CA1113829A - Fabric washing compositions containing anionic and non-anionic surfactants - Google Patents

Fabric washing compositions containing anionic and non-anionic surfactants

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Publication number
CA1113829A
CA1113829A CA327,293A CA327293A CA1113829A CA 1113829 A CA1113829 A CA 1113829A CA 327293 A CA327293 A CA 327293A CA 1113829 A CA1113829 A CA 1113829A
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CA
Canada
Prior art keywords
fabric washing
weight
washing powder
powder according
high suds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA327,293A
Other languages
French (fr)
Inventor
William D. Emery
Robin W. Huddleston
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Unilever PLC
Original Assignee
Unilever PLC
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Filing date
Publication date
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Abstract

ABSTRACT

A high sudsing fabric washing powder containing a weak detergency builder system and a defined mixture of surfactants. The mixture comprises 20-29%, based on the weight of the powder of a calcium sensitive anionic surfactant such as sodium dodecyl benzene sulphonate and from 1 to 3% by weight of the powder of a C11-24 alcohol ethoxylate containing from 5 to 30 moles, per mole of alcohol, of an alkylene oxide. Such a formulation has detergency performance equivalent to fully built products.

Description

1~13829 .

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- 1 - cC.1028 , ~' , .:
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FA~RIC WASHIN~.COMPOSI~IO~S CON~AINING A~IONIC
AND NON-ANIONIC SURFAC~AN~S I
~his in~en~ion relates to wa~hing composition~.
~here are now a number of constraint~ on the formulation of wa~hing ~ompo~ition~. ~he~e inalude the '! ' ' intended u~e, whi¢h influences product form, and legal .: .
re~triction~, which may influence phosphoru~ content and also the processing route taken. At a mare detailed level, e~en after it ha~ been decided that a particular composition is to be aimed at the fabric washing market, consideration~ as to whether the main use is to be in hand- .
washing, in twin-tub or in automatic (front lo~ding) wa~hing machine~, con~train the formulation options. For instance, it is now widely recognised that the amount of suds acceptable in a front-loading washing machine is considerably les~ than that required in a top-loading twin-.

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- 2 - 1113829 cC.1028 tub machine and a suitable low sudsing formulation must be produced for this market.
~ he practical effect of these constrai~ts has been to narrow the possible range of commercially acceptable formulations, but this has placed a premium on optimisation of particular compositions from the possible field in order to obtain best performance.
We have now discovered that very good detergenc~ and a suds level substantially higher than that produced by a low sudsing formulation can be obtained at relatively high concentrations of free calcium if the detergent active species consists of a mixture of a calcium sensitive anionic surfactant and a Cll 24 alcohol alkox~late in which the proportion of the alcohol.alkoxylate is limited.
Accordingly, the pre~ent invention provides a high ~uds fabric washing powder comprising a weak detergency builder as herein defined, characterised by the detergent active apecies being a mixture consisting of from 20 to 2~/o by weight of the powder of a calcium sensitive anionic s.urfactant and from 1 to 3% by.weight of the powder of a Cll 24 alcohol alkoxylate contai~ing from 5 to ~0 mole~ Or ' ethylene oxide or from 5 to 30 mole~ of a mix~ure of ethylene oxide and propylene oxide, per mole of alcohol, the presence of the Cll 24 alcohol alkoxylate serving to increa~e the detergency of the powder in use.. '.' ~ he term 'weak detergency builder' as u~ed herei~
mean~ a compound or mixture o~ compounds which, when the fabric wa~hing powder i~ di~olved at.a given concentration in water of given hardnes~, leaves a sufficient free 30. calcium ion concentration in bhe solution for the calcium ~alt of the anionic surfactant to be precipitated, were it not ~or the presence of the nonionic surfactant. ~hat is to say, that if the nonionic surfactant is omi~ted from the powder'formulation, the calcium ~alt of the ~nionic '.' detergent active is precipitated. However, because ~pray-dried powders normally produce a cloudy solution and`

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- 3- ca~lo28 because some of the modern detergency builders are precipitant builders (such as orthophosphates) or are in any ca~e incompletely dissolved in the wash liquor (alumino silicates) it is not a simple matter to tell whether a precipitate of the calcium salt of the anionic surfactant is being formed.
In practice, the best way of determining this is to perform a detergency test since this provides a direct measure of the effect of precipitation on the performance of the wa~hing powder.
Consequently, in order to determine whether the builder system in a particular formulation is a weak builder as herein defined, and hence whether that formulation fall~
within the scope of this application, it is necessary to perform te~ts to asse~s the detergency of the formulations in the absence of nonionic surfactant at a number of different concentrations of water hardness. ~rom the~e tests it is within the competence of a chemist skilled in the detergents art to extrapolate the concentration and water hardnés~ at which the calcium salt of the anionic surfactant is beginning to be precipitated.
A weak detergency builder-is defined aæ one which permits prqcipitation of the calcium salt of the anionic surfactant from water containing 300 ppm of water hardne~
ions, calculated as calcium ¢arbonate, at a product concentration ~f 2 gm~
Preferably, the powder contains no more than 5% by weight of phosphorus.
Examplqæ of calcium senæitive surfactants are salts, preferably sodium salts of C9 16 linear or branched alkyl benzene sulphonate~, Cl~ 22 primary alkyl sulphates or C16 22 æecondary alkyl sulphates, and mixtures of C13 20 5econdar~ alkane gulphonateæ or C12 22 vinylidène olefine ~ulphonates and hydroxy alkane sulphonates. Of these, the preferred mRterials are alkyl benzene sulphonates having an average of 12 or 13 carbon atomæ in the alkyl subætituent, , ~" ~.... . . . . . .
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1~:138Z9 _ 4 - cC.1028 C14_17 or C16_19 secondary alkane sulphonates and C14 20 primary alkane sulphates.
Satisfactory detergency properties æe obtained at as little as 20% by weight of the anionic surfactant, based on the total composition, and even better ones when the minimum level is treated as 22%. ~he anionic surfactant content cannot be increased indefinitely, since when using amounts of nonionic surfactant of between l and 3%~
as proposed above, processing difficulties set in when the anionic surfactant reaches 30-32%~ depending on the water content of the crutcher slurry and also higher levels of nonionic surfactant substantiaIly reduce the amount of foam produced. ~hus, whilst the invention extends to compositions containing between 20 and 30% of the calcium sensitive 15 anionic surfactant, it is preferred that the range should be 22 to 27%. Particularly good results are obtained when the level is 24.5 to 25.5% with a level of nonionic surfactant of from 1.5 to 2.5% by weight.
As has been mentioned already, the formulations of the invention are preferred to contain a maximum of 5% by weight of pho~phoru8. ~his i8 believed to be the level to which future legislation will settle. In our experienc.e, at phosphorus levels of 5% or les8 in hard water, the free calcium ion concentration in hard water will often be high 25 enoùgh to precipitate calcium sensitive.anionic surfactants in the abse~ce of steps to pre~ent that.
~he detergenc~ builders which may be used in the ..
compositions of this invention may be any of the ~equestrant or precipitant builders which have been suggested to replace phosphate builders, or they may be phosphate salts, or mixtures of any one of the~e, generally in amounts ~rom 10 to 30/0 by weight in the case of phosphate builders and 10 to 35% by weight in the case of non-phosphat`e.ones.
Examples of detergency builders which ma~ be used are.
ortho-, pyro- and tripolyphosphatesf aluminosilicates;
carbonates? especially the sodium carbonate/calcium : : : .

- 5 - 1~13829 cC.1028 carbonate combination; polyphosphonates such as ethane-l-hydroxy-l,l-diphosphonate; amine carboxylates such as nitrilotriacetates and ethylene diamine tetra acetates;
ether carboxylates such as oxydiacetates, oxydisuccinates, carboxymethyloxysuccinates and malonates; citrates;
mellitates; and salts of polymeric carboxylic acids such as polymaleates, polyitaconates and polyacrylates. These salts will normally contain alkali metal or ammonium cations, preferably sodium.
Mixtures of sodium ortho- and tri-polyphosphate are the preferred detergency builders, particularly mixtures in the ratio 10:1 to 1:5, preferably 5:1 to 1:1 tripolyphosphate to orthophosphate, in amounts of 10 to 30% by weight.
~he nature of the nonionic surfactant is not especially critical in the compositions of this invention provided tha~
it conforms to the definition given earlier, that is it is an ethoxylate, or mixed éthoxylate/propoxylate of a Cll 24 alcohol containing from 5 to 30 moles per mole of alcohol, of alkylene oxide.
~he alcohol may be straight chain or branched chain, primary or secondary and may be made by one of the synthetic processes, such as the 'Ziegler' or 'Oxo' processes, or may be derived from naturally occurring materials such a~
tallow.
~he alkoxylation may be carried out by conventional means using from 5 to 30, pr~ferably 15 to 25 and most preferably 15 to 20 moles of ethylene oxide, or a mixture of ethylene oxide and propylene oxide in the de~ired proportions which will depend on the degree of hydrophobic character required.
Examples of commercially available materials which are ~uitable for use in this invention are:
~ ergitols (~rade Mark) which are a series `of ethoxylates of secondar~ alcohols sold by the Union Carbide Corporation, especially ~ergitol 15-S-7, 15-S-9, 15-S-12 and 15-S-15 which are ethoxylates of a mixture of C11 15 , .
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- 6 - 1$138~9 cC.1028 alcohols and ~ergitols 45-S-12 and ~5-S-15 which are ethoxylates of a mixture of C14 and C15 alcohols, the degree of ethoxylation being shown by the postscript.
~thoxylates of primary alcohols made by the Oxo process 5 and containing about 20% of alpha branched material sold by Shell Chemicals Ltd and Shell Chemicals Inc as Dobanols and ~eodols (registered Trade Marks) respectively, especially Dobanol and ~eodol 25-7, 25-9, 25-12 and 25-15 which are ethoxylates of a mixture of C12-C15 alcohols and Dobanol 10 45-7, 45-9, 45-12 and 45-15 which are ethoxylates of a mixture of C14_15 alcohols-Ukanils (~rade Mark) which æe a series of ethox~latesof Oxo alcohols containing about 25% of alpha methyl branched and about 10% of ethyl branched material and 15 Acropols (~rade Mark) manufactured by Ugine Euhlman et Cie, especially Acropol 35-7, 35-9, 35-11 and 35-15 which are derived from a mixture of C13-C15 alcohols^
Synperonics (~rade Mark), a series of ethoxylates of alcohols containing 45-55% of alkyl branchin~, mostl~ methyl branching, sold by Imperial Chemical Industries Limited, especially those based on a C13 15 mixture of alcohols and ethoxylated to 7,9,11 and 15 units of ethylene oxide.
~ thoxylates of primary Ziegler alcohols sold as AIfo~s (~rade Mark) derived by polymerisation of ethylene, manufactured by Cono~o-Condea, especiall~ Alfol 12/14-7, 12/14-9, 12/14-12, 12/14-15 and Alfol 14/12-7, 14/12-9, 14/12-12, 14/12-15 which are ethox~lates of mixtures of C12 and C14 alcohols, Alfol 16/18-10, 16/18-18 and 16/18-25, and Alfol 16/20-10, 16/20-18. and 16/20-25 which are ethox~lates of mixtures of C16 and C18 alcohols and mixtures of C18 and C20 alcohols respectively.
Ethoxylates of primary O~o alcohols containing about 60% branched material, sometimes called Lials ~rade Mark) produced from olefins manufactured by ~iquichimica.
~astly, ethoxylates of natural alcohols, such as tallow alcohol can be used.

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- ' 7 1~138Z9 cC.10~8 Other conventional components of detergent compositions may be present in conventional amounts. Examples of these include powder flow aids such as finely divided silicas and aluminosilicates, antiredeposition agents such as sodium 5 carboxymethylcellulose, oxygen-releasing bleaching a~ents :-such as sodium perborate and sodium percarbonate, per-acid bleach precursors such as tetraacetylethylenediaminé, chlorine-releasing bleaching agents such as trichloroiso-cyanuric acid and alkali metal salts of dichloroisocyanuric .
acid, fabric softening agents such as clays of the smectite and illite types, anti-ashing aids, starches, slurry stabilisers such as copolyethylene maleic anhydride and copolyvinylmethylether maleic anhydride, usually in salt form, inorganic salts such as ~odium silicates and sodium sulphate, and usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and colourants. lhe detergent compositions usually have an alkaline pH,.generally i~ the region of pH 9-11, which is achieved by the presence of alkaline salts, especially sodium silicates such as the meta-, netural or alkaline silicates, preferably at levels up to about 15% by weight~ - .
~ h0 invention will be further described in the following Examples.

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. .. .:., - 8 - ~1138Z9 c~.1028 , ~xample 1 % by welght Component A B
Sodium C12 alkyl benzene sulphonate 20.0 27 5 ~allow alcohol ethoxylate (25 ~0) 7 Sodium tripolyphosphate (STPP)13.6 13.6 ~risodium orthophosphate 5.0 5.0 Alkaline sodium silicate 9.0 10.0 Sodium sulphate 25.3 31.9 10 Coloured STPP speckles 3.0 ~.0 Sodium polyacr~late 3.0 3.0 Enzymes 1.2 1.2 Water & minor ingredients to 100 to 100 ~hese two formulations were mixed in various proportions in order to obtain fabric washing powders containing amounts of nonionic surfactant var~ing from 0 to 7% of the powder. ~he suds performance o~ the resultant powder was then assessed using a Ross-Miles dynamic foam meter, which is an instrument-well known in the detergents art. (~he results are shown in ~able l).
~ he time taken for the lather to collapse was also measured. -.
.

1~38Z9 ~ 9 _ cC.102B

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~13829 - 10 - cC.1028 As can be seen from the ~able, products containing more than 3% nonionic surfactant had a suds stability of less than 5 minutes, which is considered unsatisfactory.
~he detergency of some of the products obtained by mixed ~ormulations A and B was also tested. A handwashing procedure was used and the detergency was assessed using-a reflectance method. ~he results are shown in ~able 2.
Table 2 R460 Reflectance (proportional to detergency) 2.5 gms/l produc.t,.concentration.in..water..of..30.
hardness f~rench~ '.
-. . . . . . _ . % nonionic. . 0 1. . 3 7 . . . ., . . .
/0 a,nionic 27 26, 24 20 . ~ .

Soil ' ,. , _ ............ . _ ' ' :'',' ER~C" 42.3 49.3 . 53.2 55.0 .' . . AS 12+ ," 47-9, 50.2 52.1 53-8 ¦ , .. .
- It can be seen that there is a general trend towards increasing detergency with increasing percentage of . ~ -nonionic surfactant. ~he difference between the deterge,ncy of the composition containing 26% by weight of anionic and . 1% by weight of ~onionic surfactant and that of the ,~
composition.containing no nonionic surfactant at all i9 more substantial than the differen¢e between the compo~ition~ containing 3 and ~/o of nonio~ic surfactant .. . .
respectiVel~. .
'~A cotton test piece soiled with a ~ynthetic sebum ,: .
and inorganic materials. , -.
.
~A cotton test piece soiled with an organic. , synthetic soil.
~he conclusion to be drawn from these two~experiments ;~
is that there is a heavy fall-off in foaming powe~ when . -the amount of nonionic surfactant ~eaches 3%, but that detergency increases rapidly with additions of ver~ small .... ,, ~

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cc . 1028 amounts of nonionic surfactant, increasing more slowl~ -therea~ter. ~he op-timum of .oaming and detergency appears to be reached at 25% alkyl benzene sulphonate and 2% tallow alcohol ethoxylate, acceptable levels being obtained at 24% and 3% respectively.

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Claims (9)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A high suds fabric washing powder comprising a detergent active compound and a detergency builder mixture of sodium tripolyphosphate and trisodium orthophosphate, wherein the detergent active species is a mixture consisting of from 20 to 29% by weight of the powder of a calcium sensitive anionic surfactant and from 1 to 3% by weight of the powder of a C11-24 alcohol alkoxylate containing from 5 to 30 moles of ethylene oxide or from 5 to 30 moles of a mixture of ethylene oxide and propylene oxide per mole of alcohol.
2. A high suds fabric washing powder according to claim 1, containing no more than 5% by weight of phosphorus.
3. A high suds fabric washing powder according to claim 1, wherein the detergency builder mixture is in a ratio of from 5:1 to 1:1, tripolyphosphate to orthophosphate.
4. A high suds fabric washing powder according to claim 1, wherein the detergency builder mixture is present in an amount of from 10 to 30% by weight.
5. A high suds fabric washing powder according to claim 1, wherein the calcium sensitive anionic surfactant contains a C9-16 linear or branched alkyl benzene sulphonate.
6. A high suds fabric washing powder according to claim 1, wherein the detergent active compound is present in an amount of from 22 to 27% by weight.
7. A high suds fabric washing powder according to claim 1, wherein the detergent active compound is present in an amount of from 24.5 to 25.5% by weight.
8. A high suds fabric washing powder according to claim 1, wherein the alcohol alkoxylate is present in an amount of 1.5 to 2.5% by weight.
9. A high suds fabric washing powder according to claim 1, wherein the alcohol alkoxylate comprises a tallow alcohol alkoxylate containing an average of 25 moles of ethylene oxide per mole of alcohol.
CA327,293A 1978-05-10 1979-05-09 Fabric washing compositions containing anionic and non-anionic surfactants Expired CA1113829A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB18671/78 1978-05-10
GB1867178 1978-05-10

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CA318,251A Division CA1078413A (en) 1975-03-18 1978-12-20 Optical waveguide and method and compositions for producing same

Publications (1)

Publication Number Publication Date
CA1113829A true CA1113829A (en) 1981-12-08

Family

ID=10116453

Family Applications (1)

Application Number Title Priority Date Filing Date
CA327,293A Expired CA1113829A (en) 1978-05-10 1979-05-09 Fabric washing compositions containing anionic and non-anionic surfactants

Country Status (8)

Country Link
JP (1) JPS54146809A (en)
AU (1) AU525730B2 (en)
BR (1) BR7902829A (en)
CA (1) CA1113829A (en)
GR (1) GR66506B (en)
IT (1) IT1109135B (en)
NZ (1) NZ190355A (en)
ZA (1) ZA792252B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6189300A (en) * 1984-10-09 1986-05-07 ライオン株式会社 Production of granular detergent composition containing nonionic surfactant
JPH0639595B2 (en) * 1985-04-01 1994-05-25 株式会社テシマ化研 Slurry composition for producing powder detergent

Also Published As

Publication number Publication date
JPS54146809A (en) 1979-11-16
IT7868213A0 (en) 1978-05-26
BR7902829A (en) 1979-11-27
NZ190355A (en) 1980-11-28
IT1109135B (en) 1985-12-16
ZA792252B (en) 1981-01-28
AU525730B2 (en) 1982-11-25
AU4681179A (en) 1979-11-15
GR66506B (en) 1981-03-24

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