CA1202853A - Cleaning compositions - Google Patents
Cleaning compositionsInfo
- Publication number
- CA1202853A CA1202853A CA000415030A CA415030A CA1202853A CA 1202853 A CA1202853 A CA 1202853A CA 000415030 A CA000415030 A CA 000415030A CA 415030 A CA415030 A CA 415030A CA 1202853 A CA1202853 A CA 1202853A
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- Prior art keywords
- alkali metal
- detergent composition
- aqueous detergent
- composition according
- ionic strength
- Prior art date
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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
- C11D3/3956—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT
Aqueous cleaning compositions of viscosity >180 centipoises at 20°C are provided containing a trialkyl amine oxide of formula R1R2R3N?O, where 13 < R1 ? 18 and R2 and R3 are C1-C4 alkyl, as the sole surfactant at a level of 0.5% to 5.0% by weight of the composition. The compositions also incorporate one or more ionisable water soluble compounds to provide an ionic strength of 3.0 g moles/dm3 minimum, and in preferred embodiments this is provided by an alkali metal hypochlorite bleach component.
Aqueous cleaning compositions of viscosity >180 centipoises at 20°C are provided containing a trialkyl amine oxide of formula R1R2R3N?O, where 13 < R1 ? 18 and R2 and R3 are C1-C4 alkyl, as the sole surfactant at a level of 0.5% to 5.0% by weight of the composition. The compositions also incorporate one or more ionisable water soluble compounds to provide an ionic strength of 3.0 g moles/dm3 minimum, and in preferred embodiments this is provided by an alkali metal hypochlorite bleach component.
Description
~ ~LZ028S3 .
CLEANING COMPOSITIONS
An~hony Francis MARTI~
Field of the Invention S This invention relates to a~ueous cleanin~ com~oæi~:~.on~
and especia.lly to chlorin~ bleach-containin~ aqueous cleanin~
compositions useful for the removal of oxidisab~e s~a~.n~ ~rom and the disinfection of hard surfaces. Compo~i~ions in accord~nce with the invention find particular. uti~it~ in ~he lOcleanin~ of ~anitary fittings such as tollets, bide~, .si.nk.s, ba~hs and shower units in addition to the disineotion of ~rains an~ the washing of tiled surfaces.
Backgro~nd of the Invention A~ueous chlorine bleaching products are ~Yell known in the ~rt and have been used or many years in a varie~y of bleac~in~ and disinfectin~ ~pplications. '~be acti.ve component of a product of this type is no~mally ~n a~
metal hypochlorite, usually at a le~el o from 1 ~o 15~ hy ~eight, and the ph~sical characteristics o~ l:he prod~2ct a):e
CLEANING COMPOSITIONS
An~hony Francis MARTI~
Field of the Invention S This invention relates to a~ueous cleanin~ com~oæi~:~.on~
and especia.lly to chlorin~ bleach-containin~ aqueous cleanin~
compositions useful for the removal of oxidisab~e s~a~.n~ ~rom and the disinfection of hard surfaces. Compo~i~ions in accord~nce with the invention find particular. uti~it~ in ~he lOcleanin~ of ~anitary fittings such as tollets, bide~, .si.nk.s, ba~hs and shower units in addition to the disineotion of ~rains an~ the washing of tiled surfaces.
Backgro~nd of the Invention A~ueous chlorine bleaching products are ~Yell known in the ~rt and have been used or many years in a varie~y of bleac~in~ and disinfectin~ ~pplications. '~be acti.ve component of a product of this type is no~mally ~n a~
metal hypochlorite, usually at a le~el o from 1 ~o 15~ hy ~eight, and the ph~sical characteristics o~ l:he prod~2ct a):e
2~hose of a clilut~ salt solution with a viscosil:y les.s ~han 20 centistokes.
In recent years, interest has developed in chlorine bleach produc~s of higher viscosity, in order t:~ p~ovide longer lasting ~dherence to ver~ical sur~aces and henc~
25~reater ~fficacyt and a number of ccmposition~ lave been disclosed that are stated to be both chemica~ .sl:~b~e and physically ~table over an extended period o I:~.m~.
. ~ Ex~,ples of such compositions are disc~osed by ~r~ish Pat~nt No. 1329036, European Published Patent Applica~io~
30 Nos. D021581t 0030~01, ~rench Published P~tent Applic~ion No. 2355909 and Bri,ish Patent ~pp~ication No. 20~3S22A.
~2~2853 These thickened compositions ineorporate one or more bleach stable surfactants as an aid in increasing viscosity ancl a preferred example of such a surfactant is an amine ~xide containing one C10-Cl~ alkyl group and ~wo lower S alkyl, usually Cl-C4 alkyl groups. The composition~ also contain a source of alkalinity and alkali metal salts of various kinds.
In order to achieve a si~nificant enhancement o VlSCosity the prior art has employed other surfactants in l0admixture with the amine oxide such as alkali metal a~y acid sal~s, alkali metal alkyl sulphate salts and saccharo.se e~ters and viscosities of up to 150 centistokes at ~.5~ a~e stated to be obtainable by this technique.
It has nou surprisingly been found that stable ~3u~ous 15chlorine bleach-containing compositions having viscosi~ie~
appreciably in excess of 150 centistokes can b~ achie~ed without the necessi~y of employing the surfactant mixture&
taught as necessary by the prior art.
This finding has also simplified the formulation of ~
20thickened chlorine bleach composition insoar as it lowe~s the level of organic components in the formulation and thereby lessens ~he problem of ensuring chemical stability as well as reducing the cost of the c~mposition.
It has also been found that compositions in accordance ~5with the invention display cleaning advantages relative to commercially available chlorine bleach co~posikions emhodyin~
the prior art.
Summary of the Invention According to the present invention there is provided a 30stable single phase aqueous detergent composition incorporating an amine oxide of formula RlR2~3N-~O
wherein Rl is an alkyl group in which the average numb~ o~
carbon atoms is such that 13 C Rl ~18 and ~2 and k3 are each independently selected ~rom the group oonsisting of 35Cl C4 alkyl radicals and C~-C4 hy~roxy alkyl radicals together wi~h at least one ionisable ~ater solul~le compotlnd ~;herein the amine oxide constitutes the sole surfactant and is p~esent in an amount of fro¢, about O.S5 to about 5.0% by wei~ht lZQZ~353 of the composition and in that the at least one water soluble inorganic salt is present in an amount to provide a total ionic strength of the composition of at least about 3.0 moles/dm , such that said composition has a viscosity o~ at 51east about 180 cp at 20C.
In one aspect of the invention the alkyl ~roup Rl consists essentially of a mixture of groups containin~ 13 and lS carbon atoms and comprising a mixture of woieties ~f structure, a) R -- CH _ CB2 -and b ) R- - C~ CH2 -, 15 the group R4 being predominantly methyl, the composit~on also being characterised by a total ionic ~trength of at least about 4.7 moles/dm3.
In a preferred aspect of the invention in which t~c~
- composition incorporates a hypochlorite bleach, Rl con~ai~s 20 an average. o~ from 14 to about 16 carbon atoms and is selected from linear moiet~es and moieties containin9 no mo~e than about 25~ methyl branching.
In this specification fluid viscosity is expressed as ~:he dynamic viscosity n in centipoises. The dynamic ~iscosity is measured by a ~rookfield RVT viscometer and for the purposes of this specification measurements are made wi~h Spindle No. 3 at 100 rpm and a liquid temperature c) 20C. Fluid viscosity can also be expressed as ~he kinem~ti~.
viscosity ~ in centistokes as measured by an Ostwald . 30 viscometer and is characterised by the expression v -n/P
wheren is t:he dynamic viscosity in centipoises and P is ~he density in g/cm3~ Compositions in accordance with the present invention have a density in the ran~e from abc~ul~ a~
to abou~ 1.25 g/cm3, typically approximatel~ 1~15 g/cm3, ~ 3~ so that the nl~merical value of the kinematic viscosik~ in centis~okes is slightly less than that of tlle dynam;c viscosity in centipoises.
