CA2185545A1 - Granular bleaching compositions - Google Patents
Granular bleaching compositionsInfo
- Publication number
- CA2185545A1 CA2185545A1 CA002185545A CA2185545A CA2185545A1 CA 2185545 A1 CA2185545 A1 CA 2185545A1 CA 002185545 A CA002185545 A CA 002185545A CA 2185545 A CA2185545 A CA 2185545A CA 2185545 A1 CA2185545 A1 CA 2185545A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- mixtures
- silicate
- alkali metal
- metal salt
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
- C11D3/394—Organic 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- 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
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
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- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Detergent Compositions (AREA)
- Medicinal Preparation (AREA)
- Cereal-Derived Products (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Cosmetics (AREA)
Abstract
A granular laundry composition is disclosed which comprises a source of available oxygen, a stabilizer like chelant together with an alkali metal salt of silicate. Such compositions allow to produce wash solutions wherein the bleaching activity is retained upon longer periods of time. Optionally said compositions may further comprise a soil suspender and be formulated so as to allow to keep the pH of the wash solution below 9.5 and thereby boost the cleaning performance on particulate soil (clay).
Description
WO 95/25160 ~ SU3 21 ~55~5 Granular'~'~~ ' ' ,g co.,~l o~
.
Technical field The present invention relates to the cleaning of fabrics under soaking 15 conditions. More s~,euiri~:~y~ granular c~"",osilio,ls for soaking fabrics are described which giYe optimum p~,ru""d"ce in cleaning andlor ~ re~ g fabrics upon long soaking periods.
Backqround of the invention It is desirable that a c~",~:,ilio,~ which is typically formulated to be used insoaking conditions retains its capacity to bleach after a long period of time.
2s This is even more desirable in ~ a such as the ui_,.lreuLiull and/or cleaning of highly soiled fabrics, such as baby napkins.
It is known in the art to use peroxy hydrate compounds in such d~)~liCd~iUI 15 Said peroxy hydrate compounds release hydrogen peroxide which is an 30 oxidizing agent, in solution.
However, the use of such peroxy hydrate compounds in ,.~",~.o~ilio,~s designed to be used upon long soaking periods has been restricted by the relative instability of said bleaches in wash solutions. Indeed, due to the reiative 35 instability of such a bleach in a wash solution, said wash solution does not retain its bleaching activity over extended periods required for cleaning and/ordi ,illrè~,li"g highly soiled fabrics. In fact, the hydrogen peroxide produced by
.
Technical field The present invention relates to the cleaning of fabrics under soaking 15 conditions. More s~,euiri~:~y~ granular c~"",osilio,ls for soaking fabrics are described which giYe optimum p~,ru""d"ce in cleaning andlor ~ re~ g fabrics upon long soaking periods.
Backqround of the invention It is desirable that a c~",~:,ilio,~ which is typically formulated to be used insoaking conditions retains its capacity to bleach after a long period of time.
2s This is even more desirable in ~ a such as the ui_,.lreuLiull and/or cleaning of highly soiled fabrics, such as baby napkins.
It is known in the art to use peroxy hydrate compounds in such d~)~liCd~iUI 15 Said peroxy hydrate compounds release hydrogen peroxide which is an 30 oxidizing agent, in solution.
However, the use of such peroxy hydrate compounds in ,.~",~.o~ilio,~s designed to be used upon long soaking periods has been restricted by the relative instability of said bleaches in wash solutions. Indeed, due to the reiative 35 instability of such a bleach in a wash solution, said wash solution does not retain its bleaching activity over extended periods required for cleaning and/ordi ,illrè~,li"g highly soiled fabrics. In fact, the hydrogen peroxide produced by
2 ~ 5 such peroxy hydrate compounds is rapidly dec~ Josed by the presence of ions of heavy metals such as iron, copper and Illdlludll~se often found in tap water as well as by the presence in the wash solution of bacteria or organic materials provided by the soiled napkins, e.g. soils like feces and urine.
Indeed, the presence of such heavy metal ions is unavoidable in the usage conditions of granuiar soaking .,ulll,uu ,it,ùna~ To overcome this problem US - 4 4û5 482 discloses the use of stabilizers like chelants, i.e. diethylene triaminop~ dC~, acid and magnesium sulfate, in granular c~lll,uuailiulls. Magnesium ~o sulfate allows to stabilize the hydrogen peroxide and to harden the water in the wash solution obtained with said granular culllpOailio~l and diethylenl:l,idl"i"e pdl~ldu~, acid neutralizes metal ions which are not ~dcu",uu~ed themselves by the oxidizing action of hydrogen peroxide.
However, there is a constant strive for the development of granular culll,uo:~iliul~5 to be used in soaking conditions, which provide a longer period of effective bleaching.
Accordingly, it is an object of the present invention to provide a granular 20 colll,uu~iliol~ Co~,ulisill9 a source of available oxygen whereby the decu,,,~,uailio,, with time of the available oxygen produced upon dissolution ofsaid COIll,u~aSiliùr~ in wa`ter is reduced.
It has now been found that the addition of an alkali metal salt of silicate, or 25 mixtures thereof, to a granular soaking cu"")osilio,- uo~ u~ g a source of available oxygen, allows to reduce the decu,,,uoai~;o,~ of available oxygen which occurs in the wash solution obtained therewith. More sueuiri~':y, it has been found that granular c~" ,posili~lls cu" ~uriail ,9 a source of available oxygen and stabilizers like chelants together with an alkali metal salt of silicate, sucn 30 as sodium silicate, allow to produce wash solutions wherein the bleaching capacity is retained upon longer periods of time as compared to the same co",posi~iù,~s but without sodium silicate. In other words, the use of an alkalimetal salt of silicate on top of other stabilizers like chelants in granular uoll~,uùsiliùns provides wash solutions which remain more active for over 245 hours and provide long term S~ dliùll andlor cleaning and/or bleaching ;P5 which are less affected by variable water supply quality or by soils ~ss~ d with highly soiled fabrics, as for example, baby napkins.
. . . _ WO95125160 2 1 8 5 5 '1~
Indeed, the presence of such heavy metal ions is unavoidable in the usage conditions of granuiar soaking .,ulll,uu ,it,ùna~ To overcome this problem US - 4 4û5 482 discloses the use of stabilizers like chelants, i.e. diethylene triaminop~ dC~, acid and magnesium sulfate, in granular c~lll,uuailiulls. Magnesium ~o sulfate allows to stabilize the hydrogen peroxide and to harden the water in the wash solution obtained with said granular culllpOailio~l and diethylenl:l,idl"i"e pdl~ldu~, acid neutralizes metal ions which are not ~dcu",uu~ed themselves by the oxidizing action of hydrogen peroxide.
However, there is a constant strive for the development of granular culll,uo:~iliul~5 to be used in soaking conditions, which provide a longer period of effective bleaching.
Accordingly, it is an object of the present invention to provide a granular 20 colll,uu~iliol~ Co~,ulisill9 a source of available oxygen whereby the decu,,,~,uailio,, with time of the available oxygen produced upon dissolution ofsaid COIll,u~aSiliùr~ in wa`ter is reduced.
It has now been found that the addition of an alkali metal salt of silicate, or 25 mixtures thereof, to a granular soaking cu"")osilio,- uo~ u~ g a source of available oxygen, allows to reduce the decu,,,uoai~;o,~ of available oxygen which occurs in the wash solution obtained therewith. More sueuiri~':y, it has been found that granular c~" ,posili~lls cu" ~uriail ,9 a source of available oxygen and stabilizers like chelants together with an alkali metal salt of silicate, sucn 30 as sodium silicate, allow to produce wash solutions wherein the bleaching capacity is retained upon longer periods of time as compared to the same co",posi~iù,~s but without sodium silicate. In other words, the use of an alkalimetal salt of silicate on top of other stabilizers like chelants in granular uoll~,uùsiliùns provides wash solutions which remain more active for over 245 hours and provide long term S~ dliùll andlor cleaning and/or bleaching ;P5 which are less affected by variable water supply quality or by soils ~ss~ d with highly soiled fabrics, as for example, baby napkins.
. . . _ WO95125160 2 1 8 5 5 '1~
3 2 l~5~5 A further advanSage is that the available oxygen decu,,,uoai~iù,l reduction effect of an alkali metal salt of silicate has also been observed in CullllJùs~ s comprising a source of available oxygen together with a bleach activator.
s Summarv of the invention Co~uosiliùl~s according to the present invention are granular ~u,,,posiliù,ls cu,,,urisill~ a source of available oxygen and diethylene triamino pe"lact:lic acid. Said ù,,luosiliu,~s further comprise an alkali metal salt of silicate or mixtures thereof.
The present invention also encol"passes the use of an alkali metal salt of silicate, or mixtures thereof in a granular laundry CulllpOait;OIl Culll~risi,lg a source of available oxygen whereby the dec~",uo~ " with time of the available oxygen produced upon dissolution of said c~ Juailiùll in water is 20 reduced.
The present invention also el~co,,,udaaes a process of treating fabrics with a source of available oxygen wherein a granular ~ul~luùailiull culllp~iaillg said source of available oxygen and an alkali metal salt of silicate or mixtures 2s thereof is dissolved in water and said fabrics are left to soak in said diluted c~ ûsiliul 1 then either washed and left to dry or rinsed and left to dry.
