Note: Descriptions are shown in the official language in which they were submitted.
~'7~S6
DETERGENT ADDITIVES AND DETERGE~T COMPOSITIONS
CONTAINING THEM
The present invention relates to additives for
detergent compositions, and to detergent composi~ions
containing them. These compositions are particularly, but
not essentially, adapted for fabric washing. The invention
x~lates more particularly to substantially phosphate-free
detergent compositions.
Fabric washing compositions conventionally contain
phospha~e detergency builders such as sodium
tripolyphosphate. In some circumstances it is thought tha~
the use of phosphates in detergent compositions can lead to
environmental problems in waste waters. There is therefore
a desire to reduce the level of phosphorus, or to eliminate
it altogether, in detergent compositions.
Water-insoluble aluminosilicate ion exchange materials
have been suggested as alternative builders to phosphates:
see, for example, GB 1,473,201 and GB 1,473,202 (Henkel).
It has been found in practice, however, that these
aluminosilicate materials, even in large amounts, tend to
be undesirably slow in their exchange of cations,
56
- 2 - C.1303
especially at low temperatures, resulting in inferior
detergency. It has accordingly been suggested that
supplementary water-soluble builders should be used in
combination with these aluminosilicates to raise the
detergency to an acceptable level. These supplementary
builders are generally materials that are efficient
sequestrant builders in their own right, for example,
alkali metal tripolyphosphates, nitrilotriacetates and
poly ~ -hydroxyacrylates. High levels of these materials
are, however, not generally desirable in detergent
compositions ~or cost or environmental reasons.
We have now discovered that surprisingly good
detergency results are obtained by using, in combination
with an aluminosilicate builder, relatively small amounts
of both an organic sequestrant builder and o an organic
precipitant builder. The detergency results obtained using
ternary systems of this ~ype have surprisingly been found
to be better than would have been expected from
consideration of the results obtained using the
corresponding binary aluminosilicate/sequestrant and
aluminosilicate/precipitant s~stems, so that decreased
amounts of the supplementary builders can be used, giving
cost savings and environmental advantages.
It is Xnown that the detergency builder properties of
aluminosilicates are enhanced by the addition of water-
soluble complexing agents such as sodium tripolyphosphate.
This effect has been explained in terms of the so-called
"carrier molecule model": see, for example, P Berth,
J. Am. Oil Chemists' Soc., 55 , 52-53 (1978). The
complexing agent is able to take up polvalent water
hardness ions (notably Ca2+, but also Mg2+) fxom solid
surfaces (such as the surface of a textile fibre) and pass
them on to the aluminosilicate ion-exchanger after
transport through the ~queous medium. The complexing agent
~'7 ~S~
C.1303
forms a chelate complex with the hardness ion which on
arrival at the surface of the aluminosilicate dissociates.
It i5 not easy to envisage a similar mechanism with
precipitant builders, since these remove hardness ions from
the wash liquor by the virtually irreversible formation of
a precipitate (insoluble calcium or magnesium salt).
It i5 thus unexpected that addition of a precipitant
builder and an aluminosilicate/sequestrant system gives a
substantial improvement in detergency builder properties.
The present invention accordingly provides, in a first
aspect, a detergent additive consisting essentially of:
(a) from about 25% to about 97% by weight of a crystalline
or amorphous alumino~ilica~e cation-exchange material,
(b) from about 3% to about 75~ by weight, in total, of
(i) an organic precipitant builder having a polyvalent
anion, which builder forms an insoluble calcium
salt, and
(ii) an organic builder which forms a soluble complex
with calcium,
the weight ratio of (i) to (ii) being from about 10:1
to about 1:10.
The organic precipitant builder is preferably one
having a divalent anion.
The aluminosilicate cation exchange material is a
crystalline or amorphous material having the general
formula:
(Cat2/n O)X A1203(SiO2)y 2
wherein Cat is a cation having valency n that is
exchangeable wi~h calcium (e.g. Na or K ); x is a
number from 0.7-1.5; y is a number from 1.3-4; and z is
'7:~S~
- 4 - C.1303
such that the bound water content is from 10~ to 28% by
weight.
Preferably a crystalline material .is used which can be
described by the unit cell content:
Nax[(Al02)x (sio2)y3zH2
wherein x and y are integers of at least 6, the ratio of x
to y being in the range of 1:1 to 1:2; and z is such that
the bound water content is from 10~ to 28% by weight.
The aluminosilicate preferably has a particle size of
10 from 0.1 to 100 micrometres, ideally between 0.1 and 10
micrometres, and an ion exchang~ capacity of at least 200
mg CaC03 per gram of aluminosilicate (anhydrous basis).
In a preferred embodiment the wat~r insol~ble
aluminosilicate is a crystalline material having the
formula described by the unit cell content:
Nal2(A102)12 (siO2)12 2
wherein z is from 20 to 30, preferably about ?7.
