CA2096955A1

CA2096955A1 - Liquid built detergent compositions

Info

Publication number: CA2096955A1
Application number: CA002096955A
Authority: CA
Inventors: Sean G. Hall; John T. Mccullins
Original assignee: Individual
Current assignee: Sb Chemicals Ltd
Priority date: 1990-11-26
Filing date: 1991-11-26
Publication date: 1992-05-27
Also published as: WO1992009677A1; ZA919331B; JPH06502662A; PT99612A; IE914108A1; NZ240753A; AU8947191A; EP0559693A1; GB9025691D0

Abstract

A liquid built detergent composition comprises a substantially anhydrous organic liquid phase having uniformly distributed therein (i) an amine salt of an anionic surfactant acid which contains one or more sulphonic acid groups and (ii) a finely divided particulate builder.

Description

rV092/09677 2 a 9 ~ rJ ~ ~ Pcr/GBg1/o2o83 LIQUID BUILT DETERGENT COMPOSITIONS
~ his invention relates to liquid built detergent compositions and to their production and use.
In recent times, mainly for reasons of manufacturing economics, aqueous heavy duty built liauid -detergents have made in-roads into the spray dried washing powder market with the result that much work has taken place both in relation to the physics and also to the chemistry of product formulationO Such built liquid detergents arz often sold in 2 litre plastics bottles. Typical of such products are those described in G~-~-2123846, G3~B-2153~39, EP-B-~; 0086614 and EP-3-0151884.
As a consequence of this commercial development the spray dried market sector has responded by the introduction of detergent concentrates which are very low in inert ingredients. ~his means that, without fillers and ~ex~enders, the product can ~e presented to the public with a ~, so-called environmentally-friendly connotation and 80 that it can be claimed that in use the product is less polluting.
This is because very much less product is used per washinq machine load because of its strength. In addition the ; associated packaging can be significantly reduced in comparison to the traditional powder pack with a resulting saving in paper and ~oard.
The use of diethanolamine dodecyl benzene sulphonate in an aqueous heavy duty detergent is mentioned in connection with Tahle 3 of AU-~-507431.
;` ~ Another advance in detergent technology occurred ` ~ when the heavy duty built liquid section of the market `
responded to the concen~rated powder products. As a result ~ there became avalla~le liquid detergent concentrates which i are typically sold in 1 litre plastics bottles. In view of ~ the greater detergent power of such concentrates the amount .. ~
of concentrate needed for a typical washing machine load is ,'' ' , .-~
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often about one haIf of the volume of an aqueous heavy duty built detergent needed for laundering the same load of washing. ~enc~ a 1 litre bot~le of concentrate can be used to wash approximately as many loads of washing as a 2 litre bottle of a convenlional aqueous heavy duty built liquid detergent. ~o~ever, to date, this sector has basically been forced to fo~Llulat~ its products either as dispersions of inorganic builders in non aqueous mi~tures of non-ionlc surîactants, as in ~ 003~05~ or ~7-~-01206~9, or as formulations OI ~ non-ionic surfactant mi~.ture in the emulsion s~a's -i t~ 2 sat~l=ated sol.ltion of one or more builders usli~s v2ge.aDle gums, or o~her emulsi ying agents, as stabilisers, as in GB-A-2148926.
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A problem arises with conventional non-aqueous built liquid detergent compositions which contain non-ionic surfactants as the sole class of surfactant in that they tend to gel upon dispersion in water.
In the case of GB-A-2148926 the surfactants in the emulsion are non-ionic surfactants whereas, in the case of EP-B-0120~59, claim 9 cites the presence of an anionic surfactant in the composition ~ut the specification completely omits to teach its use in any of -its Examples.
This omission is because it is difficult in commerce to acquire anionic surfactants, such as sodium dodecyl benzene sulphonate, in the non-pasty solid state (any that do exist are normally offered in admixture with sodium sulphate to prevent the material from being sticky and balling together ~` The prior art therefore does not make use of anionic surfactants in non-aqueous built detergent liquids and this is unfortunate because this class of detergent is ~ one of the cheapest and mot effective of all the `~ commercially available surface active agents.
; In the non-aqueous class of liquid built detergent ~ . .

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the water analogue of the ~uilt system of, for example, GB-~-2153839, is the class of anhydrous solvents known as the polyeth~lene gl~Jcols (P.E.Gs)~ Liquid members of this class are those with a molecular weight between about 100 and about 600, commonly called PEG.100, PEG.200, PEG.300 and so forth.
It would ~e dasirable wo produca a non-aqueous heavy duty built liquid det?rgent composition with an anionic surIactanc a3 an inwegral oa t o. the liquid phase in which the builders ~re dispersed by either rod, bead or ball mllll'ng, I would fu,ther be desirable to produce a non-aqueous heav~J du~y builc liquid decergent composition which does not g~l upon dispersion in water.
- ~ The present invention accordinsly seeks to provide a substantially anhydrous liquid built detergent composition containing an anionic surfactant. It further seeks to provide a substantially anhydrous liquid built detergent composition which shows little or no tendency to gel upon dispersion in water.
According to the present invention there is provided a liquid built detergent composition comprising a substantially anhydrous organic liquid phase having uniformly distributed therein (i) an amine salt of an anionic surfactant acid which contains one or more sulphonic acid groups and (ii) a finely divided particulate builder.
The organic liquid phase i-s substantially anhydrous. In other words it is preferably devoid of added water and contains only that amount of water which is ` normally present in the ingredients used in production of - the liquid built detergent composition of the invention.
` Hence a composition in accordance with the invention ''` .

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W092/09677 2 d ~ 6 ~ ~ ~ PCT/GB9t/02083 typically contains less than about 5% w/w water, more preferably less than abou~ 2% w/w water, and eve~ more preferably less than a~out 1% w/w water, e.g. about 0.5~ w/w or less, down to about 0.1% w/w or less of water, based upon the total weight of the composition.
The organic liquid phase may include a wat~r-soluble organic solvent. In this case there ia providcd a liquid built detergent composition comprising a wat2 -~` soluble organic solvent phase having uniformly distrl~ut2d therein (i) an amine salt OI an anionic sur,actant acid which contains ~ne or more sulphonic acld groups ænd (1i~ 2 finely divided particulate builder.
Normally a significant proportion of the amine saltof the anionic surfactant acid, and preferably all or it, is dissolved in the organic liquid phase, presumably in a form akin to the micelles typically found in aqueous detergent solutions, while the builder is insoluble in the organic liquid phase.
The water-soluble organic solvent may comprise a lower molecular weight alcohol, for example an alkanoL _ ; containing from 1 to 6, or more preferably 2 to 4 carDon atoms, such as ethanol, n-propanol, lso-propanol, n-butanol or the like. Another suitable class of water-soluble organic solvents is liquid water-soluble organic compounds containing two or more hydroxy groups. Examples of such - compounds include ethylene glycol,fpropylene glycol, 1,4-butylene glycol, 1,5-pentamethylene glycol, glycerol, polyalkylene glycols such as polyethylene glycoi, polypropylene glycol, and mixed polyoxyalkylene ether glycols, such as polyoxyethylene-polyoxypropylene glycols, as well as mixtures of two or~more thereof.
; A preferred type of water-soluble organic solvent is the polyethylene glycols, of which those having molecular weights of at least about 150, for example molecular~weights ,. .
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~092/09677 PCT/GB91/02083 in the range of from about 200 to about 600, are preferred.
However, any solvent that is liquid at ambient temperatures and below (e.g. down to about -10C), that is water miscible, and that will allow dispersion of the amine salt OI the anionic surfactant acid and of the builder can be used. Mixtures o~ water-soluble organic solvents can be used, if desired. For example, a mixture or an alkanol, such as ethanol or iso-propanol, and a polyethylene glycol can be used.
Normally it will be necessary to incorporate at - most a minor amount only of an organic watsr-solu~le so1vent or of a m1x~ure of organic solvents, for example, up t3 about 20% w/w of solvent based upon the total weight OI the composition A preferred range is from about 1~ w/w up to about 15% w/w of solvent based upon the total weight of the composition.
One of the purposes for which this solvent, if present, i5 added may be to adjust the viscosity of the composition to a desired value. A useful degree of control over the viscosity of the composition can be achieved, in `~ particular, by addition of a glycol such as a polyethylene glycol (e.g. polyethylene glycol PEG 200).
; Amine salts useful in the practice of the present invention can be prepared by reacting an organic amine with an anionic surfactant acid containing one or more sulphonic acid groups.
~` Particularly preferred amines are alkanolamines, such as monoethanolamine, diethanolr~mine and - triethanolamine, and heterocyclic monocyclic amines, such as morpholine.
In use the liquid built detergent compositions of the invention will be diluted with water. ~his dilution step may take place in the wash cycle of an automatic washing machine, for example. Sin-e the ~uilder is normall~
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W092/09677 2 ~ j~ J'~3, PCT/GB91/02083 alkalinP in nature and may typically contain an alkali metal ion, exchange OI cations may occur upon dilution or the li~uid built detergent composition with water. Thus the quaternary ammonium ion of -the salt OI the anionic surfactant acid present ln the composition may, for example, undergo exchange with sodlum ions from the builder. ~ence the anions o. ~he anionic sur_ac-tant 2cid may be associated in the r~sullin~ a~ueous solu~ion with, for example, sodium ions or the ions o~^ anotn~r a~ li metal, whilst the quaternary a~monlum ion, mav undergo hydrolysis to yield the free amine Since soms ~minss havo pungent or unpleasant odours, l_ ,iili no~nally ^i~ pr~~_ried ~o selec-~ as the amine salt of the anionic surfactant acid a material which upon hydrolysis of the qUaternarY ammonium ion does not release an aminP with an unpleasant odour. For this reason preferred salts of anionic surfactant acids for use in the compositionS of the invention contain alkanolammonium ions or morpholinium ions such as monoalkanolammonium, dialkanolammonium and trialkanolammonium salts of anionic surfactant acids, such as monoethanolammonium, diethanolammonium and triethanolammonium salts of anionic surfactant acids, and morpholinium salts of anionic surfactant acids. ~ ~
As builder there can be used any of the known builders such as sodium metaphosphate, sodium paraphosphate, sodium tripolyphosphate, sodium silicate, sodium carbonate, a zeolite, a layer silicate, trisodium citrate r or a mixture of two or more thereof. It is beneficial to include an anhydrous material, such as anhydrous sodium carbonate, as an ingrèdient in the formulation of a non-aqueous liquid built dete-gent composition according to the invention because the anhydrous material absorbs water to form a solid hydrate or sodium carbonate. In this way any water present or formed in the composition, can be absorbed and the , --W092/09677 ~Q ~ ~rj PCT/GB91/02083 substantially non-aqueous nature of the composition is retained, in addition to the sodium carbonate being availabl~ to acr as an alkaline ~uilder.
~ ..zmpl~s of s-lrfactant acids include alkyl benzene sulphonic acids, in whlch the alkyl group contains from about 6 to a~out 20 carbon atoms, for example from 10 to 14 carbon atoms, ~r~m2ry or secondary alkyl sul~honic acids containins Erom a~out 1~ to about 25 car~on atoms, for ex~npie from 1~ o 1~ carbon aLoms, and alpha-olefin sulphonic acids o~Laln~d ~y sulphonztlon of an alpha-olefin containing, o_ e:~ple f-rom a~ouL 10 to a~out 22 carbon , .
atoms, such as a C16 to C18 ole;ln or a mixture containing same. Besides a material containing a sulphonic acid group thPre may also be used for the production of the amine salt or salts, usually in admixture with a material containing a sulphonic acid group, a sulphated fatty alcohol; typical sulphated fatty alcohols i~clude those containing from about 10 to about 26 carbon atoms, for example a sulphated fatty alcohol mixture containing C10, C12~ C14~ C16 and C18 fatty alcohols. Typical of such a fatty alcohol mixture is-o~e containing alcohols in the following proportions: C10 3~0%, 12 57 ~' C14 20.0%, C16 9-0% and C18 11-0%-The composition of the invention may furtherinclude one or more non-ionic surfactants. Typical non-ionic surfa~tants include fatty acid monoethanolamides such as coconut fatty acid monoethanolamlde, a typical formulation for which is a mixture of monoethanolamides of fatty acids as follows: C6 0.5%, C8 6.5%, Cl0 6.0%, C12 49 5%' C14 19-5%~ C16 8-5%~ C18 (slearic) 2.0~, C18 (oleic) 6.0%, and C18 (linoleic) 1.5%. Other suita~le non-ionic surfactants include polyoxyalkylene ethers of alkanols, typically polyoxyPthylene thers of alkanols containing typically 3 or moro ethylene oxide groups, for example from about 6 to about 20 ethylene oxide residues and ~ased upon - . ..
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W092/09677 2 ~ PCT/GB91/02083 , .
alkanols containing from about 6 to about 26 carbon atoms.
Mixed polyoxyethylene oxypropylene ethers of alkanols can also be used; these can also be based on C6 to C2~ alkano1s and can contain from about 3 up to about 20 alkylene oxiae residues, i.e. a mixture of ethylene oxide and propylenQ
oxide residues. The alkanols and alkanol mixtures upon which such non-ionic surfactants are based can be producea by hydrogenation of methyl esters produced by transesterification of naturally occurring vegetable oils such as coconut oil, sunflower oil, palm oil, rape seed oil, and the li.~9, or of anLmal fats, such as t~llow o_ la=d~ '.
typical polyoxy2thylane eth2r of an alXanol i3 bas2d 12uryl alcohol condensed with approximately 8 moles of ethylene oxide. Polyoxyalkylene ethers of alkylphenols are another type of non-ionic surfactant. Mixtures of non-ionic surfactants can bé used.
The compositions of the present invention may include an amphoteric surfactant or a mixture of amphoteric surfactants. Typical amphoteric surfactants include dicarboxylated derivatives of oleic ;~idazoline, caprylo amphocarboxy glycinate, octyl imino dipropionate, octyl dimethyl betaine, complex coco iminodiglycinates, and fatty ampho polycarboxyglycinates. Often a mixture of amphoteric surfactant and non-ionic surfactant are present together in the compositions of the invention. The weight ratio o~
amphoteric surfactant to non-ionic surfactant may vary within wide limits, for example in the range of from about 1:100 to about 100:1.
Preferably a liquid built detergent composition according to the invention contains at least about 0.1~ w/w of an ~m1ne salt of an anionic surfactant acid up to about 20% w~w or more, e.g. up to about 25~ w/w, even more preferably from about 2% w/w up to about 15% w/w, based on the total weight of said composition.

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W092/09677 2 0 9 ~ ~ ~`j j PCT/GB9l/02083 _ g _ Preferably a liquid built detergent composition according to the invention comprises from about 0.16 W/W Up to about 20% or more of a non-ionic surfactant or surfactants, of an amphoteric surfactant or surfactants, or of a mixture of non-ionic and amphoteric surfactants, 2vsn more prefera~ly up to about 35~ w/w or more, e.g. up to about 50% w/w, most preferably from about 2~ up to a~ouL 35%
w/w, based on the total weight of the composition.
A liquid built detergent composition ac-ordlr.g to the invention may further comprise a bleach and, optionally, a bleach activ2tor. ~rypically such a compos tion m2y contain r-om about 0.1% w/w up to a~out 10~ w/w or mor~, e.g. up to about 15% w/w of a bleach and, optionally, rrom aDout 0.03% w/w up to about 3~ w/w or more, e.g. up to about S~w/w of a bleach activator, based upon the total weight of the composition.
Other mlnor ingredients which may be included in the composition of the invention include preservatives, optical brighteners, fragrances, foam depressants, foam boosters and/or stabilisers, soaps, dyes, pigments, buffers, corrosion inhi~ition agents, sequestration agents, anti-ingestion agents, humectants, enzymes, enzy~me stabilisers, fabric softeners, fabric conditioners, and the like.
Typical sequestration agents include ethylene diamine tetraacetic acid, nitrilotrioacetic acid, and acrylic-maleic copolymers such as those sold under the trade mark Polycarboxylate AMC. One or more of these minor ingredients can be included in the compositions of the invention as appropriate. Such other minor ingredients typically comprise not more than about 5% w/w each of the compositions of the invention, for example in the range or from about 0.001% w/w up to about 2% w/w each oased upon the total weight of the composition.
The compositions of the invention may ~e formulated ~ ' , , .
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- ~ : ' . -, W092/09677 ~n1~3~ , PCT/CB91/02083 so as to have approximately the same laundering power as conventional aqueous heavy duty built liquid detergents.
Preferably, however, the compositions of the invention will be formula~ed as conc3ntratss whlch have several times, e.g.
about 2 to abou~ 5 times, the laundering power of conventional aqueous neavy duty 9uil C liquid detergents. To this end it ls desi-~bls o fo~mulate the compositions as concentra_es in ~7hic:~ che soli~ components comprise in total at least zbout 30% ~ and ~referably at least about 45% w/w up to zbou~ ~0~ ~w or aven higher, based upon the weight of the composl~ion Th 3 i s~ ntl_n :-u the ;~_o~;ides a pro~Qs3 for the production of a liquid 9uil t decergent composition which includes the step of reacting in an organic phase an anionic surfactant acid containing one or more free sulphonic acid groups with an amine. Such an amine may be a primary amine, a secondary amine, or a tertiary amine.
In one form of the process the reaction is carried out in an organic phase which includes a water-soluble oxganic solvent. In this case there is provided in accordance with the invention a process for the production of a liquid buil~ detergent composition which includes the step of reacting an anionic surfactant acid containing one or more free sulphonic acid groups in an organic solvent phase comprising a water-soluble solvent with an amine. The amine may be a prLmary amine, a secondary amine, or a tertiary amine.
Hence the invention contemplates producing in-situ quantities of organic base salts of anionic ~urfactant sulphonic acids. By this means highly successful built liquids can be produced from solutions of an acid such as dodecylbenzene sulphonic acid in PEG 200 (polyethylene glycol 200), in alkylene oxide addition products, or in a blend of both. Such solu~ions may further contain anhydrous , ' W O 92/09677 ~ ~ " , ,~;~ r P ~ /GB91/02083 non-ionic sur~actants. The organic bases which were used wera mono-, di-, and triethanolamine and morpholine but any primary, secondary or tPrtiary amine without an unpleasant odour can 3~2 us2c3.. ~Lom these matarials very transparent pale yellow s~JruDs can be produced which are excelle~t vehicles ~or car~ing ~h2 silicate, carbonate, phosphate and polyphos?ha~e builflers which are to be micronised to give the non-aqueous bullr laund~y liquids.
As an e~ mple OL chis technology the following solution was ~repared.-.
Dodecyl ~enzene Sulphonic ~cld 67.5 gms ~3tty ~ Gl ~,~ ~3.~ (!~ .~.c 1 C' 5 0 ' E.O) 15.0 gms ~-~ Alkylene Oxlde Addition Product (Ma~lox FK 64) 100.0 gms Polyethylene Glycol 200 75.0 gms (The word "Marlox" is a trade mark).
The above ingredients were simply stirred together in any order to give an amber syrup. This solution was then converted to the quaternary ammonium salt of the sulphonic ;~ acid by titration with one of the previously mentioned amines. The resulting syrups had the following viscosity:
~' Viscosities at 25C (mPa) ~riethanolamine salt 275 Diethanolamine salt 247 Monoethanolamine salt 254 Morpholine salt 261 A further series of sim1lar syrups can be prepared by omitting the polyethylene glycol or the fatty alcohol ethoxylate.
When any of these syrups was mixed with a builder such as sodium tripolyphosphate (35%), sodium silicate ~Soluble C" powder or sodium carbonate (5% each) and micronised by milling, the result was a fully ~uilt pourable liquid laundr~I detQrgent. All the other usual minor ,, .

W092/09677 PCT/G~91/02083 ~,~3~

ingredients cculd be added and are compatible, including soaps which can be formed in-situ by having a fatty acid in . solution in the PEG mixture prior to titration with the amine.
- The invention is further illustrated in the following Examples.
EXAMPI.E 1 A liquid built detergent concentrate is ~roducod from the following ingredients:-: .
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, W092/09677 2 v ~ J ~.i PCT/GB91/02083 ~ % w/w `~ Dodecyl 3enzene Sulphonic Acid 11.5 Al~ylene Oxide Addition Product (Marlox FK 64) 12.0 Alcohol Ethoxylate (4 moles E.O.) 3.0 Coconut Fatty Acld 5.2 Triethanolamine 8.~
Polyethylene Glycol (PEG 200) 2.0 Sub-total 52.2 Sodium Silicate (Soluble C powder) 5,0 Sodium Carbonate Anhydrous (Soda Ash) 5.0 Sodium Tripolyphosphate35.0 Mlnor Ingredients ~ 3 Sub-total ~7.8 Total 100.0 :~. ===== .
All the organics, with the exception of the triethanolamine, are mixed together to yield a dar~ amber syrup. To this is added enough triethanolamine for neutralisation; the approximate end point corresponds to the syrup colour becoming a lighter yellow. To this syrup are added all the other ingredients and the mixture is then micronised in a bead mill. In this preparation the presence of the sodium carbonate is bifunctional in that it acts both as an alkaline builder in the product and a drying agent.
EXAMPLES 2 to ;
~ urther liquid built detergent concentrates were produced by admixing the following ingredients and micronising in a bead mill:

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xamplé No. 2 3 4 5 ~ ~w/w %w/w %w/w %w/w -. Diethanolamin~Q salt o~F
dodecylben~ene ~sul~honic acid 13.5 13.5 13.5 12.6 Alcohol ethoxylate (3 mole~ ~O) 7.0 7.0 7.0 10.7 ~lcohol etho~yleLe (7 molss EO) 8.3 8.3 8.3 ~lcohol al~o~ylat~ (7 moles ~O) '2.6 12.6 12.6 24.2 Polyethyl2ne ~lycol 200 5?5 5.5 5-5 -: Isopropyl alc~hol 2.5 2.5 2. 5 2.5 ::
'! Sub-total 49~4 .49~4 d9,4 50,0 ~`, .
Sodium -tripolyphosphace31.3 38.0 38.0 38.0 Sodium silicate 3- 3- 3- 3-Soda ash ~ 5 5-5 Sodium perborate 10.0 - - -TAED 1.9 - - -Sodium carboxymethyl cellulose 1.0 1.0 1.0 1.0 EDTA 1.0 0.4 1.0 1.0 Minor ingredients 2.4 3.2 _2.1 2.0 Sub-total 50 o 6 50.6 50.6 50.0 Total . 100.0 100.0 100~0 100.0 .:

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1. Alcohol ethoxylate (3 moles EO) = polyethylene glycol ether (3 moles of `: ~
ethylene oxide) of a ~` C12_15 alkanol -~ ~ mixture.

2. Alcohol a~h~-yla,e (7 mol~s EO) = polyethylene glycol ether (7 moles ` ethylene oxide) of a C12_15 21kanol mixture.
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- 3. Alcohol alko-xylate = polyethylene/propylene glycol ether (7 moles of alkylene oxide: 92%
propylene oxide/8%
ethylene oxide) of a 12-15 alkanol mixture.
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4. TAED - = tetraacetyl ethylene diamlne.
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5. ED~A = ethylene diamine tetraacetic acid.

6. Minor ingredients = enzymes, fragrance, TiO2, Bitrex (an anti-ingestion agent), :~;
and an optical brightener.
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W092/09677 2 ~ 9 ~ PCT/~B91/02083 Successful liquid built detergent concentrates resulted.
Ethanol can be used in place of lso-propanol with similarly good results.
~, EXAMPLES 6_to 9 ` The diethanolamine salt of dodecyl benz~ne sulphonic acid was replaced in the f3rmulations of ~ mpl3s 2 to 5 by an equal weight of the corresponding triethanolamine salt. Liquid built detergent conce~t_at3s ~:~ of similarly good quality were obtained in each case.
EXAML~LES lO to 21 Liquid built detergent concentra~ss wele prCdUC
by mixing the following ingredients and blending tog2th2r all the liquid ingredients in each rormulation listed, with the excepti-on of the minor ingredients. Amine salt formation from the dodecylbenzene sulphonic acid was accomplished by stoichiometric addition of the relevant amine. Then all the soLid ingredients were added, with the exception of any thermalLy la~ile enzyme present. The resulting mixture was then micronised in a ball milL to produce an easiLy flowable product which could then be inoculated with the appropriate quantity of enzyme or erzymes (if used):

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Example No. 10 11 12 13 . %w/w %w/w %w/w %w/w : Dodecylbenzene sulphonic acid 7.76 10.05 7.23 8.36 Alcohol ethoxylate (3 moles EO) 11.46 16.35 10,68 10.50 :~ Marlox FK 64 27.45 31.61 25.57 26.00 Triethanolamine 4.28 - 3.99 Diethanolam1ne - - - 3.1-Monoethanolamine - 2.70 - -Polyethylene glycol (PEG 200) - - -Iso-propanol 2.68 - 2.4g 2.50 Sub-total 53.63 60,71 49.96 50,50 Zeolite (Wessalith P) 7.17 15.44 Sodium tripolyphosphate - - 31.18 37.10 Soda ash 26.7, 12.14 - 5.00 : Sodium silicate powder (Soluble C) 5.35 3.64 2.99 3.00 EDTA 3.21 3.64 0.99 0.40 Sodium carboxymethylcellulose 1.07 1.21 0.99 loOO
Optical brightening agent :~; (DMS-X) 0.80 ` 0.97 0.90 0.90 Optical brightening agen' (CBS-X) 0.05 - - -Antifoam agent (DB 100) - - - -Tio2 0.14 0.20 0.20 0.20 Fragrance 0.85 0.97 0.83 1.00 Esters: Esperase 0.64 0.72 _ 0.60 Texmamyl SL 0.32 O.36 - O.30 Sodium perborate ~ 9-97 ~: TAED - - 1.99 '; Sub-total 46.37 39.29 50O04 49.50 Total 100 100 00 100 00 100 00 ~` ' .
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Example No. 14 15 16 17 ~w/w %w/w 96w/w %w/w Dodecylben2ena sulDhonic acid 8.36 8.36 6.16 7.41 Alcohol ethoxylate (3 moles EO) 10.;0 10.508.73 10.50 Marlox F~ 64 26.00 26.0021.62 26.00 Triethanolam1ne ~ ~ 3.40 4.08 Diethanolamin2 '.14 3.14 - _ Monoeth2~l a~,,l n ra _ _ _ _ ~olyethyl a~e gi~col (~G ~00) - - 10.19 Iso-propanol 2.50 2.50 - -Sub-totai 50.~0 50.~050.29 50.Ag Zeoiite (hessallth P) - - ~ ~
Sodium tripolyphosphate 38.00 30.6330.63 30.64 Soda ash 4.10 Sodium silicate powder (Soluble C~ 3.00 2.99 2.99 2.99 EDTA 0.40 0 99 0 99 0 99 Sodium carboxymethylcellulose 1.00 1.00 1.00 1.00 Optical brightening agent (D-~S-~) 0.90 0.90 0.90 0.90 Optical brightenlng agent (C~S--X) , -- -- -- --Antifoam agent (D~ 100) - - 0.21 ~i2 - 0.20 0.20 0.20 0.20 Fragrance 1.00 0.83 0.83 0.83 Enzymes:Esperase S~ ~ 0.60 - - -~ Termamyl S~ 0.30 - - -;" Sodium perborate ~ 9 97 9 97 9 97 ` TAED - 1.99 1.99 1.99 .~ ~ Sub-total 49.50 49.5049.71 49.50 Total 100.00100.00 100.00 100.00 "-:
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~' ` ` ' ~092/09677 ~ 3 ~ PCT/GB91/~2083 Exampl~ No. 18 19 20 21 %w/w ~w/w 96w/w ~w/w Dodecylbenzene ~ulphonic acid 6.86 8.55 7.38 8.34 Alcohol ethoxylate (3 moles EO)9.73 10.74 10.46 10.45 Marlox F~ 5' 23.17 26.60 25.90 25.95 Triethanol~mine 3.78 - 4.06 Diethanolamin~ ~ 3.21 - 3.13 Monoethanolamino Poly~thylen~ sl-~col (PEG 200) ~.63 12.78 12.45 12.47 Tso-propanol 2.i~ - 2.49 2.50 Sub-total 50.50 61.88 62.7a 62.84 Zeolite (Wessalith ~) ~ ~ ~ ~
Sodium tripolyphosphatP 38.00 28.19 30.26 30.21 Soda ash 4.10 - 3.00 3.00 Sodium silicate powder (Soluble C) 3.00 1.55 1.50 1.50 EDTA 0.40 0.40 0.20 0.40.
Sodi~m carboxymethylcellulose1.00 0.50 0O50 0.15 Optical brightening agent : (D~S-X) 0.90 - 0.40 0.;0 Optical brightening agent (CBS-X) Antifoam agent (DB 100) - 0.26 0.25 Q.25 TiC2 0.20 0.15 0.15 0.15 Fragrance 1.00 0.61 0.60 0.60 Enzymes: sperase S~ 0.60 - 0.25 0.25 :.
Termamyl 5L 0.30 - 0.15 0.15 Sodium perborate - 5.11 TAED - 1.35 - -; Sub-total . 49-50 3B.12 37.26 37.16 :~ Total 100.00 100.00 100.00 100.00 ' - -:; ',~ .
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~ W092/09677 2 ~ ~ 6 .3 ~; ~3 PCT/GB91/02083 Examples 22 to-26 :
Further liquid detergent concentrates were made according to the general procedure of Examples 10 to 21 using the following ingredients:--.

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092/09677 ~ P ~ /~B91/02083 Example No. 22 23 24 25 26 %W/W 9~W/W 96W/W!~SW/W ~T~7/W
Dodecylbenzene sulphonic acid 8.80 11.10 8.90 11.10 11.10 Alcohol ethoxylate (3 moles EO) 7.00 8.80 7.00 8.80 8.80 Alcohol ethoxylate (7 ~oles EO) 8.30 11.50 8.30 11.50 11,50 Marlox F~ 64 12.60 10.90 8.70 10.90 10.90 Triethanolamine 4.70 5.90 4.70 5~90 5.90 Polyethylene glycol (PEG 200) 6.00 12.50 g.go 12.50 12.50 Iso-propanol 2050 2.10 2.50 2.10 ~.lO
Sub-total 49.90 62.80 49.90 62.80 62.80 Zeolite (Wessalith P) - 22.75 _ 15.10 15.10 Sodium tri-polyphosphate 38.00 - 20.00 Soda ash 5.00 5.95 26.00 17.80 11.90 Sodium sili~ate powder (Soluble C) 3.00 4.00 2.00 2.00 2.00 EDTA 0.40 0.80 0.20 0.40 0.40 Sodium carboxymethyl-cellulose 1.00 1.00 0.50 0.50 0.50 Optical brightening agent (DMS-X) 0-90 0.80 0.40 0.40 0.40 TiO2 0.10 0.20 0.20 0.20 0.20 Eragrance 0.80 0.80 0.40 0.40 0.40 Enzymes:Esperase SL 0.60 0.60 0.25 0.25 Texmamyl SL~ 0.30 0.30 0.15 0.15 Sodium perborate - ~ ~ 5.00 TAED - - - - 1.30 Sub-total 50.10 37.20 50.1037.20 37.20 Total 100.00 100.00 100.00100.00100.00 ~, , ....

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W092/09677 2 ~ 7 PCT/GB91/02083 If desired a small amount of a bitter tasting material, such as Bitrex, can be added to a concentrate according to any one of ~xamples lO to 2~, in order to deter ingestion or the concantrat2 by, for example, small children. In the case of Bitrex, amounts as low as about ; 0.005 %w/w suIrice ror this purpose.
Re~e~n.co should be made to the Notes to Examples 2 to 5 or ~u-lh~- ex?lanation or 2xamples lO to 26; the words "~essalith~ itrex", "~sperase" and ~'Termamyl" are trade marXs.

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Claims

1. A liquid built detergent composition comprising a substantially anhydrous organic liquid phase having uniformly distributed therein (i) an amine salt of an anionic surfactant acid wich contains one or more sulphonic acid groups and (ii) a finely divided particulate builder.

2. A liquid built detergent composition according to claim 1, in which said organic liquid phase comprises a wtaer-soluble organic solvent.

3. A liquid built detergent composition according to claim 2, in which said water-soluble organic solvent comprises a hydroxylic solvent selected from lower molecular weight alkanols and glycols.

4. A liquid built detergent composition according to claim 2 or claim 3, in which said water-soluble organic solvent comprises an alkanol containing from 2 to 4 carbon atoms, a polyethylene glycol having a molecular weight in the range of from about 150 to about 600, or a mixture thereof.

5. A liquid built detergent composition according to claim 2 or claim 3, which comprises from about 1% w/w to about 20% w/w of said water-soluble organic solvent.

6. A liquid built detergent composition according to claim 1, claim 2 or claim 3, in which said amine salt is a salt derived from an alkanolamine or a heterocyclic monocyclic amine.

7. A liquid built detergent composition according to claim 1, claim 2 or claim 3, in which said amine salt is a salt derived from monoethanolamine, diethanolamine, triethanolamine, or morpholine.

8. A liquid built detergent composition according to claim 1, claim 2 or claim 3, in which said anionic surfactant acid comprises an alkyl benzene sulphonic acid in which the alkyl group contains from about 6 to about 20 carbon atoms, a primary or secondary alkyl sulphonic acid containing from 10 to about 26 carbon atoms, an alpha-olefin sulphonic acid obtained by sulphonation or an alpha-olefin containing from about 10 to 22 carbon atoms, or a mixture thereof.

9. A liquid built detergent composition according to claim 1, claim 2 or claim 3, which comprises from about 0.1% w/w to about 25% w/w of said amine salt.

10. A liquid built detergent composition according to claim 1, claim 2 or claim 3, in which said builder comprises sodium metaphosphate, sodium paraphosphate, sodium tripolyphosphate, sodium silicate, sodium carbonate, a zeolite, a layer silicate trisodium citrate, or a mixture of two or more thereof.

11. A liquid built detergent composition according to claim 1, claim 2 or claim 3, which comprises from about 15% w/w up to about 60% w/w of said builder.

12. A liquid built detergent composition according to claim 1, which further comprises at least one non-ionic surfactant.

13. A liquid built detergent composition according to claim 12, in which said non-ionic surfactant comprises a fatty acid monoethanolamide, a polyoxyalkylene ether of an alkanol, a polyoxyalkylene ether of an alkylphenol, or a mixture thereof.

14. A liquid built detergent composition according to claim 12 or claim 13, which comprises from about 0.1% w/w up to about 50% w/w of said non-ionic surfactant or surfactants.

15. A liquid built detergent composition according to claim 1, claim 2, claim 3, claim 12 or claim 13, which further comprises an amine salt of a sulphated fatty alcohol containing from about 10 to about 26 carbon atoms.

16. A liquid built detergent composition according to claim which further comprises a bleach.

17. A liquid built detergent composition according to claim 16, which further comprises a bleach activator.

18. A liquid built detergent composition according to claim 17, which comprises from about 0.1% w/w up to about 15% w/w of a bleach and from about 0.03% w/w up to about 5% w/w or a bleach activator.

19. A liquid built detergent composition according to claim 1, which further comprises an enzyme.

20. A liquid built detergent composition according to claim 19, which further comprises an enzyme stabiliser.

21. A liquid built detergent composition according to claim 1, claim 2, claim 3, claim 12, claim 13, claim 16, claim 17, claim 18, claim 19 or claim 20, which further comprises an amphoteric surfactant.

22. A process for the production of a liquid built detergent composition which includes the step of reacting in an organic phase the acidic form of an anionic surfactant acid containing one or more free sulphonic acid groups with an amine.