Cetailed cl~su, iuliul~ of the invention The CCIll,ùOai~iùl-a according to the present invention comprises as a first essential ingredient a source of available oxygen. By source of available 35 oxygen it is meant herein an active oxygen-releasing peroxy compound or mixtures thereof. The peroxy compound may be hydrogen peroxide or any of the addition compounds of hydrogen peroxide or organic peroxyacid or wo 95/25160 2 1 8 5 5 ~ 5r~
mixtures thereof. By addition compounds of hydrogen peroxide it is meant compounds which are formed by the addition of hydrogen peroxide to a second chemical compound, which may be for example an inorganic salt, urea or organic carboxylate, to provide the addition compound. Examples of the s addition compounds of hydrogen peroxide include inorganic perhydrate salts, the compounds hydrogen peroxide fomms with organic carboxylates, urea, and compounds in which hydrogen peroxide is clathrated.
Examples of inorganic perhydrate salts include perborate, pe,w,bù,,dL~l10 pel;Jl~apl~dl~ and p~, ' ' salts. The inorganic perhydrate salts are normally the alkali metal salts.
The alkali metal salt of pe,w,L,u"ale, perborate or mixtures thereof, are the preferred inorganic perhydrate salts for inclusion in the w,np~ailiuns in accu, dd,~-,e with the present inYention. Preferred alkali metal salt of pe(~;d,u.",dla to be used herein is sodium p~w~vnale. Sodium pelwlb~l~dl~
is available cu"""e,~ -'ly as a crystalline solid. Most cu"""e~ !y available materials include low levels of heavy metal sequestrats such as EDTA, 1-hydroxyethylidene 1, 1 d~ ua~Jllorlic acid (HEDP) or an amino-pl)ospl~ù~ e, 20 which are illC~ uldl~d during manufacturing process Preferred alkali metal salt of perborate to be used herein is sodium perborate. For the purposes of the present invention, the pe,w,L.u,lc,l~ or perborate can be ill~,~l,uo,dlt:d into detergent cu, ~,uuSi~iO~ la without additional protection.
2s Whilst heavy metals present in the sodium carbonate used to manufacture the pe,w,Lul,c,L~ can be controlled by the inclusion of sequestrats in the reaction mixture, it is preferred that the pel~,dl~Ulld~t: be protected from heavy metalspresent as impurities in other i"u~ ic. Il:- of the product. It has been found that the total level of Iron, Copper and Al ,ga"ese ions in the product should not0 exceed 25 ppm and preferably should be less than 2û ppm in order to avoid an Jl~ adverse effect on p~lwlLor~ , stability during its storage.
The Cûll,pOsiliul,S according to the present invention comprise from 10% to 80% by weight of the total Culll~uosiliu" of a source of available oxygen, 3s preferably from 15% to 50% and more preferably from 20% to 45%. When a co",posi~iu" of the present invention is used under normal conditions to produce the wash solu~ion, i.e. 15-7û9 of a c~ ailiul~ according to the ~ WO 95/25160 2 1 8 5 5 ~ 5 r~
present invention are dissolved in about 7 liters of water, said wash solution comprises from 0.3% to 11% by weight of the total wash solution of available oxygen, preferably of from 0.45% to 7% and more preFerably of from 0.6% to 6.2%. By "available oxygen" it is meant herein the active oxygen released by 5 hydro3en peroxide in the wash upon its reduction. Said hydrogen peroxide beins itself released by the active oxygen-releasing peroxy compounds, more generally defined herein under the name of source of available oxygen.
As a second essential Gompound the cu",,uo~ilio,~s of the present invention 10 Gomprise diethylene triamino pélltace~ acid as a stabilizer like chelant. Said Gheiating agent helps to control the ievel of free heavy metal ions in the wash solution, thus avoiding rapid dec~",~osi~i~n of the hydrogen peroxide released by said source of available oxygen of the ~u",posi~io,~s of the present invention.
Other suitable amino calL ox~l..'~, chelating agents may be used in the 15 G~lllpûai~iOIla of the present invention such as ethylelledid"~i"e lètldace~dLes (EDTA), N-hydroxyethylethyle,~e.Jia",i"e l~iac~t.,t~,3, Il ilu;,iace~ 3, ethy~ e~id",i"e léLla,ulu,uliOII_~ ., triethyl~ t~,;,dd")i"e h~ æ~ ;, and t:LI Idl "~Idiy,ycines, alkali metal ammonium and sl Ihstit~ It~d ammonium saltsthereof or mixtures thereof. Further suitable chelating agents include 20 ethylc~edialllille-N~N~- disuccinic acids (EDDS) or alkali metal, alkaline earth metal, ammonium, or sllhsti~t~d ammonium salts thereof, or mixtures thereof.
Particularly suitable EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof. Also others suitable chelating agents may be the organic ,ul luaiJI lurldleSl including amino alkylene poly(alkylene 2s ~ OalJl lùl 1_`~.), alkali metal ethane 1 -hydroxy di~l~o~,l lOndlèS, nitrilotrimethylene pllOapl~Orl-~3l ethylene diamine tetra methylene pl~ûa,ullOIldlès and diethylene triamine penta methylene l~llùsullulld~es. The ,ullosullo~ld~e compounds may be present either in their acid form or in the form of their metalalkali salt. Preferably the organic ,ul)osul~r~_`u compounds where present are 30 in the form of their magnesium salt.
The cOIll~oaiLiol~s according to the present invention comprise from 0.01% to 5% by weight of the total Culll~Oailiul ,s of said chelating agents, preferably from û.û5% to 2%, more preferably from 0.1% to 1%.
3s As a third essential compound the c~",,uosiliuns of the present invention further comprise an alkali metal salts of silicate or mixtures thereof. Preferred alkali wo ssnsl60 ;~ 1 8 5 5 ~, 5P~
metal salt of silicate to be used herein is sodium silicate. It has been found that the decu",posilio,1 of available oxygen produced in the wash solution upon dissolution of a culll,uuailiull of the present invention is reduced by the presence of at least 4û parts per million of sodium silicate in said wash s solution. Accordingly, the present cc",~oai~iùns comprise from û.5% to 15% by weight of the total l,u~,uOailion of an alkali metal salt of silicate, or mixtures thereof, preferably from 1% to 10% and more preferably from 2% to 7%.
Any type of alkali metal salt of silicats can be used in the colll,uo5iliol~s of the present invention including the crystalline forms as well as the amorphous forms of said alkali metal salt of silicate or mixtures thereof. Preferred herein is to use the crystalline forms as well as the amorphous forms of sodium silicate or mixtures thereof.
Suitable cr,vstalline forms of sodium silicate to be used according to the present invention are the crystalline layered silicates of the granular formuia NaMSixO2xt1 yH2o wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from û to 20, or mixtures thereof. Crystalline layered sodium silicates of this type are disclosed in EP-A-164 514 and methods for their ul~dldliùl~ are 2s disclosed in DE-A-34 17 649 and DE-A-37 42 043. For the purposes of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the a, b, g and d forms of Na2Si2Os These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS~. The most preferred material is d -Na2Si2Os NaSKS~. Crystalline layered silicates are i~-,UI,UUI~ either as dry mixed solids, or as solid Culll~ol1~llLa of au~lullle:ldlc:s with other cc,,,~û, ,e, ILa.
3s Suitable amorphous forms of sodium silicate to be used herein have the following generai formula:
WO 95125160 2 1 8 5 5 4 5 . ."J~ s ~ ~
NaMSixo2x+1 wherein M is sodium or hydrogen and x is a number from 1.9 to 4 or mixtures s thereof. PreFerred to be used herein are the amorphous fomms of Si20s Na20.
Other suitable alkali metal salt of silicate to be used herein are al~",i, IOail;~Lt:s including those having the empirical formula:
Mz(zAI02.ySiO2) wherein M is sodium potassium ammonium or s~hstit~'?~ ammonium z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at ieast about 50 milligram equivalents of CaC03 hardness per gram of anhydrous alulllill~a;i~ . Preferred alu",i"c are zeolites which have the formula:
Nazi(AI02)z (SiO2)yù.xH20 20 wherein z and y are integers of at least 6 the molar ratio of z to y is in the range from 1.0 to about 0.5 and x is an integer from about 15 to about 264.
Useful alu",i,-os;l,. d~ ion exchange materials are ~u~ kA~'y available.
These al~",i,~: c can be crystalline or amorphous in structure and can be 25 naturally-occurring alullli~losil;~ a or s~"~ ic~l'y derived. A method for producing alL""i"osili~ e ion exchange materials is disclosed in U.S. Patent 3 985 669 Krummel et al issued October 12 1976. Preferred synthetic crystalline aiL",i" :~ ion exchange materials useful herein are available under the desi~"d~i-,ns Zeolite A Zeolite P (B) and Zeolite X. In an especially 30 preferred ~ bodi~llell~ the crystalline alullli,l ion exchange material has the formula:
Na12i(AI02)12(SiO2)12u.xH20 3s wherein x is from 2û to 30 especially about 27. This material is known as Zeolite A. Preferably the al~",i,: - has a particle âize of about û.1-10 microns in diameter.
wo ssns l 60 r ~ ~ r. ~
8 2l 855~5 ~
Other suitable silicates to be used herein are for instance magnesium silicates such as Mg3(0H)4Si20s.
s The Cul~l,ùOa;liùlla according to the present invention may comprise a magnesium compound 1,vhich acts to partially stabilize the hydrogen peroxide and hardens the water in the wash solution in which the Culll,uOaitiullS are used.