An example of this material is the commercially
available product known as Zeolite type A, which is
typically:
Na20.Al2o3.2sio2 4'5H2
and is also described by the unit cell content:
12[(A102)l2-(sio2)l2~.27H2o.
The organic precipitant builder i9 a water-soluble
material which forms an insoluble calcium salt and which
has a polyvalent, preferably di~alent, anion~ Materials
~37 ~S~
- 5 - C.1303
having a divalent anion are substantially more weigh~-
effPctive as builders than are soaps; only one mole is
consumed by each gram ion of Ca2 or Mg2+ hardness
ions, as compared with two moles of soap.
The solubility product of the calcium salt of the
organic precipitant builder having a divalent anion is
preferably less than 10 8.
Advantageously the organic precipitant builder is a
compound of the formula I:
/ (CH2)nCOOY
R -X (I)
(C 2)m
wherein:
Rl is C10-C24 alkyl or alkenyl, or an arylalkyl or
15 alkylaryl group of equivalent chain length;
X is CH, CR2, N or CO~;
R2 is Cl-C3 alkyl;
Y is hydrogen or a solubilising cation, preferably alkali
metal and especially sodium;
n and m, which may be the same or diferent, are 0 or
integers from 1 to 4; and
Z is COOY or SO3Y.
One preferred group of compounds within this
definition consists of thvse in which X is CH, n is zero,
and m is 0 or 1. Thus, according to a firs~ preferred
embodiment of the invention, the organic precipitant
builder is a compound 3f the formula II.
COOY
Rl ~ CH / I (II)
(CH~)p-Z
stj
- 6 - C.1303
wherein Rl, Y and Z have the meanings given above, and p
is 0 or 1.
Especially preferred classes of compounds within the
gener~l formula II are the following:
(i) substituted malonates of the formula III:
/ COOY
Rl - CH \ (III)
COOY
(ii) substituted succinates of the formula IV:
,~ COOY
R - CH (IV)
2COOY
- and -
(iii) C~-sulphofatty acid salts of the formula V:
/ COOY
Rl - CH ~V)
S03Y
Compounds of the formulae III and IV are described,
for example, in GB 1,293,753, GB 1,342,247 and GB 1,342,340
(Unilever). Examples of such compounds include disodium
dodecyl malonate (C12-AKM), disodium hexadecenyl
succinate (C16 1-AKS), and disodium mixed C15-C18
succinate (C15 18-AKS).
Compounds of the formula V are described, for example,
in GB 1,368,736 and GB 1,380,390 (Unilever). A typical
example is disodium ~-sulphostearate (C18-SFAS)~
Blends of compounds of different chain lengths, for example
715~
- 7 - C.1303
the c~-sulpho salt of coconut fatty acids (coco-SFAS), or
of tallow fatty acids (tallow-SFAS), or of blended coconu~
and tallow fatty acids, may also advantag~ously be used.
According to a second preferred embodimen~ oE ~he
invention, the organic precipitant builder is a compound of
the formula VI:
~ ( CH2 ) VcOOY
Rl - N (VI)
( C~I2 ) wCY
or of the formula VII:
~( CH2 ) vcoy
Rl - C0 - N ~ (VII~
(CH~)wcooy
wherein Rl and Y have the meanings given above and v and
w are each 1 to 4, preferably 1 or 2.
Compounds of the formula VI in which v and w are both
1, the N-alkyl iminodiacetates, are of especial interest.
Compounds of the formula VI in which v and w are both
2, the ~ -iminodipropionates, are known amphoteric
surfactants, disclosed, for example, in GB
1,296,793 (General Mills). These materials are also known
as lath0r promoters in soap bars, a for example, in
EP 0 025 242 (Procter & Gamble), and as anti-corrosive
agents, for example, in US 2,926,108 (General Mills).
Compounds of the formula VI in which v and w are both 1,
the iminodiacetates, have also been disclosed, for example,
as scum dispersants in soap products, in US 3,630,927
(Monsanto), and as anti-corrosive agents, in US 2,368,604
(Shell). US 3,981,779 (Grace) discloses compounds of both
formulae VI and VII for use as "chelant-surfactants" for
decreasing the fouling of metals by aqueous systems.
- ~ - C.1303
GB 761,384 (California Research Corporation) discloses
detergent compositions con~aining 10 to 50~ by weight of
alkylbenzene sulphona~e and 5 to 20~ by weight of a water~
soluble salt o~ an N-(C8-C18 alkyl)-iminodiacetic acid,
the latter component acting as a foam promoter. Similarly,
GB 761,383 (California Research Corporation) discloses
combinations of alkyl sulphates and N-(C~-C18 alkyl)-
iminodicarboxylic acids. Other specifications relating to
the use of compounds of the formula VI in detergent
compositions are GB 446,737 and GB 446,813 (I G Farben).
Compounds analogous to those of formula VI but having a
shorter alkyl chain (C8 or less~ are known as sequestrant
builders, as in GB 1,383,025 (Chemische Werke Huls), and
as rancidity preventers in soaps and non-soap detergents,
as in GB 574,504 (Unilever).
The organic sequestrant builder is a water-soluble
material which forms soluble complexes with calcium,
preferably with pKCa greater than 3.0, preferably greater
than 4.0 and more preferably greater than 4.5.
Advantageously the sequestrant builder also forms complexes
with magnesium, preferably with pKMg greater than 4.0O
Examples of suitable materials include alkali metal
(especially sodium) salts of the following acids:
nitrilotriacetic acid, ethylenediamine tetracetic acid,
polyacrylic acid, poly( -hydroxyacrylic) acid,
carboxymethyloxymalonic acid, carboxymethyloxysuccinic
acid, oxydiacetic acid, oxydisuccinic acid, citric acid,
dipicolinic acid and many more. The polyacetal
carboxylates disclosed in VS 4,144,126 and
US 4,146,495 (Monsanto) and the oxidised polysaccharides
disclosed in GB 1,330,121, GB 1,330,122 and GB 1,330,123
(Unilever~ may also advantageously be used.
~9'7~
~ 9 - C.1303
Alkali metal salts of nitrilotriacetic acid (NTA),
especially the trisodium salt, are, however, the preferred
organic sequestrants used according to the present
invention. The use of NTA salts in combination with
precipitant builders having a divalent anion is especially
preferred.
The nitrilotriacetic acid compounds preferably used
according to the present invention are known sequestering
agents and may be represented by the following structural
formula
t 2 )3
wherein X, as before is hydrogen or a solubili~ing cation.
These compounds further contain C-bonded substituents of an
inert and innoxious nature such as alkyl, eg methyl or
ethyl, or haloalkyl, eg chloromethyl. The nature of said
compounds is not particularly critical with the implicit
limitation that such substituents be devoid of any tendency
to deleteriously affect the desirable properties of ~he
nitrilotriacetic acid compound.
Preferred compounds falling within the ambit of the
above-described definition and formula are nitrilotriacetic
acid, trisodium nitrilotriacetate monohydrate, tripotassium
nitrilotriacetate, disodium nitrilotriacetate and
dipotassium nitrilotriacetate.
~5 The organic precipitant builder and the organic
sequestrant builder together constitute from about 3% to
about 75% by weight of the builder mix (detergent additive)
of the invention, preferably from about 10% ~o about 60%
and especially from about 20~ to about 50%. The ratio of
30 precipitant to sequestrant is from 10:1 to 1:10t preferably
from 3:1 to 1:3 and desirably from 3:1 to 1:1.
7~5~
- 10 - C.1303
The detergent additive of the presen~ invention is an
efficient builder system yielding good detergency results
when incorporated, with detergent-active materials, in a
detergent composition.
Accordingly, in a second aspect the present invention
provides a detergent composition comprising from about 3 to
about 90~ by weight of at least one synthetic
detergent-active material, and from about 10 to about 97%
by weight of a detergent additive as previously defined.
The detergent composition of the invention contains
from about 10% ~o about 97% by weight of the detergent
additive of the invention, preferably from about 10% to
about 80~. more preferably from about 25% to about 70~,
and especially from about 28% to about 67%.
Since the detergent additive contains from about 25%
to about 97% by weight of aluminosilicate, the
aluminosilicate content of the detergent composition can
range from about 2~5% to about 94%. An aluminosilicate
content of from ~bout 10% to about 60~, especially from
about 17% to about 47%, is preferred.
Similarly, the content of organic builders
(precipitant plus sequestrant) can range from about 0.3~ to
about 73%, a range of from about 5~ to about 40%.
especially from about 7% to about 27%, being preferred.
The preferred range for the content of the precipitant
builder is from about 3~ to about 20%, especially from
about 5% to about 10%; for the sequestrant builder the
preferred range is from about 1% to about 15%, especially
from about 2% to about 10%,
The detergent compositions of the present invention
arP prefPrably substantially free of inorganic phosphate.
~7~15~
~ C.1303
This is highly desirable for the environmental reasons
mentioned earlier. Compositions according to the invention
containing no inorganic phosphate have been found to
exhibit detergency properties comparable to those of sodium
tripolyphosphate-built products.
If desired, however, the compositions may contain
inorganic phosphate, but preferably at a level not
exceeding 10% based on the whole product; a level b~low 5%
is a~vantageous, and a level below 3% is especially
preferred. Any phosphate present may, for example~ be in
the form of alkali metal (preferably sodium~ tripoly-
phospha~e, orthophosphate, pyrophosphate or polymeric
phosphate.
The detergent compositisn of the invention necessarily
includes from about 3% to about 90% by weight, preferably
from about 5% to about 40% by weight, more pxeferably from
about 10~ to about 25% by weight, of a synthetic anionic,
nonionic, amphoteric or zwitterionic detergent compound or
mixture thereof. Many suitable detergent-active compounds
are commercially available and are fully described in the
literature, for example in "Surface Active Agents and
Detergents", Volumes I and II, by Schwartz, Perry and
Berch.
The preferred detergent compounds which can be used
are synthetic anionic and nonionic compounds. The former
are usually water soluble alkali metal salts of organic
sulphates and sulphonates having alXyl radicals containing
from about 8 to about 22 carbon atoms, the term alkyl being
used to include the alkyl portion of higher aryl radicals.
Examples of suitable synthetic anionic detergent compounds
are sodium and potassium alkyl sulphates, especially those
obtained by sulphating higher (C8-C18) alcohols
produced for example from tallow or coconut oil; sodium and
7~56
~ 12 - C.1303
potassium alkyl (Cg-C~0) benzene sulphonates,
particularly sodium linear secondary alkyl (C10-Cl~)
benzene sulphonates; sodium alkyl glyceryl ether sulphates,
especially those ethers of the higher alcohols derived from
tallow or coconut oil and synthetic alcohols derived from
petroleum; sodium coconut oil fatty acid monoglyceride
sulphates and sulphonates; sodium and potassium salts of
sulphuric acid esters of higher (C~-C18) fatty
alcohol-alkylene oxide, particularly ethylene oxide,
reaction products; the reaction products of fatty acids
such as coconut fatty acids esterified with isethionic acid
and neutralised with sodium hydroxide; sodium and potassium
salts of fatty acid amides of methyl taurine; alkane
monosulphonates such as those derived by reacting
alpha-olefins (C~-C20) with sodium bisulphate and those
derived by reacting paraffins with SO~ and Cl~ and then
hydrolysing with a base to produce a random sulphonate; and
olefin sulphonates, which term is used to describe the
material made by reacting olefins, particularly C10-C20
alpha-olefins, with S03 and then neutralising and
hydrolysing the reaction product~ The preferred anionic
detergent compounds are sodium (Cll-C15) alkyl benzene
sulphonates and sodium (C16-C18) alkyl sulphates.
Examples of suitable nonionic detergent compounds
which may be used include in particular the reaction
products of alkylene oxides, usually ethylene oxide, with
alkyl (C6-C22) phenols, generally 5 to 25 EO, ie 5 to
25 units of ethylene oxide per molecule; the condensation
products of aliphatic (C8-C18) primary or secondary
linear or branched alcohols with ethylene oxide, generally
6 to 30 EO, and products made by condensation of ethylene
oxide with the reaction products of propylene oxide and
ethylenediamine. Other so-called nonionic detergent
compounds include lons chain tertiary amine oxides, long
chain tertiary phosphine oxides and dialkyl sulphoxides.
s~
- 13 - C.130
Mixtures of detergent compounds, for example mixed
anionic or mixed anionic and nonionic compounds may be used
in the detergen~ compositions, particularly in the latter
case to provide controlled low sudsing properties. This is
beneficial for compositions intended for use in
suds~intolerant automatic washing machines. Anionic
and nonionic detergent compounds are advantageously used
together in ratios of from 3:1 to 1.5:10
Amounts of amphoteric or zwitterionic deterg~nt
compounds can also be used in the compositions of the
inven~ion but this is not normally desired due to their
relatively high cost. If any amphoteric or zwitterionic
detergent compounds are used it is generally in small
amounts in compositions based on the much more commonly
used synthetic anionic and/or nonionic detergent compounds.
If desired, the composition of the invention may also
includ~ soap. The presence of small amounts of soap is
beneficial with respect to lather control and detergency.
Soaps which may be used are especially the sodium or less
desirably the potassium, salts or ClG-C2~ fatty acids~
Soaps based mainly on the longer-chain fatty acids within
this range, that is to say, with at least half of the soap
having a chain length of C16 or more, are especially
preferredO This preferred chain length distribution may be
conveniently obtained by using soaps from natural sources
such as tallow, palm oil or rapeseed oil, which may be
hardened if desired, with lesser amounts of other, shorter-
chain soaps prepared from nut oils such as cocvnut oil or
palm kernel oil.
According to a preferred embodiment of the invention,
the detergent composition also contains a bleach system.
7 ~5~i
- 14 - C.1303
The bleach system preferably comprises a peroxy bleach
compound which is an inorganic persalt, which is preferably
used in conjunction with an activator therefor. The
persalt may be, for example, sodium perborate (either the
monohydrate or the tetrahydrate) or sodium percarbonate.
The activator makes the bleaching more effective at lower
temperatures, ie in the range from ambient temperature to
about 60C, so that such bleach systems are commonly known
as low-temperature bleach systems and are well known in the
art. The inorganic persalt acts to release active oxygen
in solution, and the activator is usually an organic
compound having one or more reactive acyl residues, which
cause the formation of peracids, the lattex providing or a
more effective bleaching action at lower temperatures than
lS can be obtained by use of ~he peroxy bleach compound alone.
The ratio by weight of the peroxy bleach compound to the
activator is generally from about 20:1 to about 1:1,
preferably about 15:1 to about 2:1.
The detergent composition of the invention preferably
contains from about 5% to about 30% by weight of the peroxy
bleach compound, and about 0.1 to about 15% by weight of
the activator. The total amount of the bleach system
ingredients preferably lies within the range of from S% to
35% by weight, especially from about 6% to about 30% by
weight~
Typical examples of suitable peroxy bleach compounds
are alkali metal perborates, both tetrahydrates and
monohydrates, alkali metal percarbonates, persilicates and
perphosphates, of which sodium perborat~ is preferred.
Activators for peroxybleach compounds have been amply
described in the literature, including British patents
836,988, 855,735, 907,356, 907,358, 970,g50, 1,003,310 and
1,246,339, US patents 3~332,882 and 4,128,494, Canadian
1~9715G
- 15 - C.1303
patent 844,481 and South African patent 68/6,344. ~pecific
suitable activators include.
(a) N-diacylated and N,N'-polyacylated amines, such as
N,N,N',N'-tetraacetyl methylene diamine and
N,N,N',N'-tetraacetyl ethylene diamine,
N,N-diacetylaniline, N,~-diacetyl-p-toluidine;
1,3-diacylated hydantoins such as, for example,
1,3-diacetyl-5,5-dimethyl hydantoin and
1,3-dipropionyl hydantoin; ~4acetoxy-~N,~')-
polyacylmalonamide, for example ~-acetoxy-(N,~
diacetylmalonamide;
(b) N-alkyl-N-sulphonyl carbonamides, for example the
compounds N-methyl-N-mesyl-acetamide, N-methyl-~-
mesyl-b~n7.~m;de, N methyl-~-mesyl-p~nikrobenzamide,
and ~-methyl-N-mesyl-p-methoxybenzamide,
~c) N-acylated cyclic hydrazides, acylated triazones or
u.razoles, for example monoacetylmaleic acid hydrazide;
(d) 0,N,N-trisubstituted hydroxyl~mines, such as
O-benzoyl~ succinyl hydroxylamine,
0-acetyl-N,~-succinyl hydroxylamine,
0-p-methoxybenzoyl-N,~-succinyl-hydroxylamine,
0-p-nitrobenzoyl-N,~-succinyl-hydroxylamine and
0,~,N-triacetyl hydroxylamine;
(e) N,~'-diacyl-sulphurylamides, for example N,~'-
dimethyl-~,N'-diacetyl-sulphurylamide and N,N'-
diethyl-~,~'-dipropionyl sulphurylamide;
(f) Triacylcyanurates, for example triacetyl cyanurate and
tribenzoyl cyanurate;
(g~ Carboxylic acid anhydrides, such as benzoic anhydride,
m-chloro-benzoic anhydride, phthalic anhydride,
4-chloro-phthalic anhydride;
(h) Sugar esters, for example glucose pentaacetate;
(i) 1,3-diacyl-4,5-diacyloxy-imidazolidine, for example
1,3-diformyl~4,5~diacetoxy-imidazolidine,
1,3-diacetyl-4,5-diacetoxy-imidazolidine,
9'7:~S~
- 16 -
1,3-diacetyl-4,5-dipropionyloxy-imidazoline;
(j) Tetraacetylglycoluril and tetrapropionylglycoluril;
(k) Diacylated 2,5-diketopiperazine, such as 1,4-dia-
cetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiper-
azine and 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine;
(1) Acylation products of propylenediurea or 2,2-dim-
ethyl-propylenediurea (2,4,6,8-tetraaza-bicyclo-(3,3,1)-non-
ane-3,7-dione or its 9,9-dimethyl derivative),especially the
tetraacetyl- or the tetrapropionyl-propylenediurea or their
dimethyl derivatives;
(m) Carbonic acid esters, for example the sodium salts
of p-(ethoxycarbonyloxy)-benzoic acid and p-(propoxy-
carbonyloxy)-benzenesulphonic acid.
(n) ~ -acyloxy-(N,N') polyacyl malonamides, such as
~-acetoxy-(N,N') diacetyl malonamide.
The N-diacylated and N,N'-polyacylatedamines
mentioned under (a) are of special interest, particularly
N,N,N' ,N' --tetra-acetyl-ethylenediamine (TAED).
It is preferred to use the activator in ~ranular
form, preferably wherein the activator is finely divided as
described in G.B. 2,053,998B (Unilever). SpeciEically, it is
preferred to have an activator of an average particle size of
less than 150 micrometres, which gives significant improve-
ment in bleach efficiency. The sedimentation losses, when
using an activator with an average particle size of less than
150 /um, are substantially decreased. Even better bleach per-
formance is obtained if the average particle size of the
activator is less than 100 /um. However, too small a particle
size gives increased decomposition, dust-for~ation and hand-
ling problems, and although particle sizes below 100 ~um canprovide for an improved bleaching efficiency, it is desirable
that the activator should not have more than 20~
7:~S~i
- 17 - C.1303
by weight o particles with a size of less than 50 /um.
On the other hand, the activator may have a cer~ain amount
of particles of a size greater ~han 150 /um, but it
should not contain more than 5~ by weight of particles
> 300 /um, and not more than 20% by weight of particles
~ 200 /um, preferably > 150 /um. It is to be
understood that these particle sizes refer to the activator
presen~ in the granules, and not to the granules
themselves. The latter have a particle SiZ2, the major
part of it ranging from 100 to 2000 /um~ preferably 250
to 1000 /um. Up to 5~ by weight of granules with a
particle size of > 1700 /um and up to 10% by weight of
granules C 250 /um is tolerable. The granules
incorporating ~he activator, pr~ferably in this
inely~divided form, may be obtained by granulating a
suitable carrier material, such as sodium
tripolyphosphate and/or potassium tripolyphosphate with
activator particles of the required size. Other
granulation methods, e.g. using organic and/or inorganic
granulativn aids, can also be usefully applied. The
granules can be subsequently dried, if required.
Basically, any granulation process is applicable, as long
as the granule contains the activator, and as long as the
other materials present in the granule do not negatively
affect the activator.
It is particularly preferred to include in the
detergent compositions a stabiliser for the bleach
system, for example ethylene diamine tetramethylene
phosphonate and diethylene triamine pentamethylene
phosphonate. These stabilisers can be used in acid or
salt form, especially in calcium, magnesium, zinc or
aluminium salt form, as described in our UK Patent
Application No. 2 048 930.
- 18 ~ C.1303
Apart from the components already mentioned, the
detergent compositions of the invention can contain any of
the conventional aclditives in the amoun~s in which such
materials are normally employed in fabric washing detergent
compositions. Examples of these addit.ives include lather
boosters such as alkanolamides, particularly the
monoethanolamides derived from palm kernel fatty acids and
coconut fatty acids; lather depressants such as alkyl
phosphates, silicones, or alkyl phosphonic acids
incorporated in petroleum jelly, wax or mineral oil;
an~i-redeposition agents such as sodium carboxymethyl-
cellulose and cellulose ethers: fabric softening agents;
inorganic salts such as sodium sulphate and sodium
carbonate; and, usually present in very minor amounts,
fluorescent agents, perfumes, enzymes such as proteases and
amylases.
It may be desirable to include in the composition an
amount of an alkali metal silicate, particularly sodium
ortho-, meta- or preferably neutral or alkaline silicate.
The presence of such alkali metal silicates at levels of at
least about 1~, and preferably from about 5% to about 15~
by weight of the composition, is advantageous in decreasing
the corrosion of metal parts in washing machines, besides
giving processing benefits and generally improved powder
properties. The more highly alkaline ortho- and meta-
silicates would normally only bP used at lower amounts
within this range~ in admixture with the neutral or
alkaline silicates.
The composition of the invention is preferably
alkaline, but not too strongly alkaline as this could
result in fabric damage and also be hazardous for domestic
usage. In practice the composition should desirably give a
pH of from about 805 to about 11 in use in aqueous wash
solutionu It is preferred in particu]ar for domes~ic
7:~S~
- 19 - C.1303
products to have a pH of from about 9.0 to about 10.5 as
lower pH's tend to be less effective for optimum detergency
building, and more highly alkaline products can be
hazardous if misused~ The pH is measured at the lowest
normal usage concentration of 0.1~ w/v of the product in
water of 12H (Ca), ~French permanent hardness, calcium
only) a~ 50C so that a satisfactory degree of alkalinity
can be assured in use at all normal product concentrations.
If necessary, up to 10~ by weight of alkali metal
carbonate, preferably sodium carbonate, may be included in
order to raise the pH and to maintain adequate buffer
capacity in the presence of acidic soils.
If carbonate or phosphates are present it may be
desirable ~o include in the composition of the invention
one or more antideposition agents, to decrease any tendency
to form inorganic deposits on washed fabrics. The amount
of any such antideposition agent is normally from about
0.1~ to about 5~ by weight, preferably from about 0.2% to
about 1.5% by weigh~ of the composition. The preferred
antideposition agent~ are anionic polyelectrolytes,
especially polymeric aliphatic carboxylates, or organic
phosphonates.
The detergent compositions of the invention should
desirably be in free-flowing particulate, for example,
powdered or granular form, and can be produced by any of
the techniques commonly employed in the manufacture o such
washing compositions, for exampl~, by slurry-making and
spray-drying processes. It is preferred that the process
used to form the compositions should result in a product
having a moisture content of not more than about 12~, more
preferably from about 4% to about 10~ by weight.
The detergent compositions of the invention may also
be in the form of bars or tablets, or in liquid form.
156
- 20 - C.1303
The invention will now be illustrated by the following
non-limiting Examples.
E~AMPLES
In the Examples that follow, the detergencies of wash
liquors incorporating various builder systems were compared
by measuring the reflectance of a clay-soiled
polyester/cotton test cloth before and after washing in the
Tergotometer. The reflectances were measured using a Carl
Zeiss Elrepho Reflectometer and the xeflectance increase on
washing toR) was taken as a measure of detergency.
In each case a wash liquor was prepared using the
ingredients stated below in the concentrations stated
below, in 40FH (Ca) or 20FH ~Ca) water. The wash liquor
was allowed to equilibrate for 15 minutes. Test cloth
pieces (four pieces per litre, each measuring 76.2 mm x
76.2 mm) were then added and a 20-minute wash at 80C, pH
10.0 and 55 rpm ayitation was carried out, followed by a
rinse in water of the same hardness as that of the water
used to prepare the wash liquor.
The ingredients and concentrations were as follows:
g/litre
Sodium C10-Cl3 linear alkylbenzene 0.195
sulphonate
C14-C15 alcohol ethoxylate (11 E0) 0.09
25 Hardened tallow soap 0.06
Alkaline silicate 0.15
~:~9~7~5~
- 21 - C.1303
g/litre
Sodium sulphate 2.00
Detergent additive according to the invention
(as specified in Examples) 1.00-5.00
I~ will be seen that the detergent additive according
to the invention was used at concentrations of from 1~00 to
5.00 g/litre, and the other components of the composition
were used at a constant total concentration of 2.495
g/litre, so that the total concentration ranged from 3.495
to 7.495 g/litre. Thus the percentage of the total
composition constituted by the detergent addi~ive o the
invention at Pach concentration of the latter was as
follows:
Concentra~ion
-% detergent additive
(of detergent (total) in composition
additive
1,00 3~495 28061
1.50 3.995 37.55
202.00 4.495 44.49
2.50 4.995 50.05
3.00 5.495 54.60
4.00 6.495 61.5g
5.00 7.495 66.71
A11 percentages given in the Examples are by we.ight
and are based on the anhydrous materials.
~t7~S~
- 22 - C.1303
EXAMPLE 1
The detergencies of compositions containing a t~rnary
builder system (detergent additive) according to the
invention were compared at two different concentrations and
water hardnesses, with those of control compositions
containing single or binary builder systems. The
aluminosilicate used was zeolite A, the organic precipitant
was disodium dodecylmalonate (C12AKM), and the organic
sequestrant was trisodium nitrilo~riacetate (NTA). The
results were as follows:
Re~lectance AR
In 20FH Ca In 40FH Ca
Concentration, g/l 1.0 1.5 2.5 4.0
Detergent additive
60% zeolite~25~ C12
AKM/15% NTA 22,6 26.0 25.4 28.5
85% zeolite 15%/~TA 18.5 24.5 20.1 26.7
75% zeolite/25% Cl2
20 AK~ 17.4 24.0 21.~ 25.8
100% zeolite 16.4 20.8 16.5 25.0
~:~9~S-~;
- 23 - C.1303
EX~MPLE 2
A similar procedure to that of Example 1 was carried
out using the organic sequestrant trisodium
carboxymethyloxysuccinate (CMOS~ instead of NTA~ The
results were as follows:
Reflectance ~
In 20~FH Ca In 40FH Ca
water wat~r
Concentration, g/l 1.0 2.0 4.0 5.0
~ r
Detergent additive
60% zeolite/25% C12
AKM/15% CMOS 18.5 26.9 26.5 27.0
85% zeolite/15% CMOS 16.8 23.5 24.1 24.7
75% zeolite/25
5 C12AKM 17.4 26.1 25.8 26.~
100% zeolite 16.4 25.1 25.0 25.8
EXAMPLE 3
A similar procedure to that of Example 1 was carried
out using the organic sequestrant poly ( ~-hydrcxy
acrylate) (P~AC) instead of ~TA. The tests at 2.5 g/l and
in 40 FH (Ca ) water were carried out using a different
test cloth, one with a predominantly fatty soil. The
results were as follows:
'7~
- 2~ - C.1303
Reflectance ~R
In 40FH Ca In 40DFH Ca
water water
(fatty test cloth) (clay-soiled
test clo~h )
Concentration, g/l 2.5 3.0
Detergent addit.ive
60% zeolite/25~ C12
~KM/15% PHAC 29.1 28.0
10 85~ zeolite/15% PHAC 28.1 25.6
75% zeolite/25% C12
AKM . 28.0 2~.1
100% zeolite 26.6 19.8
EXAMPLE 4
15 A similar procedure to ~hat o Example 1 was carried
out using as organic sequestrant a polyacryla~e (Versicol
E7) instead of NTA~ The test~ were carried out at 3.0 g/l
and in 40D~H (Ca 2~3 water, and the results were a~
follows:
20 Detergent additive Reflectance ~R
60% zeolite/25% C12
AKM/15~ polyacrylate 25.3
85% zeolite/15%
polyacrylate 22.0
5G
25 - C.1303
De~ergent additiveReflectance oR
75~ zeolite/25~ C12
AKM 24.1
100~ zeolite 19.8
EX~MPLE 5
A similar procedure to that of Example 1 was carried
out using as organic sequestrant tetrasodium
ethylenediamine-tetraacetate (EDTA) instead of ~TA, at 3.0
g/l and in 40~ FH (Ca2+) water. The results were as
follows:
Detergent additiveReflectance AR
60~ ~eolite/25~ C12
AKM/15% EDTA 26.3
85~ zeolite/15% EDTA 22.6
75% zeolite/25% C12
AKM 24.1
100% zeolite 19.8
EXAMPLE 6
A similar procedure to that of Example 1 was carried
out using as organic sequestrant tetrasodium oxydisuccinate
(ODS) instead of NTA, at 3.0 g/l and in 40 FH (Ca
water. The resul~s were as follows:
56
- 26 - C.1303
Detergent additiveReflectance
60% zeolite/25% C12
AKM/15% ODS 24.9
85% zeolite/15% ODS23.4
75~ zeolite/25~ C12
AKM 24.1
100~ zeolite 19.8
EXAMPLE 7
A similar procedure to that of Example 1 was carried
out using as organic sequestrant instead of NTA, an
oxidised starch as described in GB 1,330,121. ~he tests
were carried ou~ at 3.0 g/l in 40 FH (Ca2 7 water and
the results were as follows:
Detergent additiveReflectance ~R
15 60% 7.eolite/25% C12
AKM/15% oxidised starch 25.2
85% zeolite/15% oxidised
starch 21.1
75% zeolite/25% C12
25 AKM 24.1
100~ zeolite 19.8
7~5~
- 27 - ~.1303
EXAMPLE 8
A similar procedure to that of Example 1 was carried
out using as organic precipitant, instead of C12 AKM,
disodium hexadecenyl succ'nate (C16 AKS). The tests were
carried out in 40 FH (Ca ) water and the resul~s were
as follows:
Reflectance R
Concentration, g/l 2.0 2.5 4.0
Detergent additive
10 60% zeolite/25% C16
AKS/15% NTA 19.5 25.9 27O2
85% zeolite/15% NTA 15.9 21.2 25.0
75% zeolite/25~ C16
AKS 16.2 20.3 24.5
15 100% zeolite 14.6 17.3 23.0
EXAMPLE 9
A similar procedure to that of Example 1 was carried
out using, as organic precipitant, instead of C12 AKM,
disodium C~-sulphostearate (C18 SFAS). The tests were
carried out in 40 FH ~Ca +) water and the results were
as follows:
7 ~ 5~
- 28 - C.1303
Reflectar.ce ~R
Concentration, g/l 2.5 3.0 4.0
Detergent additive
60% zeolite/25% C18
5 SFAS/15% NTA 22.7 24.8 27.1
85% zeolite/15% NTA 21.2 23.5 25~0
75% zeolite/25% Cl~
SFAS 19.6 21.5 23.4
100% zeolite 17.2 19.5 23.0
10 EXAMPL~ 1~
A similar procedure to that of Example 1 was carried
out using, as organic precipitant, instead of C12AKM,
disodium he~adecyliminodiacetate (C16IMA). The tests
were carried out at a total builder concentration of 4 g/
litre in 40FH (Ca ) water. Tests were carried out
using both a clay-soiled test cloth and a test cloth soiled
with a mixture o~ organic and particulate soilsO The
results were as follows:
97~5~
- 29 - C.1303
Reflec~ance ( ~ R)
Detergent additive Clay-soiled Mixed-soil
test cloth test cloth
100% zeoli~e 14.0 31.5
90% zeolite/10% NTA 16.5 32.9
80% zeolite/20~ C16IMA 13.6 31.1
70% zeolite/20% C16IMA/
10~ NTA 17.3 33.5
70% zeolite/30~ C16IMA 15.0 not tested
10 60% ~.eolite/30% C16IMA/
10% NTA 18.0 no~ tested
80% zeolite/20% STP 17.4 34.1
