CA2209667A1 - Detergent composition - Google Patents
Detergent compositionInfo
- Publication number
- CA2209667A1 CA2209667A1 CA 2209667 CA2209667A CA2209667A1 CA 2209667 A1 CA2209667 A1 CA 2209667A1 CA 2209667 CA2209667 CA 2209667 CA 2209667 A CA2209667 A CA 2209667A CA 2209667 A1 CA2209667 A1 CA 2209667A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- detergent composition
- surfactant
- weight
- chain lengths
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Abstract
A detergent composition is disclosed which contains a surfactant system having alkyl sulfate and nonionic surfactant components, and a detergency builder comprising zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP). Granular and liquid detergent compositions are preferred and methods of making such compositions are disclosed.
Description
DETERGENT COMPOSITION
,.
The present invention relates to a detergent composition comprising a surfactant system and a zeolite component as a sequestering agent for water hardness.
Detergent compositions containing synthetic detergents, particularly linear alkyl benzene sulfonate salts are well known in the art and are in widespread commercial use. Conventionally the linear alkyl benzene sulfonate salt forms part of a surfactant mixture in association with one or more other anionic or nonionic surfactants.
Current environmental concern has focused on the undesirability of deriving detergent components from non-renewable hydrocarbon sources. Interest ~ has ther~fore increased in the formulation of well-pe,ror",ing deteryentcompositions comprising surfactant systems which are environmentally compatible and ~refer~bly derived from renewable natural sources.
An example of an anionic surfactant which is readily derivable from renewable natural sources and which could replace the alkyl benzene sulfonate component either partially or in total is alkyl sulfate surfactant.
Deterge,1l compositions including alkyl sulfate surfactant derived from naturally occurring fats and oils are known in the art. For example, GB-A-1,399,966, in the name of the Procter & Gamble Company, discloses a detergel,l composition containing alkyl sulfate su, raclal,t derived from tallowoil, or from coconut oil.
The detergency pe~ rorl"ance characteristics of surfactants having alkyl chains are known to depend on the nature and length of the alkyl chain. For example, EP-A-342,917 describes a surfactant system, derived preferably from natural feedstock material, comprising an anionic surfactant the major ingredient of which is an alkyl sulfate of mixed alkyl chain length such that atleast 10% by weight of the alkyl chains present in the alkyl sulfate are C12 chains and at least 20% by weight of the alkyl chains are C1 8 chains.
It has been recently established that good detergency performance over a range of laundry wash temperatures may be obtained for surfactant systems containing an alkyl sulfate surfactant having a high proportion of alkyl chain lengths greater than C14, in combination with a nonionic surfactant.
A surfactant system containing alkyl sulfate surfactant of mixed alkyl chain length such that the level ~f C12 and C18 alkyi chain lengths is minimised, and wherein the C14 and C16 alkyl chain lengths form the major part, in combination with a nonionic surfactant, which provides particularly good detergency pelrorl"a"ce over a wide range of temperatures, is described in the Applicant's copending PCT Application No. US94/06943.
It has however, now been found that for the above described alkyl sulfate and nonionic co"laining surfactant systems to perform satisfactorily as components of a detergent composition designed pri",a,ily for laundering purposes it is important for the composition to contain a builder system providing effective control of hardness ions, particularly calcium ions.
Conventionally, water soluble inorganic phosphates, such as sodium tripolyphosphate, have been used as builders for laundry deterge"~s.
More recently, alkali metal aluminosilicate ion-exchangers, particularly crystalline water insoluble sodium aluminosilicate zeolites, have been proposed as replacements for the inorganic phosphates.
For example, EP 21 491A (Procter & Gamble) discloses detergent compositions containing a builder system which includes zeolite A, X
or P (B) or a mixture thereof. EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes their use as detergency builders.
However, it is known that there are certain problems in the use of water insoluble zeolites as detergency builders, as compared with water soluble builders such as phosphates. In particular, most zeolites including zeolite A act relatively slowly to sequester the calcium ions.
It has been found that this slow sequestration of calcium ions can co,npro~ise the effective working of surfactant systems which require more rapid control of water hardness. In particular the performance of the hereinabove described surfactant systems containing alkyl sulfate and nonionic surfactants have been found to be cor"~ror"ised when used in a detergent composition employing a builder system having a significant zeolite A content. Performance is particularly cor,l~ ro",ised under hard feed water conditions.
Surprisingly the Applicant has now found that good detergency pe,ror",a"ce is obtained when zeolite MAP is used particularly as a substitute for zeolite A in combination with the su,ractant system containing alkyl sulfate surfactants having a high proportion of alkyl chain lengths greater than C1 4 in combination with nonionic surfactant.
According to the present invention there is provided a detergent composition co"lai"i"g (a) an alkyl sulfate sulracta"t system comprising a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20% by weight of the alkyl chains are of chain length less than C14;
(~) a nonionic surfactant; and (c) a zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP) In a prefer,ed aspect of the present invention the alkyl sulfate surfactant system is derived from natural sources and cor,~prises a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that from 30% to 80% by weight of the alkyl chain lengths are C14 from 30% to 50% by weight of the alkyl chain lengths are C16 and less than 10% by weight of the alkyl chain lengths are C1 8 In another preferred aspect of the present invention the composition contains an alkyl ethoxysulfate surfactant as an anionic cosurfactant.
In a further prefened aspect of the present invention the nonionic surfactant is a hydrohobic nonionic surfactant preferably an alkoxylated nonionic surfactant having a hydrophilic lipophilic balance (hlb) value of less than 9.5.
The composition is preferably free of alkyl benzene sulfonate.
Detailed description of the invention Alkyl sulfate surfactant The first essential component of the detergent compositions of the invention is an alkyl sulfate su,ractarl~ system comprising a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20% by weight of the alkyl chain lengths are of chain length less than C14 The alkyl sulfate surfactant system is prererably present in the detergent compositions at a level of from 1% to 50% prererably from 3% to 30% most prer~:, cbly from 5% to 20% by weight of the cGmposilio~ ,s.
r, eferdbly the alkyl sulfate su~ ractal1~ system is derived from natural sQurces and in a particularly p,efer,ed execution comprises a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that from 35% to 70% most prererably from 40% to 60% of the alkyl chains are C14 from 30% to 50% prererably from 30% to 40% most preferably from 32% to 38% of the alkyl chains are C16 less than 10%
preferably less than 5% most preferably less than 3% of the alkyl chains areC1g.
By derived from natural sources it is meant herein that the alkyl chain portion of the surfactant is derived from naturally occurring fats and oil.
Natural oils and fats provide feedstock material encompassing a range of alkyl chain lengths. The alkyl chains are predominantly linear, in contrast to the branched nature of feedstock obtained from synthetic sources. For example, tallow fat contains a high proportion (typically about 70%) Of C18 alkyl chains. Coconut and palm oil on the other hand contain a high proportion ~f C12 alkyl chains (typically about 55%) and lesser proportions of C147 C16 and C18 alkyl chain lengths.
Alkyl chains derived from natural oils and fats typically have chains with even numbers of carbon atoms, most typically C12- C14, C16 and C18 The alkyl chains may contain a small prcpG,lion of unsaturated, e.g.: alkenyl, chains which if desired may be hydrogenated, or "hardened" to minimize these impurity levels. Typically the alkyl sulfate su, rdcLa"t is prod! ~ced from alcohols obtained by reduction of the natural oils and fats. Examples of natural oils and fats include those derived from coconl;lt, babassu, palm kernel, beef tallow, kapok, olive, peanut, sesame and te~seerl Alkyl sulfate su,racLd"l of the desired alkyl chain length distribution is obtained from natural feedstock, meaning natural oils or fats, or any mixtures thereof, or the natural alcohols derived thert:r,.r", by any suitable physical process which allows for the separalion of such feedstock into different components with the desired alkyl chain length distributions.
Suitable physical processes would include, for example, distillation processes. The separation of feedstock material into dirrerel,~ components of desired composition is often referred to in the industry as "cutting" of the feedstock (into desired "cuts"). The different components (or cuts) may then be used as such, or blended, as appropriate to allow for derivation of the alkyl sulfate su, racla,-l with the desired alkyl chain length distribution.
Alkyl ethoxYsulfate su~ ra~La, IL
t~ .
In addition to the alkyl sulfate surfactant the detergent compositions ,ureferdbly also contain an alkyl ethoxysulfate surfactant. The weight ratio of the alkyl sulfate surfactant to the alkyl ethoxysulfate surfactant is preferablyfrom 2:1 to 19:1 more preferably from 3:1 to 12:1 and most prererably from 3.5:1 to 10:1.
The alkyl ethoxysulfate surfactant is preferably a water soluble C12-C1g alkyl ethoxysulfate surfactant containing an average of from 1 to 7 moles ethylene oxide per mole derived from the condensation product of a C12-C1g alcohol wherein said C12-C1g alcohol is most preferably derived from natural sources. Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
Preferred are C12-C14 alkyl ethoxysulfate salts with an average of from one to five ethoxy groups per mole, and most preferably with an average of from one to three ethoxy groups per mole.
Nonionic surfactant The second essential component of the deterge,)l composition according to the present invention is a nonionic su, fdclal ,~.
The nonionic surfactant is preferably present in the detergent compositions at a level of from 1% to 50%, prererably from 2% to 20%, most preferably from 3% to 10% by weight of the compositions.
The nonionic surfactant is preferably a hydrophobic nonionic su,ractanl, particularly an alkoxylated nonionic surfactant, having a hydrophilic lipophilic balance (hlb) value of < 9.5, more preferably < 1 0.5.
Examples of suitable hydrophobic alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of Iess than 5 alkylene oxide groups per molecule.
The alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.
Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula:
R-O-(CnH2nO)YH
wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most prefer~bly from 10 to 22 carbon atomsl y is from 0.5 to 3.5 and n is 2 or 3.
Preferred nonionic surfactants include primary C11 -C1 s aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight.
A particularly prererl ed aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.
Specific examples of suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C1s alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
Another class of nonionic sufactants comprises alkyl polyglucoside compounds of general formula RO(CnH2nO)tzx wherein Z is a moiety derived from glucose; R is a saturated hydro~hobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds . including less than 10% unreacted fatty alcohol and less than 50%short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
WO 96/21705 PCTtUS96/00214 Zeolite MAP builder According to the present invention the detergency builder system is based on zeolite MAP, optionally in conjunction with one or more supplementary builders. The amount of zeolite MAP employed may range, for example, from 5 to 60 wt.%, more preferably from 15 to 40 wt.%.
Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, ~rererably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
Zeolite P having a Si:AI ratio of 1.33 or less may be prepared by the following steps:
(i) mixing together a sodium aluminate having a mole ratio Na2O:AI2O3 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio SiO2:Na20 within the range of from 0.8 to 3.4 with vigorous stirring at a ter"peral-lre within the range of from 25~C to boiling point usually 95~C, to give a gel having the following co""~osition; Al2O3: (1.75-3.5) SiO2: (2.3-7.5) Na2O :P
(80450)H20;
(ii) ageing the gel composition for 0.5 to 10 hours, preferably 2 to 5 hours, at a temperature within the range of from 70~C to boiling point, usually to 95~C, with sufficient stirring to maintain any solids present in suspension;
(iii) separating the crystalline sodium aluminosilicate thus formed, washing to a pH within the range of from 10 to 12.5, and drying"~referably at a temperature not exceeding 1 50~C, to a moisture content of not less than 5 wt.%
Preferred drying methods are spray-drying and flash drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.
Commercial sodium metasilicate pentahydrate dissolved in water and commercial sodium silicate solution (waterglass) are both suitable silica sources for the production of zeolite P in accordance with the invention. The reactants may be added together in any order either rapidly or slowly. Rapid addition at ambient temperature, and slow addition at elevated temperature (90-95~C) both give the desired product.
Vigorous stirring of the gel during the addition of the reacta, lls, and at least moderate stirring during the subsequent ageing step, however, appear to be essential for the for",aliGn of pure zeolite P. In the absence of stirring, various mixtures of crystalline and amorphous materials may be obtained.
Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the sla".lard method described in GB 1473201 (Henkel). The calcium binding ca,uacily is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
-Although zeolite MAP like other zeolites contains water of hydldlioll,for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.
The amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.
According to one embodiment of the invention the zeolite MAP
detergent builder is in powder form.
-Additional deterqent components In addition to the essential alkyl sulfate and nonionic surfactant components, the detergent composition according to the invention can include one or more other s~" racta, lls selected from anionics, zwitterionics, ampholytics and cationics.
Many suitable detergent-active compounds are available and fully described in the literature (for example "Surface Active Agents and Detergents" Volumes I and ll by Schwartz, Perry and Berch).
Examples of suitable additional anionic surfactants include olefin sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates. Sodium salts are generally preferred.
In addition to zeolite MAP, the builder system may contain an organic or inor~,a"ic cobuilder.
Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form. Suitable inorganic cobuilders include carbonates and amorphous and crystalline lamellar sodium silicates.
Suitable lamellar silicates have the composition:
NaMSix02x+1 . yH20 where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Such materials are described in US Patents No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG). Especially preferled are compounds in which x = 2 and y = O.
The synthetic material is commercially available from Hoechst AG as -Na2 Si2Os (SKS6) and is described in US Patent No. 4664830.
The total amount of deteryency builder in the granular composition typically ranges from 10 to 80 wt.%, more prefe, dbiy from 15 to 60 wt%
W O96121705 PCTnUS96/00214 and most preferably from 10 to 4~ wt.%.
Detergent compositions according to the invention may also suitably contain a bleach system. This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
The bleach system prererably comprises a peroxy bleach compound, ,ureferably an inorganic persalt, optionally in conjunction with a precursor. Suitable persalts include sodium perbor~le monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred.
Prefer,ed bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors.
Other materials which may be present in the detergent compositions of the invention include, for example, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
The detergent co""~osilion according to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositions are preferred.
The cleterge,1l col"~.ositions of the invention may be prepared by any suitable method. The particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
~ In processes based around a spray-drying tower, a base powder is first prepared by spray-drying a slurry and then other components ~ unsuitable for processing via the slurry can be sprayed on or admixed (postdosed). The lipase enzyme will generally be post-dosed.
The zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated post-tower. The lamellar silicate, where this is employed, is also incorporated via a non-tower process and is preferably postdosed.
Alternatively, particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.
The granular detergent compositions of the invention may be prepared to any suitable bulk density. The compositions preferably have a bulk density of at least 400 g/l preferably at least 550 g/l, most preferably at least 700 g/l and, with particular preference at least 800 g/l.
The benefits of the present invention are particularly evident in powders of high bulk density, for example, of 700 g/l or above. Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry 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 EP340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
The detergent composition of the invention may be formulated as a liquid detergent composition which may be aqueous or anhydrous.
The term "liquid" used herein includes pasty viscous formulations such as gels. The liquid detergent composition generally has a pH of from 6.5to 10.5.
The total amount of detergency builder in the liquid composition is preferably from ~ to 70% of the total liquid composition.
Illustrative compositions according to the present invention are presented in the following Examples.
In the detergent compositions, the abbreviated component identifications have the following meanings:
246AS : Sodium alkyl sulfate surfactant containing a alkyl chain length weight distribution of 15% C12 alkyl chains, 45% C14 alkyl chains, 35% C16 alkyl chains, 5% C1g alkyl chains TAS : Sodium alkyl sulfate surfactant containing predominantly C16 - C1g alkyl chains derived from tallow oil.
24AE3S : C12-C14 alkyl ethoxysulfate containing an average of three ethoxy groups per mole 35E3 : A C 13-15 primary alcohol condensed with an average of 3 moles of ethylene oxide 25E3 : A C12-C1s primary alcohol cG"densed with an average of 3 moles of ethylene oxide Carbonate : Anhydrous sodium carbonate Perborate : Sodium perboraletetrahydrate Percarbonate : Sodium percarL,G"ate TAED : Tetra acetyl ethylene diamine Silicate : Amorphous Sodium Silicate (SiO2:Na20 ratio normally follows) Zeolite MAP : Hydrated sodium aluminosilicate zeolite MAP
~ having a silicon to aluminium ratio of 1.07 MA/M : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.
Enzyme : Proteolytic enzyme sold by Novo Industries AS of activity 4.0 KNPU.
Example 1 The following granular laundry detergent compositions were prepared (parts by weight) in accordance with the invention.
A B C D E
246AS 7.6 6.5 4.8 6.8 TAS - - - - 8.6 24AE3S 2.4 - 1.2 1.7 25E3 3.26 - - - 6.3 35E3 - 5.0 5.0 5.0 Zeolite MAP 20.0 25.0 20.0 25.0 31.0 Carbonate 15.0 15.0 20.0 10.0 12.0 MA/M 4.25 4.25 4.25 4.25 2.0 Perborate - 16.0 - 16.0 20.0 Percarbonate 20.0 - 20.0 TAED 5.0 5.0 5.0 5.0 6.7 Enzyme 1.4 1.4 1.4 1.4 1.4 Silicate (2.0 4.0 - - 4.0 3.0 ratio) Water and miscellaneous (Including suds suppressor, sodium sulphate, perfume) to balance
,.
The present invention relates to a detergent composition comprising a surfactant system and a zeolite component as a sequestering agent for water hardness.
Detergent compositions containing synthetic detergents, particularly linear alkyl benzene sulfonate salts are well known in the art and are in widespread commercial use. Conventionally the linear alkyl benzene sulfonate salt forms part of a surfactant mixture in association with one or more other anionic or nonionic surfactants.
Current environmental concern has focused on the undesirability of deriving detergent components from non-renewable hydrocarbon sources. Interest ~ has ther~fore increased in the formulation of well-pe,ror",ing deteryentcompositions comprising surfactant systems which are environmentally compatible and ~refer~bly derived from renewable natural sources.
An example of an anionic surfactant which is readily derivable from renewable natural sources and which could replace the alkyl benzene sulfonate component either partially or in total is alkyl sulfate surfactant.
Deterge,1l compositions including alkyl sulfate surfactant derived from naturally occurring fats and oils are known in the art. For example, GB-A-1,399,966, in the name of the Procter & Gamble Company, discloses a detergel,l composition containing alkyl sulfate su, raclal,t derived from tallowoil, or from coconut oil.
The detergency pe~ rorl"ance characteristics of surfactants having alkyl chains are known to depend on the nature and length of the alkyl chain. For example, EP-A-342,917 describes a surfactant system, derived preferably from natural feedstock material, comprising an anionic surfactant the major ingredient of which is an alkyl sulfate of mixed alkyl chain length such that atleast 10% by weight of the alkyl chains present in the alkyl sulfate are C12 chains and at least 20% by weight of the alkyl chains are C1 8 chains.
It has been recently established that good detergency performance over a range of laundry wash temperatures may be obtained for surfactant systems containing an alkyl sulfate surfactant having a high proportion of alkyl chain lengths greater than C14, in combination with a nonionic surfactant.
A surfactant system containing alkyl sulfate surfactant of mixed alkyl chain length such that the level ~f C12 and C18 alkyi chain lengths is minimised, and wherein the C14 and C16 alkyl chain lengths form the major part, in combination with a nonionic surfactant, which provides particularly good detergency pelrorl"a"ce over a wide range of temperatures, is described in the Applicant's copending PCT Application No. US94/06943.
It has however, now been found that for the above described alkyl sulfate and nonionic co"laining surfactant systems to perform satisfactorily as components of a detergent composition designed pri",a,ily for laundering purposes it is important for the composition to contain a builder system providing effective control of hardness ions, particularly calcium ions.
Conventionally, water soluble inorganic phosphates, such as sodium tripolyphosphate, have been used as builders for laundry deterge"~s.
More recently, alkali metal aluminosilicate ion-exchangers, particularly crystalline water insoluble sodium aluminosilicate zeolites, have been proposed as replacements for the inorganic phosphates.
For example, EP 21 491A (Procter & Gamble) discloses detergent compositions containing a builder system which includes zeolite A, X
or P (B) or a mixture thereof. EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes their use as detergency builders.
However, it is known that there are certain problems in the use of water insoluble zeolites as detergency builders, as compared with water soluble builders such as phosphates. In particular, most zeolites including zeolite A act relatively slowly to sequester the calcium ions.
It has been found that this slow sequestration of calcium ions can co,npro~ise the effective working of surfactant systems which require more rapid control of water hardness. In particular the performance of the hereinabove described surfactant systems containing alkyl sulfate and nonionic surfactants have been found to be cor"~ror"ised when used in a detergent composition employing a builder system having a significant zeolite A content. Performance is particularly cor,l~ ro",ised under hard feed water conditions.
Surprisingly the Applicant has now found that good detergency pe,ror",a"ce is obtained when zeolite MAP is used particularly as a substitute for zeolite A in combination with the su,ractant system containing alkyl sulfate surfactants having a high proportion of alkyl chain lengths greater than C1 4 in combination with nonionic surfactant.
According to the present invention there is provided a detergent composition co"lai"i"g (a) an alkyl sulfate sulracta"t system comprising a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20% by weight of the alkyl chains are of chain length less than C14;
(~) a nonionic surfactant; and (c) a zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP) In a prefer,ed aspect of the present invention the alkyl sulfate surfactant system is derived from natural sources and cor,~prises a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that from 30% to 80% by weight of the alkyl chain lengths are C14 from 30% to 50% by weight of the alkyl chain lengths are C16 and less than 10% by weight of the alkyl chain lengths are C1 8 In another preferred aspect of the present invention the composition contains an alkyl ethoxysulfate surfactant as an anionic cosurfactant.
In a further prefened aspect of the present invention the nonionic surfactant is a hydrohobic nonionic surfactant preferably an alkoxylated nonionic surfactant having a hydrophilic lipophilic balance (hlb) value of less than 9.5.
The composition is preferably free of alkyl benzene sulfonate.
Detailed description of the invention Alkyl sulfate surfactant The first essential component of the detergent compositions of the invention is an alkyl sulfate su,ractarl~ system comprising a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20% by weight of the alkyl chain lengths are of chain length less than C14 The alkyl sulfate surfactant system is prererably present in the detergent compositions at a level of from 1% to 50% prererably from 3% to 30% most prer~:, cbly from 5% to 20% by weight of the cGmposilio~ ,s.
r, eferdbly the alkyl sulfate su~ ractal1~ system is derived from natural sQurces and in a particularly p,efer,ed execution comprises a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that from 35% to 70% most prererably from 40% to 60% of the alkyl chains are C14 from 30% to 50% prererably from 30% to 40% most preferably from 32% to 38% of the alkyl chains are C16 less than 10%
preferably less than 5% most preferably less than 3% of the alkyl chains areC1g.
By derived from natural sources it is meant herein that the alkyl chain portion of the surfactant is derived from naturally occurring fats and oil.
Natural oils and fats provide feedstock material encompassing a range of alkyl chain lengths. The alkyl chains are predominantly linear, in contrast to the branched nature of feedstock obtained from synthetic sources. For example, tallow fat contains a high proportion (typically about 70%) Of C18 alkyl chains. Coconut and palm oil on the other hand contain a high proportion ~f C12 alkyl chains (typically about 55%) and lesser proportions of C147 C16 and C18 alkyl chain lengths.
Alkyl chains derived from natural oils and fats typically have chains with even numbers of carbon atoms, most typically C12- C14, C16 and C18 The alkyl chains may contain a small prcpG,lion of unsaturated, e.g.: alkenyl, chains which if desired may be hydrogenated, or "hardened" to minimize these impurity levels. Typically the alkyl sulfate su, rdcLa"t is prod! ~ced from alcohols obtained by reduction of the natural oils and fats. Examples of natural oils and fats include those derived from coconl;lt, babassu, palm kernel, beef tallow, kapok, olive, peanut, sesame and te~seerl Alkyl sulfate su,racLd"l of the desired alkyl chain length distribution is obtained from natural feedstock, meaning natural oils or fats, or any mixtures thereof, or the natural alcohols derived thert:r,.r", by any suitable physical process which allows for the separalion of such feedstock into different components with the desired alkyl chain length distributions.
Suitable physical processes would include, for example, distillation processes. The separation of feedstock material into dirrerel,~ components of desired composition is often referred to in the industry as "cutting" of the feedstock (into desired "cuts"). The different components (or cuts) may then be used as such, or blended, as appropriate to allow for derivation of the alkyl sulfate su, racla,-l with the desired alkyl chain length distribution.
Alkyl ethoxYsulfate su~ ra~La, IL
t~ .
In addition to the alkyl sulfate surfactant the detergent compositions ,ureferdbly also contain an alkyl ethoxysulfate surfactant. The weight ratio of the alkyl sulfate surfactant to the alkyl ethoxysulfate surfactant is preferablyfrom 2:1 to 19:1 more preferably from 3:1 to 12:1 and most prererably from 3.5:1 to 10:1.
The alkyl ethoxysulfate surfactant is preferably a water soluble C12-C1g alkyl ethoxysulfate surfactant containing an average of from 1 to 7 moles ethylene oxide per mole derived from the condensation product of a C12-C1g alcohol wherein said C12-C1g alcohol is most preferably derived from natural sources. Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
Preferred are C12-C14 alkyl ethoxysulfate salts with an average of from one to five ethoxy groups per mole, and most preferably with an average of from one to three ethoxy groups per mole.
Nonionic surfactant The second essential component of the deterge,)l composition according to the present invention is a nonionic su, fdclal ,~.
The nonionic surfactant is preferably present in the detergent compositions at a level of from 1% to 50%, prererably from 2% to 20%, most preferably from 3% to 10% by weight of the compositions.
The nonionic surfactant is preferably a hydrophobic nonionic su,ractanl, particularly an alkoxylated nonionic surfactant, having a hydrophilic lipophilic balance (hlb) value of < 9.5, more preferably < 1 0.5.
Examples of suitable hydrophobic alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of Iess than 5 alkylene oxide groups per molecule.
The alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.
Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula:
R-O-(CnH2nO)YH
wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most prefer~bly from 10 to 22 carbon atomsl y is from 0.5 to 3.5 and n is 2 or 3.
Preferred nonionic surfactants include primary C11 -C1 s aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight.
A particularly prererl ed aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.
Specific examples of suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C1s alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
Another class of nonionic sufactants comprises alkyl polyglucoside compounds of general formula RO(CnH2nO)tzx wherein Z is a moiety derived from glucose; R is a saturated hydro~hobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds . including less than 10% unreacted fatty alcohol and less than 50%short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
WO 96/21705 PCTtUS96/00214 Zeolite MAP builder According to the present invention the detergency builder system is based on zeolite MAP, optionally in conjunction with one or more supplementary builders. The amount of zeolite MAP employed may range, for example, from 5 to 60 wt.%, more preferably from 15 to 40 wt.%.
Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, ~rererably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
Zeolite P having a Si:AI ratio of 1.33 or less may be prepared by the following steps:
(i) mixing together a sodium aluminate having a mole ratio Na2O:AI2O3 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio SiO2:Na20 within the range of from 0.8 to 3.4 with vigorous stirring at a ter"peral-lre within the range of from 25~C to boiling point usually 95~C, to give a gel having the following co""~osition; Al2O3: (1.75-3.5) SiO2: (2.3-7.5) Na2O :P
(80450)H20;
(ii) ageing the gel composition for 0.5 to 10 hours, preferably 2 to 5 hours, at a temperature within the range of from 70~C to boiling point, usually to 95~C, with sufficient stirring to maintain any solids present in suspension;
(iii) separating the crystalline sodium aluminosilicate thus formed, washing to a pH within the range of from 10 to 12.5, and drying"~referably at a temperature not exceeding 1 50~C, to a moisture content of not less than 5 wt.%
Preferred drying methods are spray-drying and flash drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.
Commercial sodium metasilicate pentahydrate dissolved in water and commercial sodium silicate solution (waterglass) are both suitable silica sources for the production of zeolite P in accordance with the invention. The reactants may be added together in any order either rapidly or slowly. Rapid addition at ambient temperature, and slow addition at elevated temperature (90-95~C) both give the desired product.
Vigorous stirring of the gel during the addition of the reacta, lls, and at least moderate stirring during the subsequent ageing step, however, appear to be essential for the for",aliGn of pure zeolite P. In the absence of stirring, various mixtures of crystalline and amorphous materials may be obtained.
Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the sla".lard method described in GB 1473201 (Henkel). The calcium binding ca,uacily is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
-Although zeolite MAP like other zeolites contains water of hydldlioll,for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.
The amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.
According to one embodiment of the invention the zeolite MAP
detergent builder is in powder form.
-Additional deterqent components In addition to the essential alkyl sulfate and nonionic surfactant components, the detergent composition according to the invention can include one or more other s~" racta, lls selected from anionics, zwitterionics, ampholytics and cationics.
Many suitable detergent-active compounds are available and fully described in the literature (for example "Surface Active Agents and Detergents" Volumes I and ll by Schwartz, Perry and Berch).
Examples of suitable additional anionic surfactants include olefin sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates. Sodium salts are generally preferred.
In addition to zeolite MAP, the builder system may contain an organic or inor~,a"ic cobuilder.
Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form. Suitable inorganic cobuilders include carbonates and amorphous and crystalline lamellar sodium silicates.
Suitable lamellar silicates have the composition:
NaMSix02x+1 . yH20 where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Such materials are described in US Patents No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG). Especially preferled are compounds in which x = 2 and y = O.
The synthetic material is commercially available from Hoechst AG as -Na2 Si2Os (SKS6) and is described in US Patent No. 4664830.
The total amount of deteryency builder in the granular composition typically ranges from 10 to 80 wt.%, more prefe, dbiy from 15 to 60 wt%
W O96121705 PCTnUS96/00214 and most preferably from 10 to 4~ wt.%.
Detergent compositions according to the invention may also suitably contain a bleach system. This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
The bleach system prererably comprises a peroxy bleach compound, ,ureferably an inorganic persalt, optionally in conjunction with a precursor. Suitable persalts include sodium perbor~le monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred.
Prefer,ed bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors.
Other materials which may be present in the detergent compositions of the invention include, for example, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
The detergent co""~osilion according to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositions are preferred.
The cleterge,1l col"~.ositions of the invention may be prepared by any suitable method. The particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
~ In processes based around a spray-drying tower, a base powder is first prepared by spray-drying a slurry and then other components ~ unsuitable for processing via the slurry can be sprayed on or admixed (postdosed). The lipase enzyme will generally be post-dosed.
The zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated post-tower. The lamellar silicate, where this is employed, is also incorporated via a non-tower process and is preferably postdosed.
Alternatively, particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.
The granular detergent compositions of the invention may be prepared to any suitable bulk density. The compositions preferably have a bulk density of at least 400 g/l preferably at least 550 g/l, most preferably at least 700 g/l and, with particular preference at least 800 g/l.
The benefits of the present invention are particularly evident in powders of high bulk density, for example, of 700 g/l or above. Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry 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 EP340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
The detergent composition of the invention may be formulated as a liquid detergent composition which may be aqueous or anhydrous.
The term "liquid" used herein includes pasty viscous formulations such as gels. The liquid detergent composition generally has a pH of from 6.5to 10.5.
The total amount of detergency builder in the liquid composition is preferably from ~ to 70% of the total liquid composition.
Illustrative compositions according to the present invention are presented in the following Examples.
In the detergent compositions, the abbreviated component identifications have the following meanings:
246AS : Sodium alkyl sulfate surfactant containing a alkyl chain length weight distribution of 15% C12 alkyl chains, 45% C14 alkyl chains, 35% C16 alkyl chains, 5% C1g alkyl chains TAS : Sodium alkyl sulfate surfactant containing predominantly C16 - C1g alkyl chains derived from tallow oil.
24AE3S : C12-C14 alkyl ethoxysulfate containing an average of three ethoxy groups per mole 35E3 : A C 13-15 primary alcohol condensed with an average of 3 moles of ethylene oxide 25E3 : A C12-C1s primary alcohol cG"densed with an average of 3 moles of ethylene oxide Carbonate : Anhydrous sodium carbonate Perborate : Sodium perboraletetrahydrate Percarbonate : Sodium percarL,G"ate TAED : Tetra acetyl ethylene diamine Silicate : Amorphous Sodium Silicate (SiO2:Na20 ratio normally follows) Zeolite MAP : Hydrated sodium aluminosilicate zeolite MAP
~ having a silicon to aluminium ratio of 1.07 MA/M : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.
Enzyme : Proteolytic enzyme sold by Novo Industries AS of activity 4.0 KNPU.
Example 1 The following granular laundry detergent compositions were prepared (parts by weight) in accordance with the invention.
A B C D E
246AS 7.6 6.5 4.8 6.8 TAS - - - - 8.6 24AE3S 2.4 - 1.2 1.7 25E3 3.26 - - - 6.3 35E3 - 5.0 5.0 5.0 Zeolite MAP 20.0 25.0 20.0 25.0 31.0 Carbonate 15.0 15.0 20.0 10.0 12.0 MA/M 4.25 4.25 4.25 4.25 2.0 Perborate - 16.0 - 16.0 20.0 Percarbonate 20.0 - 20.0 TAED 5.0 5.0 5.0 5.0 6.7 Enzyme 1.4 1.4 1.4 1.4 1.4 Silicate (2.0 4.0 - - 4.0 3.0 ratio) Water and miscellaneous (Including suds suppressor, sodium sulphate, perfume) to balance
Claims (9)
1. A detergent composition containing (a) an alkyl sulfate surfactant system comprising a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20% by weight of the alkyl chains are of chain length less than C14;
(b) a nonionic surfactant; and (c) a zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP).
(b) a nonionic surfactant; and (c) a zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP).
2. A detergent composition according to Claim 1 wherein said alkyl sulfate surfactant system is derived from natural sources and comprises a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that from 30% to 80% by weight of the alkyl chain lengths are C14 from 30% to 50% by weight of the alkyl chain lengths are C16 and less than 10% by weight of the alkyl chain lengths are C18.
3. A detergent composition according to either of Claims 1 or 2 wherein said alkyl sulfate surfactant is present at a level of from 5% to 20% by weight of the composition
4. A detergent composition according to any of Claims 1 to 3 containing an alkyl ethoxysulfate surfactant as an anionic cosurfactant.
5. A detergent composition according to Claim 4 wherein said alkyl ethoxysulfate is present at a level such that the weight ratio of the alkyl sulfate surfactant to the alkyl ethoxysulfate surfactant is from 3:1 to 12:1.
6. A detergent composition according to any of Claims 1 to 5 wherein said nonionic surfactant has a hydrophilic lipophilic balance (hlb) value of less than 9.5.
7. A detergent composition according to Claim 6 wherein the nonionic surfactant is an alkoxylated nonionic surfactant.
8. A detergent composition according to Claim 7 wherein said alkoxylated nonionic surfactant is selected from the alkylene oxide adducts of fatty alcohols having the general formula:
R-O-(CnH2nO)yH
wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.
R-O-(CnH2nO)yH
wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.
9. A detergent composition according to any of Claims 1 to 8 wherein said zeolite builder is present at a level of from 5% to 60% by weight of the composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9500592.2 | 1995-01-12 | ||
| GB9500592A GB2296919A (en) | 1995-01-12 | 1995-01-12 | Detergent composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2209667A1 true CA2209667A1 (en) | 1996-07-18 |
Family
ID=10767941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2209667 Abandoned CA2209667A1 (en) | 1995-01-12 | 1996-01-05 | Detergent composition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0802957A4 (en) |
| AR (1) | AR000715A1 (en) |
| BR (1) | BR9607176A (en) |
| CA (1) | CA2209667A1 (en) |
| GB (1) | GB2296919A (en) |
| WO (1) | WO1996021705A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19807805A1 (en) | 1998-02-26 | 1999-09-02 | Henkel Kgaa | A combination of surfactants containing special anionic surfactants |
| MY133398A (en) * | 1999-07-09 | 2007-11-30 | Colgate Palmolive Co | Fabric cleaning composition containing zeolite |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE7T1 (en) * | 1977-06-29 | 1979-12-07 | Procter & Gamble | DETERGENT COMPOSITIONS |
| GB8310698D0 (en) * | 1983-04-20 | 1983-05-25 | Procter & Gamble | Detergent compositions |
| DE3469159D1 (en) * | 1983-08-22 | 1988-03-10 | Henkel Kgaa | Stabilized aqueous zeolite suspension |
| GB8504733D0 (en) * | 1985-02-23 | 1985-03-27 | Procter & Gamble Ltd | Detergent compositions |
| GB8617255D0 (en) * | 1986-07-15 | 1986-08-20 | Procter & Gamble Ltd | Laundry compositions |
| GB8811447D0 (en) * | 1988-05-13 | 1988-06-15 | Procter & Gamble | Granular laundry compositions |
| GB8811672D0 (en) * | 1988-05-17 | 1988-06-22 | Unilever Plc | Detergent composition |
| CA2001927C (en) * | 1988-11-03 | 1999-12-21 | Graham Thomas Brown | Aluminosilicates and detergent compositions |
| CA2083331C (en) * | 1991-11-26 | 1998-08-11 | Johannes H. M. Akkermans | Detergent compositions |
| GB9305599D0 (en) * | 1993-03-18 | 1993-05-05 | Unilever Plc | Detergent compositions |
| GB2288187A (en) * | 1994-03-31 | 1995-10-11 | Procter & Gamble | Detergent composition |
| GB2287949A (en) * | 1994-03-31 | 1995-10-04 | Procter & Gamble | Laundry detergent composition |
| GB2288813A (en) * | 1994-04-28 | 1995-11-01 | Procter & Gamble | Granular Detergent Composition |
-
1995
- 1995-01-12 GB GB9500592A patent/GB2296919A/en not_active Withdrawn
-
1996
- 1996-01-05 CA CA 2209667 patent/CA2209667A1/en not_active Abandoned
- 1996-01-05 WO PCT/US1996/000214 patent/WO1996021705A1/en not_active Application Discontinuation
- 1996-01-05 EP EP96902617A patent/EP0802957A4/en not_active Withdrawn
- 1996-01-05 BR BR9607176A patent/BR9607176A/en not_active Application Discontinuation
- 1996-01-12 AR AR10099896A patent/AR000715A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9607176A (en) | 1997-11-11 |
| EP0802957A4 (en) | 1999-11-24 |
| AR000715A1 (en) | 1997-08-06 |
| EP0802957A1 (en) | 1997-10-29 |
| MX9705330A (en) | 1997-10-31 |
| WO1996021705A1 (en) | 1996-07-18 |
| GB2296919A (en) | 1996-07-17 |
| GB9500592D0 (en) | 1995-03-01 |
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