Detergent additive compositions

A detergent additive composition in the form of an extrudate comprising about 75% to about 95% of particulate infusible solids comprising storage-sensitive detergent-additive material and about 5% to about 25% of ethoxylated nonionic surfactant. The storage-sensitive detergent additive material is preferably an organic peroxy acid bleach precursor. When added to detergent compositions, the additive compositions have excellent storage stability and water-dispersibility characteristics.

TECHNICAL FIELD 
The Present invention relates to detergent additive compositions, methods 
for making thereof, and use thereof in granular detergent compositions. In 
particular, it relates to detergent additive compositions having improved 
storage stability within a full detergent composition. 
BACKGROUND OF THE INVENTION 
It is widely recognized that the function of a detergent additive material 
can be significantly impaired in a detergent composition by interaction 
between the additive material and other components of the composition. For 
example, enzymes, perfumes and bleach activators can be deleteriously 
effected by interaction with peroxy bleaches; cationic fabric conditioners 
can be deleteriously effected by interaction with anionic surfactants; and 
fluorescers can be deleteriously effected by interaction with peroxy 
bleaches or cationic surfactants. Moreover, the consumer acceptibility of 
a product can also be significantly reduced as the result of physical 
interactions between a detergent additive and other components of a 
detergent composition. For instance, a speckled detergent containing a 
water-soluble dye can lose its aesthetic appeal as a result of migration 
of the dye into the detergent base powder, an effect which can be 
significantly enhanced by the presence in the detergent composition of a 
nonionic surfactant component. Physical segregation problems in the case 
of abnormally-sized additive materials can also contribute to reduce 
aesthetic appeal and effectiveness of a detergent composition. 
Numerous attempts have been made, of course, to improve the 
storage-stability characteristics of detergent additive materials such as 
bleach activators and the like, but such attempts have in general 
encountered only limited success. The main approach to the problem has 
been to protect the additive material from its hostile environment by 
agglomerating, coating or encapsulating the material with a 
non-hygroscopic, preferably hydrophobic material. Conventionally, organic 
materials have found the greatest favour as coating agents because such 
materials readily form a substantially cohesive and continuous plastic 
matrix in which the additive material can be embedded. British Patent Nos. 
1,204,123, 1,441,416, and 1,395,006 are representative of this general 
approach. Unfortunately, however, protection of sensitive ingredients 
within an organic plastic matrix as practiced in the art can have a 
detrimental effect on the dispersibility or dissolution characteristics of 
the ingredient in water. This is of particular significance in the case of 
bleach activators because poor dispersibility can lead directly to 
problems of "pinpoint spotting" and fabric damage. 
Accordingly, the present invention provides detergent additive compositions 
having improved storage stability together with excellent release and 
dispersibility characteristics in wash water. In particular, it provides 
detergent additive compositions comprising bleach activators which are 
stable to storage in bleach-containing detergent compositions but which 
disperse readily in water to provide effective low temperature bleaching 
performance. The invention also provides detergent additive compositions 
having improved physical and processing characteristics. 
SUMMARY OF THE INVENTION 
According to the present invention, there is provided a detergent additive 
composition in the form of an extrudate comprising by weight thereof: 
(a) from about 75% to about 95% of particulate, infusible solids having a 
particle size distribution such that at least about 50% thereof passes a 
250 micrometer screen and comprising storage-sensitive detergent additive 
material, and 
(b) from about 5% to about 25% of ethoxylated nonionic surfactant melting 
in the range from about 20.degree. C. to about 60.degree. C., 
the composition being prepared by mixing the particulate infusible solids 
and ethoxylated nonionic surfactant in liquid form to form a substantially 
homogeneous friable mass, and mechanically extruding the friable mass by 
means of a screw with radial discharge through an apertured screen to form 
extrudate in the form of elongate particles having an average lateral 
dimension in the range from 0.5 millimeters to 2 millimeters, and an 
average longitudinal dimension in the range from about 1 mm to about 6 mm. 
With regard to the solids component, this has a particle size distribution 
such that at least about 50%, more preferably at least about 80% thereof 
passes a 250 micrometer screen. Highly preferred solid materials have a 
particle size distribution such that at least about 50%, especially at 
least about 80% thereof passes a 150 micrometer or even a 100 micrometer 
screen. The particulate solids are described herein as "infusible" by 
which is meant that in the anhydrous form, they melt at temperatures in 
excess of about 100.degree. C. and preferably in excess of about 
150.degree. C. The particulate solids component can consist essentially 
completely of a storage-sensitive detergent additive material, or it can 
consist of a mixture of storage-sensitive additive material with a 
particulate diluent or dispersant as described below. 
In preferred compositions, the extrudate comprises from about 80% to about 
92%, preferably from about 84% to about 90% particulate solids, and from 
about 8% to about 20%, more preferably from about 10% to about 16% of 
ethoxylated nonionic surfactant. A solids level of 84% to 90% and a 
surfactant level of 10% to 16% is particularly desirable for detergent 
additive materials or diluents having a melting point of about 150.degree. 
C. or higher. Detergent additive materials having lower melting point 
(about 100.degree. C. to about 145.degree. C.) may require higher nonionic 
surfactant levels for optimum processing and this tends to lead to reduced 
water-dispersibility. Accordingly, it is preferred to use low melting 
detergent additive materials in combination with at least 5%, more 
preferably at least 10% of high melting diluent. 
Control of the particle size of the extrudate itself is also of importance 
for securing optimum storage stability and release characteristics. 
Preferably, the extrudate has a particle size distribution such that at 
least 50%, more preferably at least 80% thereof passes a 2 millimeter 
screen onto a 500 micrometer screen. Highly preferred extrudates have a 
particle size distribution such that at least 50%, especially at least 80% 
thereof passes a 1.4 millimeter screen onto a 840 micrometer screen. It is 
a noteable feature of the present invention that extrudates having these 
optimum particle sizes can be produced directly by extrusion without 
requiring a post-extrusion sizing step such as cutting, seiving or 
spheronizing and with minimum or no need for recycling waste material. 
Some mechanical agitation of the particles after extrusion may be 
desirable however, for optimum size control. 
The ethoxylated nonionic surfactant component of the present composition 
has a melting point in the range from about 20.degree. C. to about 
60.degree. C., preferably from about 22.degree. C. to about 40.degree. C., 
more preferably from about 25.degree. C. to about 36.degree. C. Highly 
suitable nonionic surfactants of this type are ethoxylated primary or 
secondary C.sub.9 -C.sub.18 alcohols having an average degree of 
ethoxylation from about 3 to about 30, more preferably from about 5 to 
about 14. 
Turning to the storage-sensitive detergent additive material, this can be a 
unifunctional or multifunctional material selected from bleaching 
auxiliaries, photoactivators, fluorescers, dyes, perfumes, germicides, 
enzymes, suds controllers, fabric conditioners and the like. Highly 
preferred detergent additive materials, however, are organic peroxyacid 
bleach precursors, sometimes called herein bleach activators. Another 
highly preferred detergent additive material is a porphine-type 
photoactivator discussed in more detail below. 
As mentioned earlier, the detergent additive material can be in admixture 
with a particulate diluent or dispersant. 
Suitable dispersants herein include water-insoluble natural or synthetic 
silica or silicates, water-soluble inorganic salt materials and 
water-soluble organic poly-acids or salts thereof having a melting point 
(anhydrous) of at least 100.degree. C., preferably at least about 
150.degree. C. 
In general terms, the detergent additive compositions herein are made by 
(a) mixing the particulate infusible solids comprising storage-sensitive 
detergent additive material and liquid ethoxylated nonionic surfactant to 
form a substantially homogeneous, friable mass, and 
(b) mechanically extruding the friable mass. 
By "friable" is meant that the mixture of particulate solids and liquid 
ethoxylated nonionic surfactant prior to extrusion has a moist, somewhat 
crumbly texture. This is to be contrasted with the cohesive, plastic state 
which forms at higher ratios of nonionic surfactant:total solids. 
As specified herein, the friable mixture of solids and nonionic surfactant 
is mechanically extruded by means of a screw with radial discharge through 
an apertured screen to form extrudate in the form of elongate particles 
having an average lateral dimension in the range from about 500 
micrometers to about 2 millimeters, preferably from about 840 micrometers 
to about 1.4 millimeters, and an average longitudinal dimension in the 
range from about 1 millimeter to about 6 millimeters, preferably from 
about 1.5 millimeters to about 3 millimeters. Preferably, the particles 
have an average longitudinal:average lateral dimension ratio of from about 
1.1:1 to about 3:1, more preferably from 1.3:1 to about 1.8:1. In this 
context, "average" refers to a simple number-average. 
The present invention further provides granular detergent compositions 
containing the detergent additive compositions described herein. Preferred 
granular detergent compositions comprise: 
(a) from about 40% to about 99.9% of spray-dried powder comprising 
(i) from about 1% to about 20% of organic surfactant selected from anionic, 
zwitterionic and ampholytic surfactants and mixtures thereof, 
(ii) from about 5% to about 93.9% of detergency builder, and 
(iii) from about 5% to about 18% moisture, 
(b) from about 0.1% to about 20% of the detergent additive composition, and 
optionally 
(c) up to about 25% of ethoxylated nonionic surfactant in intimate mixture 
with the spray-dried base powder and detergent additive composition, and 
(d) up to about 35% by weight of peroxysalt bleaching agent 
The individual components of the instant compositions will now be discussed 
in detail.

A preferred class of detergent additive material is an organic peroxyacid 
bleach precursor. Examples of the various classes of peroxyacid bleach 
precursors include: 
(a) Esters 
Esters suitable as peroxy compound precursors in the present invention 
include esters of monohydric substituted and unsubstituted phenols, 
substituted aliphatic alcohols in which the substituent group is electron 
withdrawing in character, mono- and disaccharides, N-substituted 
derivatives of hydroxylamine and esters of imidic acids. The phenol esters 
of both aromatic and aliphatic mono- and dicarboxylic acids can be 
employed. The aliphatic esters can have 1 to 20 carbon atoms in the acyl 
group, examples being phenyl laurate, phenyl myristate, phenyl palmitate 
and phenyl stearate. Of these, 1-acetoxy benzoic acid and methyl o-acetoxy 
benzoate are especially preferred. Diphenyl succinate, diphenyl azeleate 
and diphenyl adipate are examples of phenyl aliphatic dicarboxylic acid 
esters. Aromatic esters include phenyl benzoate, diphenyl phthalate and 
diphenyl isophthalate. 
A specific example of an ester of a substituted aliphatic alcohol is 
trichloroethyl acetate. Examples of saccharide esters include glucose 
penta-acetate and sucrose octa-acetate. An exemplary ester of 
hydroxylamine is acetyl aceto hydroxamic acid. 
These and other esters suitable for use as peroxy compound precursors in 
the present invention are fully described in British patent specification 
Nos. 836988 and 1147871. 
A further group of esters are the acyl phenol sulphonates and acyl alkyl 
phenol sulphonates. An example of the former is sodium acetyl phenol 
sulphonate (alternatively described as sodium p-acetoxy benzene 
sulphonate). Examples of acyl alkyl phenol sulphonates include sodium 
2-acetoxy 5-dodecyl benzene sulphonate, sodium 2-acetoxy 5-hexyl benzene 
sulphonate and sodium 2-acetoxy capryl benzene sulphonate. The preparation 
and use of these and analogous compounds is given in British patent 
specification Nos. 963135 and 1147871. 
Esters of imidic acids have the general formula: 
##STR1## 
wherein X is substituted or unsubstituted C.sub.1 --C.sub.20 alkyl or aryl 
and Y can be the same as X and can also be --NH.sub.2. An example of this 
class of compounds is ethyl benzimidate wherein Y is C.sub.6 H.sub.5 and X 
is ethyl. 
Other specific esters include p-acetoxy acetophenone and 
2,2-di-(4-hydroxyphenyl)propane diacetate. This last material is the 
diacetate derivative of 2,2-di(4-hydroxyphenyl)propane more commonly known 
as Bisphenol A which is an intermediate in the manufacture of 
polycarbonate resins. Bisphenol A diacetate and methods for its 
manufacture are disclosed in German DAS No. 1260479 published February 
8th, 1968 in the name of VBB Chemiefaserwork Schwarza "Wilhelm Piesh". 
(b) Imides 
Imides suitable as organic peroxy compound precursors in the present 
invention are compounds of formula: 
##STR2## 
in which R.sub.1 and R.sub.2, which can be the same or different are 
independently chosen from a C.sub.1 -C.sub.4 alkyl group or an aryl group 
and X is an alkyl, aryl or acyl radical (either carboxylic or sulphonic). 
Typical compounds are those in which R.sub.1 is a methyl, ethyl, propyl or 
phenyl group but the preferred compounds are those in which R.sub.2 is 
also methyl, examples of such compounds being N,N-diacetylaniline, 
N,N-diacetyl-p-chloroaniline and N,N-diacetyl-p-toluidine. Either one of 
R.sub.1 and R.sub.2 together with X may form a heterocyclic ring 
containing the nitrogen atom. An illustrative class having this type of 
structure is the N-acyl lactams, in which the nitrogen atom is attached to 
two acyl groups, one of which is also attached to the nitrogen in a second 
position through a hydrocarbyl linkage. A particularly preferred example 
of this class is N-acetyl caprolactam. The linkage of the acyl group to 
form a heterocyclic ring may itself include a heteroatom, for example 
oxygen, and N-acyl saccharides are a class of precursors of this type. 
Examples of cyclic imides in which the reactive centre is a sulphonic 
radical are N-benzene sulphonyl phthalimide, N-methanesulphonyl 
succinimide and N-benzene sulphonyl succinimide. These and other 
N-sulphonyl imides useful herein are described in British patent 
specification No. 1242287. 
Attachment of the nitrogen atoms to three acyl groups occurs in the 
N-acylated dicarboxylic acid imides such as the N-acyl phthalimides, 
N-acyl succinimides, N-acyl adipimides and N-acyl glutarimides. Imides of 
the above-mentioned types are described in British patent specification 
No. 855735 the disclosures of which are hereby incorporated specifically 
herein by reference. 
Two further preferred groups of materials in this class are those in which 
X in the above formula is either a second diacylated nitrogen atom i.e. 
substituted hydrazines, or a difunctional hydrocarbyl groups such as a 
C.sub.1 -C.sub.6 alkylene group further substituted with a diacylated 
nitrogen atom i.e. tetra acylated alkylene diamines. 
Particularly preferred compounds are N,N,N',N'-tetra acetylated compounds 
of formula: 
##STR3## 
in which x can be 0 or an integer between 1 and 6, examples are tetra 
acetyl methylene diamine (TAMD) where x=1, tetra acetyl ethylene diamine 
(TAED) where x=2, and tetra acetyl hexamethylene diamine (TAHD) where x=6. 
Where X=0 the compound is tetra acetyl hydrazine (TAH). These and 
analogous compounds are described in British patent specification Nos. 
907,356, 907,357,and 907,358. 
Acylated glycourils form a further group of compounds falling within the 
general class of imide peroxy compound precursors. These materials have 
the general formula: 
##STR4## 
in which at least two of the R groups represent acyl radicals having 2 to 
8 carbon atoms in their structure. The preferred compound is tetra acetyl 
glycouril in which the R groups are all CH.sub.3 CO-- radicals. The 
acylated glycourils are described in British patent specification Nos. 
1246338, 1246339, and 1247429. 
Other imide-type compounds suitable for use as peroxy compound precursors 
in the present invention are the N-(halobenzoyl) imides disclosed in 
British patent specification No. 1247857, of which N-m-chloro benzoyl 
succinimide is a preferred example, and poly imides containing an 
N-bonded-COOR group, e.g. N-methoxy carbonyl phthalimide, disclosed in 
British patent specification No. 1244200. 
N-acyl and N,N'-diacyl derivatives of urea are also useful peroxy compound 
precursors for the purposes of the present invention, in particular 
N-acetyl dimethyl urea, N,N'-diacetyl ethylene urea and N,N'-diacetyl 
dimethyl urea. Compounds of this type are disclosed in Netherlands Patent 
Application No. 6504416 published 10th October, 1966. Other urea 
derivatives having inorganic persalt activating properties are the mono- 
or di-N-acylated azolinones disclosed in British patent specification No. 
1379530. 
Acylated hydantoin derivatives also fall within this general class of 
organic peroxy compound precursors. The hydantoins may be substituted e.g. 
with lower alkyl groups and one or both nitrogen atoms may be acylated. 
Examples of compounds of this type are N-acyl hydantoin, N,N-diacetyl, 
5,5-dimethyl hydantoin, 1-phenyl, 3-acetyl hydantoin and 1-cyclohexyl, 
3-acetyl hydantoin. These and similar compounds are described in British 
patent specification Nos. 965672 and 1112191. 
Another class of nitrogen compounds of the imide type are the N,N-diacetyl 
methylene diformamides of which N,N-diacetyl methylamine diformamide is 
the preferred member. This material and analogous compounds are disclosed 
in British patent specification No. 1106666. 
(c) Imidazoles 
N-acyl imidazoles and similar five-membered ring systems form a further 
series of compounds useful as inorganic peroxy compound precursors. 
Specific examples are N-acetyl benzimidazole, N-benzoyl imidazole and its 
chloro- and methyl-analogues. Compounds of this type are disclosed in 
British patent specification Nos. 1234762, 1311765 and 1395760. 
(d) Oximes 
Oximes and particularly acylated oximes are also a useful class of organic 
peroxy compound precursors for the purpose of this invention. Oximes are 
derivatives of hydroxylamine from which they can be prepared by reaction 
with aldehydes and ketones to give aldoximes and ketoximes respectively. 
The acyl groups may be C.sub.1 -C.sub.12 aliphatic or aromatic in 
character, preferred acyl groups being acetyl, propionyl, lauroyl, 
myristyl and benzoyl. Compounds containing more than one carbonyl group 
can react with more than one equivalent of hydroxylamine and the commonest 
class of dioximes are those derived from 1,2-diketones and ketonic 
aldehydes, such as dimethyl glyoxime 
##STR5## 
The acylated derivatives of this compound are of particular value as 
organic peroxy compound precursors, examples being diacetyl dimethyl 
glyoxime, dibenzoyl dimethyl glyoxime and phthaloyl dimethyl glyoxime. 
(e) Carbonates 
Substituted and unsubstituted aliphatic, aromatic and alicyclic esters of 
carbonic and pyrocarbonic acid have also been proposed as organic peroxy 
compound precursors. Typical examples of such esters are p-carboxy phenyl 
ethyl carbonate, sodium-p-sulphophenyl ethyl carbonate, 
sodium-p-sulphophenyl n-propyl carbonate and diethyl pyrocarbonate. The 
use of such esters as inorganic persalt activators in detergent 
compositions is set forth in British patent specification No. 970950. 
In addition to the foregoing classes, numerous other materials can be 
utilised as organic peroxy compound percursors including triacyl 
guanidines of formula: 
##STR6## 
wherein R is alkyl, preferably acetyl or phenyl, prepared by the acylation 
of guanidine salt. Other classes of compounds include acyl sulphonamides, 
e.g. N-phenyl N-acetyl benzene sulphonamide as disclosed in British patent 
specification No. 1003310 and triazine derivatives such as those disclosed 
in British patent specification Nos. 1104891 and 1410555. Particularly 
preferred examples of triazine derivatives are the di- and triacetyl 
derivatives of 2,4,6,-trihydroxy-1,3,5-triazine, 
2-chloro-4,6-dimethoxy-S-triazine and 2,4-dichloro 6-methoxy-S-triazine. 
Piperazine derivatives such as 1,4-diacylated 2,5-diketo piperazine as 
described in British patent specification Nos. 1339256 and 1339257 are 
also useful as are water-soluble alkyl and aryl chloroformates such as 
methyl, ethyl and phenyl chloroformate disclosed in British patent 
specification No. 1242106. 
Of the foregoing classes of activators, the preferred classes are those 
that produce a peroxycarboxylic acid on reaction with an inorganic 
persalt. In particular the preferred classes are the imides, oximes and 
esters especially the phenol esters and imides. 
Specific preferred materials are solid and are incorporated in the instant 
compositions in finely divided form, i.e., with an average particle size 
of less than about 500.mu., more preferably less than about 250.mu., 
especially less than about 150.mu.. Highly preferred materials include 
methyl o-acetoxy benzoate, sodium-p-acetoxy benzene sulphonate, Bisphenol 
A diacetate, tetra acetyl ethylene diamine, tetra acetyl hexamethylene 
diamine and tetra acetyl methylene diamine. 
The invention is especially suited to the stabilization of multifunctional 
photoactivator/dyes belonging to the porphine class of general formula 
##STR7## 
wherein each X is (.dbd.N--) or (.dbd.CY--), and the total number of 
(.dbd.N--) groups is 0, 1, 2, 3 or 4; wherein each Y, independently, is 
hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or 
heteroaryl; wherein each R, independently, is hydrogen or pyrrole 
substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl, or 
wherein adjacent pairs of R's are joined together with orthoarylene groups 
to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 
2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), 
Cd(II), Mg(II), Ca(II), Al(III), Sc(III), or Sn(IV); wherein B is an 
anionic, nonionic or cationic solubilizing group substituted into Y or R; 
wherein M is a counterion to the solubilizing groups; and wherein s is the 
number of solubilizing groups; wherein, when B is cationic, M is an anion 
and s is from 1 to 8; when B is nonionic, B is polyethoxylate, M is zero, 
s is from 1 to 8, and the number of condensed ethylene oxide molecules per 
prophine molecule is from 8 to 50; when B is anionic and proximate, M is 
cationic and s is from 3 to 8; when B is anionic and remote, M is cationic 
and s is from 2 to 8; and when B is sulphonate the number of sulphonate 
groups is no greater than the number of aromatic and heterocyclic 
substituent groups. 
As used herein, a solubilizing group attached to a carbon atom displaced 
more than 5 carbon atoms away from the porphine core is referred to as 
"remote"; otherwise it is "proximate." 
Highly preferred materials of this general type are the zinc phthalocyanine 
tri- and tetrasulphonates and mixtures thereof. Materials of this general 
class were originally disclosed for use in detergent compositions in 
British Pat. Nos. 1,372,035 and 1,408,144 and are discussed in detail in 
European Patent Application 3861. The photo-activators can provide fabric 
bleaching effects in built detergent compositions in the presence of 
visible light and atmospheric oxygen and can also synergistically enhance 
the bleaching effect of conventional bleaching agents such as sodium 
perborate. The porphine bleach is preferably used in an amount such that 
the level of porphine in final detergent composition is in the range from 
about 0.001% to about 0.5%, more preferably from about 0.002% to about 
0.02%, especially from about 0.003% to about 0.01% by weight. 
The porphine is preferably incorporated into the detergent additive 
composition as an intimate mixture with a hydratable water-soluble 
crystalline salt, especially tetrasodium tripolyphosphate hydrated to an 
extent of about 55% to about 65% of its maximum hydration capacity. The 
additive composition will preferably comprise from about 0.05% to 2%, more 
preferably from about 0.1% to 0.5% by weight of porphine. 
The invention can also be applied to give improved additive compositions 
based on enzymes, fluorescers, perfumes, suds suppressors, fabric 
conditioners, soil suspending agents, peroxyacid bleaches and the like. 
Preferred enzymatic materials include the commercially available amylases 
and neutral and alkaline proteases conventionally incorporated into 
detergent compositions. Suitable enzymes are discussed in U.S. Pat. Nos. 
3,519,570 and 3,533,139. Examples of suitable enzymes include the 
materials sold under the Registered Trade Marks Maxatase and Alcalase. 
Anionic fluorescent brightening agents are well-known materials, examples 
of which are disodium 
4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'disu 
lphonate, disodium 
4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2'-disulpho 
nate, disodium 
4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, 
disodium 
4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino 
)stilbene-2,2'-disulphonate, disodium 
4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2'-disulphonate, 
disodium 4,4'-bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-y 
lamino)stilbene-2,2'disulphonate and sodium 
2(stilbyl-4"-(naptho-1',2':4,5)-1,2,3-triazole-2"-sulphonate. 
Other fluorescers to which the invention can be applied include the 
1,3-diaryl pyrazolines and 7-alkylaminocoumarins. 
With regard to the ethoxylated nonionic surfactant component, this can be 
broadly defined as compounds produced by the condensation of ethylene 
oxide groups (hydrophilic in nature) with an organic hydrophobic compound, 
which may be aliphatic or alkyl aromatic in nature. The length of the 
polyoxyethylene group which is condensed with any particular hydrophobic 
group can be readily adjusted to yield a water-soluble compound having the 
desired degree of balance between hydrophilic and hydrophobic elements. 
Examples of suitable nonionic surfactants include: 
1. The polyethylene oxide condensates of alkyl phenol, e.g. the 
condensation products of alkyl phenols having an alkyl group containing 
from 6 to 12 carbon atoms in either a straight chain or branched chain 
configuration, with ethylene oxide, the said ethylene oxide being present 
in amounts equal to 3 to 30, preferably 5 to 14 moles of ethylene oxide 
per mole of alkyl phenol. The alkyl substituent in such compounds may be 
derived, for example, from polymerised propylene, di-isobutylene, octene 
and nonene. Other examples include dodecylphenol condensed with 9 moles of 
ethylene oxide per mole of phenol; dinonylphenol condensed with 11 moles 
of ethylene oxide per mole of phenol; nonylphenol and di-isooctylphenol 
condensed with 13 moles of ethylene oxide. 
2. The condensation product of primary or secondary aliphatic alcohols 
having from 8 to 24 carbon atoms, in either straight chain or branched 
chain configuration, with from 3 to about 30 moles, preferably 5 to about 
14 moles of ethylene oxide per mole of alcohol. Preferably, the aliphatic 
alcohol comprises between 9 and 18 carbon atoms and is ethoxylated with 
between 3 and 30, desirably between 5 and 14 moles of ethylene oxide per 
mole of aliphatic alcohol. The preferred surfactants are prepared from 
primary alcohols which are either linear (such as those derived from 
natural fats or, prepared by the Ziegler process from ethylene, e.g. 
myristyl, cetyl, stearyl alcohols), or partly branched such as the 
Dobanols and Neodols which have about 25% 2-methyl branching (Dobanol and 
Neodol being Trade Names of Shell or Synperonics, which are understood to 
have about 50% 2-methyl branching (Synperonic is a Trade Name of I.C.I.) 
or the primary alcohols having more than 50% branched chain structure sold 
under the Trade Name Lial by Liquichimica. Specific examples of nonionic 
surfactants falling within the scope of the invention include Dobanol 
45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-3, Dobanol 91-6, Dobanol 
91-8, Synperonic 6, Synperonic 14, the condensation products of coconut 
alcohol with an average of between 5 and 12 moles of ethylene oxide per 
mole of alcohol, the coconut alkyl portion having from 10 to 14 carbon 
atoms, and the condensation products of tallow alcohol with an average of 
between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow 
portion comprising essentially between 16 and 22 carbon atoms. Secondary 
linear alkyl ethoxylates are also suitable in the present compositions, 
especially those ethoxylates of the Tergitol series having from about 9 to 
15 carbon atoms in the alkyl group and up to about 11, especially from 
about 3 to 9, ethoxy residues per molecule. 
3. The compounds formed by condensing ethylene oxide with a hydrophobic 
base formed by the condensation of propylene oxide with propylene glycol. 
The molecular weight of the hydrophobic portion generally falls in the 
range of about 1500 to 1800. Such synthetic nonionic detergents are 
available on the market under the Trade Name of "Pluronic" supplied by 
Wyandotte Chemicals Corporation. 
Various optional ingredients can be incorporated into the additive and 
detergent compositions of the present invention in order to increase 
efficacy, particularly in the area of detergency and stain removal. The 
total amount of such optional ingredients lies in the range 1%-70%, 
preferably 1%-30% of the additive composition when incorporated directly 
therein, or in the range 40%-99.9%, preferably 90%-99.5% when incorporated 
in the non-additive portion of a detergent composition. 
The detergent additive compositions of the invention can include a 
particulate dispersant, either in intimate mixture with the detergent 
additive material, or more preferably as a surface-coating agent on the 
extrudate at a level of from about 1% to 3%, especially from about 1.1% to 
2.5% by weight of the composition. The dispersant is preferably a 
water-insoluble silica or silicate, a water-soluble inorganic salt, or an 
organic polyacid or salt thereof. Water-insoluble silicates can be 
selected from aluminosilicates of the clay or zeolite classes or can be a 
magnesium silicate type of material. Aluminosilicates of the clay variety 
are preferably sheet-like natural clays, especially those selected from 
the smectite-type and kaolinite-type groups. Highly suitable smectite-type 
clays include alkali and alkaline-earth metal montmorillonites, saponites 
and hectorites; highly suitable kaolinite-type materials include kaolinite 
itself, calcined kaolin and metakaolin. 
Other suitable water-insoluble silicates include aluminosilicates of the 
zeolite type, particularly those of the general formula Na.sub.z 
(AlO.sub.2).sub.z (SiO.sub.2).sub.y xH.sub.2 O wherein z and y are 
integers of at least about 6, the molar ratio of z to y is in the range 
from about 1.0 to about 0.5 and x is a number such that the moisture 
content of the aluminosilicate is from about 10% to about 28% by weight 
thereof. Particularly preferred materials of the zeolite class are those 
prepared from clay themselves, especially A-type zeolites prepared by 
alkali treatment of calcined kaolin. 
Another suitable water-insoluble silicate is a magnesium silicate of 
formula n MgO:SiO.sub.2 wherein n is in the range from about 0.25 to about 
4.0. 
Suitable water-soluble inorganic salts include magnesium sulphate or 
chloride, sodium bicarbonate as well as the calcium or magnesium 
complexing agents useful as detergency builders. These are discussed in 
detail below. 
Suitable organic acids include lactic acid, glycollic acid and ether 
derivatives thereof as disclosed in Belgium Patents Nos. 821,368, 821,369 
and 821,370; succinic acid, malonic acid, (ethylenedioxy) diacetic acid, 
maleic acid, diglyollic acid, tartaric acid, tartronic acid and fumaric 
acid; citric acid, aconitic acid, citraconic acid, carboxymethyloxy 
succinic acid, lactoxysuccinic acid, and 2-oxa-1,1,3-propane tricarboxylic 
acid; oxydisuccinic acid, 1,1,2,2-ethane tetracarboxylic acid, 
1,1,3,3-propane tetracarboxylic acid, and 1,1,2,3-propane tetracarboxylic 
acid; cyclopentane-cis, cis, cis-tetracarboxylic acid, cyclopentadienide 
pentacarboxylic acid, 2,3,4,5-tetrahydrofuran-cis, cis, 
cis-tetracarboxylic acid, 2,5-tetrahydrofuran-cis-cis dicarboxylic acid, 
1,2,3,4,5,6-hexane-hexacarboxylic acid, mellitic acid, pyromellitic acid 
and the phthalicacid derivatives disclosed in British Patent 1,425,343; 
ethylene diamine tetra(methylenephosphonic acid), diethylene triamine 
penta(methylenephosphonic acid) and the acid salts of the above organic 
acids. Of the above, the preferred organic acids are citric, glycollic and 
lactic acids and the two phosphonic acids. 
As well as being a dispersant, the above acidic materials also have a pH 
regulating function, of course, and this can be particular valuable in the 
case of extrudate containing bleach activators. 
A highly preferred ingredient of the detergent compositions of the 
invention is a surfactant or mixture of surfactants, especially an anionic 
surfactant or a mixture thereof with nonionic, cationic, zwitterionic and 
ampholytic surfactant. The surfactant is preferably present in the 
non-additive portion of the composition at a level of from about 1% to 
about 20%, more preferably from about 3% to about 16% of the total 
composition. A typical listing of the classes and species of these 
surfactants is given in U.S. Pat. No. 3,663,961 issued to Norris on May 
23, 1972 and incorporated herein by reference. 
Suitable synthetic anionic surfactants are water-soluble salts of alkyl 
benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, 
paraffin sulfonates, alphaolefin sulfonates, alpha-sulfo-carboxylates and 
their esters, sulfonates, alpha-sulfo-carboxylates and their esters, alkyl 
glyceryl ether sulfonates, fatty acid monoglyceride sulfates and 
sulfonates, alkyl phenol polyethoxy ether sulfates, 
2-acyloxy-alkane-1-sulfonate, and beta-alkyloxy alkane sulfonate. 
A particularly suitable class of anionic surfactants includes water-soluble 
salts, particularly the alkali metal, ammonium and alkanolammonium salts 
or organic sulfuric reaction products having in their molecular structure 
an alkyl or alkaryl group containing from about 8 to about 22, especially 
from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric 
acid ester group. (Included in the term "alkyl" is the alkyl portion of 
acyl groups). Examples of this group of synthetic detergents which form 
part of the detergent compositions of the present invention are the sodium 
and potassium alkyl sulfates, especially those obtained by sulfating the 
higher alcohols (C.sub.8-18) carbon atoms produced by reducing the 
glycerides of tallow or coconut oil and sodium and potassium alkyl benzene 
sulfonates, in which the alkyl group contains from about 9 to about 15, 
especially about 11 to about 13, carbon atoms, in straight chain or 
branched chain configuration, e.g. those of the type described in U.S. 
Pat. No. 2,220,099 and 2,477,383 and those prepared from alkylbenzenes 
obtained by alkylation with straight chain chloroparaffins (using 
aluminium trichloride catalysis) or straight chain olefins (using hydrogen 
fluoride catalysis). Especially valuable are linear straight chain alkyl 
benzene sulfonates in which the average of the alkyl group is about 11.8 
carbon atoms, abbreviated as C.sub.11.8 LAS. 
Other anionic detergent compounds herein include the sodium C.sub.10-18 
alkyl glyceryl ether sulfonates, especially those ethers of higher 
alcohols derived from tallow and coconut oil; sodium coconut oil fatty 
acid monoglyceride sulfonates and sulfates; and sodium or potassium salts 
of alkyl phenol ethylene oxide ether sulfate containing about 1 to about 
10 units of ethylene oxide per molecule and wherein the alkyl groups 
contain about 8 to about 12 carbon atoms. 
Other useful anionic detergent compounds herein include the water-soluble 
salts or esters of .alpha.-sulfonated fatty acids containing from about 6 
to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon 
atoms in the ester group; water-soluble salts of 
2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms 
in the acyl group and from about 9 to about 23 carbon atoms in the alkane 
moiety; alkyl ether sulfates containing from about 10 to 18, especially 
about 12 to 16, carbon atoms in the alkyl group and from about 1 to 12, 
especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; 
water-soluble salts of olefin sulfonates containing from about 12 to 24, 
preferably about 14 to 16, carbon atoms, especially those made by reaction 
with sulfur trioxide followed by neutralization under conditions such that 
any sultones present are hydrolysed to the corresponding hydroxy alkane 
sulfonates; water-soluble salts of paraffin sulfonates containing from 
about 8 to 24, especially 14 to 18 carbon atoms, and .beta.-alkyloxy 
alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl 
group and from about 8 to 20 carbon atoms in the alkane moiety. 
The alkane chains of the foregoing non-soap anionic surfactants can be 
derived from natural sources such as coconut oil or tallow, or can be made 
synthetically as for example using the Ziegler or Oxo processes. Water 
solubility can be achieved by using alkali metal, ammonium or 
alkanolammonium cations; sodium is preferred. Magnesium and calcium are 
preferred cations under circumstances described by Belgian patent No. 
843,636 invented by Jones et al, issued Dec. 30, 1976. Mixtures of anionic 
surfactants are contemplated by this invention; a preferred mixture 
contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl 
group or paraffin sulfonate having 14 to 18 carbon atoms and either an 
alkyl sulfate having 8 to 18, preferably 12 to 18, carbon atoms in the 
alkyl group, or an alkyl polyethoxy alcohol sulfate having 10 to 16 carbon 
atoms in the alkyl group and an average degree of ethoxylation of 1 to 6. 
Nonionic surfactants suitable for use in the detergent component of the 
present compositions include the alkoxylated surfactants previously 
described. Again, highly suitable nonionic surfactants of this type are 
ethoxylated primary or secondary C.sub.9-15 alcohols having an average 
degree of ethoxylation from about 3 to about 9. Desirably, the total level 
of nonionic surfactant in the instant compositions is such as to provide a 
weight ratio of nonionic surfactant:anionic surfactant in the range from 
about 1:4 to about 4:1. 
The addition of a water-soluble cationic surfactant to the present 
compositions has been found to be useful for improving the greasy stain 
removal performance. Suitable cationic surfactants are those having a 
critical micelle concentration for the pure material of at least 200 ppm 
and preferably at least 500 ppm specified at 30.degree. C. and in 
distilled water. Literature values are taken where possible, especially 
surfact tension or conductimetric values--see Critical Micelle 
Concentrations of Aqueous Surfactant System, P. Mukerjee and K. J. Mysels, 
NSRDS--NBS 37 (1971). 
A highly preferred group of cationic surfactants of this type have the 
general formula: 
EQU R.sup.1.sub.m R.sup.2.sub.4-m N Z 
wherein R.sup.1 is selected from C.sub.8-20 alkyl, alkenyl and alkaryl 
groups; R.sup.2 is selected from C.sub.1-4 alkyl and benzyl groups; Z is 
an anion in number to give electrical neutrality; and m is 1, 2 or 3; 
provided that when m is 2 R.sup.1 has less than 15 carbon atoms and when m 
is 3, R.sup.1 has less than 9 carbon atoms. 
Where m is equal to 1, it is preferred that R.sup.2 is a methyl group. 
Preferred compositions of this mono-long chain type include those in which 
R.sup.1 is C.sub.10 to C.sub.16 alkyl group. Particularly preferred 
compositions of this class include C.sub.12 alkyl trimethylammonium halide 
and C.sub.14 alkyl trimethylammonium halide. 
Where m is equal to 2, the R.sup.1 chians should have less than 14 carbon 
atoms. Particularly preferred cationic materials of this calss include 
di-C.sub.8 alkyldimethylammonium halide and di-C.sub.10 
alkyldimethylammonium halide materials. 
Where m is equal to 3, the R.sup.1 chains should be less than 9 carbon 
atoms in length. An example is trioctyl methyl ammonium chloride. 
Another highly preferred group of cationic compounds have the general 
formula: 
R.sup.1 R.sup.2.sub.m R.sup.3.sub.3-m N.sup.+ A wherein R.sup.1 represents 
a C.sub.6-24 alkyl or alkenyl group or a C.sub.6-12 alkaryl group, each 
R.sup.2 independently represents a (C.sub.n H.sub.2n O).sub.x H group 
where n is 2, 3 or 4 and x is from 1 to 14, the sum total of C.sub.n 
H.sub.2n O groups in R.sup.2.sub.m being from 1 to 14, each R.sup.3 
independently represents a C.sub.1-12 alkyl or alkenyl group, an aryl 
group or a C.sub.1-6 alkaryl group, m is 1, 2 or 3, and A is an anion. 
In this group of compounds, R.sup.1 is selected from C.sub.6-24 alkyl or 
alkenyl groups and C.sub.6-12 alkaryl groups; R.sup.3 is selected from 
C.sub.1-12 alkyl or alkenyl groups and C.sub.1-16 alkaryl groups. When m 
is 2, however, it is preferred that the sum total of carbon atoms in 
R.sup.1 and R.sup.3.sub.3-m is no more than about 20 with R.sup.1 
representing a C.sub.8-18 alkyl or alkenyl group More preferably the sum 
total of carbon atoms in R.sup.1 and R.sup.1 .sub.3-m is no more than 
about 17 with R.sup.1 representing a C.sub.10-16 alkyl or alkenyl group. 
When m is 1, it is again preferred that the sum total of carbon atoms in 
R.sup.1 and R.sup.3.sub.3-m is no more that about 17 with R.sup.1 
representing a C.sub.10-16 alkyl or alkaryl group. 
Additionally in this group of compounds, the total number of alkoxy 
radicals in polyalkoxy groups (R.sup.2.sub.m) directly attached to the 
cationic charge centre should be no more than 14. Preferably, the total 
number of such alkoxy groups is from 1 to 7 with each polyalkoxy group 
(R.sup.2) independently containing from 1 to 7 alkoxy groups; more 
preferably, the total number of such alkoxy groups is from 1 to 5 with 
each polyalkoxy group (R.sup.2) independently containing from 1 to 3 
alkoxy groups. Especially preferred are cationic surfactants having the 
formula: 
EQU R.sup.1 (C.sub.n H.sub.2n OH).sub.m (CH.sub.3).sub.3m N.sup.+ A 
wherein R.sup.1 is as defined immediately above, n is 2 or 3 and m is 1, 2 
or 3. 
Particularly preferred cationic surfactants of the class having m equal to 
1 are dodecyl dimethyl hydroxyethyl ammonium salts, dodecyl dimethyl 
hydroxypropyl ammonium salts, myristyl dimethyl hydroxyethyl ammonium 
salts and dodecyl dimethyl dioxyethylenyl ammonium salts. When m is equal 
to 2, particularly preferred cationic surfactants are dodecyl 
dihydroxyethyl methyl ammonium salts, dodecyl dihydroxypropyl methyl 
ammonium salts, dodecyl dihydroxyethyl ethyl ammonium salts, myristyl 
dihydroxyethyl methyl ammonium salts, cetyl dihydroxyethyl methyl ammonium 
salts, stearyl dihydroxyethyl methyl ammonium salts, oleyldihydroxyethyl 
methyl ammonium salts, and dodecyl hydroxy ethyl hydroxypropyl methyl 
ammonium salts. When m is 3, particularly preferred cationic surfactants 
are dodecyl trihydroxyethyl ammonium salts, myristyl trihydroxyethyl 
ammonium salts, cetyl trihydroxyethyl ammonium salts, stearyl 
trihydroxyethyl ammonium salts, oleyl trihydroxy ethyl ammonium salts, 
dodecyl dihydroxyethyl hydroxypropyl ammonium salts and dodecyl 
trihydroxypropyl ammonium salts. 
In the above, the usual inorganic salt counterions can be employed, for 
example, chlorides, bromides and borates. Salt counterions can also be 
selected from organic acid anions, however, such as the anions derived 
from organic sulphonic acids and from sulphuric acid esters. A preferred 
example of an organic acid anion is a C.sub.6-12 alkaryl sulphonate. 
Of all the above cationic surfactants, especially preferred are dodecyl 
dimethyl hydroxyethyl ammonium salts and dodecyl dihydroxyethyl methyl 
ammonium salts. 
Additional preferred cationic surfactants are fully disclosed in British 
patent application No. 79-25946 and incorporated herein by reference. 
The above water-soluble cationic surfactants can be employed in 
nonionic/cationic surfactant mixtures in a weight ratio of from about 10:6 
to about 20:1, more preferably from about 10:2 to about 10:6, and 
particularly from about 10:3 to 10:5. 
Other optional ingredients which can be added to the present composition 
either as part of the additives or as a separate particulate admixture 
include surfactants other than the nonionic and cationic surfactants 
specified hereinbefore, suds modifiers, chelating agents, 
anti-redeposition and soil suspending agents, optical brighteners, 
bactericides, anti-tarnish agents, enzymatic materials, fabric softeners, 
antistatic agents, perfumes, antioxidants and bleach catalysts. 
U.S. Pat. No. 3,933,672 issued Jan. 20, 1976, to Bartollota et al., 
incorporated herein by reference, discloses a silicone suds controlling 
agent. The silicone material can be represented by alkylated polysiloxane 
materials such as silica aerogels and xerogels and hydrophobic silicas of 
various types. The silicone material can be described as siloxane having 
the formula: 
##STR8## 
wherein x is from about 20 to about 2,000 and R and R' are each alkyl or 
aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. The 
polydimethylsiloxanes (R and R' are methyl) having a molecular weight 
within the range of from about 200 to about 2,000,000, and higher, are all 
useful as suds controlling agents. Additional suitable silicone materials 
wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl or 
aryl hydrocarbyl groups exhibit useful suds controlling properties. 
Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, 
methyl-, ethyl-, phenylmethylpolysiloxanes and the like. Additional useful 
silicone suds controlling agents can be represented by a mixture of an 
alkylated siloxane, as referred to hereinbefore, and solid silica. Such 
mixtures are prepared by affixing the silicone to the surface of the solid 
silica. A preferred silicone suds controlling agent is represented by a 
hydrophobic silanated (most preferably trimethylsilanated) silica having a 
particle size in the range from about 10 millimicrons to 20 millimicrons 
and a specific surface area above about 50 m.sup.2 /g. intimately admixed 
with dimethyl silicone fluid having a molecular weight in the range from 
about 500 to about 200,000 at a weight ratio of silicone to silanated 
silica of from about 1:1 to about 1:2. The silicone suds suppressing agent 
is advantageously releasably incorporated in a water-soluble or 
water-dispersible, substantially non-surface-active detergent-impermeable 
carrier. 
Particularly useful suds suppressors are the self-emulsifying silicone suds 
suppressors, described in German Patent Application DTOS No. 2,646,126 
published Apr. 28, 1977 and incorporated herein by reference. An example 
of such a compound is DS-544, commercially available from Dow Corning, 
which is a siloxane/glycol copolymer. 
Suds modifiers as described above are used at levels of up to approximately 
5%, preferably from 0.1 to 2% by weight of the nonionic surfactant. They 
can be incorporated into the particulates of the present invention or can 
be formed into separate particulates that can then be mixed with the 
particulates of the invention. The incorporation of the suds modifiers as 
separate particulates also permits the inclusion therein of other suds 
controlling materials such as C.sub.20 -C.sub.24 fatty acids, 
microcrystalline waxes and high MWt copolymers of ethylene oxide and 
propylene oxide which would otherwise adversely affect the dispersibility 
of the matrix. Techniques for forming such suds modifying particulates are 
disclosed in the previously mentioned Bartolotta et al U.S. Pat. No. 
3,933,672. 
The detergent compositions of the invention can also contain from about 5% 
to about 93.9% of detergency builder, preferably from about 20% to about 
70% thereof. 
Suitable detergent builder salts useful herein can be of the polyvalent 
inorganic and polyvalent organic types, or mixtures thereof. Non-limiting 
examples of suitable water-soluble, inorganic alkaline detergent builder 
salts include the alkali metal carbonates, borates, phosphates, 
polyphosphates, tripolyphosphates and bicarbonates. 
Examples of suitable organic alkaline detergency builder salts are: 
(1) water-soluble amino polyacetates, e.g. sodium and potassium 
ethylendiaminetetraacetates, nitrilotriacetates, and 
N-(2-hydroxyethyl)nitrilodiacetates; 
(2) water-soluble salts of phytic acid, e.g. sodium and potassium phytates; 
(3) water-soluble polyphosphonates, including, sodium, potassium and 
lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium 
and lithium salts of methylenediphosphonic acid and the like. 
(4) water-soluble polycarboxylates such as the salts of lactic acid, 
glycollic acid and ether derivatives thereof as disclosed in Belgian 
Patent Nos. 821,368, 821,369 and 821,370; succinic acid, malonic acid, 
(ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric 
acid, tartronic acid and fumaric acid; citric acid, aconitic acid, 
citraconic acid, carboxymethyloxysuccinic acid, lactoxysuccinic acid, and 
2-oxy-1,1,3-propane tricarboxylic acid; oxydisuccinic acid, 1,1,2,2-ethane 
tetracarboxylic acid, 1,1,3,3-propane tetracarboxylic acid and 
1,1,2,3-propane tetracarboxylic acid; cyclopentane-cis, cis, 
cis-tetracarboxylic acid, cyclopentadienide pentacarboxylic acid, 
2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylic acid, 
2,5-tetrahydrofuran-cis-dicarboxylic acid, 
1,2,3,4,5,6-hexane-hexacarboxylic acid, mellitic acid, pyromellitic acid 
and the phthalic acid derivatives disclosed in British Pat. No. 1,425,343. 
Mixtures of organic and/or inorganic builders can be used herein. One such 
mixture of builders is disclosed in Canadian Patent No. 755,038, e.g. a 
ternary mixture of sdium tripolyphosphate, trisodum nitrilotriacetate, and 
trisodium ethane-1-hydroxy-1,1-diphosphate. 
A further class of builder salts is the insoluble alumino silicate type 
which functions by cation exchange to remove polyvalent mineral hardness 
and heavy metal ions from solution. A preferred builder of this type has 
the formulation Na.sub.z (AlO.sub.2).sub.z (SiO.sub.2).sub.y.xH.sub.2 O 
wherein z and y are integers of at least 6, the molar ratio of z to y is 
in the range from 1.0 to about 0.5 and x is an integer from about 15 to 
about 264. Compositions incorporating builder salts of this type form the 
subject of British patent specification No. 1,429,143 published Mar. 24, 
1976, German Patent Application No. OLS 2,433,485 published Feb. 6, 1975, 
and OLS 2,525,778 published Jan. 2, 1976, the disclosures of which are 
incorporated herein by reference. 
The detergent compositions of the invention can also be supplemented by 
bleaches, especially sodium perborate tetrahydrate or sodium percarbonate 
at levels from about 5% to about 93.9%. The compositions also preferably 
include from about 0.05% to about 0.6% (acid basis), preferably from about 
0.06% to about 0.3% of aminopolyphosphonic acid, or salt thereof, having 
the general formula: 
##STR9## 
wherein n is an integral number from 0 to 3, and each R is individually 
hydrogen or CH.sub.2 PO.sub.3 H.sub.2 provided that at least half of the 
radicals represented by R are CH.sub.2 PO.sub.3 H.sub.2. Preferred 
aminopolyphosphonic acids are selected from nitrilotri(methylenephosphonic 
acid), ethylene-diaminetetra(methylenephosphonic acid), 
diethylenetriamine(pentamethylenephosphonic acid), and mixtures thereof. 
An alkali metal, or alkaline earth metal, silicate can also be present. The 
alkali metal silicate is preferably from about 3% to about 8%. Suitable 
silicate solids have a molar ratio of SiO.sub.2 /alkali metal.sub.2 O in 
the range from about 1.0 to about 3.3, more preferably from 1.5 to 2.0. 
Other suitable ingredients include soil-suspending agents such as the 
water-soluble salts of carboxymethyl cellulose and of methyl 
vinylether/maleic anhydride copolymer, nonionic cellulose materials such 
as hydroxyethyl cellulose, and polyethylene glycols. 
In the Examples which follow, the abbreviations used have the following 
designation: 
LAS: Linear C.sub.12 alkyl benzene sulphonate 
TAS: Sodium tallow alcohol sulfate 
TlAE.sub.n : Tallow alcohol ethoxylated with n moles of ethylene oxide per 
mole of alcohol 
CTMAC: Coconut trimethyl ammonium chloride 
CDMAC: Coconut alkyl dihydroxyethyl methyl ammonium chloride 
Dobanol 45-E-7: A C.sub.14-15 oxo-alcohol with 7 moles of ethylene oxide, 
marketed by Shell 
Dobanol 45-E-4: A C.sub.14-15 oxo alcohol with 4 moles of ethylene oxide, 
marketed by Shell 
Dobanol 91-E-3: A C.sub.9-11 oxo alcohol with 4 moles of ethylene oxide, 
marketed by Shell 
TAED: Tetraacetyl ethylene diamine 
AOBS: Sodium p-acetoxy benzene sulphonate 
TAHD: Tetraacetyl hexamethylene diamine 
Imvite: Sodium montmorillonite marketed by IMV, Nevada U.S.A. 
ZPT: Zinc phthalocyanine tetrasulphonate 
Silicate: Sodium silicate having an SiO.sub.2 :Na.sub.2 O ratio of 1.6. 
Wax: Microcrystalline wax-Witcodur 272 M.pt 87.degree. C. 
Silicone Prill: Comprising 0.14 parts by weight of an 85:15 by weight 
mixture of silanated silica and silicone, granulated with 1.3 parts of 
sodium tripolyphosphate, and 0.56 parts of tallow alcohol condensed with 
25 molar proportions of ethylene oxide 
Gantrez AN119: Trade Name for maleic anhydride/vinyl methyl ether 
copolymer, believed to to have an average molecular weight of about 
240,000, marketed by GAF. This was prehydrolysed with NaOH before 
addition. 
Brightener: Disodium 
4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'-disulpho 
nate. 
Dequest 2060: Trade Name for diethylene triamine penta(methylene phosphonic 
acid), marketed by Monsanto. 
Dequest 2041: Trade Name for ethylenediamine tetra (methylene phosphonic 
acid), marketed by Monsanto. 
The present invention is illustrated by the following examples: 
EXAMPLES I-VI 
The following additive compositions are each prepared by admixing the 
particulate solid components and nonionic surfactant at a temperature of 
about 45.degree. to form a homogeneous, friable matrix which is then 
extruded through an XTRUDER (Registered Trade Mark) EXKS-1 in radial 
discharge mode. 
______________________________________ 
Examples 
I II III IV V VI 
______________________________________ 
TAED -- 80 -- -- -- 87 
AOBS -- -- 50 -- -- -- 
TAHD -- -- -- -- 70 -- 
ZPT 1 -- -- -- -- -- 
Sodium tripolyphosphate 
87 -- -- -- -- -- 
(Anhydrous) 
Imvite -- -- 34 -- -- -- 
Dequest 2060 -- -- -- -- 5 -- 
Dequest 2041 -- 6 -- -- -- -- 
LAS (spray dried) 
-- -- -- 39 -- -- 
Sodium perborate 
-- -- -- 50 -- -- 
tetrahydrate (average 
particle size .about.50.mu.) 
Magnesium sulphate 
-- -- -- 1 -- -- 
Gantrez AN119 -- -- -- -- 10 -- 
TAE.sub.11 12 14 16 10 15 13 
______________________________________ 
The above products are non-bleeding, free-flowing granular compositions 
having high granule strength, low dust and low moisture pick-up on storage 
at 32.degree. and 80% relative humidity, and they have excellent storage 
stability and rapid dispersibility in aqueous detergent media. 
EXAMPLES VII-XII 
The following detergent compositions are prepared by dry-mixing the 
additive compositions of Examples I to VI and where appropriate, the 
sodium perborate tetrahydrate, silicone prill and enzyme with auxiliary 
granular, spray-dried mixtures containing all remaining components apart 
from nonionic surfactant, which is added as a final spray-on. 
______________________________________ 
Examples 
VII VIII IX X XI XII 
______________________________________ 
LAS 6 12 -- 2 8 7 
TAS 2 -- 10 -- -- 2 
CTMAC -- -- 3 -- 2 -- 
CDMAC -- -- -- 1 -- -- 
Dobanol 45-E-4 -- -- -- 4 -- -- 
Dobanol 45-E-7 -- -- 5 8 5 -- 
Dobanol 91-E-3 -- 2 -- -- -- -- 
Sodium tripolyphosphate 
33 40 30 60 45 24 
Silicate 10 8 -- -- 9 6 
Dequest 2041 -- -- -- -- 0.3 
0.1 
Dequest 2060 0.5 -- -- -- -- -- 
Wax -- -- -- 1 2 -- 
Gantrez AN119 -- -- 0.5 
-- 0.4 
1 
Brightener 0.5 -- 0.5 
-- 0.3 
0.3 
Additive I 2 -- -- -- -- -- 
Additive II -- 5 -- -- -- -- 
Additive III -- -- 10 -- -- -- 
Additive IV -- -- -- 7 -- -- 
Additive V -- -- -- -- 12 -- 
Additive VI 2 -- -- -- -- 2 
Sodium perborate 
30 25 25 15 10 22 
tetrahydrate (average 
particle size .about.300.mu.) 
Akalaze enzyme 1 -- -- -- -- 1 
Silicone prill 1 2 2 -- -- 1 
Sodium sulphate, 
moisture, miscellaneous 
To 100 
______________________________________ 
The above products are free-flowing granular compositions having excellent 
detergency performance on bleachable stains and displaying excellent 
physical and chemical storage characteristics. 
EXAMPLES XIII to XVIII 
The following additive compositions are each prepared by spraying the 
nonionic surfactant onto the particulate solid components (other than 
surface coating agent) at a temperature of about 40.degree. C. to form a 
homogeneous friable mass which is then extruded through an XTRUDER (RTM) 
EXD-100 in radial discharge mode using 1.2 mm screens. The extrudate is 
then coated with the surface-coating agent as specified. Finally the 
additive compositions XIII to XVIII are incorporated in the detergent 
compositions of Examples VII to XII replacing Additives I to VI 
respectively. The numbers are parts by weight. 
______________________________________ 
Examples 
XIII XIV XV XVI XVII XVIII 
______________________________________ 
Extrudate 
TAED 87 80 76 76 80 78 
Dequest 2041 -- 6 -- 7 6 -- 
Dequest 2060 -- -- 5 -- -- 5 
TAE.sub.11 13 14 15 12 12 14 
Magnesium sulphate 
-- -- 2 -- -- 2 
Gantrez AN114 
-- -- 2 5 -- 1 
Surface 
Coating Agent 
Magnesium silicate 
2.0 1.5 -- -- -- -- 
(MgO:SiO.sub.2 = 0.3125) 
Imvite -- -- 2.5 
1.8 
-- -- 
Zeolite A -- -- -- -- 2.0 1.4 
______________________________________ 
The above products are non-bleeding, free-flowing granular compositions 
having high granule strength, low dust and low moisture pick-up on storage 
at 32.degree. and 80% relative humidity, and they have excellent storage 
stability and rapid dispersibility in aqueous detergent media.