:12~ 8S3 Detailed Description of the InventiOn ~ he invention will be described primarily with reference to an aqueous composition containing an alkali metal hypochlorite bleach, the latter providing the majority, and preferably substantially all, of the ionic strength requirement. However, the invention also embraces non-bleach.
compositions in which the ionic stren~th is provided b~ any ionisable alkali or alkali earth metal compound.
. Bleach composition embodiments of the present invention 1~ therefore c~mprise an amine oxide of defined structure and an alkali metal hypochlorite there being sufficient ionisable inorganic salt present to provide an ionic stren~th of at least about 3.0 moles/dm3.
The alkali metal hypochlorite may be a ~ithium, po~as~ium 15 or sodium hypochlorite and the level of hypochlorite in the composition is normaIly arranged to lie in the ran~e rom about 1% to about 12%, preferably from about S~ to about 10%
by weight. Customarily hypochlorite bleach compositions contain approximately 6% or g% hypochlorite by weight.
20 However~ ~he activi~y of chlorine bleaching composition~ is co~ventionally expressed in terms of the weight percentage of available chlorine in the-composition, and the actual wei~ht percentage of bleaching species is arranged to provide the desired level of eavailable chlorine'. The preferred 25 hypochlorite species is sodium hypochlorite which contains 95O3~ available chlorine.
Al~ali metal hypochlorites are commercially available as aqueous solutions containing from about 5% to about lS~ b~
weight 'available chlorinel a~d the bulk supplie~s normall~
30 produce material having available chlo~ine contents towa~ds the upper er;d of this ~ange viz. ~rom about 1~ to about 1 by weightO ~hese commercially available hy~ochlori~e solutions contain other salts as byproducts or con~aminants, more specifi.cally free alkalinity in the form of al.kali me~al hydroxide and al~ali metal carbonate, and alkal~ metal chloride. I.ow levels of other species such as sodium chlora~e are also believed to be formed durin~ h~pochlorite manufacture but their chemical stability is su~ficiently low :~20Z8S3 that they have lar~ely decomposed by the time the hypochlorite is employed in product formulations. The levels o~ the byproduct materials depend on the processin~
conditions employed in the manufacture of the hypochloxite 5 but in general they fall within the ranges 0.2 - 1.0~ alkali metal hydroxide 0.01 - 0.1% alkali metal carbonate 10.0 ~ 18~0% alkali metal chloride expressed as a weight percentage of the hypochlorite solution 10 as suppliedD
Amine oxides useful in the present ~nvention hav~ the formula RlR~R3N-~0 wherein Rl is an alkyl group in - which the number of carbon atoms is 13 < R~ and n2 and R3 are Cl-C4 alkyl groups or C2-C4 hydroxy 15 alkyl groups. The amine oxide is present in an amount of from about 0.5% to about 5%, more preferably rom ahout 0.5%
to about 2.5~ and, in preferred embodiments of the invention in which the Rl average chain length ~ 14 carbon atoms, from about 1~ to about 1.5~ by weight of the composition.
" 20 The Rl group may be linear o~ branched and may be derived from natural or synthetic hydrocarbon sources. For the purposes of the present invention linear groups are defined as including moieties incorporating up to about 25~ methyl branching, predominantly in the 2-position relative ~o ~he nitrogen atom of the amine oxide~
~sethyl branchin~ on the alkyl chain also predominates in those amine oxides useful in the present invention in which the Rl group is branchedl rather ~han linear in natllre.
Commercially available sources of these amina oxides are normally a mixture of ~ 2 R CH~--CH2 N -- O
~Z:0;~853 which arises as a result of the processing route used to form the precursor alcohol or aldehyde. This route involves carbonylating or hydroformylating an olefin, prefe~ably a linear^~-olefin and leads to a mixture of the desired branched chain aldehyde or alcohol of the same carhon number. For olefin startin~ mater~als.haVing a ran~e o~
carbon chain lenqth, the resultant alcohol or aldehyde mixture contains compounds of different carbon numbe~ and i~omers containing straight chain and 2-alkyl branched chaln 10 alkyl groups. A typical mixture useful in the p~esent invention comprises from about 65 to about 75~ b~ wei~ht C13 and from about 35 to about 25% by weight C15 am~.ne oxides with approximately 50% by weight stra~ght cl)ain and 50% by weight 2-alkyl branched chain where the 2~alkyl ~roup 15 i8 predominantly methyl. These are available from ICI unde~
the trade mark Synprolam 35 DktO as a 30~ aqueou~ æolution.
The branched chain amine oxides and mixtu~es the~eo~ with linear chain amine oxides are used at levels to~ards the upper end of the range viz. ~ about 2~ by weisht of the 20 composition and typically from about 2.0~ to abo~ .5~ b~
weight.
Althougll the above-described mixture of strclight chain and branched chain alkyl dimethyl amine oxides h~ een found to provide the benefits of the invention, their use doe~ no~
25 constitute the most preferred.execution o~ the h~pochlorite bleach aspect of the invention. This is because an ionic stren~th of at least about 4.7 moles/dm3 i~ )eguired ~:o acbieve the target viscosity and this level of ~onic stren~th is believed to make the storage stability of ~he hypochlorite bleach less t:han that which is considered desirahle for the expected shel.f life of the product. For t~)e hypochlorite bleach aspect of the composition, the pree~ed amin~ ox~de structure is one in which Rl has an average chain len~th in the range Cl~-C16 and is a linear group, linea~ ~ein~
defir,ed as including moieties contalning up to about 25%
2~m~thyl branching. Compositions ~ontaining the~e p~eferred ~2028~i3 amine oxicles require a lower amine oxid~ level viz. < about 2.0~, more typically from about 1~ to about 1.5% and also a lower ionic strength viz. about 3.0 moles/dm3 minimum in order to achieve target viscosity. Both of these reductions in ingredient level le~d to improved stora~e stability and also lo~er the cost of the product.
The ionisable water soluble compound ~hich forms the other major component of the compositions o~ the invention is a non-surface active organic, or inorganic, compound which must be present in an amount to provide an ionic s~ength o~
at least about 3.0 moles/dm .
The ionisable compound~s) can be inorganic in nakure eg.
hydroxide~sulphate, halide (particularly chloride~ carbona~eO
nitrate~ orthophosphate~ pyrophosphate, polyphosplla~.e o~
sil~cate, ,or organic such as citrate, formate, acetate or ~uccinate. In a preferred aspect of the invention ln which sodium hypochlorite bleach is incorporated, the hypochlori~e itself, toyether with the sodium hydroxide, chloride and chlorate associated with the bleach provides the, or a majo~
proportion o the ionisable oompounds requir~d by the I inYention. In the preferred hypochlo~ite bleach-containing ~mbodiments of the invention, certain inorganic compounds such as si:Licates, and organic compounds incorporating oxidisable groups axe unstable and should be avoided.
The :ionic strength of the composition is calculated by ~eans of the expression Total Ionic Strength I = ~ C,Z; 2 where Ci is ~he molar concentration o~ ~he ionic species in 9 moles/dm Zi is the valency of the species..
The ~unction CiZ2 is calculated for each of the ionic species in solution, these functions are su~med ~nd divided by two to give the composition ionic stre~qth~
~ZOZ853 ~ he ionisable alkali metal compound normally comprises a caustic alkali suoh as sodium or po~assium hydroxide ei~he~
alone or in admixture with alkali metal salts. ~he level o sodium hydroxide necessary ~o provide a total composition ionic strength of 3.0 moles~dm3 where the composition contains only the amine oxide would be approximately 11% ~o 12% by weight of the composition dependent on the dens~y o~:
the solution~ More preferably, for product safety reasons, the at least one ionisable compound comprises a mixturc~ o 10 caustic alkali in an amount of from about 0.5~ to aboul ~
weight of the composition together with one or more alkali metal sal~s in an amount of at least about 10% by wei~ht, more usually at least 15-20~o In that aspect of the invention directed to ~i~uid 15 de~ergent compositions sui~able for cleaning hard surfaGes such as walls and windows, the ionisable compound ~an in~ de any of the water soluble inorganic and organic builder and sequestrant. salts normally incorporated in such produ~:s.
Compounds classifiable and well-~nown in the art as de~ex~en~
20 builder salts include the nitrilotriacetates, polycarboxylates, citrates, ortho- and pyro-phosphates, and mixtures of any of these. Metal ion sequestrants include al~
of the above, plus materials like ethylenediaminetetra-aceta~e, the amino-polyphosphonates and phosphates 25 ~DEQUEST~. A wide variety of poly-functional organic acids and salts is disclosed in ~ur-opean Patent ~pplication Publication No 0040882 which contains examples o the use o~:
such materials in various cleaning compositions. In q~ner~ll the builder~sequestrant will comprise from about ~ to abont.
30 25% of the composition. Citric acid ~2% ~0% as sodium citrate) is a preferred builder.
In the aspect of the invention in which ~ hypo~h~or;l:e bleach is incorporated the bleach itself, oontainin~ ~.he range of by-product materials previously mentioned, prov~d~s 35 a major por~ion of ~he ioni~ strength requirement, ViY. a~
least about 3.0 moles/dm assuming an available chlorine level of about 9% in the composition. In practice thereore it is usually only necessary to add alkali meta1 hydroxide ~n ~ .
lZV;Z~3~3 _ g a to~al composition basis. In this aspect of the inventlon ~t is particularly preferred that the, or the ma~or part o~
the, amine oxide should have an ~1 alkyl chaln length in the range from 14 to about 16 carbon atoms. A desirable 5 optional component of compositions in accordance with the invention i~ a perfume which i8 present at a level of ~rom about 0.01% to about 0.5% preferably rom about ~.05% to about 0.2~% by weight of ~he composition.
The compositions are made by conventional mixin~
~technigues. Although any order of mixing can be used, presolut~on o the alkali ~etal hydroxide and any alkali metal salt ~s desirable and these are normally added to a solution of the amine oxide. Perfume is then added under high shear agitation together with any addit~onal water ~o Sprov~de the desired product concentrat~on. In the aspect o the invention in wh~ch an alkali metal hypochlorite bleach 18 included, this component ls added last.
The invention is illustrated in the following example~
in which percentages are expressed by weight of the 20 composition unless otherwise stated.
In the examples reference to ingredients have been abbreviated as follows:
C13D~O Cl~ alkyl dimeth~l amine oxlde in ~hich the alkyl group is 95~ C13 and approximately 50% of the alkyl groups contain methyl branching on the 2-carbon atom.
ClsDUO Cl~ al~yl dimethyl amine oxide in which the alkyl ~roup is 95~ Cls and approximatel~
50~ of the alkyl group~
contain methyl branching on the 2-carbon atom.
3s C13-Cls DMAO C13-Cls alkyl dimethyl amine oxide in which the alk~l group is 67% C13~ 33% C15 and the alkyl groups contain approximatel~ 50% methyl branching on the 2~carbon atom. Available from Imperial Chemical Industries Ltd under the Trade Mark Synprolam 35DMO.
~'~OZ8S3 1 o --C14~MAO Cl~ alkyl dimethyl amine oxlde in which the alkyl group is-a predominantly linear Cl~ (~g4%) moiety.
Available f~om Albri~t ~ on Ltd as Empige~O~
N~A Trisodium ni~rilotriacetate EDTA Tetra sodium eth~lene diamine tetra acetate EDTMP Octa sodium ethylene diamine tetra methylene phosphonate NaPyro Tetra sodium p~ropho~phate Na citrate ~risodium cit~ate K Pyro Tetra potassium py~ophosph~e Na me'llitate Hexasodium benzene hexacarboxyla~e 1.09 of pelleted sodium hydroxide, equivalent to 0.5~ o~ the finished product composition, was dissolved in 7.~ ml ~of~
20 water and 8~0 g anhydrous sodium carbonate wa~ added to the ~olution. This solution was then added to 16.6 g oP a 30~ by weigh~ solu~ion of C13 15 alkyl ~imethyl amine oxide ~available ~Erom ICI as Synprolam 35DMO). ~inally this mixture was blended with hi~h shear agitation into 167~ o~ a 25sodium hypochlorite solution~ containing 11.5% by weight of a~ailable chlorine.
~Supplied by British Drug Hous~s Ltd as GPR hypochlorite This composition had the following analysis, in percent 30by weig~t and had a density of 1.25 g~cm2.
NaOCl 10.1 ~= 9~6% available chlorine~ 1.6~ moles/dm3 NaCl 13O5 2~B%
NaClO3 0.8 0.09 Na2CO3 4.1 0.~8 ~
35NaOH lrO 0~31 Q
Amine 2.5 oxide Water 67.8 & ~isc 100 . O
1;20Z8S3 _ 11 This p~oduct was a singie phase solution havin~ a dynamic viscosity a~s measured at 20C with a Brookfield viscometer using the No. 3 spindle at 100 rpm was 165 cp fresh and 180 cp after 24 hours.
The ionic strength of this composition was as calculated follows: ~ CiZi I = 2 ,[1.68]~12.88~+t0.09~[2x~.48i~[0.31~ ~Ca~ions~
~ [1.681~2.88]~[0.091+[4x0.48]~t0.31J ~An~.ons) - 6~45 moles/dm3 EXA~PLE 2 20 9 poudered anhydrous sodi~m carbonate alld 2~ 9 pelleted sodium hydroxide were dissolved in ~,00 ml ~of~
water. 66.6 9 of a 30% solution of a C13J15 alk~l dimethyl amine oxide sold under the trade name Synprolam 35 nMO b~ ICI
Ltd, was added to the alkaline salt solutioll wi~h hi~h shea~
agitation. The mixture was then added to 720 ~ o a ~odium hypochlorite solution containin~ 10~ available chlorine sold 20 by British Drug Houses Ltd and further soft wa~e~ was added to provide a final compo~ition containing:
7.6~ sodium hypochlorite t_ 7.2~ available chlorine) 2.5% sodium hydroxide 2.1% sodium carbonate 13.5Q sodium chlGride 2.0% C13/1~ Amine Oxide 72.3% water and miscellaneous 100 ~, O 96 The ionic strength I of this composition was ound ~o ~e ~..61 moles/dm3 and the dy~amic viscosity, measured b~ means o~ a Brookfield RVT viscometer tSpindle No. 3 at 100 rpm) at 20C wzs 220 cp as measured 2~ hours after ~he so~u~ion ~a.5 prepared. The density of the solution w~as 1.25 gfcm3 so tha~
- the calculated kir.ematic viscosity v was 215.6 centistokes~
, . . . ... . .. .
lZ()2853 EXA~PLE 3 ~he following composition was prepared using the technique employed in Example 2.
Sodium hypochlorite 8.4~ (~ 8.0% available chlorine) Sodium hydroxide4.5%
Sodium chloride 12.7%
~13~15 amine oxide* 2.0%
Perfume 0.1 ~ater & misc. 72.3%
100.
Synprolam DMO
~he density of this solution was 1.25 g/cm3 and on thi~
basis the ionic strength of tbe com~osition was calcula~ed ~o-be 5.50 moles/dm3. Its viscosity 5after 24 hours) wa~ ~0 15 centipoises.
EXA~tPLE 4 The following compositions, prepared according to the ; technique of Example 1 illustrate the criticality of the Yarious features of the invention.
- (a) (b) (c~ (d) Sodium hypochlorite 8.4 8.4 8.4 8.4 Sodium hydroxide 4.5 4.5 O.S 0.5 Sodium chloride 12.7 12.7 12.7 12.7 C12tl4 linear alkyl _ - 2.0 dimethyl amine oxide C13/15 branched alkyl2.0 - 2;0 ~.5 dimetllyl amine oxide Water ~ misc. 72.4 72.4 7~.4 76~
~iscosity centipGises 20C 220 20 90 105 30 (24 hrs after preparation) Composition Ionic strength I moles dm3 5.50 5.50 4.~0 ~.~0 ~ Composition ~a) is in accordance with the present invention whilst compositions ~b), (c) and ~d) are illustrative of prior art products. Comparison of compositions (a) and tb) ~Z(~Z853 demonstrates the different viscosit~ behaviour of products containing a) amine oxides of average chain length C C13 and b) amine oxide of average chain length > C13 both products being at the same ionic strength. Comparison of compositions (a) and ~c) illustrates the role of ionic strength in providing the product viscosities o~ the presen~
invention. In particular it should be noted that, for amine oxides havin~ a chain length at the lower end of the range found to be useful in the invention, an ionic streng~h ~ 5.0 moles/dm3 is required i.e. appreciably higher than the recited minimum of 3.3 moles~dm3. Comparison of compositions (c) and (d) shows that ~or this amine oxide chain length, increasing amine oxide concentr~tion does ~c~i:
compensate for the shortfall in ionic strength d~spl~e~
these compositions.
The composition set out in Example 4(a) and designa~ed X
I was tested for its hard surface cleaning ability re~ativ~ l:n ¦ ~ commercially available chlorine bleach product designate~
i 20 II and having the following approximate analysis:
Available chlorine 8.0 C12/14 linear alkyl 1.0 dimethyl Amine oxide Sodium laurate 0.5.
~5 Sodium hydroxide 0.2 Water & ~isc~ To 100 A synthetic soil was made up comprising by volume ~ part:s qround garden soil, 4 parts roast lamb fat and 1 part mi~.k.
The soil was made up by mixin~ the fat and ~arden soi~
heating and stirring to melt the fat and then dispersinc~ ~h~
milk in the mixture.
15 cm square ceramic tiles were each soiled with ~0 m~ c~
thP above soil~ which was applied by pad and then allowed t:o dry for one hour or overni~ht ~18 hours).
A soiled tile was then clamped with the soiled sUt~ e uppermost at an angle sf 30 to the vertical and the soiled lZ~)~Z853 surface was divided equally into Left hand and Right hand areas. 14 ml of Product I was applied by syringe on to the Lef~ ~and area and the same volume of Product Il was applied to the Right Hand area, each application being arranged to cover the whole surface of the respective area. The areas were then lef t to drain for 10 minutes or ovexnight (18 hours) before being rinsed for 1~ seconds with water at a rate of 8.5 litres/minute and a temperature o 20C usin~ a split rinsing head to treat both LH and RH areas simultaneously. Four replicate tests were oarried out in two of which the tile areas to which the products were applied were also reversed.
Assessment of cleaning differences between L~ and ~l areas was carried out by visual grad~ ng usiny ~ 1-4 s~ale, higher values denoting enhanced cleanin~ Results are given below in which the cleaninq per~ormance of ~roduct I is expressed as a difference rela~ive to that of Product II.
Time elapsed after soiling treatment CleaningYardstick t ~ Difference 1 hr 10 mins ~ +0 . 78 a . 6B
18 hrs 10 mins +1D50 0~32 1 hr 18 hrs ~1.47 0.38 18 hrs 18 hrs +1~69 0.~3 It can be seen that Product I provides significantly better soil cleaning than Product II under the conditions o~
the Test.
Example 6 The following composi~ion was prepared ac~ording to the technique of Example 1:
-~Z(~z8s3l 5 ~e) (f) (g) (h) (~) Cl3DMAO 1.2 Cl4D~IAO 1~2 1.5 1.75 C15DMAO 1~2 NaOH 1.0 NaOCl 9.o NaCl g.o NaCL03 0.6 ,>
Water & Uisc. to 100 1~ ~iscosity (cp) 350 l9~ 30 ~,45 3~4 The density of each of these compositions was 1.15 g/ml and the ionic strength for each composi~ion was calculated to be 3.5 molJdm3. The product YisCosity was me~suKed at 2Q~C
using the tech~ique of Example lo It can be seen that an amine oxide alkyl chain len~th of C~3 is reguired in order to achieve the recited viscosity minimum of 180 centipoises. An increase in the level of C13DMAO to 5~ by weight of the composition did ~ot produce the desired YiSCosity increase.
?o EXAMPLE 7 ! The follawing compositions are in accordance with the invention.
7 l.Z~Z853 ~k~ m) (n) (o) (p). (q) (r C13 Cls DMAo 2 . 5 _ 2 . ~ 0 C14 Dl`lAO _ 1.4 - 1.5 1.5 _ 1.. 8 l.~
NaOH 0.5 0.6 0.5 0.5 0.6 0.6 0.5 0,5 NaPyro 5 R Pyro ~ - 12 Na citrate 10 15 ~ 0 ~,0 Na mellitate ~ 15 NTA - ~ 15 ~5 - ~-EDTA ~ ~
EDTMP 0.2 0.2 0.2 -- 0.~. - 0.
Pe~fume 0~1 0.1 0-l 061 0-1 0~1 0.1 0.
Wat~r & Misc To 100 Ionic Strën~th I 4.96 3.9d, 5.03 7.81 4.~ b.3(1 5~0 5.5 15 (9 moles/dlm ) product density basis 1.15 g/c~n3 All of the compositions exhibit viscosil:ies ;.n excess o ~00 centipoises at ~0C after 24 hours.
. --
In recent years, interest has developed in chlorine bleach produc~s of higher viscosity, in order t:~ p~ovide longer lasting ~dherence to ver~ical sur~aces and henc~
25~reater ~fficacyt and a number of ccmposition~ lave been disclosed that are stated to be both chemica~ .sl:~b~e and physically ~table over an extended period o I:~.m~.
. ~ Ex~,ples of such compositions are disc~osed by ~r~ish Pat~nt No. 1329036, European Published Patent Applica~io~
30 Nos. D021581t 0030~01, ~rench Published P~tent Applic~ion No. 2355909 and Bri,ish Patent ~pp~ication No. 20~3S22A.
~2~2853 These thickened compositions ineorporate one or more bleach stable surfactants as an aid in increasing viscosity ancl a preferred example of such a surfactant is an amine ~xide containing one C10-Cl~ alkyl group and ~wo lower S alkyl, usually Cl-C4 alkyl groups. The composition~ also contain a source of alkalinity and alkali metal salts of various kinds.
In order to achieve a si~nificant enhancement o VlSCosity the prior art has employed other surfactants in l0admixture with the amine oxide such as alkali metal a~y acid sal~s, alkali metal alkyl sulphate salts and saccharo.se e~ters and viscosities of up to 150 centistokes at ~.5~ a~e stated to be obtainable by this technique.
It has nou surprisingly been found that stable ~3u~ous 15chlorine bleach-containing compositions having viscosi~ie~
appreciably in excess of 150 centistokes can b~ achie~ed without the necessi~y of employing the surfactant mixture&
taught as necessary by the prior art.
This finding has also simplified the formulation of ~
20thickened chlorine bleach composition insoar as it lowe~s the level of organic components in the formulation and thereby lessens ~he problem of ensuring chemical stability as well as reducing the cost of the c~mposition.
It has also been found that compositions in accordance ~5with the invention display cleaning advantages relative to commercially available chlorine bleach co~posikions emhodyin~
the prior art.
Summary of the Invention According to the present invention there is provided a 30stable single phase aqueous detergent composition incorporating an amine oxide of formula RlR2~3N-~O
wherein Rl is an alkyl group in which the average numb~ o~
carbon atoms is such that 13 C Rl ~18 and ~2 and k3 are each independently selected ~rom the group oonsisting of 35Cl C4 alkyl radicals and C~-C4 hy~roxy alkyl radicals together wi~h at least one ionisable ~ater solul~le compotlnd ~;herein the amine oxide constitutes the sole surfactant and is p~esent in an amount of fro¢, about O.S5 to about 5.0% by wei~ht lZQZ~353 of the composition and in that the at least one water soluble inorganic salt is present in an amount to provide a total ionic strength of the composition of at least about 3.0 moles/dm , such that said composition has a viscosity o~ at 51east about 180 cp at 20C.
In one aspect of the invention the alkyl ~roup Rl consists essentially of a mixture of groups containin~ 13 and lS carbon atoms and comprising a mixture of woieties ~f structure, a) R -- CH _ CB2 -and b ) R- - C~ CH2 -, 15 the group R4 being predominantly methyl, the composit~on also being characterised by a total ionic ~trength of at least about 4.7 moles/dm3.
In a preferred aspect of the invention in which t~c~
- composition incorporates a hypochlorite bleach, Rl con~ai~s 20 an average. o~ from 14 to about 16 carbon atoms and is selected from linear moiet~es and moieties containin9 no mo~e than about 25~ methyl branching.
In this specification fluid viscosity is expressed as ~:he dynamic viscosity n in centipoises. The dynamic ~iscosity is measured by a ~rookfield RVT viscometer and for the purposes of this specification measurements are made wi~h Spindle No. 3 at 100 rpm and a liquid temperature c) 20C. Fluid viscosity can also be expressed as ~he kinem~ti~.
viscosity ~ in centistokes as measured by an Ostwald . 30 viscometer and is characterised by the expression v -n/P
wheren is t:he dynamic viscosity in centipoises and P is ~he density in g/cm3~ Compositions in accordance with the present invention have a density in the ran~e from abc~ul~ a~
to abou~ 1.25 g/cm3, typically approximatel~ 1~15 g/cm3, ~ 3~ so that the nl~merical value of the kinematic viscosik~ in centis~okes is slightly less than that of tlle dynam;c viscosity in centipoises.
:12~ 8S3 Detailed Description of the InventiOn ~ he invention will be described primarily with reference to an aqueous composition containing an alkali metal hypochlorite bleach, the latter providing the majority, and preferably substantially all, of the ionic strength requirement. However, the invention also embraces non-bleach.
compositions in which the ionic stren~th is provided b~ any ionisable alkali or alkali earth metal compound.
. Bleach composition embodiments of the present invention 1~ therefore c~mprise an amine oxide of defined structure and an alkali metal hypochlorite there being sufficient ionisable inorganic salt present to provide an ionic stren~th of at least about 3.0 moles/dm3.
The alkali metal hypochlorite may be a ~ithium, po~as~ium 15 or sodium hypochlorite and the level of hypochlorite in the composition is normaIly arranged to lie in the ran~e rom about 1% to about 12%, preferably from about S~ to about 10%
by weight. Customarily hypochlorite bleach compositions contain approximately 6% or g% hypochlorite by weight.
20 However~ ~he activi~y of chlorine bleaching composition~ is co~ventionally expressed in terms of the weight percentage of available chlorine in the-composition, and the actual wei~ht percentage of bleaching species is arranged to provide the desired level of eavailable chlorine'. The preferred 25 hypochlorite species is sodium hypochlorite which contains 95O3~ available chlorine.
Al~ali metal hypochlorites are commercially available as aqueous solutions containing from about 5% to about lS~ b~
weight 'available chlorinel a~d the bulk supplie~s normall~
30 produce material having available chlo~ine contents towa~ds the upper er;d of this ~ange viz. ~rom about 1~ to about 1 by weightO ~hese commercially available hy~ochlori~e solutions contain other salts as byproducts or con~aminants, more specifi.cally free alkalinity in the form of al.kali me~al hydroxide and al~ali metal carbonate, and alkal~ metal chloride. I.ow levels of other species such as sodium chlora~e are also believed to be formed durin~ h~pochlorite manufacture but their chemical stability is su~ficiently low :~20Z8S3 that they have lar~ely decomposed by the time the hypochlorite is employed in product formulations. The levels o~ the byproduct materials depend on the processin~
conditions employed in the manufacture of the hypochloxite 5 but in general they fall within the ranges 0.2 - 1.0~ alkali metal hydroxide 0.01 - 0.1% alkali metal carbonate 10.0 ~ 18~0% alkali metal chloride expressed as a weight percentage of the hypochlorite solution 10 as suppliedD
Amine oxides useful in the present ~nvention hav~ the formula RlR~R3N-~0 wherein Rl is an alkyl group in - which the number of carbon atoms is 13 < R~ and n2 and R3 are Cl-C4 alkyl groups or C2-C4 hydroxy 15 alkyl groups. The amine oxide is present in an amount of from about 0.5% to about 5%, more preferably rom ahout 0.5%
to about 2.5~ and, in preferred embodiments of the invention in which the Rl average chain length ~ 14 carbon atoms, from about 1~ to about 1.5~ by weight of the composition.
" 20 The Rl group may be linear o~ branched and may be derived from natural or synthetic hydrocarbon sources. For the purposes of the present invention linear groups are defined as including moieties incorporating up to about 25~ methyl branching, predominantly in the 2-position relative ~o ~he nitrogen atom of the amine oxide~
~sethyl branchin~ on the alkyl chain also predominates in those amine oxides useful in the present invention in which the Rl group is branchedl rather ~han linear in natllre.
Commercially available sources of these amina oxides are normally a mixture of ~ 2 R CH~--CH2 N -- O
~Z:0;~853 which arises as a result of the processing route used to form the precursor alcohol or aldehyde. This route involves carbonylating or hydroformylating an olefin, prefe~ably a linear^~-olefin and leads to a mixture of the desired branched chain aldehyde or alcohol of the same carhon number. For olefin startin~ mater~als.haVing a ran~e o~
carbon chain lenqth, the resultant alcohol or aldehyde mixture contains compounds of different carbon numbe~ and i~omers containing straight chain and 2-alkyl branched chaln 10 alkyl groups. A typical mixture useful in the p~esent invention comprises from about 65 to about 75~ b~ wei~ht C13 and from about 35 to about 25% by weight C15 am~.ne oxides with approximately 50% by weight stra~ght cl)ain and 50% by weight 2-alkyl branched chain where the 2~alkyl ~roup 15 i8 predominantly methyl. These are available from ICI unde~
the trade mark Synprolam 35 DktO as a 30~ aqueou~ æolution.
The branched chain amine oxides and mixtu~es the~eo~ with linear chain amine oxides are used at levels to~ards the upper end of the range viz. ~ about 2~ by weisht of the 20 composition and typically from about 2.0~ to abo~ .5~ b~
weight.
Althougll the above-described mixture of strclight chain and branched chain alkyl dimethyl amine oxides h~ een found to provide the benefits of the invention, their use doe~ no~
25 constitute the most preferred.execution o~ the h~pochlorite bleach aspect of the invention. This is because an ionic stren~th of at least about 4.7 moles/dm3 i~ )eguired ~:o acbieve the target viscosity and this level of ~onic stren~th is believed to make the storage stability of ~he hypochlorite bleach less t:han that which is considered desirahle for the expected shel.f life of the product. For t~)e hypochlorite bleach aspect of the composition, the pree~ed amin~ ox~de structure is one in which Rl has an average chain len~th in the range Cl~-C16 and is a linear group, linea~ ~ein~
defir,ed as including moieties contalning up to about 25%
2~m~thyl branching. Compositions ~ontaining the~e p~eferred ~2028~i3 amine oxicles require a lower amine oxid~ level viz. < about 2.0~, more typically from about 1~ to about 1.5% and also a lower ionic strength viz. about 3.0 moles/dm3 minimum in order to achieve target viscosity. Both of these reductions in ingredient level le~d to improved stora~e stability and also lo~er the cost of the product.
The ionisable water soluble compound ~hich forms the other major component of the compositions o~ the invention is a non-surface active organic, or inorganic, compound which must be present in an amount to provide an ionic s~ength o~
at least about 3.0 moles/dm .
The ionisable compound~s) can be inorganic in nakure eg.
hydroxide~sulphate, halide (particularly chloride~ carbona~eO
nitrate~ orthophosphate~ pyrophosphate, polyphosplla~.e o~
sil~cate, ,or organic such as citrate, formate, acetate or ~uccinate. In a preferred aspect of the invention ln which sodium hypochlorite bleach is incorporated, the hypochlori~e itself, toyether with the sodium hydroxide, chloride and chlorate associated with the bleach provides the, or a majo~
proportion o the ionisable oompounds requir~d by the I inYention. In the preferred hypochlo~ite bleach-containing ~mbodiments of the invention, certain inorganic compounds such as si:Licates, and organic compounds incorporating oxidisable groups axe unstable and should be avoided.
The :ionic strength of the composition is calculated by ~eans of the expression Total Ionic Strength I = ~ C,Z; 2 where Ci is ~he molar concentration o~ ~he ionic species in 9 moles/dm Zi is the valency of the species..
The ~unction CiZ2 is calculated for each of the ionic species in solution, these functions are su~med ~nd divided by two to give the composition ionic stre~qth~
~ZOZ853 ~ he ionisable alkali metal compound normally comprises a caustic alkali suoh as sodium or po~assium hydroxide ei~he~
alone or in admixture with alkali metal salts. ~he level o sodium hydroxide necessary ~o provide a total composition ionic strength of 3.0 moles~dm3 where the composition contains only the amine oxide would be approximately 11% ~o 12% by weight of the composition dependent on the dens~y o~:
the solution~ More preferably, for product safety reasons, the at least one ionisable compound comprises a mixturc~ o 10 caustic alkali in an amount of from about 0.5~ to aboul ~
weight of the composition together with one or more alkali metal sal~s in an amount of at least about 10% by wei~ht, more usually at least 15-20~o In that aspect of the invention directed to ~i~uid 15 de~ergent compositions sui~able for cleaning hard surfaGes such as walls and windows, the ionisable compound ~an in~ de any of the water soluble inorganic and organic builder and sequestrant. salts normally incorporated in such produ~:s.
Compounds classifiable and well-~nown in the art as de~ex~en~
20 builder salts include the nitrilotriacetates, polycarboxylates, citrates, ortho- and pyro-phosphates, and mixtures of any of these. Metal ion sequestrants include al~
of the above, plus materials like ethylenediaminetetra-aceta~e, the amino-polyphosphonates and phosphates 25 ~DEQUEST~. A wide variety of poly-functional organic acids and salts is disclosed in ~ur-opean Patent ~pplication Publication No 0040882 which contains examples o the use o~:
such materials in various cleaning compositions. In q~ner~ll the builder~sequestrant will comprise from about ~ to abont.
30 25% of the composition. Citric acid ~2% ~0% as sodium citrate) is a preferred builder.
In the aspect of the invention in which ~ hypo~h~or;l:e bleach is incorporated the bleach itself, oontainin~ ~.he range of by-product materials previously mentioned, prov~d~s 35 a major por~ion of ~he ioni~ strength requirement, ViY. a~
least about 3.0 moles/dm assuming an available chlorine level of about 9% in the composition. In practice thereore it is usually only necessary to add alkali meta1 hydroxide ~n ~ .
lZV;Z~3~3 _ g a to~al composition basis. In this aspect of the inventlon ~t is particularly preferred that the, or the ma~or part o~
the, amine oxide should have an ~1 alkyl chaln length in the range from 14 to about 16 carbon atoms. A desirable 5 optional component of compositions in accordance with the invention i~ a perfume which i8 present at a level of ~rom about 0.01% to about 0.5% preferably rom about ~.05% to about 0.2~% by weight of ~he composition.
The compositions are made by conventional mixin~
~technigues. Although any order of mixing can be used, presolut~on o the alkali ~etal hydroxide and any alkali metal salt ~s desirable and these are normally added to a solution of the amine oxide. Perfume is then added under high shear agitation together with any addit~onal water ~o Sprov~de the desired product concentrat~on. In the aspect o the invention in wh~ch an alkali metal hypochlorite bleach 18 included, this component ls added last.
The invention is illustrated in the following example~
in which percentages are expressed by weight of the 20 composition unless otherwise stated.
In the examples reference to ingredients have been abbreviated as follows:
C13D~O Cl~ alkyl dimeth~l amine oxlde in ~hich the alkyl group is 95~ C13 and approximately 50% of the alkyl groups contain methyl branching on the 2-carbon atom.
ClsDUO Cl~ al~yl dimethyl amine oxide in which the alkyl ~roup is 95~ Cls and approximatel~
50~ of the alkyl group~
contain methyl branching on the 2-carbon atom.
3s C13-Cls DMAO C13-Cls alkyl dimethyl amine oxide in which the alk~l group is 67% C13~ 33% C15 and the alkyl groups contain approximatel~ 50% methyl branching on the 2~carbon atom. Available from Imperial Chemical Industries Ltd under the Trade Mark Synprolam 35DMO.
~'~OZ8S3 1 o --C14~MAO Cl~ alkyl dimethyl amine oxlde in which the alkyl group is-a predominantly linear Cl~ (~g4%) moiety.
Available f~om Albri~t ~ on Ltd as Empige~O~
N~A Trisodium ni~rilotriacetate EDTA Tetra sodium eth~lene diamine tetra acetate EDTMP Octa sodium ethylene diamine tetra methylene phosphonate NaPyro Tetra sodium p~ropho~phate Na citrate ~risodium cit~ate K Pyro Tetra potassium py~ophosph~e Na me'llitate Hexasodium benzene hexacarboxyla~e 1.09 of pelleted sodium hydroxide, equivalent to 0.5~ o~ the finished product composition, was dissolved in 7.~ ml ~of~
20 water and 8~0 g anhydrous sodium carbonate wa~ added to the ~olution. This solution was then added to 16.6 g oP a 30~ by weigh~ solu~ion of C13 15 alkyl ~imethyl amine oxide ~available ~Erom ICI as Synprolam 35DMO). ~inally this mixture was blended with hi~h shear agitation into 167~ o~ a 25sodium hypochlorite solution~ containing 11.5% by weight of a~ailable chlorine.
~Supplied by British Drug Hous~s Ltd as GPR hypochlorite This composition had the following analysis, in percent 30by weig~t and had a density of 1.25 g~cm2.
NaOCl 10.1 ~= 9~6% available chlorine~ 1.6~ moles/dm3 NaCl 13O5 2~B%
NaClO3 0.8 0.09 Na2CO3 4.1 0.~8 ~
35NaOH lrO 0~31 Q
Amine 2.5 oxide Water 67.8 & ~isc 100 . O
1;20Z8S3 _ 11 This p~oduct was a singie phase solution havin~ a dynamic viscosity a~s measured at 20C with a Brookfield viscometer using the No. 3 spindle at 100 rpm was 165 cp fresh and 180 cp after 24 hours.
The ionic strength of this composition was as calculated follows: ~ CiZi I = 2 ,[1.68]~12.88~+t0.09~[2x~.48i~[0.31~ ~Ca~ions~
~ [1.681~2.88]~[0.091+[4x0.48]~t0.31J ~An~.ons) - 6~45 moles/dm3 EXA~PLE 2 20 9 poudered anhydrous sodi~m carbonate alld 2~ 9 pelleted sodium hydroxide were dissolved in ~,00 ml ~of~
water. 66.6 9 of a 30% solution of a C13J15 alk~l dimethyl amine oxide sold under the trade name Synprolam 35 nMO b~ ICI
Ltd, was added to the alkaline salt solutioll wi~h hi~h shea~
agitation. The mixture was then added to 720 ~ o a ~odium hypochlorite solution containin~ 10~ available chlorine sold 20 by British Drug Houses Ltd and further soft wa~e~ was added to provide a final compo~ition containing:
7.6~ sodium hypochlorite t_ 7.2~ available chlorine) 2.5% sodium hydroxide 2.1% sodium carbonate 13.5Q sodium chlGride 2.0% C13/1~ Amine Oxide 72.3% water and miscellaneous 100 ~, O 96 The ionic strength I of this composition was ound ~o ~e ~..61 moles/dm3 and the dy~amic viscosity, measured b~ means o~ a Brookfield RVT viscometer tSpindle No. 3 at 100 rpm) at 20C wzs 220 cp as measured 2~ hours after ~he so~u~ion ~a.5 prepared. The density of the solution w~as 1.25 gfcm3 so tha~
- the calculated kir.ematic viscosity v was 215.6 centistokes~
, . . . ... . .. .
lZ()2853 EXA~PLE 3 ~he following composition was prepared using the technique employed in Example 2.
Sodium hypochlorite 8.4~ (~ 8.0% available chlorine) Sodium hydroxide4.5%
Sodium chloride 12.7%
~13~15 amine oxide* 2.0%
Perfume 0.1 ~ater & misc. 72.3%
100.
Synprolam DMO
~he density of this solution was 1.25 g/cm3 and on thi~
basis the ionic strength of tbe com~osition was calcula~ed ~o-be 5.50 moles/dm3. Its viscosity 5after 24 hours) wa~ ~0 15 centipoises.
EXA~tPLE 4 The following compositions, prepared according to the ; technique of Example 1 illustrate the criticality of the Yarious features of the invention.
- (a) (b) (c~ (d) Sodium hypochlorite 8.4 8.4 8.4 8.4 Sodium hydroxide 4.5 4.5 O.S 0.5 Sodium chloride 12.7 12.7 12.7 12.7 C12tl4 linear alkyl _ - 2.0 dimethyl amine oxide C13/15 branched alkyl2.0 - 2;0 ~.5 dimetllyl amine oxide Water ~ misc. 72.4 72.4 7~.4 76~
~iscosity centipGises 20C 220 20 90 105 30 (24 hrs after preparation) Composition Ionic strength I moles dm3 5.50 5.50 4.~0 ~.~0 ~ Composition ~a) is in accordance with the present invention whilst compositions ~b), (c) and ~d) are illustrative of prior art products. Comparison of compositions (a) and tb) ~Z(~Z853 demonstrates the different viscosit~ behaviour of products containing a) amine oxides of average chain length C C13 and b) amine oxide of average chain length > C13 both products being at the same ionic strength. Comparison of compositions (a) and ~c) illustrates the role of ionic strength in providing the product viscosities o~ the presen~
invention. In particular it should be noted that, for amine oxides havin~ a chain length at the lower end of the range found to be useful in the invention, an ionic streng~h ~ 5.0 moles/dm3 is required i.e. appreciably higher than the recited minimum of 3.3 moles~dm3. Comparison of compositions (c) and (d) shows that ~or this amine oxide chain length, increasing amine oxide concentr~tion does ~c~i:
compensate for the shortfall in ionic strength d~spl~e~
these compositions.
The composition set out in Example 4(a) and designa~ed X
I was tested for its hard surface cleaning ability re~ativ~ l:n ¦ ~ commercially available chlorine bleach product designate~
i 20 II and having the following approximate analysis:
Available chlorine 8.0 C12/14 linear alkyl 1.0 dimethyl Amine oxide Sodium laurate 0.5.
~5 Sodium hydroxide 0.2 Water & ~isc~ To 100 A synthetic soil was made up comprising by volume ~ part:s qround garden soil, 4 parts roast lamb fat and 1 part mi~.k.
The soil was made up by mixin~ the fat and ~arden soi~
heating and stirring to melt the fat and then dispersinc~ ~h~
milk in the mixture.
15 cm square ceramic tiles were each soiled with ~0 m~ c~
thP above soil~ which was applied by pad and then allowed t:o dry for one hour or overni~ht ~18 hours).
A soiled tile was then clamped with the soiled sUt~ e uppermost at an angle sf 30 to the vertical and the soiled lZ~)~Z853 surface was divided equally into Left hand and Right hand areas. 14 ml of Product I was applied by syringe on to the Lef~ ~and area and the same volume of Product Il was applied to the Right Hand area, each application being arranged to cover the whole surface of the respective area. The areas were then lef t to drain for 10 minutes or ovexnight (18 hours) before being rinsed for 1~ seconds with water at a rate of 8.5 litres/minute and a temperature o 20C usin~ a split rinsing head to treat both LH and RH areas simultaneously. Four replicate tests were oarried out in two of which the tile areas to which the products were applied were also reversed.
Assessment of cleaning differences between L~ and ~l areas was carried out by visual grad~ ng usiny ~ 1-4 s~ale, higher values denoting enhanced cleanin~ Results are given below in which the cleaninq per~ormance of ~roduct I is expressed as a difference rela~ive to that of Product II.
Time elapsed after soiling treatment CleaningYardstick t ~ Difference 1 hr 10 mins ~ +0 . 78 a . 6B
18 hrs 10 mins +1D50 0~32 1 hr 18 hrs ~1.47 0.38 18 hrs 18 hrs +1~69 0.~3 It can be seen that Product I provides significantly better soil cleaning than Product II under the conditions o~
the Test.
Example 6 The following composi~ion was prepared ac~ording to the technique of Example 1:
-~Z(~z8s3l 5 ~e) (f) (g) (h) (~) Cl3DMAO 1.2 Cl4D~IAO 1~2 1.5 1.75 C15DMAO 1~2 NaOH 1.0 NaOCl 9.o NaCl g.o NaCL03 0.6 ,>
Water & Uisc. to 100 1~ ~iscosity (cp) 350 l9~ 30 ~,45 3~4 The density of each of these compositions was 1.15 g/ml and the ionic strength for each composi~ion was calculated to be 3.5 molJdm3. The product YisCosity was me~suKed at 2Q~C
using the tech~ique of Example lo It can be seen that an amine oxide alkyl chain len~th of C~3 is reguired in order to achieve the recited viscosity minimum of 180 centipoises. An increase in the level of C13DMAO to 5~ by weight of the composition did ~ot produce the desired YiSCosity increase.
?o EXAMPLE 7 ! The follawing compositions are in accordance with the invention.
7 l.Z~Z853 ~k~ m) (n) (o) (p). (q) (r C13 Cls DMAo 2 . 5 _ 2 . ~ 0 C14 Dl`lAO _ 1.4 - 1.5 1.5 _ 1.. 8 l.~
NaOH 0.5 0.6 0.5 0.5 0.6 0.6 0.5 0,5 NaPyro 5 R Pyro ~ - 12 Na citrate 10 15 ~ 0 ~,0 Na mellitate ~ 15 NTA - ~ 15 ~5 - ~-EDTA ~ ~
EDTMP 0.2 0.2 0.2 -- 0.~. - 0.
Pe~fume 0~1 0.1 0-l 061 0-1 0~1 0.1 0.
Wat~r & Misc To 100 Ionic Strën~th I 4.96 3.9d, 5.03 7.81 4.~ b.3(1 5~0 5.5 15 (9 moles/dlm ) product density basis 1.15 g/c~n3 All of the compositions exhibit viscosil:ies ;.n excess o ~00 centipoises at ~0C after 24 hours.
. --
Claims (11)
1. A stable single phase aqueous detergent composition incorporating an amine oxide of formula R1R2R3N--O
wherein R1 is an alkyl group in which the average number of carbon atoms is such that 13 < R1 ? 18 and R2 and R3 are each independently selected from the group consisting of C1-C4 alkyl radicals and C2-C4 hydroxy alkyl radicals together with at least one ionisable water soluble compound wherein the amine oxide constitutes the sole surfactant and is present in an amount of from about 0.5% to about 5.0% by weight of the composition and in that the at least one water soluble inorganic salt is present in an amount to provide a total ionic strength of the composition of at least about 3.0 moles/dm3, such that said composition has a viscosity of at least about 180 cp at 20°C.
wherein R1 is an alkyl group in which the average number of carbon atoms is such that 13 < R1 ? 18 and R2 and R3 are each independently selected from the group consisting of C1-C4 alkyl radicals and C2-C4 hydroxy alkyl radicals together with at least one ionisable water soluble compound wherein the amine oxide constitutes the sole surfactant and is present in an amount of from about 0.5% to about 5.0% by weight of the composition and in that the at least one water soluble inorganic salt is present in an amount to provide a total ionic strength of the composition of at least about 3.0 moles/dm3, such that said composition has a viscosity of at least about 180 cp at 20°C.
2. An aqueous detergent composition according to Claim 1 wherein the alkyl group R1 consists essentially of a mixture of groups containing 13 and 15 carbon atoms and comprising a mixture of moieties of structure, a) and b) the group R4 being predominantly methyl, the composition also being characterised by a total ionic strength of at least about 4.7 moles/dm3.
3. An aqueous detergent composition according to Claim 2 wherein a) and b) are present in approximately equal proportions by weight.
4. An aqueous detergent composition according to Claim 1 wherein the ionisable water soluble compound is selected from the group consisting of an alkali metal organic and inorganic builder or sequestrant salts.
5. An aqueous detergent composition according to Claim 4 wherein the ionisable water soluble compound is selected from the group consisting of alkali metal carbonates, citrates, pyrophosphates, aminopolyacetates, aminopolyphosphonates and mixtures thereof.
6. An aqueous detergent composition according to Claim 3 wherein substantially all of the ionic strength is provided by a mixture of alkali metal hypochlorite, alkali metal chloride and alkali metal hydroxide.
7. An aqueous detergent composition according to either one of the claims 5 and 6 wherein the composition incorporates bleach stable perfume.
8. An aqueous detergent composition according to Claim l wherein R1 contains an average of from 14 to about 16 carbon atoms and is selected from linear moieties and moieties containing no more than about 25% methyl branching.
9. An aqueous detergent composition according to Claim 8 wherein substantially all of the ionic strength is provided by a mixture of alkali metal hypochlorite, alkali metal chloride and alkali metal hydroxide.
10. An aqueous detergent composition according to Claim composed of from about 1% to about 1.5% C14 linear alkyl dimethyl amine oxide, from about 9.0% to about 9.5% sodium hypochlorite, from about 9.0% to about 9.5% sodium chloride and from about 0.5% to about 1.5% sodlum hydroxide.
11. An aqueous detergent composition according to Claim 10 wherein the composition incorporated a bleach stable perfume.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8133642 | 1981-11-07 | ||
| GB8133642 | 1981-11-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1202853A true CA1202853A (en) | 1986-04-08 |
Family
ID=10525715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000415030A Expired CA1202853A (en) | 1981-11-07 | 1982-11-05 | Cleaning compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0079697B2 (en) |
| AT (1) | ATE17595T1 (en) |
| CA (1) | CA1202853A (en) |
| DE (1) | DE3268705D1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0110544A1 (en) * | 1982-11-02 | 1984-06-13 | Imperial Chemical Industries Plc | Bleaching compositions |
| DE3380736D1 (en) * | 1983-10-14 | 1989-11-23 | Procter & Gamble | Cleaning compositions |
| GB8330158D0 (en) * | 1983-11-11 | 1983-12-21 | Procter & Gamble Ltd | Cleaning compositions |
| GB8332271D0 (en) * | 1983-12-02 | 1984-01-11 | Unilever Plc | Bleaching composition |
| GB8333426D0 (en) * | 1983-12-15 | 1984-01-25 | Ici Plc | Bleaching compositions |
| GB8630845D0 (en) * | 1986-12-24 | 1987-02-04 | Ici Plc | Bleaching compositions |
| US4946619A (en) * | 1988-07-19 | 1990-08-07 | The Clorox Company | Solubilization of brighter in liquid hypochlorite |
| US5034150A (en) * | 1989-05-03 | 1991-07-23 | The Clorox Company | Thickened hypochlorite bleach solution and method of use |
| US5705467A (en) * | 1991-10-22 | 1998-01-06 | Choy; Clement K. | Thickened aqueous cleaning compositions and methods of use |
| US5279758A (en) * | 1991-10-22 | 1994-01-18 | The Clorox Company | Thickened aqueous cleaning compositions |
| GB9213578D0 (en) * | 1992-06-26 | 1992-08-12 | Unilever Plc | Improvements to bleaching compositions |
| WO1995003383A1 (en) * | 1993-07-23 | 1995-02-02 | The Procter & Gamble Company | Thickened aqueous detergent compositions with improved cleaning performance with short chain surfactants |
| AU683523B2 (en) * | 1993-12-29 | 1997-11-13 | Reckitt Benckiser Inc. | Thickened alkali metal hypochlorite compositions |
| US8470755B1 (en) | 2012-03-23 | 2013-06-25 | The Procter & Gamble Company | Liquid cleaning and disinfecting compositions comprising a zinc inorganic salt |
| US9133417B2 (en) * | 2012-03-23 | 2015-09-15 | The Procter & Gamble Company | Liquid cleaning and disinfecting compositions comprising an assymetrically branched amine oxide |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA797201A (en) * | 1965-06-22 | 1968-10-22 | The Procter & Gamble Company | Liquid detergent composition |
| NL134221C (en) * | 1969-08-29 | Unilever Nv | ||
| GB2003522B (en) * | 1977-09-02 | 1982-02-24 | Ici Ltd | Bleaching and cleaning compositions |
| US4352678A (en) * | 1978-10-02 | 1982-10-05 | Lever Brothers Company | Thickened abrasive bleaching compositions |
| GB2051162A (en) * | 1979-05-30 | 1981-01-14 | Reckitt & Colmann Prod Ltd | Thickened aqueous alkali metal hypochlorite solutions |
| NL7908798A (en) * | 1979-12-05 | 1981-07-01 | Unilever Nv | LIQUID, THICKENED CHLORINE BLEACH. |
-
1982
- 1982-10-26 AT AT82305666T patent/ATE17595T1/en not_active IP Right Cessation
- 1982-10-26 DE DE8282305666T patent/DE3268705D1/en not_active Expired
- 1982-10-26 EP EP82305666A patent/EP0079697B2/en not_active Expired - Lifetime
- 1982-11-05 CA CA000415030A patent/CA1202853A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3268705D1 (en) | 1986-03-06 |
| EP0079697B2 (en) | 1990-03-14 |
| EP0079697B1 (en) | 1986-01-22 |
| ATE17595T1 (en) | 1986-02-15 |
| EP0079697A1 (en) | 1983-05-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |