl)-4-methoxyphenol;
(iii) tert-butylhydroquinone (TBHQ), also known as 1, 4-benzenediol.
21~731 ~
wos6/061sl - 8 - r~l,r~ 1~709 The oDtio~l m-tA1 ion se~uestr~nt Advantageously, the composition of the invention may also contain a seguestrant for transition metal ions.
Pre~erred seguestrants include aminopolycarboxylates, for example, ethylenediaminetetraacetic acid or its salts; or aminopolyphosphonates, for example, ethylenediamine tetramethylenephosphonic acid (ETDMP) or its salts (De~uest (Trade Mark) 2041 and 2047 ex Monsanto) or higher phosphonates such as diethylenetriamine pentamethylenephosphonic acid (DETPMP) and its salts (De~uest (Trade Mark) 2~60 or 2061). ~ =
Such phosphonates are conventionally incorporated into 15 detergent compositions containing peroxy bleach compounds, as bleach stabilisers; but in the context of the present invention seguestrants are advantageously present whether or not a bleach system is also present.
The oDtion~l bleach svstPm Compositions of the invention may if desired contain a bleach system. However, the invention is not concerned with 2S bleach stability and is egually applicable to non-bleaching f ormulations .
Suitable peroxy bleach compounds include organic peroxyacids, and inorganic persalts such as the alkali metal 30 perborates, percarbonates, perphosphates, persilicates and persulphates . Preferred; nor~ni c persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. me peroxy bleach compound is suitably present in an amount of from 5 to 35 wt96, preferably from 10 to 35 25 wt~.
21 ~731 t WO 96tO6151 9 1 ~ t The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 1 to 8 wt%, 5 preferably from 2 to 5 wt96. Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. An especially preferred bleach precursor suitable for use~ in the present invention is 10 N,N,N~,N~-tetracetyl ethylenediamine (TAED).
As previously indicated, a bleach stabiliser (heavy metal se~uestrant ) may also be present . Suitable sequestrants are discussed above.
If desired, the bleach system may also include a transition metal bleach catalyst as described and claimed in EP 458 3g7A, EP 458 398A and EP 509 787A (Unilever).
Other ol~tio~l incrre~ients The compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase 25 detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%. However, compositions containing little or no sodium carbonate are also within the scope of the invention .
Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
2~:8~3 1 W096/061SI _ lo r~
--One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt~i.
Other materials that may be present in detergent 5 compositions of the invention include sodium silicate;
antiredeposition ayents such as cellulosic polymers; other soil release or antiredeposition polymers; fluorescers;
inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; detergent enzymes, 10 for example, proteases, lipases, r~ qes and amylases;
dyes; coloured speckles; perfumes~ foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.
PreD~ration ~n~ bulk densitv The invention is of especial value for compact detergent powders in which ingredients are in especially close 20 proximity, for example, compositions having bulk densities of 650 g/l or more, and especially of 750 g/l or more.
Detergent compositions of high bulk density are generally prepared either by post-tower densification of spray-dried 25 powder, or by wholly non-spray-drying~Drocesses such as mixing and granulation. In both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
Preferred processes for preparing compositions of the invention will include the step of mixing and granulating ingredients in a high-speed mixer/densifier to form a base 35 powder of high bulk density, and optionally postdosing ingredients unsuitable for such processing.
21 ~13~ l WO 96/06151 r~
The antioxidant may either ~e included in the high bulk density base powder, or postdosed. It is desirable that the antioxidant should be distributed as homogeneously as possible through the final product.
According to one preferred process, a solution or suspension of the antioxidant in nonionic surfactant or in a nonionic surfactant/fatty acid soap mixture is mixed into the base powder before the postdosing of any solid ingredients.
Alternatively, the the antioxidant may be postdosed in particulate form, either as such or in the form of granules also containing a carrier material, for example, zeolite or sodium carbonate, and optionally a binder, for example, sodium 15 silicate ,r acrylate or acrylate/maleate polymer.
20 ~XAMPT,~c:
The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated.
2~731 1 WO 96/061~1 - 12 ~ ~ /r.- . '^7709 es 1 to 6 High bulk density bleaching detergent compositions were 5 prepared to the following general formulation:
Coconut alcohol sulphate 5 . 52 Nonionic 7EO 7 . 50 10Nonionic 3EO 5-Zeolite MAP 34.76 Sodium soap 1. 95 Sodium carbonate :: 3.13 Sodium carboxymethylcellulose 0 . 85 15BHT see below Percarbonate, TAED etc 3 0 . 07 EDTMP (Dequest 2047) 0.42 Enzymes 1. 42 Perfume 0 . 45 20 Foam control/fluorescer granules 3.50 Water and salts to 100. O0 The composition was ~repared as follows. A high bulk density base powder was prepared-by mixing and granulating 25 surfactants, zeolite, sodium carbonate and sodium carboxymethylcellulose in a continuous high-speed mixer/densifier (Lodige (Trade Mark~ Recycler). Bleach ingredients, further sodium carbonate, enzyme granules and foam control/fluorescer granules were subsequently postdosed.
3 0 EDTMP was included in the base in some compositions, and postdosed in others.
2~ ~73 l 1 wo 96/06151 1 3 1 ~1/~ . v, The BET was introduced by two different methods:
(a) into the base powder (in the high-speed mixer~granulator) as a nonionic surfactant/soap/BHT mixture; or (b) postdosed in powder form.
Compositions were prepared as follows:
~x~ Antiox; ~l~nt ~
0 . 2296 BHT, postdosed Postdosed 2 0 . 4~v BHT, postdosed Postdosed 15 3 0.1% BHT, postdosed In base 4 0.2~ BHT, postdosed In base 5 0 . 3~v BET, postdosed In base 6 0 . 4~v BHT, postdosed In base ~x~mnl e 7 A similar formulation was prepared containing sodium perborate instead of sodium.. percarbonate. It ~on~ine~
postdosed EDTMP, and 0 . 29~i BHT postdosed.
2 ~
WO96/06151 _ ~4_ r~.,~ ,v, les 8 to 10 High bulk density non-bleaching deter~ent cPmpPsitions were prepared to the following general formulation:
Coconut alcohol sulphate 6.35 Nonionic 7EO 8. 63 Nonionic 3EO 5 . 75 Sodium soap 2 . 24 10 Zeolite MAP 39.99 :
Sodium carbonate l . 26 Sodium carboxymethylcellulose ~: 0. 98 =
BHT see below Sodium citrate (2H2O) 22.18 15EDTMP ( De(auest 2 0 47 ) 1. 43 Enzymes 1. 2 4 Perfume 45 Foam control/fluorescer granules 3.20 Water and salts to 100. 00 The method of preparation was as follows: a high bulk density base powder was prepared as described in Examples 1 to 6; sodium citrate, enzyme granules and foam 25 control/fluorescer granules were s~bse~uently postdosed.
EDTMP was postdosed. Compositions were prepared as follows:
~am~ Antioxi ~nt EDTMP
30 8 0.30% BHT postdosed postdosed 9 0.1% BHT + 0.1% BHA postdosed postdosed 0. 05% BHT + 0 . D5% BHA postdosed postdosed * * *
2~ ~73 l 1 wo 96/06151 1 3 1 ~1/~ . v, The BET was introduced by two different methods:
(a) into the base powder (in the high-speed mixer~granulator) as a nonionic surfactant/soap/BHT mixture; or (b) postdosed in powder form.
Compositions were prepared as follows:
~x~ Antiox; ~l~nt ~
0 . 2296 BHT, postdosed Postdosed 2 0 . 4~v BHT, postdosed Postdosed 15 3 0.1% BHT, postdosed In base 4 0.2~ BHT, postdosed In base 5 0 . 3~v BET, postdosed In base 6 0 . 4~v BHT, postdosed In base ~x~mnl e 7 A similar formulation was prepared containing sodium perborate instead of sodium.. percarbonate. It ~on~ine~
postdosed EDTMP, and 0 . 29~i BHT postdosed.
2 ~
WO96/06151 _ ~4_ r~.,~ ,v, les 8 to 10 High bulk density non-bleaching deter~ent cPmpPsitions were prepared to the following general formulation:
Coconut alcohol sulphate 6.35 Nonionic 7EO 8. 63 Nonionic 3EO 5 . 75 Sodium soap 2 . 24 10 Zeolite MAP 39.99 :
Sodium carbonate l . 26 Sodium carboxymethylcellulose ~: 0. 98 =
BHT see below Sodium citrate (2H2O) 22.18 15EDTMP ( De(auest 2 0 47 ) 1. 43 Enzymes 1. 2 4 Perfume 45 Foam control/fluorescer granules 3.20 Water and salts to 100. 00 The method of preparation was as follows: a high bulk density base powder was prepared as described in Examples 1 to 6; sodium citrate, enzyme granules and foam 25 control/fluorescer granules were s~bse~uently postdosed.
EDTMP was postdosed. Compositions were prepared as follows:
~am~ Antioxi ~nt EDTMP
30 8 0.30% BHT postdosed postdosed 9 0.1% BHT + 0.1% BHA postdosed postdosed 0. 05% BHT + 0 . D5% BHA postdosed postdosed * * *
Claims (4)
1 A particulate detergent composition comprising an organic surfactant system comprising anionic and/or nonionic non-soap surfactants, a detergency builder system and other detergent ingredients to 100 wt%, characterised in that:
(i) the composition contains more than 5 wt% of C8-20 primary alcohol sulphate and/or at least 8 wt% of an ethoxylated C8-20 alcohol nonionic surfactant and/or more than 15 wt% of total non-soap organic surfactant, (ii) the detergency builder system comprises alkali metal aluminosilicate, (iii) the composition further comprises from 0.01 to 5 wt% of an antioxidant, all percentages being based on the total composition.
(i) the composition contains more than 5 wt% of C8-20 primary alcohol sulphate and/or at least 8 wt% of an ethoxylated C8-20 alcohol nonionic surfactant and/or more than 15 wt% of total non-soap organic surfactant, (ii) the detergency builder system comprises alkali metal aluminosilicate, (iii) the composition further comprises from 0.01 to 5 wt% of an antioxidant, all percentages being based on the total composition.
2 A detergent composition as claimed in claim 1, characterised in that the organic surfactant system comprises C8-20 primary alcohol sulphate and ethoxylated C8-20 alcohol nonionic surfactant.
3 A detergent composition as claimed in claim 2, characterised in that the composition contains more than 5 wt%
of primary alcohol sulphate.
of primary alcohol sulphate.
4 A detergent composition as claimed in claim 2, characterised in that the composition contains more than 15 wt% of the surfactant system (i), which system comprises C8-20 primary alcohol sulphate and ethoxylated C8-20 alcohol nonionic surfactant.
A detergent composition as claimed in claim 2, characterised in that the surfactant system (i) comprises C8-20 primary alcohol sulphate and ethoxylated C8-20 alcohol nonionic surfactant in a ratio of less than 1:1.
6 A detergent composition as claimed in claim 1, characterised in that the composition comprises at least 10 wt% of ethoxylated nonionic surfactant.
7 A detergent composition as claimed in claim 1, characterised in that the antioxidant (iii) is a sterically hindered phenol.
8 A detergent composition as claimed in claim 7, characterised in that the antioxidant (iii) is selected from butylated hydroxytoluene, butylated hydroxyanisole, and tert-butylhydroquinone.
9 A detergent composition as claimed in claim 1, characterised in that it comprises from 0.05 to 2 wt% of antioxidant (iii).
A detergent composition as claimed in claim 1, characterised in that it also comprises a sequestrant for transition metal ions.
11 A detergent composition as claimed in claim 10, characterised in that the sequestrant comprises an aminopolycarboxylate or aminopolyphosphonate.
12 A detergent composition as claimed in claim 10, characterised in that the sequestrant comprises ethylenediamine tetramethylenephosphonic acid or a salt thereof.
13 A detergent composition as claimed in claim 1, characterised by a bulk density of at least 650 g/l.
14 A detergent composition as claimed in claim 1, characterised in that it is not the product of a spray-drying process.
A process for the preparation of a particulate detergent composition as claimed in claim 1, which includes the step of mixing and granulating ingredients in a high-speed mixer/densifier to form a base powder of high bulk density and optionally postdosing ingredients unsuitable for processing in a high-speed mixer/densifier, characterised in that a solution or suspension of the antioxidant in nonionic surfactant is mixed with the base powder before the postdosing of any solid ingredients.
16 A process for the preparation of a particulate detergent composition as claimed in claim 1, which includes the step of mixing and granulating ingredients in a high-speed mixer/densifier to form a base powder of high bulk density and optionally postdosing ingredients unsuitable for processing in a high-speed mixer/densifier, characterised in that the antioxidant is postdosed in particulate form.
A detergent composition as claimed in claim 2, characterised in that the surfactant system (i) comprises C8-20 primary alcohol sulphate and ethoxylated C8-20 alcohol nonionic surfactant in a ratio of less than 1:1.
6 A detergent composition as claimed in claim 1, characterised in that the composition comprises at least 10 wt% of ethoxylated nonionic surfactant.
7 A detergent composition as claimed in claim 1, characterised in that the antioxidant (iii) is a sterically hindered phenol.
8 A detergent composition as claimed in claim 7, characterised in that the antioxidant (iii) is selected from butylated hydroxytoluene, butylated hydroxyanisole, and tert-butylhydroquinone.
9 A detergent composition as claimed in claim 1, characterised in that it comprises from 0.05 to 2 wt% of antioxidant (iii).
A detergent composition as claimed in claim 1, characterised in that it also comprises a sequestrant for transition metal ions.
11 A detergent composition as claimed in claim 10, characterised in that the sequestrant comprises an aminopolycarboxylate or aminopolyphosphonate.
12 A detergent composition as claimed in claim 10, characterised in that the sequestrant comprises ethylenediamine tetramethylenephosphonic acid or a salt thereof.
13 A detergent composition as claimed in claim 1, characterised by a bulk density of at least 650 g/l.
14 A detergent composition as claimed in claim 1, characterised in that it is not the product of a spray-drying process.
A process for the preparation of a particulate detergent composition as claimed in claim 1, which includes the step of mixing and granulating ingredients in a high-speed mixer/densifier to form a base powder of high bulk density and optionally postdosing ingredients unsuitable for processing in a high-speed mixer/densifier, characterised in that a solution or suspension of the antioxidant in nonionic surfactant is mixed with the base powder before the postdosing of any solid ingredients.
16 A process for the preparation of a particulate detergent composition as claimed in claim 1, which includes the step of mixing and granulating ingredients in a high-speed mixer/densifier to form a base powder of high bulk density and optionally postdosing ingredients unsuitable for processing in a high-speed mixer/densifier, characterised in that the antioxidant is postdosed in particulate form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9417140.2 | 1994-08-24 | ||
| GB9417140A GB9417140D0 (en) | 1994-08-24 | 1994-08-24 | Detergent compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2187311A1 true CA2187311A1 (en) | 1996-02-29 |
Family
ID=10760361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002187311A Abandoned CA2187311A1 (en) | 1994-08-24 | 1995-07-08 | Detergent compositions |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0777715A1 (en) |
| AU (1) | AU2983095A (en) |
| BR (1) | BR9508807A (en) |
| CA (1) | CA2187311A1 (en) |
| CZ (1) | CZ53097A3 (en) |
| GB (1) | GB9417140D0 (en) |
| HU (1) | HUT77100A (en) |
| PL (1) | PL318787A1 (en) |
| SK (1) | SK24097A3 (en) |
| TR (1) | TR199500943A2 (en) |
| WO (1) | WO1996006151A1 (en) |
| ZA (1) | ZA955934B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7084100B2 (en) | 2004-04-28 | 2006-08-01 | The Procter & Gamble Company | Antioxidant compositions |
| GB0511313D0 (en) * | 2005-06-03 | 2005-07-13 | Unilever Plc | Incorporation of antioxidant in detergent composition |
| EP1987120B2 (en) † | 2006-02-24 | 2013-09-11 | Unilever PLC | Fast release granules |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7411994A (en) * | 1973-09-17 | 1975-03-19 | Unilever Nv | Enzyme granules with improved storage stability - by incorporating an antioxidant |
| GB1550350A (en) * | 1975-12-19 | 1979-08-15 | Shell Int Research | Detergent compositions comprising an alkyl polyoxyalkylene ether non-ionic surfactant and a bisphenol |
| EP0283252B1 (en) * | 1987-03-17 | 1992-10-07 | The Procter & Gamble Company | Bleaching compositions |
| DE3888116T2 (en) * | 1987-12-09 | 1994-08-04 | Procter & Gamble | Bleach. |
| TW244358B (en) * | 1992-10-12 | 1995-04-01 | Kao Corp |
-
1994
- 1994-08-24 GB GB9417140A patent/GB9417140D0/en active Pending
-
1995
- 1995-07-08 EP EP95925861A patent/EP0777715A1/en not_active Withdrawn
- 1995-07-08 HU HU9701689A patent/HUT77100A/en unknown
- 1995-07-08 AU AU29830/95A patent/AU2983095A/en not_active Abandoned
- 1995-07-08 BR BR9508807A patent/BR9508807A/en not_active Application Discontinuation
- 1995-07-08 CZ CZ97530A patent/CZ53097A3/en unknown
- 1995-07-08 PL PL95318787A patent/PL318787A1/en unknown
- 1995-07-08 CA CA002187311A patent/CA2187311A1/en not_active Abandoned
- 1995-07-08 WO PCT/EP1995/002709 patent/WO1996006151A1/en not_active Application Discontinuation
- 1995-07-08 SK SK240-97A patent/SK24097A3/en unknown
- 1995-07-17 ZA ZA955934A patent/ZA955934B/en unknown
- 1995-08-02 TR TR95/00943A patent/TR199500943A2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CZ53097A3 (en) | 1997-07-16 |
| WO1996006151A1 (en) | 1996-02-29 |
| EP0777715A1 (en) | 1997-06-11 |
| SK24097A3 (en) | 1997-08-06 |
| AU2983095A (en) | 1996-03-14 |
| HUT77100A (en) | 1998-03-02 |
| ZA955934B (en) | 1997-01-17 |
| BR9508807A (en) | 1998-01-06 |
| GB9417140D0 (en) | 1994-10-12 |
| PL318787A1 (en) | 1997-07-07 |
| TR199500943A2 (en) | 1996-06-21 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |