CA2126847A1 - Granular percarbonate laundry bleach containing layered silicate stabilizer - Google Patents
Granular percarbonate laundry bleach containing layered silicate stabilizerInfo
- Publication number
- CA2126847A1 CA2126847A1 CA002126847A CA2126847A CA2126847A1 CA 2126847 A1 CA2126847 A1 CA 2126847A1 CA 002126847 A CA002126847 A CA 002126847A CA 2126847 A CA2126847 A CA 2126847A CA 2126847 A1 CA2126847 A1 CA 2126847A1
- Authority
- CA
- Canada
- Prior art keywords
- percarbonate
- layered silicate
- granular
- sodium
- weight
- 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
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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
- C11D3/395—Bleaching agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
2126847 9312843 PCTABSCORE2 A granuler bleaching composition is disclosed which comprises an alkali metal salt of percarbonate and a crystalline layered silicate or mixtures thereof. Preferred compositions further comprise an anhydrous acidifiant agent. The compositions provide effective bleaching and are as stable as perborate based bleaching compositions.
Description
W0 93/12843 2 1 ~ ? 1 i7 Pcr/us92/ll~22 GRANULAR PER~ARBONi~TE LAUNDRY BLEACH CONTAININ6 LAYERED SILICATE STABILIZER
~h~~
The present inv~ntion relates to blea~hir~g r~mpositions f or laundry. Granular lalmdry bleaching cc~mpositions are described which comprise percarbonate as the bleaching specie, said c:ompositions beirlg stable upon storage.
~
The inorganic perhydrate blea ::h most widely used in the context of laundry bleaching is sodi~am perbsrate in the f orm of either the monohydrate or tetrahydrate . However, con ::erns abe~ut the lmpact of boron salts on the envirorlment have led to an increas ing int~rest in other perhydrate salts, o~ which sodium percarbonate is the most r~adily availabl~ . -WO 93/128~3 PCr~US92/11222 3 ~ ~ 7 2 Detergent :ompositions containing sodium percarbonate are known in the art. Percarborlate salts, partic:ularly sodium percarbonate, are attractive perhydrates for use in detergent composition because they :lis~;olve r~adily in water, are weight efficient and, after giving up their available oxygen, provide a u~;e~ul source of c:arbonate ions f or detergency purposes ~
However, the inclusion of percarbonate salts in detergent cc~mpositions has been res . ricted ~it~er~o by th~ r~lative instability of the bl ach both as~is and in use. Sodium percarbonate loses its av~ilable oxys~en at a signif icant rate in the presence of ion~; o~ heav~r metals suc:~ as iron;
copper and manganese and also in the presenc . o~ moi~tur~, the~;e ef f ects being acc:ele;rated at temperatur~s in exce&;~;
of about 3 0 C .
Moisture and h~a~y metal ion~ are un2voidable components of conventional granular laundry treatment co~apcssiti~ns. Al~;o pQrcarbunate dec~mposition du~. to ~aoisture becomes ~ore o~E
an issu~ during sto~age as laumdry tr~a~m~nt procluct~; ara oft~n stor~d in humid environ~Dent~; wh~n th~ procluct picks up moisture. This has result~d in ~nargin~lly acceptable perc:arbonate bleach stability un~r Northern Europ~an summer con~itior~s, where the average maximum temperature over the hottest months is from 21C to 25C, arld unacceptable stability under temperatllres hi~her than this.
Such conditions are f ound in the Middle East and Ss:)uthern ~sia and also in Southern Europ~ where average maximu temperature~ are in the 27C to 33C range for the ht~test summer month.
There has theref ore been much activity by workers in the - field to increase percarbonate stability so as to mak~ it a viabl~ component of detergerlt f ormulations . This activity has tendes3 to concentrate on the protection of the
~h~~
The present inv~ntion relates to blea~hir~g r~mpositions f or laundry. Granular lalmdry bleaching cc~mpositions are described which comprise percarbonate as the bleaching specie, said c:ompositions beirlg stable upon storage.
~
The inorganic perhydrate blea ::h most widely used in the context of laundry bleaching is sodi~am perbsrate in the f orm of either the monohydrate or tetrahydrate . However, con ::erns abe~ut the lmpact of boron salts on the envirorlment have led to an increas ing int~rest in other perhydrate salts, o~ which sodium percarbonate is the most r~adily availabl~ . -WO 93/128~3 PCr~US92/11222 3 ~ ~ 7 2 Detergent :ompositions containing sodium percarbonate are known in the art. Percarborlate salts, partic:ularly sodium percarbonate, are attractive perhydrates for use in detergent composition because they :lis~;olve r~adily in water, are weight efficient and, after giving up their available oxygen, provide a u~;e~ul source of c:arbonate ions f or detergency purposes ~
However, the inclusion of percarbonate salts in detergent cc~mpositions has been res . ricted ~it~er~o by th~ r~lative instability of the bl ach both as~is and in use. Sodium percarbonate loses its av~ilable oxys~en at a signif icant rate in the presence of ion~; o~ heav~r metals suc:~ as iron;
copper and manganese and also in the presenc . o~ moi~tur~, the~;e ef f ects being acc:ele;rated at temperatur~s in exce&;~;
of about 3 0 C .
Moisture and h~a~y metal ion~ are un2voidable components of conventional granular laundry treatment co~apcssiti~ns. Al~;o pQrcarbunate dec~mposition du~. to ~aoisture becomes ~ore o~E
an issu~ during sto~age as laumdry tr~a~m~nt procluct~; ara oft~n stor~d in humid environ~Dent~; wh~n th~ procluct picks up moisture. This has result~d in ~nargin~lly acceptable perc:arbonate bleach stability un~r Northern Europ~an summer con~itior~s, where the average maximum temperature over the hottest months is from 21C to 25C, arld unacceptable stability under temperatllres hi~her than this.
Such conditions are f ound in the Middle East and Ss:)uthern ~sia and also in Southern Europ~ where average maximu temperature~ are in the 27C to 33C range for the ht~test summer month.
There has theref ore been much activity by workers in the - field to increase percarbonate stability so as to mak~ it a viabl~ component of detergerlt f ormulations . This activity has tendes3 to concentrate on the protection of the
2$43 2 ~ . 7 PCT/US92/1 1222 perc:arbonate by coating the crystal 1 ine product or ~y inclusion of stabilising agents during its manufacture, or both. Thus, while it has proved possible ts:~ incorporate percarbonate salts in conventional deterg~nt compo-~ition so as to have acceptable percarbonate stability over periods ref lecting normal produ5t shelf liJ~e, the percarbonate salts have proved ::omplex and ~xpensiv@ to manuf acture . This has restrict~d their broadscale utilisation, as evidenc:ed by the relatively s~all number of commercially available products containing percarbonate.
It is therefc)re an object of the present inver1tion to pre~vide a granular laundry bleaGhing compc)sition ~-~ incorporating an alkali metal percarbonate ~leach, said bleach displaying :Lmproved ~tabilityD
It is a ~Eurther obj ect of the present inventioll to proYide a granular laundry bleachinq compositiQn ince~rporating an alkali meta.l percarbonate ble;~c:h displaying improved stability, in which the percarbonate blea~h does ne~t require complex protectiorl techniques.
It has now been ~ound that these obj ect~ could be ~et by f s~nnulating a composition coJnprising an alkali metal sa~t of p~rcarbonate to~ether with a crystalline lay~r~d silicate or mixtures thereof.
Granular bleat:hir~g compositions comprising percarbonate have been desc:ribed for instance in FR 2, 385, 837, US
4, 428, 914 and GB 1, 553, 505. Crystalline layered silicate and their method5 of preparation have been described for instance in EP-A-164 ~14, DE-A-34 17 649 and l)E-A-37 42 043 arld their application to the f ield of laundry treatment ~as been descri~ed in applicant ' s copending British applicatiorls GB 90 21 761. 3, GB 90 18157 . 9 and GB 91 08639 . 7 .
It is therefc)re an object of the present inver1tion to pre~vide a granular laundry bleaGhing compc)sition ~-~ incorporating an alkali metal percarbonate ~leach, said bleach displaying :Lmproved ~tabilityD
It is a ~Eurther obj ect of the present inventioll to proYide a granular laundry bleachinq compositiQn ince~rporating an alkali meta.l percarbonate ble;~c:h displaying improved stability, in which the percarbonate blea~h does ne~t require complex protectiorl techniques.
It has now been ~ound that these obj ect~ could be ~et by f s~nnulating a composition coJnprising an alkali metal sa~t of p~rcarbonate to~ether with a crystalline lay~r~d silicate or mixtures thereof.
Granular bleat:hir~g compositions comprising percarbonate have been desc:ribed for instance in FR 2, 385, 837, US
4, 428, 914 and GB 1, 553, 505. Crystalline layered silicate and their method5 of preparation have been described for instance in EP-A-164 ~14, DE-A-34 17 649 and l)E-A-37 42 043 arld their application to the f ield of laundry treatment ~as been descri~ed in applicant ' s copending British applicatiorls GB 90 21 761. 3, GB 90 18157 . 9 and GB 91 08639 . 7 .
3 PCr/lJS92/11222 3 3 ll ~ 4 The composition5 according to the present invention also allow adequate control of the pH in the bl~achin~ liquor, giving appropriate balance between bleachis~g performance and f abric: saf ety .
Summar~of ~ e inventiorl CompGsitions as:cording to the present invention are granular bleaching compositions comprising Dlore than 209c and Ul? to 80~6 by weight of the total compo~;ition of asa alkall me~al s~lt of percarbc~Jlate h7 each and from 5% to 80~c by weight of the total c:omposition of a crystalline layered silicate of formula Na~Six02x+1.~H20 wherein M is sodium or ~-~ hydrogen "c is a number cf fro~n 1. 9 to 4 and y ' s a number oP from 0 to 20, or mixtures thereof. Pr~ferred compositions herein further c:~prise aal a~hydrous acidifying ager~t, prE~f~rably citric: acid.
etailed dese:~iptioL~
A~ a f ir~t e~s~ntial c:omponen~ ha co~o5ition!~ according to t~e pr~sent invention ~o~pris~ an alkali ~etal salt of p~rcarbonate, pre~erably sodiu~ percarbonat~ Sodiu~
percarbonate is available commercially as a cry~;t21lline solid. Most c:o~erc:ially available material includ~s a low level o~ a heavy metal s~questrant such as EI~TA, 1-hydroxyethylid~n~ diphosp~oslic ac:id (HEDP) or an amino-phosphonate, t~at is incvrporated duria~g 2~e manuf acturing process. Fs:~r the purpose~ o~E the pr@~ent inventiorl, the perc:arbclrlate c:an be incorporated into detergent composition~ without addi~ional protection.
Whilst heavy metals presl2nt in the sodium carbonate used to manuf acture tlhe percarbonate c~n b~ controlled by the inclusion of se~uestrants in the reaction mixture, it is pref erred that the percarbonate be protected f rom heavy WO 93/12843 ~ U 3 i; PCI/US92/1122 metals present as impurities in other ingredients of the product O It has been f ound that the total level of Iron, copper and Manganese ions in the product should not excç~ed ~5 ppm and pref rably should be les~ than 20 ppm in order tc~ avoid an unacceptably adverse ef f ect on perc:arbonate stability ~
The composi~ions ac:c:ording to the pr~serlt invention c:omprise moxe than 2 0% by weight of the total composil:ion of percarbonate, up to 80% by weight of the total compositiorl, preferably ~rom 409~ to 50%.
The s~cond ess@ntial t:omponer:t of the inv@ntiDn is a ~-~ crys~alline layered sili~ate. The c:rystalline layered silicates suitable for u-ce herein are s: the granular f ormul2 NaMSix02x+l Y~20 wherein ~ is sodiuDI or hydrogen, x is a number frola l. 9 to
Summar~of ~ e inventiorl CompGsitions as:cording to the present invention are granular bleaching compositions comprising Dlore than 209c and Ul? to 80~6 by weight of the total compo~;ition of asa alkall me~al s~lt of percarbc~Jlate h7 each and from 5% to 80~c by weight of the total c:omposition of a crystalline layered silicate of formula Na~Six02x+1.~H20 wherein M is sodium or ~-~ hydrogen "c is a number cf fro~n 1. 9 to 4 and y ' s a number oP from 0 to 20, or mixtures thereof. Pr~ferred compositions herein further c:~prise aal a~hydrous acidifying ager~t, prE~f~rably citric: acid.
etailed dese:~iptioL~
A~ a f ir~t e~s~ntial c:omponen~ ha co~o5ition!~ according to t~e pr~sent invention ~o~pris~ an alkali ~etal salt of p~rcarbonate, pre~erably sodiu~ percarbonat~ Sodiu~
percarbonate is available commercially as a cry~;t21lline solid. Most c:o~erc:ially available material includ~s a low level o~ a heavy metal s~questrant such as EI~TA, 1-hydroxyethylid~n~ diphosp~oslic ac:id (HEDP) or an amino-phosphonate, t~at is incvrporated duria~g 2~e manuf acturing process. Fs:~r the purpose~ o~E the pr@~ent inventiorl, the perc:arbclrlate c:an be incorporated into detergent composition~ without addi~ional protection.
Whilst heavy metals presl2nt in the sodium carbonate used to manuf acture tlhe percarbonate c~n b~ controlled by the inclusion of se~uestrants in the reaction mixture, it is pref erred that the percarbonate be protected f rom heavy WO 93/12843 ~ U 3 i; PCI/US92/1122 metals present as impurities in other ingredients of the product O It has been f ound that the total level of Iron, copper and Manganese ions in the product should not excç~ed ~5 ppm and pref rably should be les~ than 20 ppm in order tc~ avoid an unacceptably adverse ef f ect on perc:arbonate stability ~
The composi~ions ac:c:ording to the pr~serlt invention c:omprise moxe than 2 0% by weight of the total composil:ion of percarbonate, up to 80% by weight of the total compositiorl, preferably ~rom 409~ to 50%.
The s~cond ess@ntial t:omponer:t of the inv@ntiDn is a ~-~ crys~alline layered sili~ate. The c:rystalline layered silicates suitable for u-ce herein are s: the granular f ormul2 NaMSix02x+l Y~20 wherein ~ is sodiuDI or hydrogen, x is a number frola l. 9 to
4 and y is a nu~b~r from 0 to 20, or mixt~res 'chereofO
Crystalline layç~r~d sodium :ilic:ate~3 of thi~; type are disclosed in EP-A-~ 64 514 z~nd methods for their prepara~isn are disclo~gd in DE A-34 17 649 a~3d DE-A-37 4~ 043. Fs:~r the purposes of tha present invention, x in tll~ gen~ral f ormula abov~ h~s a value of 2, 3 or 4 and is pref erably 2 .
More pref erably M i~ æodium and y is 0 and pref erred examples of this formula comprise the Q~ and S' fE:~rms of Na2si2o5 These materials are available from Boechst AG
FRt; as respectively NaSKS 5, NaSKS-7, NaSKS ll and NaSKS 6.
The most preferred material is 5'- Na2Si205, 11~aSKS-6.
Crystalline layered silicates are incorporated eith~r as dry mixed solids, or as solid components of agglomerates with o~her compone~ats.
WO g3/12843 PCr/US92/11222 1 ~",.;`, i7 6 The oompositions according to the present irlvention comprise from 5% to 80% by weight of t~e ts~kal composition of said crystalline layered silicates or mixtures thereo~, preferably ~rom 15% to 25%.
As an optional but highly pr~f erred component, the compositions according to the present invention further c:omprise an anhydrous acidifying agent or ~ixtur~s thereo~.
The purpose of said acidifying agent i~: to c:o3~tr0l the alkalinity generated by the percarbonatP in the bleaching liquor. Said agent need to be inc:orporated in the produc~
in an anhydrous form, and to have a good ~;tability in oxi!tlizing environm~nt. Suitabl~ anhydrou~ acidifying agents f or u e hereir~ are carboxylic acids suc:h a~; citric acid " succinic acid, adipic ac:id, glutaric: acid, 3 chetoglutaric acid, citramalic: acid, tartaric acid and maleic at:id. Other suitable ac:idifying agents include sodium bicarbonate, sodium s~ arbonate and silicic ac:id . Highly pref ~rr~d f or u~;~ her~in is c:itric acid .
Indeed, citric acid is c:o~nercially availaJ~le in anhydxou~;
i~on~, it additio~ally acts as a builder and a ch~lant, and it is ~aiod~radable. The compo~itions ac:cordirlg to th~
pre~;ent inverltion comprise from up to l5% by wQig~t o~ t~e total composition of anhydrous citric ac:id, pre~era~ly fro~la 29~ to 8%, most pre~erably about 5%.
Compositions in accordance with the in~vention s::an also comprise csp~ional ingredients such as optical bri~hteners, anti dusting agents such as olef ines and waxes, enzymes, c:helants, dispersants, surf actal~ts, soil release agents, photoaetivated bleach2s such as Zn phthalocyanine sulphonate, dyes, pi~nents and perfumes are examples of suc:h optional in~redients and can be added in varyir~g amounts as desired.
.. 7 WO g3/12843 P~r/US92/11222 Optional but highly preferred ingredient are peroxy car~oxylic acids bleach or precursor~ thereof, commonly referred to as bleach activa~ors, which are pre~erably added in a prilled or a~glomerated form. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and ~B 2 143 231 and a method for their formation into a prilled form iB descrIbed in European Published Patent Application EP-A-62 523. Preferred examples of such compounds are tetracetyl ethylene diamine tTAED3, sod~um 3, 5, 5 trimeth~l hexanoyloxybenzene ~ulphonate 9 diperoxy dodecanoic acid as descri~ed for instance in US 4 818 425 and non~lamide of peroxyadipic acid as described ~or inst~nce in US 4 2~9 201 and n nonanoyloxybenz~nesulphonate (NO3S)~ and acetyl triethyl citrate (ATC) such as describ~.d i~ European Patent application 91~70207.7.
~he compositions according to the pr~sent invention naturally comprise inorganic f~ r salts such as alkali m@tal carb3nat~s bicarbonates and sulphates. Such fillers, for in~t~nce sodium ~icar~onate, may also act as acidify.ing age~t a~ dQscribed herein above. Accordingly, ~odium pQrcarbonate i~ a preferred filler ~aterial for.use herein~
Th~ compositions according to the presen~ invention can be made by a variety of methods well known în the ar~, including dry-mixing, spray dryin~, agglomeration and granulation and combinations thereo~.
The compositlons according to the present invention can be prepared wit~ diffexent bulk d~nsities, from conven ional granular products to s~-called "conc~ntrated" products (i.e. with a bulk den~ity above 600g/l).
wa~93/12843 ~''J i ~ i I PCr/US92/11222 Examples 1 ) Part A
The foll~wing ~xamples will illustrate t~e present invention. The fe~llowing granular compc~sitioTIs ar~ m~de by dry-mixing the listed ingredients in t~e listed proportion~
Co~positions 1 2 3 4 5 6 Sodiu~ p~rcarbonate :40.0 35.û 54.0 55.0 46.0 47.0 TAED : 8.7 7.6 11~7 - 9.5 Silicate lsyeredl SXS-6: 25.0 30.0 20.0 lO.0 18.0 20.0 Anhydrous citri~ acid : 10 . 0 12 . 0 12 . O S . 0 5 . 0 5 . O
'Sodiu~ sulphate : 15 . 3 14 . 3 1. 0 20 . O O . 5 15 . O
Sodium bica~onate : - - - 5.0 18.0 NOBS : - - - - - 10 . 3 ~inors :_up to 100 ~ _ :
The foll~wing co~npo~itions wer~! ~ade by mixing the li.ted inç~ients in the li~ted proportiorl~. The self ~e~ting rates of th~ produ t~; w~re ~nonitor~d a~ follows. q!h~
product is ~ade and put in a bottle. The bottl~ i~ n put in an o~r~n which is heated up to 70c. A prob~ in the product allows to monitor the temper~ture of the produc:t.
As soon as the produc:t reach~s 7 û c, th2 bottle i~ c~ rad and t~e sy~;tem i~ lated in aLn adiaba~ictthenno bell which ~aint~ins the t~peratu:re o f the oven cog~ ta~t at 7 0 c as bov~ . This places t~e product in adiabati conditions and f rom thereon, the temperature of ~e produc:t i~ monitored. The temperature inc:rea~e thus m~asur~d is due tc7 the self-heating c~f the product (runaway r~ctiorl).
The re-cults below list t~ree self heating rates, all irl c/hour: SHRl is the av~rage temp~rat:ure incr~a~;e ~n~as~ed during the f irst two ho~s o~ adiabakic c:l~nditio3ls; SHR2 ic the average temperature increase measured during the tllree W0 93~12843 2 1 ~ P~/US9~/11222 following hc~urs, and SHR3 is the average temperature increase measured beyond 5 hours. The ta}:~le below lists the results obtained for various c~mpositions, witl~ and withou~ crystalline layered 5i `1 icate. In some c:ase the runaway reaction was out of control and ~xperiment~ had t:o be interrupt~d f or saf ety r~a~;ons . Such experime~t . are ~arked "~oc" (out of cvntrol).
Compositions 7 7a 13 8a 9 9a Sodium percarbonate 47.0 47.0 ~7.0 47.047.0 47.0 TAED 10.2 10.2 10.2 10.2 ").2 1û.2 -S ilica~e SKS - 620 . O - - 20 . O - ~ 20 . O - -Citric acid 10.0 10.0 8.0 8.0 8.0 8.0 Sodium Sulphate11. 7 31. 7 13 . 7 33 . 7 9 . 225~ . 2 Sodium bicarb~nace ~ --- --- 4.5 4.5 SHRl* 2.3 4.5 2.2 4.0 2.5 3.9 S~2** ~.6 8.9 0.6 ~.0 0.5 7.7 S~IR3*** 0 ooc 0 ooc 0 o~c Co~apositiotls 10 lOa 11 11~1 12 12 Sodiw~l ~ercarbonat~ 47.0 47.0 47.0 47.047.0 47.0 TAED 10.2 10.2 10.2 10.2 10.210.2 Sil~c~te SKS-6 18.0 -- 20~0 -- 42.8 ~--Citric acid 7 . 0 7 . O 5 . 0 5 . O
S~diu~ Sulphate16 . 7 34 . 7 16 . 7 35 . 7 - _42 . 8 Sodium blc~r~onate
Crystalline layç~r~d sodium :ilic:ate~3 of thi~; type are disclosed in EP-A-~ 64 514 z~nd methods for their prepara~isn are disclo~gd in DE A-34 17 649 a~3d DE-A-37 4~ 043. Fs:~r the purposes of tha present invention, x in tll~ gen~ral f ormula abov~ h~s a value of 2, 3 or 4 and is pref erably 2 .
More pref erably M i~ æodium and y is 0 and pref erred examples of this formula comprise the Q~ and S' fE:~rms of Na2si2o5 These materials are available from Boechst AG
FRt; as respectively NaSKS 5, NaSKS-7, NaSKS ll and NaSKS 6.
The most preferred material is 5'- Na2Si205, 11~aSKS-6.
Crystalline layered silicates are incorporated eith~r as dry mixed solids, or as solid components of agglomerates with o~her compone~ats.
WO g3/12843 PCr/US92/11222 1 ~",.;`, i7 6 The oompositions according to the present irlvention comprise from 5% to 80% by weight of t~e ts~kal composition of said crystalline layered silicates or mixtures thereo~, preferably ~rom 15% to 25%.
As an optional but highly pr~f erred component, the compositions according to the present invention further c:omprise an anhydrous acidifying agent or ~ixtur~s thereo~.
The purpose of said acidifying agent i~: to c:o3~tr0l the alkalinity generated by the percarbonatP in the bleaching liquor. Said agent need to be inc:orporated in the produc~
in an anhydrous form, and to have a good ~;tability in oxi!tlizing environm~nt. Suitabl~ anhydrou~ acidifying agents f or u e hereir~ are carboxylic acids suc:h a~; citric acid " succinic acid, adipic ac:id, glutaric: acid, 3 chetoglutaric acid, citramalic: acid, tartaric acid and maleic at:id. Other suitable ac:idifying agents include sodium bicarbonate, sodium s~ arbonate and silicic ac:id . Highly pref ~rr~d f or u~;~ her~in is c:itric acid .
Indeed, citric acid is c:o~nercially availaJ~le in anhydxou~;
i~on~, it additio~ally acts as a builder and a ch~lant, and it is ~aiod~radable. The compo~itions ac:cordirlg to th~
pre~;ent inverltion comprise from up to l5% by wQig~t o~ t~e total composition of anhydrous citric ac:id, pre~era~ly fro~la 29~ to 8%, most pre~erably about 5%.
Compositions in accordance with the in~vention s::an also comprise csp~ional ingredients such as optical bri~hteners, anti dusting agents such as olef ines and waxes, enzymes, c:helants, dispersants, surf actal~ts, soil release agents, photoaetivated bleach2s such as Zn phthalocyanine sulphonate, dyes, pi~nents and perfumes are examples of suc:h optional in~redients and can be added in varyir~g amounts as desired.
.. 7 WO g3/12843 P~r/US92/11222 Optional but highly preferred ingredient are peroxy car~oxylic acids bleach or precursor~ thereof, commonly referred to as bleach activa~ors, which are pre~erably added in a prilled or a~glomerated form. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and ~B 2 143 231 and a method for their formation into a prilled form iB descrIbed in European Published Patent Application EP-A-62 523. Preferred examples of such compounds are tetracetyl ethylene diamine tTAED3, sod~um 3, 5, 5 trimeth~l hexanoyloxybenzene ~ulphonate 9 diperoxy dodecanoic acid as descri~ed for instance in US 4 818 425 and non~lamide of peroxyadipic acid as described ~or inst~nce in US 4 2~9 201 and n nonanoyloxybenz~nesulphonate (NO3S)~ and acetyl triethyl citrate (ATC) such as describ~.d i~ European Patent application 91~70207.7.
~he compositions according to the pr~sent invention naturally comprise inorganic f~ r salts such as alkali m@tal carb3nat~s bicarbonates and sulphates. Such fillers, for in~t~nce sodium ~icar~onate, may also act as acidify.ing age~t a~ dQscribed herein above. Accordingly, ~odium pQrcarbonate i~ a preferred filler ~aterial for.use herein~
Th~ compositions according to the presen~ invention can be made by a variety of methods well known în the ar~, including dry-mixing, spray dryin~, agglomeration and granulation and combinations thereo~.
The compositlons according to the present invention can be prepared wit~ diffexent bulk d~nsities, from conven ional granular products to s~-called "conc~ntrated" products (i.e. with a bulk den~ity above 600g/l).
wa~93/12843 ~''J i ~ i I PCr/US92/11222 Examples 1 ) Part A
The foll~wing ~xamples will illustrate t~e present invention. The fe~llowing granular compc~sitioTIs ar~ m~de by dry-mixing the listed ingredients in t~e listed proportion~
Co~positions 1 2 3 4 5 6 Sodiu~ p~rcarbonate :40.0 35.û 54.0 55.0 46.0 47.0 TAED : 8.7 7.6 11~7 - 9.5 Silicate lsyeredl SXS-6: 25.0 30.0 20.0 lO.0 18.0 20.0 Anhydrous citri~ acid : 10 . 0 12 . 0 12 . O S . 0 5 . 0 5 . O
'Sodiu~ sulphate : 15 . 3 14 . 3 1. 0 20 . O O . 5 15 . O
Sodium bica~onate : - - - 5.0 18.0 NOBS : - - - - - 10 . 3 ~inors :_up to 100 ~ _ :
The foll~wing co~npo~itions wer~! ~ade by mixing the li.ted inç~ients in the li~ted proportiorl~. The self ~e~ting rates of th~ produ t~; w~re ~nonitor~d a~ follows. q!h~
product is ~ade and put in a bottle. The bottl~ i~ n put in an o~r~n which is heated up to 70c. A prob~ in the product allows to monitor the temper~ture of the produc:t.
As soon as the produc:t reach~s 7 û c, th2 bottle i~ c~ rad and t~e sy~;tem i~ lated in aLn adiaba~ictthenno bell which ~aint~ins the t~peratu:re o f the oven cog~ ta~t at 7 0 c as bov~ . This places t~e product in adiabati conditions and f rom thereon, the temperature of ~e produc:t i~ monitored. The temperature inc:rea~e thus m~asur~d is due tc7 the self-heating c~f the product (runaway r~ctiorl).
The re-cults below list t~ree self heating rates, all irl c/hour: SHRl is the av~rage temp~rat:ure incr~a~;e ~n~as~ed during the f irst two ho~s o~ adiabakic c:l~nditio3ls; SHR2 ic the average temperature increase measured during the tllree W0 93~12843 2 1 ~ P~/US9~/11222 following hc~urs, and SHR3 is the average temperature increase measured beyond 5 hours. The ta}:~le below lists the results obtained for various c~mpositions, witl~ and withou~ crystalline layered 5i `1 icate. In some c:ase the runaway reaction was out of control and ~xperiment~ had t:o be interrupt~d f or saf ety r~a~;ons . Such experime~t . are ~arked "~oc" (out of cvntrol).
Compositions 7 7a 13 8a 9 9a Sodium percarbonate 47.0 47.0 ~7.0 47.047.0 47.0 TAED 10.2 10.2 10.2 10.2 ").2 1û.2 -S ilica~e SKS - 620 . O - - 20 . O - ~ 20 . O - -Citric acid 10.0 10.0 8.0 8.0 8.0 8.0 Sodium Sulphate11. 7 31. 7 13 . 7 33 . 7 9 . 225~ . 2 Sodium bicarb~nace ~ --- --- 4.5 4.5 SHRl* 2.3 4.5 2.2 4.0 2.5 3.9 S~2** ~.6 8.9 0.6 ~.0 0.5 7.7 S~IR3*** 0 ooc 0 ooc 0 o~c Co~apositiotls 10 lOa 11 11~1 12 12 Sodiw~l ~ercarbonat~ 47.0 47.0 47.0 47.047.0 47.0 TAED 10.2 10.2 10.2 10.2 10.210.2 Sil~c~te SKS-6 18.0 -- 20~0 -- 42.8 ~--Citric acid 7 . 0 7 . O 5 . 0 5 . O
S~diu~ Sulphate16 . 7 34 . 7 16 . 7 35 . 7 - _42 . 8 Sodium blc~r~onate
5~R1* 2.7 4.1 2.~ 4.1 2.2 4.0 SHR2** 0.6 8.3 0.4 ~.2 0 310.8 SH1~3*** 0 ooc 0 ooc 0 ooc Comments:
Compositions 7-12 show good thermal stability, and no ~emperature inc:rease is reported after 5 hours storage and beyond. ~n t~a~
absence of crystalline layered silicate i.e. in co~positio~
7a 12a, self-heating rates measured were so high that experi~ents had to b~ stopped for saf~ty purposes.
Compositions 7-12 show good thermal stability, and no ~emperature inc:rease is reported after 5 hours storage and beyond. ~n t~a~
absence of crystalline layered silicate i.e. in co~positio~
7a 12a, self-heating rates measured were so high that experi~ents had to b~ stopped for saf~ty purposes.
Claims (7)
1. A granular bleaching composition comprising more than 20% and up to 80% by weight of the total composition of an alkali metal salt of percarbonate bleach and from 5%
to 80% by weight of the total composition of a crystalline layered silicate of formula NaMSixO2x+1?yH2O
wherein M is sodium or hydrogen, x is a number of from 1.9 to 4 and y is a number of from 0 to 20, or mixtures thereof.
to 80% by weight of the total composition of a crystalline layered silicate of formula NaMSixO2x+1?yH2O
wherein M is sodium or hydrogen, x is a number of from 1.9 to 4 and y is a number of from 0 to 20, or mixtures thereof.
2. A granular bleaching composition according to claim 1 which comprises from 40% to 50% by weight of the total composition of a percarbonate bleach.
3. A granular bleaching composition according to any of the preceding claims, characterized in that it comprises from 15% to 25% by weight of the total composition of said crystalline layered silicate or mixtures thereof.
4. A granular bleaching composition according to any of the preceding claims, characterized in that the crystalline layered silicate is of the formula NaMSixO2x+1?yH2O, wherein x is 2, M is sodium and y is 0.
5. A granular bleaching composition according to any of the preceding claims, characterized in that it further comprises an anhydrous acififying agent.
6. A granular bleaching composition according to claim 5 wherein said anhydrous acidifying agent is anhydrous citric acid.
7. A granular bleaching composition according to claim 6 which comprises up to 15%, preferably from 2% to 12%, most preferably 5% by weight of the total composition of anhydrous citric acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92200005A EP0550077A1 (en) | 1992-01-03 | 1992-01-03 | Granular laundry bleaching composition |
| EP92200005.4 | 1992-01-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2126847A1 true CA2126847A1 (en) | 1993-07-08 |
Family
ID=8210346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002126847A Abandoned CA2126847A1 (en) | 1992-01-03 | 1992-12-24 | Granular percarbonate laundry bleach containing layered silicate stabilizer |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0550077A1 (en) |
| JP (1) | JPH07502770A (en) |
| KR (1) | KR940703911A (en) |
| CN (1) | CN1075749A (en) |
| AU (1) | AU666918B2 (en) |
| BR (1) | BR9207019A (en) |
| CA (1) | CA2126847A1 (en) |
| MA (1) | MA22754A1 (en) |
| MX (1) | MX9207671A (en) |
| RU (1) | RU94035995A (en) |
| WO (1) | WO1993012843A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0639639B2 (en) * | 1993-08-17 | 2010-07-28 | The Procter & Gamble Company | Detergent compositions comprising percarbonate bleaching agents |
| EP0745664B1 (en) * | 1994-02-25 | 1998-05-13 | Eka Chemicals AB | Bleaching agent |
| ES2190450T3 (en) * | 1994-03-14 | 2003-08-01 | Procter & Gamble | GRANULAR WHITENING COMPOSITIONS. |
| DE4408359A1 (en) * | 1994-03-14 | 1995-09-21 | Henkel Kgaa | Storage-stable fixed hydrogen peroxide-containing multicomponent mixtures in solid form, process for their preparation and their use |
| DE4424005A1 (en) * | 1994-07-07 | 1996-01-11 | Henkel Kgaa | Powdery bleach and detergent |
| EP0695800A3 (en) * | 1994-08-04 | 1997-10-15 | Hoechst Ag | Washing composition |
| JPH09511533A (en) * | 1994-09-19 | 1997-11-18 | ザ、プロクター、エンド、ギャンブル、カンパニー | Granular bleaching composition |
| DE4439083A1 (en) * | 1994-11-02 | 1996-05-09 | Henkel Kgaa | Direct synthesis of crystalline disilicate from water glass solution |
| DE69628784T2 (en) | 1995-04-12 | 2004-02-12 | Cleantabs A/S | Bleach tablets |
| DE19525197A1 (en) * | 1995-07-11 | 1997-01-16 | Hoechst Ag | Granular detergent builder |
| DE19532558A1 (en) * | 1995-09-04 | 1997-03-06 | Henkel Kgaa | Multi-component mixtures in solid form containing hydrogen peroxide with stable storage, process for their preparation and their use (II) |
| GB9605534D0 (en) * | 1996-03-15 | 1996-05-15 | Unilever Plc | Detergent compositions |
| GB2353800A (en) * | 1999-09-02 | 2001-03-07 | Procter & Gamble | Antibacterial detergent compositions |
| US20090032063A1 (en) * | 2007-07-30 | 2009-02-05 | Haas Geoffrey R | Solid cleaning composition and method of use |
| GB0805908D0 (en) * | 2008-04-01 | 2008-05-07 | Reckitt Benckiser Inc | Laundry treatment compositions |
| FR3072390B1 (en) * | 2017-10-18 | 2019-12-20 | Quadrimex Chemical Sas | EXTEMPORANEOUS COMPOSITION COMPRISING A MIXTURE OF TWO PRODUCTS FOR THE DESTRUCTION OF ORGANOPHOSPHORUS AND / OR ORGANOSULFUR POLLUTANTS |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951838A (en) * | 1973-10-10 | 1976-04-20 | E. I. Du Pont De Nemours And Company | Silica sol stabilizers for improving the stability of sodium percarbonate in solid bleaches and detergents |
| DE3413571A1 (en) * | 1984-04-11 | 1985-10-24 | Hoechst Ag, 6230 Frankfurt | USE OF CRYSTALLINE LAYERED SODIUM SILICATES FOR WATER SOFTENING AND METHOD FOR WATER SOFTENING |
| 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 |
| US5087895A (en) * | 1988-02-02 | 1992-02-11 | Motorola, Inc. | Miniature microstrip/cavity oscillator |
| DE3812555A1 (en) * | 1988-04-15 | 1989-10-26 | Hoechst Ag | STORAGE-STABILIZED DETERGENT WITH REINFORCED WHITENING EFFECT |
| DE3812556A1 (en) * | 1988-04-15 | 1989-10-26 | Hoechst Ag | DETERGENT WITH STORAGE-STABILIZED BLEACHING SYSTEM |
| DE3929896A1 (en) * | 1989-09-08 | 1991-03-14 | Hoechst Ag | DISHWASHING LIQUID |
-
1992
- 1992-01-03 EP EP92200005A patent/EP0550077A1/en not_active Ceased
- 1992-12-24 RU RU94035995/04A patent/RU94035995A/en unknown
- 1992-12-24 BR BR9207019A patent/BR9207019A/en not_active Application Discontinuation
- 1992-12-24 JP JP5511910A patent/JPH07502770A/en active Pending
- 1992-12-24 CA CA002126847A patent/CA2126847A1/en not_active Abandoned
- 1992-12-24 AU AU34224/93A patent/AU666918B2/en not_active Ceased
- 1992-12-24 KR KR1019940702293A patent/KR940703911A/en active IP Right Grant
- 1992-12-24 WO PCT/US1992/011222 patent/WO1993012843A1/en active Application Filing
- 1992-12-30 MX MX9207671A patent/MX9207671A/en not_active Application Discontinuation
- 1992-12-30 MA MA23046A patent/MA22754A1/en unknown
-
1993
- 1993-01-02 CN CN93101189A patent/CN1075749A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| MX9207671A (en) | 1994-05-31 |
| AU3422493A (en) | 1993-07-28 |
| CN1075749A (en) | 1993-09-01 |
| AU666918B2 (en) | 1996-02-29 |
| KR940703911A (en) | 1994-12-12 |
| MA22754A1 (en) | 1993-07-01 |
| WO1993012843A1 (en) | 1993-07-08 |
| BR9207019A (en) | 1995-12-05 |
| JPH07502770A (en) | 1995-03-23 |
| EP0550077A1 (en) | 1993-07-07 |
| RU94035995A (en) | 1996-06-20 |
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