The CullIpOai~iul~S of the present invention preferably comprise from 0.1% to 5%10 by weight of the total ,u~,uosiliol~ of magnesium compounds, e.g. magnesium sulfate, and preferably from 0.5% to 3%.
The ~,ullluOaiLiulls according to the present invention may naturally comprise inorganic filler salts such as alkali metal cdluol,~,L~s, bi~dluull. ~,~ and 15 sulphates. Such fillers for instance sodium bicdlL,u,,dL~, may also act as acidifyin3 agent as described herein after. Accordingly, sodium ~iCdlLJUlldLe and sodium sulphate are the preferred filler materials for use herein.
20 The present invention makes possible the production of a cu,,,~siLiu,, which provides stain removal, cleaning, deûr~ dliol~, whitening, bleaching and/or d,ai"r~ iul, d~e"u'~"g on the i"y,c~dirl,~a included therein. Co,ll,uuailiOI~S in accu,dd"ce with the invention can thus comprise optional i, Iyl~,iie:l ,Ls such as optical b,iyl,lel~e,a, anti dusting agents such as olefines and waxes, enzymes, 2s other chelarlts, ~iSp~ladllla, surfactants, soil release agents, soil suspenders, builders, photoactivated bleaches such as Zn phthalocyanine sulphonate, dyes, dye transfer inhibitors, pigments and perfumes. Said optional i"yl t:~ie, lls can be added in varying amounts as desired.
30 Indeed, particularly preferred herein are uulll,uOailiul15 which beside theirprolonged bleaching properties, i.e. Ionger period of effective bleaching provided upon dissolution of said cu~uùsilion in water, further provide good cleaning pe,ru,,,,d,,ce on fabrics soiled with mud/clay containing soils, such as socks. Accordingly the cull"~ailions herein may further comprise a soil 3s suspender. Suitable soil suspenders, also dch"o.~'~iyed in the art under the name of "anti-,ed~ agents", to be used in the ,u,,,pùsilio~s of the present invention include cellulose derivatives such as methylcellulose, wo 95/25160 2 1 8 ~, r~ 4 5PC~
carboxymethylcellulose and hydroxyethycellulose, homo-or co-polymeric polycarboxylic acids or their salts and polyamino compounds. Polymers of this type include the polyacrylates and copol~" ,~, ~ of maleic anhydride with ethylene, methylvinyl ether, acrylic acid or methacrylic acid, the maleic s anhydride constituting at least 20 mole percent of the copolymer disclosed in detail in EP-A-137 669. Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight of from 1 0û0 to 10000 and more preferably of from 2û00 to 8û00.
10 Accordingly the ,,o"",~sili~ns of the present invention comprise up to 20% byweight of the total c~ ,u~i~io,, of a soil suspender, or mixtures thereof, preferably from 3% to 15% by weight and more preferably from 5% to 14% and most preferably from 7 to 14%.
15 As an optimal but highly preferred cu,~,,uull~ the c~",~.osiliù,~s according to the present invention further comprise an acidifying system. The purpose of said acidifying system is to control the alkalinity generated by the source of available oxygen and any alkaline compûunds present in the wash solution.
Said system comprises anhydrous acidifying agent, or mixtures thereof, which 20 needs to be i"~,u~,uul ' i in the product in an anhydrous form, and to have agood stability in oxidizing environment. Suitable anhydrous acidifying agents for use herein are carboxylic acids such as citric acid, succinic acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid and maleic acid or their salts or mixtures thereof. Other suitable acidifying agents include 2s sodium bicdl ~u"ale, sodium sesquicd, ~u"dle and silicic acid. Preferred acidifying system to be used herein comprise citric acid and/or sodium citrate and optionally bicdl ~ondl~. Highly preferred as the acidifying system is citricacid. Indeed, citric acid is uu,,,,,,t:,-,ially available in anhydrous form, it a~di~io~ y acts as a builder and a chelant, and it is bi~dey,~dable. The 30 cu,,,,uûsiliulls according to the present invention comprise from up to 20% by weight of the total cu",,uosiliu,~ of anhydrous citric acid, preferably from 5% to 15%, most preferably about 10%.
It has been found that by formulating the uu~,uosiliol)s of the present invention, 35 especially the ones which further comprise a soil suspender, to control pH inthe wash solution and keep it below 9.5, said cu,,,,oosiliù~)s are able of boosting the cleaning pe,ru""d-,ce on mud/clay c~"lai"i,~g soil. Accordingly preferred WO95/25160 2 ~ T~
uo~,poailions to be used according to the present invention comprise an acidifying system, the weight ratio of the source of available oxygen, alkali metal salt of silicate together with carbonate, if present, to said acidifying system being inferior to 4, preferably inferior to 3.5.
s Optional but highly preferred ill~ ta are peroxy carboxylic acids bleach or precursors thereof, commonly referred to as bleach activators, which are preferably added in a prilled or a~ ",e,d~d form. Examples of suitable 10 compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 23~ and a method for their formation into a prilled form is described in European Published Patent Application EP-A-62 523. Preferred examples of such compounds are tetracetyl ethylene diamine, (TAED), sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dudeLdl ,oi-, acid as 15 described for instance in US 4 818 425 and nonylamide of peroxyadipic acid asdescribed for instance in US 4 259 201 and n-nonanoylox~b~"~t~,~esulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in European patent 91870207.7. Also particularly preferred are N-acyl ,d,UIUId~, selected from the group consisting of sllhstitlJt~d or uns~hstit~lt~d benzoyl 20 Cd~)l Uldl,ldl 11, octanyl Cd~.ll uld~,lal 11, nonanoyl Cd,Ul uld~.lal 11, hexanoyl Cd~)l Uldl,ldl 11, decanoyl Cd,ul Uld-,ldl 11, undecenoyl Capl ulal~ld~ formyl Ud,UI UldUIdl 11, acetyl Cd,Ul UldUIdl 11, propanoyl Cdul UldUIdl 11, butanoyl W,UI ula~.Ldl 11 pentanoyl Cd,ulUlal,lalll. The Culll~uailiullS of the present invention may comprise one of the above " le:l ,liù,~ed bleach activators or mixtures thereof 2s Preferred mixtures of bleach activators to be used in the ,u~,uosiliùns of the present invention comprise n-nonanoylox~lu~ esulphonate (NOBS~ together with a second bleach activator having a low tendency to generâte diacyl peroxide but which delivers in the wash mainly peracid. Said second bleach 30 activators include tetracetyl ethylene diamine (TAED), acetyl triethyl citrate (ATC), acetyl ud,ululd~,ldll~, benzoyl ca~lulduLdl~l and the like, or mixtures thereof. Said mixtures of bleach activators are preferably used in the ~Illbudi~ l of the present invention where the C~lll,uOailiûl~s of the present invention, especially the ones which further comprise a soil suspender, are 3s formulated to allow the control of the pH in the wash solution below 9.5.
Indeed, it has been found that the above ",~"lioned c~lll,u~ailiul~s of the present invention which further comprise a mixture of bleach activators WO 95/25160 11 I ~ U~ O2SO3 ,u, ",urisi"~ n-nûnanoyloxyb~ en~sulphûnate and said second bleach activatûr, allow tû boûst particulate sûil (clay) cleaning pa~ru""a~ue while exhibiting at the same time gûûd p~lrUlllldll-~e on diacyl perûxide sensitive soil (e.g. beta-carotene) and ûn peracid sensitive sûil (e.g. bûdy soils).
Accordingly in an ~"ILoui",a"l of the present inventiûn the c~,,,pûsiliu,,:, maycomprise mûre than 3% by weight of the total ~,u,,,pûsiliu,, of n-nonanûylûx~e, ~ e:,ulphonate, préferably frûm 4% to 1 û% and more preferably from 5% to 7% and mûre than û.5% by weight of the tûtal cr.,,,,uo:~iliùl~ of said second bleach activatûr, or mixtures thereof, preferably from 2% to 8% and more preferably from 5% to 7% .
The c~l~l,uOailiûl~ according to the present invention can be made by a variety 5 of methods well knûwn in the art, including dry-mixing, spray drying, a~!Jlu" ,~ .,lion and granulation and ~,~" IL;, ICII;OI ~5 thereof.
The cu,,,,uosili~,~s according to the present invention can be prepared with 20 different bulk densities, frûm conventional granular products to so-called "uul~c~l ,t, ~l~d" products (i.e. with a bulk density above 600911).
The present invention also e,~c~",,uasses the use of an alkali metal salt of 25 silicate, or mixture thereof, in a granular r~r.",,uùsiliu" uu"~p~isi"9 a source of available oxygen, whereby the decu,,,,uo~ilio,~ with time of the available oxygen produced upon dissolution of said co"".osi~io,~ in water is reduced.
30 By ''d~,,,,.,osiliû,~ of available oxygen is reduced" it is meant herein that the amount of available oxygen in the wash solution is higher when said wash solution is produced with the c~"~ û~itions of the present invention as compared to the same cu,,,i,osiliùns but without an alkali metal salt of silicate, - even if measured after 24 hours. The available oxygen clecu",posiLioll 3s reduction effect of an alkali metal salt of silicate, i.e. the higher available oxygen retention phel,u,na"u" through the wash, may be measured using a standard indirect redox titration with iodide and thiosulfate as titratin3 agents WO 95/25160 P~
~ ~ 8 ~ 12 and starch as indicator. This method is reported in the literature, see for instance "Analisi Chimica Quantitativa, Emilio Bottari, Arnaldo Liberti, 1983, page 308".
s The present invention aiso e,~ ""~asses the use of an acidifying system in a laundry cu",posiliu~ u~p~isi"~ a source of available oxygen, an alkali metal salt of silicate and optionally carbonate, v~herein the weight ratio of the source of available oxygen, alkali metal salt of silicate together with carbonate, if present, to said acidifying system is inferio! to 4, whereby the pH in the dilution 10 Culll,uuailiull (wash solution) obtained upon diâsolution of said cu",pùsili,o,l in water is kept below 9.5, whereby the cleaning pe,ru""d"ce on mudlclay Cullld;llillg soil is improved. In a preferred ~",uodi",~"l said cu",uosiliu"
further comprise a soil suspender and/or a chelating agent, andlor a bleach activator. In a further preferred ~",bodi",t",l said culll~Joai~iul) comprises a15 mixture of bleach activators, said mixture cu",~,risi"g n-nonanoyloxybt"l~l1es.llphonate and a second bleach activator, said second bleach activator being selected from the group of tetracetyl ethylene diamine, acetyl triethyl citrate, acetyl Cd,ulUId~,ldlll, benzoyl cau,ula~,ld,,, or mixtures thereof, preferably said cu",~osi~iù,) comprises more than 3% by weight of the 20 total Culll,uOailiull of n-nonanoyloxy~e"~nesulphonate and more than û.5% by weight of the total COIll,uua;~iull of said second bleach activator.
The present invention also 3nco",~asses a process of treating fabrics with a source of available oxygen wherein a granular C~ uai~iull wlll,u,isi"g said 2s source of available oxygen and an alkali metal salt of silicate, or mixture thereof, is diluted in water and said fabrics are left to soak in said diluted cu",,uùsi~;on (wash solution), then either rinsed and left to dry or washed and left to dry.
30 By "washed" it is meant herein that the soaking step carried out according tothe process of treating fabrics of the present invention may be followed by a washing step, said washing step includes washing with an automatic washing machine andlor washing by hand.
The culll~Josiliùl)s of the present invention are particularly suitab~e to be used for treating baby napkins, linen and clothing co"ld",i"dl~d by body exudates.
WO95/25160 r_l,l,.. ..
13 2 1 ~
Depending on their lesl,euli;e formulation said c~"~uosili~",s are alsoparticularly suitable to be used for treating socks and linen and clothing co, lldll ,i, . by mud/clay soils. The cu,,,~osiliu,ls of the present inventions are also particularly suitable to be used upon long soaking periods in both hot and s cold water.
Ex~el il l lel ILdl data 1 ) Part A
The following cu,,,p~ iù,~s are made with the listed illyre~ie"La in the listed ~, u~u, liù~ ,s.
Co"",usilions (% by wêight) 15 ll lul ediél ,~
Sodium perw,l,~" 3û 30 30 30 Sodium carbonate 30 30 30 3û
Citric acid 5 5 5 5 20 Polyacrylate 2 2 2 2 Sodium Li~ dl L,oll 25 25 25 25 LAS~ 5 5 5 5 Sodium silicate / 5 / 5 Magnesiumsulphate / 1 1.2 1.2 25 DETMPA~ / l û.3 0.3 Minors and water up to 1 oo%
30 LAS ~ is linear sodium alkyl benzene sulfonate.
DETMPA~ is diethylen triamino péllldCeli. acid.
~ .
WO 95/25160 r~,l"
2)PartB 21 85545 The c~,,,,uosiliù~s above were evaluated in terms of the amount of available oxygen present in the wash solutions produced by using respectively said S Culll~Oai liu~s.
The eApe~i"~ l was conducted to replicate the realistic soaking conditions.
For this purpose we used hard water (17gr/us gallon) and stains standards on cotton of blood, wine, coffee, grass and sebum From the EMPA institute.
The wash solutions were prepared by dissolving 3û grams of each of the c~ uaiLiùl~â 1, 2, 3 and 4 in 7 liters of water. These wash solutions were prepared at 60C and held for 24 hours at an ambient temperature of about 25C. The available oxygen content remaining in each of the wash solutions was measured at time 1 hour, 6 hours, 16 hours and 24 hours.
The method used for measuring the available oxygen content remainin3 in the wash solutions was a standard indirect redox titration with iodide and thiosulfate as titrating agents and starch as indicator.
The table below lists the results obtained for the above mentioned culll~ailiO~Is with and without sodium silicate, in terms of % of available oxygen (AvO2) retained in the wash solutions at different times following the pdld~iUI) of said wash solutions with said c~""~osili~ns.
Co" ,!,osi~iùl ,s 1 2 3 4 (% of AvO2 retained) 1 hour 1ûO 10û 100 100 6 hours 1 78 87 96 30 16 hours / 58 73 89 24 hours 31 55 66 88 The results show that a c~",posilio,~ co",~.,isi"g pe,ud,uol,d~e and sodium silicate (c~",~o:,iliù,~ 2) as compared to the same cu",~ailion but without 35 sodium silicate (c~,,,,uùsiliùll 1), allows to produce a wash solution wherein the amount oF available oxygen is higher, even after a long soaking period, e.g. 24 hours. This clearly shows that the use of sodium silicate allows to reduce the w095/25160 2 1 8 5 5 ~ 5 decomposition of available oxygen produced in the wash solution and thereby allows to retain the bleaching capacity of said wash solution upon longer periods of time. The results obtained with c~,,,pc,siliu,,s 2 and 3 are equivalents. Indeed, sodium silicate allows to obtain the same benefits as compared to others known stabilizers like chelants. However, when adding sodium silicate on top of said other stabilizers like chelants such as diethylene triamino p~ dC~IiC acid and magnesium sulphate in a ~",l~u~ designed to prepare a washlsûaking solution, the available oxygen in said wash solution is i~ll~ill~d to up to 88% of the initial available oxygen after 24 hours. This 0 translates in an overall improved pe~rulllldll~e ~so~ with the use of the cu~,uusil;ol la of the present invention, e.g. better Uiiil II~I..liOl~ and/or cleaning.
ExamPles 15 Further examples of cull~,u~ailiOlla according to the present invention are the following. The following ctj",~,osiliol1s are made with the listed illyl~ llla in the listed ~lu~ ulliu"s.
Cu"luosiliol)a (% by weight) "t~
Sodium pe,w,bù,~dl~ 34 26 26 30 30 Sodium perborate monohydrate I I I I 1 27 2s TAED 2 1 2 / 6 Sodium sulfate 30 30 30 25 25 Citric acid 5 5 5 10 10 10 Sodium tjiCdl uu, Idl~ ~ 9 25 19 30 LAS~ 7 5 7 6 6 5 Nonionic / I 1 1 1 2 Sodium silicate 4 3.5 4 5.9 5.9 Zeolites I I I I 1 10 Magnesium sulphate 1.2 1.2 1.2 3s DETMPA~ û.3 0.3 û.3 0.2 0.2 0.3 Polyacrylate / I 1 1û 10 10 Minors and water up to 100%
WO 95/25160 1 ~,I/~J.,.
16 21 ~5~5 LAS ~ is linear sodium alkyl benzene sulfonate.
DETMPA~ is diethylen triamino ,u~"lacelic acid.
s The co",uosiLiù,~s above when used to produc~ a soak solution show an overall improved pe, ru""c"~3 compared to the product cu~ "y available. These c~,,,,uosiliù,~s are efficient in terms of cleaning, cle~du,i~i,,g, bleaching, ~ ;. Irt ~ u and/or stain removal. For example c~,,,,uosiliu,, 5 when used upon 10 soaking conditions for treating fabrics (e.g. Iinen and/or clothing) delivers at the same time optimized pe,ru""anc~ on particulate soil (clay), on diacyl peroxide sensitive soil (e.g. beta-carotene) and on peracid sensitive soil (e.g. shirts collars, body soil).
s Summarv of the invention Co~uosiliùl~s according to the present invention are granular ~u,,,posiliù,ls cu,,,urisill~ a source of available oxygen and diethylene triamino pe"lact:lic acid. Said ù,,luosiliu,~s further comprise an alkali metal salt of silicate or mixtures thereof.
The present invention also encol"passes the use of an alkali metal salt of silicate, or mixtures thereof in a granular laundry CulllpOait;OIl Culll~risi,lg a source of available oxygen whereby the dec~",uo~ " with time of the available oxygen produced upon dissolution of said c~ Juailiùll in water is 20 reduced.
The present invention also el~co,,,udaaes a process of treating fabrics with a source of available oxygen wherein a granular ~ul~luùailiull culllp~iaillg said source of available oxygen and an alkali metal salt of silicate or mixtures 2s thereof is dissolved in water and said fabrics are left to soak in said diluted c~ ûsiliul 1 then either washed and left to dry or rinsed and left to dry.
Cetailed cl~su, iuliul~ of the invention The CCIll,ùOai~iùl-a according to the present invention comprises as a first essential ingredient a source of available oxygen. By source of available 35 oxygen it is meant herein an active oxygen-releasing peroxy compound or mixtures thereof. The peroxy compound may be hydrogen peroxide or any of the addition compounds of hydrogen peroxide or organic peroxyacid or wo 95/25160 2 1 8 5 5 ~ 5r~
mixtures thereof. By addition compounds of hydrogen peroxide it is meant compounds which are formed by the addition of hydrogen peroxide to a second chemical compound, which may be for example an inorganic salt, urea or organic carboxylate, to provide the addition compound. Examples of the s addition compounds of hydrogen peroxide include inorganic perhydrate salts, the compounds hydrogen peroxide fomms with organic carboxylates, urea, and compounds in which hydrogen peroxide is clathrated.
Examples of inorganic perhydrate salts include perborate, pe,w,bù,,dL~l10 pel;Jl~apl~dl~ and p~, ' ' salts. The inorganic perhydrate salts are normally the alkali metal salts.
The alkali metal salt of pe,w,L,u"ale, perborate or mixtures thereof, are the preferred inorganic perhydrate salts for inclusion in the w,np~ailiuns in accu, dd,~-,e with the present inYention. Preferred alkali metal salt of pe(~;d,u.",dla to be used herein is sodium p~w~vnale. Sodium pelwlb~l~dl~
is available cu"""e,~ -'ly as a crystalline solid. Most cu"""e~ !y available materials include low levels of heavy metal sequestrats such as EDTA, 1-hydroxyethylidene 1, 1 d~ ua~Jllorlic acid (HEDP) or an amino-pl)ospl~ù~ e, 20 which are illC~ uldl~d during manufacturing process Preferred alkali metal salt of perborate to be used herein is sodium perborate. For the purposes of the present invention, the pe,w,L.u,lc,l~ or perborate can be ill~,~l,uo,dlt:d into detergent cu, ~,uuSi~iO~ la without additional protection.
2s Whilst heavy metals present in the sodium carbonate used to manufacture the pe,w,Lul,c,L~ can be controlled by the inclusion of sequestrats in the reaction mixture, it is preferred that the pel~,dl~Ulld~t: be protected from heavy metalspresent as impurities in other i"u~ ic. Il:- of the product. It has been found that the total level of Iron, Copper and Al ,ga"ese ions in the product should not0 exceed 25 ppm and preferably should be less than 2û ppm in order to avoid an Jl~ adverse effect on p~lwlLor~ , stability during its storage.
The Cûll,pOsiliul,S according to the present invention comprise from 10% to 80% by weight of the total Culll~uosiliu" of a source of available oxygen, 3s preferably from 15% to 50% and more preferably from 20% to 45%. When a co",posi~iu" of the present invention is used under normal conditions to produce the wash solu~ion, i.e. 15-7û9 of a c~ ailiul~ according to the ~ WO 95/25160 2 1 8 5 5 ~ 5 r~
present invention are dissolved in about 7 liters of water, said wash solution comprises from 0.3% to 11% by weight of the total wash solution of available oxygen, preferably of from 0.45% to 7% and more preFerably of from 0.6% to 6.2%. By "available oxygen" it is meant herein the active oxygen released by 5 hydro3en peroxide in the wash upon its reduction. Said hydrogen peroxide beins itself released by the active oxygen-releasing peroxy compounds, more generally defined herein under the name of source of available oxygen.
As a second essential Gompound the cu",,uo~ilio,~s of the present invention 10 Gomprise diethylene triamino pélltace~ acid as a stabilizer like chelant. Said Gheiating agent helps to control the ievel of free heavy metal ions in the wash solution, thus avoiding rapid dec~",~osi~i~n of the hydrogen peroxide released by said source of available oxygen of the ~u",posi~io,~s of the present invention.
Other suitable amino calL ox~l..'~, chelating agents may be used in the 15 G~lllpûai~iOIla of the present invention such as ethylelledid"~i"e lètldace~dLes (EDTA), N-hydroxyethylethyle,~e.Jia",i"e l~iac~t.,t~,3, Il ilu;,iace~ 3, ethy~ e~id",i"e léLla,ulu,uliOII_~ ., triethyl~ t~,;,dd")i"e h~ æ~ ;, and t:LI Idl "~Idiy,ycines, alkali metal ammonium and sl Ihstit~ It~d ammonium saltsthereof or mixtures thereof. Further suitable chelating agents include 20 ethylc~edialllille-N~N~- disuccinic acids (EDDS) or alkali metal, alkaline earth metal, ammonium, or sllhsti~t~d ammonium salts thereof, or mixtures thereof.
Particularly suitable EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof. Also others suitable chelating agents may be the organic ,ul luaiJI lurldleSl including amino alkylene poly(alkylene 2s ~ OalJl lùl 1_`~.), alkali metal ethane 1 -hydroxy di~l~o~,l lOndlèS, nitrilotrimethylene pllOapl~Orl-~3l ethylene diamine tetra methylene pl~ûa,ullOIldlès and diethylene triamine penta methylene l~llùsullulld~es. The ,ullosullo~ld~e compounds may be present either in their acid form or in the form of their metalalkali salt. Preferably the organic ,ul)osul~r~_`u compounds where present are 30 in the form of their magnesium salt.
The cOIll~oaiLiol~s according to the present invention comprise from 0.01% to 5% by weight of the total Culll~Oailiul ,s of said chelating agents, preferably from û.û5% to 2%, more preferably from 0.1% to 1%.
3s As a third essential compound the c~",,uosiliuns of the present invention further comprise an alkali metal salts of silicate or mixtures thereof. Preferred alkali wo ssnsl60 ;~ 1 8 5 5 ~, 5P~
metal salt of silicate to be used herein is sodium silicate. It has been found that the decu",posilio,1 of available oxygen produced in the wash solution upon dissolution of a culll,uuailiull of the present invention is reduced by the presence of at least 4û parts per million of sodium silicate in said wash s solution. Accordingly, the present cc",~oai~iùns comprise from û.5% to 15% by weight of the total l,u~,uOailion of an alkali metal salt of silicate, or mixtures thereof, preferably from 1% to 10% and more preferably from 2% to 7%.
Any type of alkali metal salt of silicats can be used in the colll,uo5iliol~s of the present invention including the crystalline forms as well as the amorphous forms of said alkali metal salt of silicate or mixtures thereof. Preferred herein is to use the crystalline forms as well as the amorphous forms of sodium silicate or mixtures thereof.
Suitable cr,vstalline forms of sodium silicate to be used according to the present invention are the crystalline layered silicates of the granular formuia NaMSixO2xt1 yH2o wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from û to 20, or mixtures thereof. Crystalline layered sodium silicates of this type are disclosed in EP-A-164 514 and methods for their ul~dldliùl~ are 2s disclosed in DE-A-34 17 649 and DE-A-37 42 043. For the purposes of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the a, b, g and d forms of Na2Si2Os These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS~. The most preferred material is d -Na2Si2Os NaSKS~. Crystalline layered silicates are i~-,UI,UUI~ either as dry mixed solids, or as solid Culll~ol1~llLa of au~lullle:ldlc:s with other cc,,,~û, ,e, ILa.
3s Suitable amorphous forms of sodium silicate to be used herein have the following generai formula:
WO 95125160 2 1 8 5 5 4 5 . ."J~ s ~ ~
NaMSixo2x+1 wherein M is sodium or hydrogen and x is a number from 1.9 to 4 or mixtures s thereof. PreFerred to be used herein are the amorphous fomms of Si20s Na20.
Other suitable alkali metal salt of silicate to be used herein are al~",i, IOail;~Lt:s including those having the empirical formula:
Mz(zAI02.ySiO2) wherein M is sodium potassium ammonium or s~hstit~'?~ ammonium z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at ieast about 50 milligram equivalents of CaC03 hardness per gram of anhydrous alulllill~a;i~ . Preferred alu",i"c are zeolites which have the formula:
Nazi(AI02)z (SiO2)yù.xH20 20 wherein z and y are integers of at least 6 the molar ratio of z to y is in the range from 1.0 to about 0.5 and x is an integer from about 15 to about 264.
Useful alu",i,-os;l,. d~ ion exchange materials are ~u~ kA~'y available.
These al~",i,~: c can be crystalline or amorphous in structure and can be 25 naturally-occurring alullli~losil;~ a or s~"~ ic~l'y derived. A method for producing alL""i"osili~ e ion exchange materials is disclosed in U.S. Patent 3 985 669 Krummel et al issued October 12 1976. Preferred synthetic crystalline aiL",i" :~ ion exchange materials useful herein are available under the desi~"d~i-,ns Zeolite A Zeolite P (B) and Zeolite X. In an especially 30 preferred ~ bodi~llell~ the crystalline alullli,l ion exchange material has the formula:
Na12i(AI02)12(SiO2)12u.xH20 3s wherein x is from 2û to 30 especially about 27. This material is known as Zeolite A. Preferably the al~",i,: - has a particle âize of about û.1-10 microns in diameter.
wo ssns l 60 r ~ ~ r. ~
8 2l 855~5 ~
Other suitable silicates to be used herein are for instance magnesium silicates such as Mg3(0H)4Si20s.
s The Cul~l,ùOa;liùlla according to the present invention may comprise a magnesium compound 1,vhich acts to partially stabilize the hydrogen peroxide and hardens the water in the wash solution in which the Culll,uOaitiullS are used.
The CullIpOai~iul~S of the present invention preferably comprise from 0.1% to 5%10 by weight of the total ,u~,uosiliol~ of magnesium compounds, e.g. magnesium sulfate, and preferably from 0.5% to 3%.
The ~,ullluOaiLiulls according to the present invention may naturally comprise inorganic filler salts such as alkali metal cdluol,~,L~s, bi~dluull. ~,~ and 15 sulphates. Such fillers for instance sodium bicdlL,u,,dL~, may also act as acidifyin3 agent as described herein after. Accordingly, sodium ~iCdlLJUlldLe and sodium sulphate are the preferred filler materials for use herein.
20 The present invention makes possible the production of a cu,,,~siLiu,, which provides stain removal, cleaning, deûr~ dliol~, whitening, bleaching and/or d,ai"r~ iul, d~e"u'~"g on the i"y,c~dirl,~a included therein. Co,ll,uuailiOI~S in accu,dd"ce with the invention can thus comprise optional i, Iyl~,iie:l ,Ls such as optical b,iyl,lel~e,a, anti dusting agents such as olefines and waxes, enzymes, 2s other chelarlts, ~iSp~ladllla, surfactants, soil release agents, soil suspenders, builders, photoactivated bleaches such as Zn phthalocyanine sulphonate, dyes, dye transfer inhibitors, pigments and perfumes. Said optional i"yl t:~ie, lls can be added in varying amounts as desired.
30 Indeed, particularly preferred herein are uulll,uOailiul15 which beside theirprolonged bleaching properties, i.e. Ionger period of effective bleaching provided upon dissolution of said cu~uùsilion in water, further provide good cleaning pe,ru,,,,d,,ce on fabrics soiled with mud/clay containing soils, such as socks. Accordingly the cull"~ailions herein may further comprise a soil 3s suspender. Suitable soil suspenders, also dch"o.~'~iyed in the art under the name of "anti-,ed~ agents", to be used in the ,u,,,pùsilio~s of the present invention include cellulose derivatives such as methylcellulose, wo 95/25160 2 1 8 ~, r~ 4 5PC~
carboxymethylcellulose and hydroxyethycellulose, homo-or co-polymeric polycarboxylic acids or their salts and polyamino compounds. Polymers of this type include the polyacrylates and copol~" ,~, ~ of maleic anhydride with ethylene, methylvinyl ether, acrylic acid or methacrylic acid, the maleic s anhydride constituting at least 20 mole percent of the copolymer disclosed in detail in EP-A-137 669. Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight of from 1 0û0 to 10000 and more preferably of from 2û00 to 8û00.
10 Accordingly the ,,o"",~sili~ns of the present invention comprise up to 20% byweight of the total c~ ,u~i~io,, of a soil suspender, or mixtures thereof, preferably from 3% to 15% by weight and more preferably from 5% to 14% and most preferably from 7 to 14%.
15 As an optimal but highly preferred cu,~,,uull~ the c~",~.osiliù,~s according to the present invention further comprise an acidifying system. The purpose of said acidifying system is to control the alkalinity generated by the source of available oxygen and any alkaline compûunds present in the wash solution.
Said system comprises anhydrous acidifying agent, or mixtures thereof, which 20 needs to be i"~,u~,uul ' i in the product in an anhydrous form, and to have agood stability in oxidizing environment. Suitable anhydrous acidifying agents for use herein are carboxylic acids such as citric acid, succinic acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid and maleic acid or their salts or mixtures thereof. Other suitable acidifying agents include 2s sodium bicdl ~u"ale, sodium sesquicd, ~u"dle and silicic acid. Preferred acidifying system to be used herein comprise citric acid and/or sodium citrate and optionally bicdl ~ondl~. Highly preferred as the acidifying system is citricacid. Indeed, citric acid is uu,,,,,,t:,-,ially available in anhydrous form, it a~di~io~ y acts as a builder and a chelant, and it is bi~dey,~dable. The 30 cu,,,,uûsiliulls according to the present invention comprise from up to 20% by weight of the total cu",,uosiliu,~ of anhydrous citric acid, preferably from 5% to 15%, most preferably about 10%.
It has been found that by formulating the uu~,uosiliol)s of the present invention, 35 especially the ones which further comprise a soil suspender, to control pH inthe wash solution and keep it below 9.5, said cu,,,,oosiliù~)s are able of boosting the cleaning pe,ru""d-,ce on mud/clay c~"lai"i,~g soil. Accordingly preferred WO95/25160 2 ~ T~
uo~,poailions to be used according to the present invention comprise an acidifying system, the weight ratio of the source of available oxygen, alkali metal salt of silicate together with carbonate, if present, to said acidifying system being inferior to 4, preferably inferior to 3.5.
s Optional but highly preferred ill~ ta are peroxy carboxylic acids bleach or precursors thereof, commonly referred to as bleach activators, which are preferably added in a prilled or a~ ",e,d~d form. Examples of suitable 10 compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 23~ and a method for their formation into a prilled form is described in European Published Patent Application EP-A-62 523. Preferred examples of such compounds are tetracetyl ethylene diamine, (TAED), sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dudeLdl ,oi-, acid as 15 described for instance in US 4 818 425 and nonylamide of peroxyadipic acid asdescribed for instance in US 4 259 201 and n-nonanoylox~b~"~t~,~esulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in European patent 91870207.7. Also particularly preferred are N-acyl ,d,UIUId~, selected from the group consisting of sllhstitlJt~d or uns~hstit~lt~d benzoyl 20 Cd~)l Uldl,ldl 11, octanyl Cd~.ll uld~,lal 11, nonanoyl Cd,Ul uld~.lal 11, hexanoyl Cd~)l Uldl,ldl 11, decanoyl Cd,ul Uld-,ldl 11, undecenoyl Capl ulal~ld~ formyl Ud,UI UldUIdl 11, acetyl Cd,Ul UldUIdl 11, propanoyl Cdul UldUIdl 11, butanoyl W,UI ula~.Ldl 11 pentanoyl Cd,ulUlal,lalll. The Culll~uailiullS of the present invention may comprise one of the above " le:l ,liù,~ed bleach activators or mixtures thereof 2s Preferred mixtures of bleach activators to be used in the ,u~,uosiliùns of the present invention comprise n-nonanoylox~lu~ esulphonate (NOBS~ together with a second bleach activator having a low tendency to generâte diacyl peroxide but which delivers in the wash mainly peracid. Said second bleach 30 activators include tetracetyl ethylene diamine (TAED), acetyl triethyl citrate (ATC), acetyl ud,ululd~,ldll~, benzoyl ca~lulduLdl~l and the like, or mixtures thereof. Said mixtures of bleach activators are preferably used in the ~Illbudi~ l of the present invention where the C~lll,uOailiûl~s of the present invention, especially the ones which further comprise a soil suspender, are 3s formulated to allow the control of the pH in the wash solution below 9.5.
Indeed, it has been found that the above ",~"lioned c~lll,u~ailiul~s of the present invention which further comprise a mixture of bleach activators WO 95/25160 11 I ~ U~ O2SO3 ,u, ",urisi"~ n-nûnanoyloxyb~ en~sulphûnate and said second bleach activatûr, allow tû boûst particulate sûil (clay) cleaning pa~ru""a~ue while exhibiting at the same time gûûd p~lrUlllldll-~e on diacyl perûxide sensitive soil (e.g. beta-carotene) and ûn peracid sensitive sûil (e.g. bûdy soils).
Accordingly in an ~"ILoui",a"l of the present inventiûn the c~,,,pûsiliu,,:, maycomprise mûre than 3% by weight of the total ~,u,,,pûsiliu,, of n-nonanûylûx~e, ~ e:,ulphonate, préferably frûm 4% to 1 û% and more preferably from 5% to 7% and mûre than û.5% by weight of the tûtal cr.,,,,uo:~iliùl~ of said second bleach activatûr, or mixtures thereof, preferably from 2% to 8% and more preferably from 5% to 7% .
The c~l~l,uOailiûl~ according to the present invention can be made by a variety 5 of methods well knûwn in the art, including dry-mixing, spray drying, a~!Jlu" ,~ .,lion and granulation and ~,~" IL;, ICII;OI ~5 thereof.
The cu,,,,uosili~,~s according to the present invention can be prepared with 20 different bulk densities, frûm conventional granular products to so-called "uul~c~l ,t, ~l~d" products (i.e. with a bulk density above 600911).
The present invention also e,~c~",,uasses the use of an alkali metal salt of 25 silicate, or mixture thereof, in a granular r~r.",,uùsiliu" uu"~p~isi"9 a source of available oxygen, whereby the decu,,,,uo~ilio,~ with time of the available oxygen produced upon dissolution of said co"".osi~io,~ in water is reduced.
30 By ''d~,,,,.,osiliû,~ of available oxygen is reduced" it is meant herein that the amount of available oxygen in the wash solution is higher when said wash solution is produced with the c~"~ û~itions of the present invention as compared to the same cu,,,i,osiliùns but without an alkali metal salt of silicate, - even if measured after 24 hours. The available oxygen clecu",posiLioll 3s reduction effect of an alkali metal salt of silicate, i.e. the higher available oxygen retention phel,u,na"u" through the wash, may be measured using a standard indirect redox titration with iodide and thiosulfate as titratin3 agents WO 95/25160 P~
~ ~ 8 ~ 12 and starch as indicator. This method is reported in the literature, see for instance "Analisi Chimica Quantitativa, Emilio Bottari, Arnaldo Liberti, 1983, page 308".
s The present invention aiso e,~ ""~asses the use of an acidifying system in a laundry cu",posiliu~ u~p~isi"~ a source of available oxygen, an alkali metal salt of silicate and optionally carbonate, v~herein the weight ratio of the source of available oxygen, alkali metal salt of silicate together with carbonate, if present, to said acidifying system is inferio! to 4, whereby the pH in the dilution 10 Culll,uuailiull (wash solution) obtained upon diâsolution of said cu",pùsili,o,l in water is kept below 9.5, whereby the cleaning pe,ru""d"ce on mudlclay Cullld;llillg soil is improved. In a preferred ~",uodi",~"l said cu",uosiliu"
further comprise a soil suspender and/or a chelating agent, andlor a bleach activator. In a further preferred ~",bodi",t",l said culll~Joai~iul) comprises a15 mixture of bleach activators, said mixture cu",~,risi"g n-nonanoyloxybt"l~l1es.llphonate and a second bleach activator, said second bleach activator being selected from the group of tetracetyl ethylene diamine, acetyl triethyl citrate, acetyl Cd,ulUId~,ldlll, benzoyl cau,ula~,ld,,, or mixtures thereof, preferably said cu",~osi~iù,) comprises more than 3% by weight of the 20 total Culll,uOailiull of n-nonanoyloxy~e"~nesulphonate and more than û.5% by weight of the total COIll,uua;~iull of said second bleach activator.
The present invention also 3nco",~asses a process of treating fabrics with a source of available oxygen wherein a granular C~ uai~iull wlll,u,isi"g said 2s source of available oxygen and an alkali metal salt of silicate, or mixture thereof, is diluted in water and said fabrics are left to soak in said diluted cu",,uùsi~;on (wash solution), then either rinsed and left to dry or washed and left to dry.
30 By "washed" it is meant herein that the soaking step carried out according tothe process of treating fabrics of the present invention may be followed by a washing step, said washing step includes washing with an automatic washing machine andlor washing by hand.
The culll~Josiliùl)s of the present invention are particularly suitab~e to be used for treating baby napkins, linen and clothing co"ld",i"dl~d by body exudates.
WO95/25160 r_l,l,.. ..
13 2 1 ~
Depending on their lesl,euli;e formulation said c~"~uosili~",s are alsoparticularly suitable to be used for treating socks and linen and clothing co, lldll ,i, . by mud/clay soils. The cu,,,~osiliu,ls of the present inventions are also particularly suitable to be used upon long soaking periods in both hot and s cold water.
Ex~el il l lel ILdl data 1 ) Part A
The following cu,,,p~ iù,~s are made with the listed illyre~ie"La in the listed ~, u~u, liù~ ,s.
Co"",usilions (% by wêight) 15 ll lul ediél ,~
Sodium perw,l,~" 3û 30 30 30 Sodium carbonate 30 30 30 3û
Citric acid 5 5 5 5 20 Polyacrylate 2 2 2 2 Sodium Li~ dl L,oll 25 25 25 25 LAS~ 5 5 5 5 Sodium silicate / 5 / 5 Magnesiumsulphate / 1 1.2 1.2 25 DETMPA~ / l û.3 0.3 Minors and water up to 1 oo%
30 LAS ~ is linear sodium alkyl benzene sulfonate.
DETMPA~ is diethylen triamino péllldCeli. acid.
~ .
WO 95/25160 r~,l"
2)PartB 21 85545 The c~,,,,uosiliù~s above were evaluated in terms of the amount of available oxygen present in the wash solutions produced by using respectively said S Culll~Oai liu~s.
The eApe~i"~ l was conducted to replicate the realistic soaking conditions.
For this purpose we used hard water (17gr/us gallon) and stains standards on cotton of blood, wine, coffee, grass and sebum From the EMPA institute.
The wash solutions were prepared by dissolving 3û grams of each of the c~ uaiLiùl~â 1, 2, 3 and 4 in 7 liters of water. These wash solutions were prepared at 60C and held for 24 hours at an ambient temperature of about 25C. The available oxygen content remaining in each of the wash solutions was measured at time 1 hour, 6 hours, 16 hours and 24 hours.
The method used for measuring the available oxygen content remainin3 in the wash solutions was a standard indirect redox titration with iodide and thiosulfate as titrating agents and starch as indicator.
The table below lists the results obtained for the above mentioned culll~ailiO~Is with and without sodium silicate, in terms of % of available oxygen (AvO2) retained in the wash solutions at different times following the pdld~iUI) of said wash solutions with said c~""~osili~ns.
Co" ,!,osi~iùl ,s 1 2 3 4 (% of AvO2 retained) 1 hour 1ûO 10û 100 100 6 hours 1 78 87 96 30 16 hours / 58 73 89 24 hours 31 55 66 88 The results show that a c~",posilio,~ co",~.,isi"g pe,ud,uol,d~e and sodium silicate (c~",~o:,iliù,~ 2) as compared to the same cu",~ailion but without 35 sodium silicate (c~,,,,uùsiliùll 1), allows to produce a wash solution wherein the amount oF available oxygen is higher, even after a long soaking period, e.g. 24 hours. This clearly shows that the use of sodium silicate allows to reduce the w095/25160 2 1 8 5 5 ~ 5 decomposition of available oxygen produced in the wash solution and thereby allows to retain the bleaching capacity of said wash solution upon longer periods of time. The results obtained with c~,,,pc,siliu,,s 2 and 3 are equivalents. Indeed, sodium silicate allows to obtain the same benefits as compared to others known stabilizers like chelants. However, when adding sodium silicate on top of said other stabilizers like chelants such as diethylene triamino p~ dC~IiC acid and magnesium sulphate in a ~",l~u~ designed to prepare a washlsûaking solution, the available oxygen in said wash solution is i~ll~ill~d to up to 88% of the initial available oxygen after 24 hours. This 0 translates in an overall improved pe~rulllldll~e ~so~ with the use of the cu~,uusil;ol la of the present invention, e.g. better Uiiil II~I..liOl~ and/or cleaning.
ExamPles 15 Further examples of cull~,u~ailiOlla according to the present invention are the following. The following ctj",~,osiliol1s are made with the listed illyl~ llla in the listed ~lu~ ulliu"s.
Cu"luosiliol)a (% by weight) "t~
Sodium pe,w,bù,~dl~ 34 26 26 30 30 Sodium perborate monohydrate I I I I 1 27 2s TAED 2 1 2 / 6 Sodium sulfate 30 30 30 25 25 Citric acid 5 5 5 10 10 10 Sodium tjiCdl uu, Idl~ ~ 9 25 19 30 LAS~ 7 5 7 6 6 5 Nonionic / I 1 1 1 2 Sodium silicate 4 3.5 4 5.9 5.9 Zeolites I I I I 1 10 Magnesium sulphate 1.2 1.2 1.2 3s DETMPA~ û.3 0.3 û.3 0.2 0.2 0.3 Polyacrylate / I 1 1û 10 10 Minors and water up to 100%
WO 95/25160 1 ~,I/~J.,.
16 21 ~5~5 LAS ~ is linear sodium alkyl benzene sulfonate.
DETMPA~ is diethylen triamino ,u~"lacelic acid.
s The co",uosiLiù,~s above when used to produc~ a soak solution show an overall improved pe, ru""c"~3 compared to the product cu~ "y available. These c~,,,,uosiliù,~s are efficient in terms of cleaning, cle~du,i~i,,g, bleaching, ~ ;. Irt ~ u and/or stain removal. For example c~,,,,uosiliu,, 5 when used upon 10 soaking conditions for treating fabrics (e.g. Iinen and/or clothing) delivers at the same time optimized pe,ru""anc~ on particulate soil (clay), on diacyl peroxide sensitive soil (e.g. beta-carotene) and on peracid sensitive soil (e.g. shirts collars, body soil).
Claims (21)
1. A granular composition comprising a source of available oxygen, and diethylene triamino pentacetic acid characterized in that said composition further comprises an alkali metal salt of silicate or mixtures thereof.
2. A composition according to claim 1 which comprises from 10% to 80% by weight of the total composition of said source of available oxygen, preferably from 15% to 50% and more preferably from 20% to 45%.
3. A composition according to any of the preceding claims wherein said source ofavailable oxygen is an active oxygen-releasing peroxy compound, or mixtures thereof, preferably an alkali metal salt of percarbonate, perborate or mixtures thereof, and more preferably sodium percarbonate or sodium perborate or mixtures thereof.
4. A composition according to any of the preceding claims which comprises from 0.5% to 15% by weight of the total composition of said alkali metal salt of silicate, preferably from 1% to 10% and more preferably from 2% to 7%.
5. A composition according to any of the preceding claims wherein said alkali metal salt of silicate is sodium silicate.
6. A composition according to claim 5 wherein said sodium silicate is in an amorphous form, in a crystalline form or mixtures thereof.
7. A composition according to claim 6 wherein said sodium silicate in an amorphous form is of the general formula:
NaMSixO2x+1 wherein M is sodium or hydrogen and x is a number from 1.9 to 4, or mixtures thereof.
NaMSixO2x+1 wherein M is sodium or hydrogen and x is a number from 1.9 to 4, or mixtures thereof.
8. A composition according to claim 6 wherein said sodium silicate in a crystalline form is a crystalline layered silicate of the granular formula NaMSixO2x+1yH2O
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or mixtures thereof.
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or mixtures thereof.
9. A composition according to claim 6 wherein said sodium silicate is a zeolite of the formula Nazf(AIO2)z (SiO2)yù.xH2O
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from about 1.0 to about 0.5, and x is an integer from about 15 to about 264.
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from about 1.0 to about 0.5, and x is an integer from about 15 to about 264.
10. A composition according to any of the preceding claims wherein said composition further comprises magnesium sulfate.
11. A composition according to any of the preceding claims wherein said composition further comprises up to 20% by weight of the total composition of a soil suspender, or mixtures thereof, preferably from 3% to 15% and more preferably from 5% to 14%.
12. A composition according to any of the preceding claims wherein said composition further comprises an acidifying system, said acidifying system preferably comprising citric acid and/or sodium citrate and optionally bicarbonate.
13. A composition according to claim 12 wherein the weight ratio of the source of available oxygen, alkali metal salt of silicate together with carbonate, if present, to said acidifying system is inferior to 4, preferably inferior to 3.5.
14. A composition according to any of the preceding claims wherein said composition further comprises a bleach activator or mixtures thereof.
15. A composition according to claim 14 wherein said composition comprises n-nonanoyloxybenzenesulphonate and a second bleach activator, said second bleach activator being selected from the group of tetracetyl ethylene diamine, acetyl triethyl citrate, acetyl caprolactam, benzoyl caprolactam or mixtures thereof, preferably said composition comprises more than 3% by weight of the total composition of n-nonanoyloxybenzenesulphonate and more than 0.5% by weight of the total composition of said second bleach activator.
16. The use of an alkali metal salt of silicate, or mixtures thereof, in a granular laundry composition comprising a source of available oxygen, whereby the decomposition with time of the available oxygen produced upon dissolution of said composition in water is reduced.
17. The use of an alkali metal salt of silicate according to claim 16, in a granular laundry composition wherein said composition further comprises a chelating agent, a soil suspender, a bleach activator, an acidifying system or mixtures thereof.
18. The use of an acidifying system, in a laundry composition comprising a source of available oxygen, alkali metal salt of silicate and optionally carbonate, wherein the weight ratio of the source of available oxygen, alkali metal salt ofsilicate together with carbonate, if present, to said acidifying system is inferior to 4, whereby the pH in the dilution composition (wash solution) obtained upon dissolution of said composition in water is kept below 9.5, whereby the cleaningperformance on mud/clay containing soil is improved.
19. The use of an acidifying system according to claim 18, in a laundry composition wherein said composition further comprises a chelating agent, a soil suspender, a bleach activator, or mixtures thereof.
20. The use of an acidifying system according to claim 19, in a laundry composition wherein said composition comprises n-nonanoyloxybenzenesulphonate and a second bleach activator, said second bleach activator being selected from the group of tetracetyl ethylene diamine, acetyl triethyl citrate, acetyl caprolactam, benzoyl caprolactam or mixtures thereof, preferably said composition comprises more than 3% by weight of the total composition of n-nonanoyloxybenzenesulphonate and more than 0.5% by weight of the total composition of said second bleach activator.
21. A process of treating fabrics with a source of available oxygen wherein a granular composition comprising said source of available oxygen and an alkali metal salt of silicate, or mixtures thereof, is diluted in water and said fabrics are left to soak in said diluted composition, then either washed and left to dry or rinsed and left to dry.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP94870046 | 1994-03-14 | ||
| EP94870046.3 | 1994-03-14 | ||
| US30817794A | 1994-09-19 | 1994-09-19 | |
| US08/308,177 | 1994-09-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2185545A1 true CA2185545A1 (en) | 1995-09-21 |
Family
ID=26137755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002185545A Abandoned CA2185545A1 (en) | 1994-03-14 | 1995-03-02 | Granular bleaching compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0750661B1 (en) |
| AT (1) | ATE233313T1 (en) |
| AU (1) | AU702365B2 (en) |
| CA (1) | CA2185545A1 (en) |
| DE (1) | DE69529739T2 (en) |
| ES (1) | ES2190450T3 (en) |
| FI (1) | FI963633A (en) |
| NO (1) | NO963834L (en) |
| PL (1) | PL316252A1 (en) |
| WO (1) | WO1995025160A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2311542A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Percarbonate bleach composition |
| CA2664572C (en) | 2006-09-25 | 2015-06-16 | Wockhardt Research Centre | Substituted piperidinophenyl oxazolidinones |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE567330A (en) * | 1957-05-03 | |||
| US3951838A (en) * | 1973-10-10 | 1976-04-20 | E. I. Du Pont De Nemours And Company | Silica sol stabilizers for improving the stability of sodium percarbonate in solid bleaches and detergents |
| US4215990A (en) * | 1978-04-14 | 1980-08-05 | Purex Corporation | Peroxygen bleaching and laundering compositions |
| FI64639C (en) * | 1978-09-27 | 1983-12-12 | Unilever Nv | BLEKNINGS- OCH RENGOERINGSKOMPOSITION |
| US4405482A (en) * | 1980-09-01 | 1983-09-20 | Richardson-Vicks Pty. Limited | Sanitizing formulation |
| FR2493294A1 (en) * | 1980-11-04 | 1982-05-07 | Air Liquide | STABILIZING COMPOSITIONS FOR PEROXIDE PRODUCTS |
| US4448705A (en) * | 1982-05-20 | 1984-05-15 | Colgate-Palmolive Company | Monoperoxyphthalic acid bleaching composition containing DTPMP |
| US4664837A (en) * | 1982-10-04 | 1987-05-12 | Colgate Palmolive Co. | Bleaching and laundering composition containing magnesium monoperoxyphthalate a chelating agent, a peroxygen compound and phthalic anhydride |
| GB8311865D0 (en) * | 1983-04-29 | 1983-06-02 | Procter & Gamble Ltd | Bleach compositions |
| DE3416669A1 (en) * | 1984-05-05 | 1985-11-07 | Hoechst Ag, 6230 Frankfurt | SOFTENING DETERGENT |
| DE3526405A1 (en) * | 1985-07-24 | 1987-02-05 | Henkel Kgaa | LAYERED SILICATES WITH RESTRICTED SOURCE, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN DETERGENT AND CLEANING AGENTS |
| DE3812556A1 (en) * | 1988-04-15 | 1989-10-26 | Hoechst Ag | DETERGENT WITH STORAGE-STABILIZED BLEACHING SYSTEM |
| ES2071494T3 (en) * | 1990-11-14 | 1995-06-16 | Procter & Gamble | PROCEDURE FOR THE PREPARATION OF COMPOSITIONS FOR NON-PHOSPHATE DISHWASHERS WITH OXYGEN BLEACHING SYSTEMS. |
| US5055217A (en) * | 1990-11-20 | 1991-10-08 | Lever Brothers Company, Division Of Conopco, Inc. | Polymer protected bleach precursors |
| EP0550077A1 (en) * | 1992-01-03 | 1993-07-07 | The Procter & Gamble Company | Granular laundry bleaching composition |
| ZA935690B (en) * | 1992-08-28 | 1995-02-06 | Crosfield Joseph & Sons | Alkall containing silica solution |
-
1995
- 1995-03-02 WO PCT/US1995/002503 patent/WO1995025160A1/en active IP Right Grant
- 1995-03-02 PL PL95316252A patent/PL316252A1/en unknown
- 1995-03-02 ES ES95912000T patent/ES2190450T3/en not_active Expired - Lifetime
- 1995-03-02 DE DE69529739T patent/DE69529739T2/en not_active Expired - Fee Related
- 1995-03-02 AU AU19361/95A patent/AU702365B2/en not_active Ceased
- 1995-03-02 AT AT95912000T patent/ATE233313T1/en not_active IP Right Cessation
- 1995-03-02 EP EP95912000A patent/EP0750661B1/en not_active Expired - Lifetime
- 1995-03-02 CA CA002185545A patent/CA2185545A1/en not_active Abandoned
-
1996
- 1996-09-13 FI FI963633A patent/FI963633A/en unknown
- 1996-09-13 NO NO963834A patent/NO963834L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0750661B1 (en) | 2003-02-26 |
| AU702365B2 (en) | 1999-02-18 |
| DE69529739D1 (en) | 2003-04-03 |
| AU1936195A (en) | 1995-10-03 |
| WO1995025160A1 (en) | 1995-09-21 |
| ATE233313T1 (en) | 2003-03-15 |
| PL316252A1 (en) | 1997-01-06 |
| NO963834D0 (en) | 1996-09-13 |
| FI963633A0 (en) | 1996-09-13 |
| NO963834L (en) | 1996-09-13 |
| DE69529739T2 (en) | 2003-12-18 |
| FI963633A (en) | 1996-09-13 |
| EP0750661A1 (en) | 1997-01-02 |
| ES2190450T3 (en) | 2003-08-01 |
| EP0750661A4 (en) | 1998-10-07 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |