[0001] This invention relates to detergent compositions, and, in particular, to detergent
compositions adapted for fabric washing.
[0002] It is known that laundry compositions function more efficiently in soft water than
in water containing significant amounts of dissolved "hardness" cations such as calcium
ion, magnesium ion and the like. Zeolites or other cation exchange materials were
frequently used to pre-soften water. Such pre-softening procedures require an additional
expense to the user occasioned by the need to purchase the softener appliance.
[0003] The most usual means whereby fabrics can be optionally laundered under hard water
conditions involves the use of water-soluble builder salts and/or chelators to sequester
the undesirable hardness cations and to effectively remove them from interaction with
the fabrics and detergent materials in the laundering liquor. The most efficacious
material of this type has been sodium tripolyphosphate and this builder has been in
almost universal use during the last ten years. However, the use of such water-soluble
builders, especially phosphates, introduces into the water supply certain materials
which, in improperly treated sewage effluents, may be undesirable. Accordingly, a
means for providing water-softening builders in detergent compositions without the
need for such large quantities of soluble builder additives is desirable.
[0004] A variety of methods have been suggested for providing builder and water-softoning
action concurrently with the washing cycle of a home laundering operation, but without
the need for water-soluble detergent additives.
[0005] One recently develpad method for removing water hadness cations in dotorgent solutions
involves the use of certain water-insoluble symthetic aluminonil icates in detergent
compositions. A multitude of patent applications have apperared in recent years relating
to these materials. Among these can be mentioned British Patent Specifications No.
1,429,143; No. 1,473,201 and No. 1,473,202; German Offenlegungsschriften No. 2,529,685
and No. 2,532,501; Dutch Patent Application No. 75.11455; U.S. Patent No. 3,985,669
and Belgian Patent No. 835,492.
[0006] Despite the advances which have been made in replacing phosphate builders by aliminosilicate
materials, it is in practice found that detergent compositions built with aluminosilicates
are still deficient in a number of areas of detergency performance compared with the
commerical phosphate built detergents of today. One such area of deficiency is in
the field of oxidizable stain cleaning. In part this deficiency would appear to reflect
the poorer peptizing ability of aluminosilicate materials. Also of importance, however,
is the fact that aluminosilicates and perbleach components such as perborates, can
interact antagonistically, thereby reducing the bleaching effectiveness of compositions
containing these materials.
[0007] The essence of the present invention lies in the discovery that compositions based
on certain crystalline aluminosilicates and having specifically defined low levels
of polyphosphonate sequestering agents and specific in-use pH characteristics, have
excellent all round detergency performance and especially good cleaning performance
on oxidizable-type stains. Moreover, these benefits are delivered in the absence of
per-bleach components so that the invention makes it possible to reduce or to eliminate
such materials entirely.
[0008] Furthermore, unlike traditional compositions based on per-bleach materials which
have optimum effectiveness at a pH well above the optimum pH (8 to 9) of conventional
enzyme components, the instant compositions have optimum bleach effectiveness at about
the same pH as these enzyme materials making it possible to secure excellent bleaching
and enzyme performance from a single composition.
[0009] Polyphosphonates have already been suggested for use in detergent compositions containing
aluminosilicate. For example, German Offenlegungsschrift 2,544,035, 2,539,071 and
2,527,388, all disclose the use of various polyphosphonates notably as dispersing
agents in aluminosilicate built products. However, it appears that the usefulness
of polyphosphonates in improving bleachable-stain performance in low pH aluminosilicate
built products has not hitherto been recognized.
[0010] Accordingly, the present invention provides a detergent composition comprising
(a) from 2% to 75% of a surfactant selected from anionic, nonionic, zwitterionic and
amphoteric surfactants and mixtures thereof;
(b) from 5% to 60% of a water-insoluble crystalline aluminosilicate ion exchange material
of the formula

wherein M is a calcium-exchange cation; 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 264; said aluminosilicate ion exchange material having a particle size diameter
from about 0.1 to about 10 microns;
(c) from 0.01 to 4% by weight of a polyphosphonic acid or salt thereof, and
(d) a pH regulating agent in an amount such that a 1% aqueous solution of the detergent
composition has a pH in the range from 7.0 to 9.5.
[0011] The various essential and optional components of the composition of the invention
will now be discussed.
Organic Detergent
[0012] The detergent active component of the present compositions can be anionic, nonionic
ampholytic or zwitterionic in nature or can be mixtures thereof.
[0013] The deteryent compositions of the invention coutain the active system in an amount
of from about 2% to about 75% by weight. For solid granular compositions, the active
systens is generally in the range from about 4% to about 30%, more preferably from
about 6% to about 15% of the compositions. In liquid compositions, higher active contents,
for example about 20% to about 70% are normally employed. A typical- listing of anionic,
nonionic, zwitterionic and amphoteric surfactants useful herein appears in USP 3,925,678
incorporated herein by reference. The following list of detergent compounds which
can be used in the instant compositions is representative of such materials.
[0014] Water-seluble salts of the higher fatty acids, i.e. "soaps", are useful as the anionic
detergent component of the compositions herein. This class of detergents includes
ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium
salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably
from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification
of fats and soils or by the neutralization of free fatty acids. Particularly use-
ful are the sodium and potassium salts of the mixtures of fatty acids derived from
coconut oil and tallow, ie. sodium or potassium tallow and coconut soap.
[0015] A highly preferred class of anionic detergents includes water-soluble salts, particularly
the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction
products having in their molecular structure an alkyl 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
8-C
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 carbon atoms, in straight chain or branched chain configuration,
eg. those of the type described in USP 2,220,099 and 2,477,383. 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
11.8 LAS.
[0016] A preferred alkyl ether sulfate surfactant component of the present invention is
a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean)
carbon chain length within the range of about 12 to 16 carbon atoms, preferably from
about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation
of from about 1 to 4 mols of ethylene oxide.
[0017] Other anionic detergent compounds herein include the sodium 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.
[0018] Other useful anionic detergent compounds herein include the water-soluble salts of
esters of a-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-acyloxy-alkane-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 20 carbon atoms in the alkyl group
and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulronates
containing from about 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates
containing from about 8 to 24, especially 14 to 18 carbon atoms, and β-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.
[0019] Anionic surfactant mixtures can also be employed, for example 5:1 to 1:5 mixtures
of an alkyl benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical
and mixtures thereof, the cation being an alkali metal preferably sodium; and from
about 2% to about 15% by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon
atoms in the alkyl radical and from 1 to 30 ethoxy groups and mixtures thereof, having
an alkali metal cation, preferably sodium.
[0020] Water-soluble nonionic synthetic detergents are also useful as the detergent component
of the instant composition. Such nonionic detergent materials can be broadly defined
as compounds prouduced by the condensation of alkylene oxide groups (hydrophilic in
nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic
in nature. The length of the polyoxyalkylene 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.
[0021] Examples of suitable nonionic detergents include:
1. The polyethylene oxide condensates of alkyl phenol, eg. 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 5 to 25 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
dodccylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol
condensed with 15 moles of ethylene oxide per mole of phenol; nonylphenol condensed
with 20 moles of ethylene oxide per mole of nonylphenol and di-iso-octylphenol condensed
with 15 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 1 to about 30 moles of alkylene oxide per mole of alcohol. Preferably, the aliphatic
alcohol comprises between 9 and 15 carbon atoms and is ethoxylated with between 2
and 12, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol.
Such nonionic surfactants are preferred from the point of view of providing good to
excellent detergency performance on fatty and greasy soils, and in the presence of
hardness sensitive anionic surfactants such as alkyl benzene sulphonates. The preferred
surfactants are prepared from primary alcohols which are either linear (such as those
derived from natural fats of prepared by the Ziegler process from ethylene, eg. 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 arc understood to have about 50% 2-methyl branching (Synperionic
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, Dcbanol 45-11, 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 aleohol, the tallow portion
comprising essentially between 16 and 22 carbon atoms. Secondary linear alkyl ethexylates
arc also suitable in the present compositions, espocially these ethoxylates of the
Tergitol series having from about 9 to 16 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.
[0022] Semi-polar nonionic detergents include water-soluble amine oxides containing one
alkyl moiety of from about 10 to 28 carbon atoms and 2 moieties selected from the
group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about
3 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety
of about 10 to 23 carbon atoms and 2 moieties selected from the group consisting of
alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and
water-soluble sulfoxide detergents containing one alkyl moiety of from about 10 to
28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl
moieties of from 1 to 3 carbon atoms.
[0023] Ampholytic detergents include derivatives of aliphatic or aliphatic derivatives of
heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight
chain or branched and wherein one of the aliphatic substituents contains from about
8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing
group.
[0024] Zwitterionic detergents inclde derivatives of aliphatic quaternary ammon lum, phosphonium
and sulfonium compounds in which the aliphatic moieties can be straight chain or bnranched,
and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms
and one contains an anionic water-solubilizing group. Further use of zwitterionic
detergents are discussed in US Patents Nos. 3,925,262 and 3,929, 678.
[0025] It is to be recegnised that any of the foregoing detergents can be used separately
herein or as mixtures.
[0026] A highly preferred mixture of surfactants is an anionic/ nonionic mixture, especially
a mixture of a C
8-C
22 alkyl benzene sulfonate and a C
10-C
20 alkanol ethoxylated with from 3 to 30 moles of ethylene oxide per mole of alkanol.
Highly preferred mixtures include C
12 alkyl benzene sulfonate and C
14-C
15 alcohol-(7)-ethoxylate, in ratios of from 5:1 to 1:3, preferably 3:1 to 1:1. In still
more preferred compositions, a fatty acid soap is added to the above-described mixture,
preferably a C
10-C
20 soap at a level of from 1% to 5%.
The Polyphosphonate
[0027] Preferred polyphosphonates are those of the general formula

where n is at least 2, M is an alkali metal, ammonium or substituted ammonium cation
and Z is a connecting organic moiety having an effective covalency equal to n. Preferably
Z is a hydrocarbyl or a hydrocarbyl substituted amino radical. Various specific classes
of polyphosphonates useful in the present invention, are indicated below.
[0028] The polyphosphonate can be derived from acids selected from the group consisting
of those of the formulae:

wherein R
1 and R
2 are hydrogen or CH
2OH; n is an integer of from 3. to 10; R
3 is hydrogen, alkyl containing from 1 to about 20 carbon atoms, alkenyl containing
from 2 to about 20 carbon atoms, aryl (e.g., phenyl and naphthyl), phenylethenyl,
benzyl, halogen (e.g. chlorine, bromine, and fluorine), amino, substituted amino (e.g.,
dimethylamino, diethylamino, N-hydroxy-N-ethylamino, acetylamino), -CH
2COOH, -CH
2PO
3H
2, - CH(PO
3H
2) (OH) or -CH
2CH(PO
3H
2)
2; and R
4 is hydrogen, lower alkyl (e.g., chlorine, bromine and fluorine), hydroxyl, -CH
2CCOH, -CH
2PO
3H
2, or -CH
2CH
2PO
3H
2.
[0029] Operable polyphosphonates of the above formula (i) include propane-1,2,3-triphosphonic
acid; butane-1,2,3,4-tetraphosphonic acid, hexane-1,2,3,4,5,6-hexaphosphonic acid;
hexane-1-hydroxy-2,3,4,5,6-pentaphosphonic acid; hexane-1,6- dihydroxy-2,3,4,5-tetraphosphonic
acid; pentane-1,2,3,4,5-pentaphosphonic acid; heptane-1,2,3,4,5,6,7-heptaphosphonic
acid; octane-1,2,3,4,5,6,7,8-octaphosphoic acid; nonane-1,2,3,4,5,6,7,8,9-nonaphosphonic
acid; decane-1,2,3,4,5,6,-7,8,9,10-decaphosphonic acid; and the salts of these acids,
e.g., sodium, potassium, calcium, magnesium, ammonium, triethanolammonium, diethaanelammonium,
and monoethanolammonium salts.
[0030] Among the operable polyphosphonates encompassed by the above formula (ii) are ethane-1-hydroxy-1,
1-diphosphonic acid; methanediphosphonic acid; methanehydroxydiphosphonic acid; ethane-1,1,2-triphosphonic
acid; propane-1,1,3,3-tetraphosphonic acid; ethane-2-phenyl-1,1, diphosphonic acidiethane-2-naphthyl-1,
1-diphosphonic acid; methanophenyl- diphosphonic acid; ethane-1-amino-1, 1-diphosphonic
acid methanedichlorodiphosphonic acid; nonane-5,5-diphosphonic acid; n-pentane-1,1-diphosphonic
acid; methanedifluorodiphos- phonic acid; methanedibromediphosphenic acid; propane-2,2-
diphosphonic acid; ethane-2-carboxy-1, 1-diphosphonic acid; propane-1-hydroxy-1,1,3-triphosphonic
acid; ethane-2, hydroxy-1,1,2-triphosphonic acid; ethane-1-hydroxy-1,1,2-triphosphenic
acid; propane-1,3-diphenyl-2, 2-diphosphonic acid, nonane-1, 1-diphosphonic acid;
hexadecane-1, 1-diphosphonic acid; pent-4-one-1-hydroxy-1, 1-diphosphonic acid; octadec-9-ene-1-hydroxy-1,1-diphosphonic
acid; 3-phenyl-1, 1-diphosphonoprop-2-ene; octane-1,1-diphosphonic acid; dodecane-1,1-diphosphonic
acid; phenylaminomethanediphosphonic acid; naphthylamino- methane-diphosphonic acid;
N,N-dimethylaminomethanediphosphonic acid; N-(2-hydroxyethyl)-aminomethanediphoic
acid; N-acetylaminomethanediphosphonic acid; aminomethanediphos- phonic acid; and
the salts of these acids, e.g., sodium, potassium, calcium, magnesium, ammonium, triethanolanunonium,
diethanolammonium and monoethanolammonium salts.
[0031] Mixtures of any of the foregoing phosphonic acids and/or salts can be used in the
compositions of this invention. Methods of preparing these classes of materials are
described in U.S. Patent No. 3,488,419.
[0032] For the purpose of this invention, it is preferred that the polyphosphonates arc
free of hydroxyl groups.
[0033] Another useful and preferred class of polyphosphonates are the amino poly(alkylene
phosphonates),particularly those having the general formula

wherein n is anintegral number from O to 14, and each R is individually hydrogen or
CH
2PO
3H
2 or a water-soluble salt thereof, provided that at least half of the radicals represented
by R are CH
2Po
3H
2 radicals or water-soluble salts thereof. Especially preferred is the polyphosphonate
having the general formula

wherein each R
1 is CH
2PO
3H
2 or a water-soluble salt thereof and m is from 0 to 2. Examples of compounds within
this class are aminotri-(methylenephosphonic acid),
[0034] . ethylene diamine tetra (methylenephosphonic acid)and diethylene triamine penta(methylene
phosphonic acid). Of these, ethylene diamine tetra(methylene phosphonic acid) is the
most beneficial and is preferred.
[0035] Preferred polyphosphonates can also be defined in terms of their calcium and iron
sequestering ability as reflected in their calcium and iron logarithmic stability
constants, pK
Ca++ and
pKFe3+. These are defined by reference to the equilibrium.

where M is the metal cation and A is the polyphosphonate anion predominating in aqueous
solution at the in-use pH of the detergent composition.
[0036] The equilibrium constant is therefore

and

Preferably, the polyphosphonate has a pK
Ca++ of less than about 6, more preferably less than about 5 and especially less than
about 4. The value of pK
Fe3+, on the other hand is preferably greater than about 6, more preferably greater
than about 9, and especially greater than about 12. Literature values of stability
constants are taken where possible, (see Stability Constants of Metal-Ion Complexes,
Special Publication No 25, the Chemical Society, London). Otherwise, the stability
constant is defined at 25
0C and at 0.1 molar KCl, using a glass electrode method of measurement as described
in Complexation in Analytical Chemistry by Anders Ringbcm (1963)
The pH Regulating Agent
[0037] The pH regulating agent can be selected from inorganic or organic acids or acid salts
or mixtures of such materials. A preferred inorganic agent is sodium or potassium
bicarbonate. Suitable organic agents include lactic acid, glycollic acid and ether
derivatives thereof as disclosed in Belgium Patents 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 carboxymethyloxysuccinic 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, cyclo- pentadienide 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 Patent 1,425,343; and the acid salts
of the above organic acids. Of the above, the preferred organic acids are citric,
glycollic and lactic acids.
[0038] The pH regulating agent is present in an amount sufficient to provide a pH in 1%
aqueous solution of the detergent composition, in the range from about 7 to 9.5, preferably
from about 7 to 9, especially from about 7.5 to 8.5. Generally, from about 5 to 25%,
especially from about 10 to 20% of the regulating agent is sufficient for this purpose.
The Aluminosilicate Builder
[0039] The aluminosilicate ion exchange materials used herein are prepared by a process
which results in the formation of materials which are particularly suitable for use
as detergency builders and water softeners. Specifically, the aluminosilicates herein
have both a higher calcium ion exchange capacity and a higher exchange rate than similar
materials previously suggested as dctergcncy builders. Such high calcium ion exchange
rate and capacity appear to be a function of several interrelated factors which result
from the method of preparing said aluminosilicate icn exchange materials.
[0040] It is highly preferred that these ion exchange builder materials are in the "sodium
form".
[0041] A second essential feature of the ion exchange builder materials herein is that they
be in a hydrated form ie. contain 10% to 28%, preferably 10% to 22% of water. Highly
preferred aluminosilicates herein frequently contain from about 18% to about 22% water
in their crystal matrix. It has been found, for example, that less highly hydrated
aluminosilicates, eg. those containing about 6% water, do not function effectively
as ion exchange builders when employed in the context of a laundry detergent composition.
[0042] A third essential feature of the ion exchange builder materials herein is their particle
size range. Proper selection of small particle sizes results in fast, highly efficient
builder materials.
[0043] The method set forth below for preparing the aluminosilicates herein takes into consideration
all of the foregoing essential elements. First, the method avoids contamination of
the aluminosilicate product by cations other than sodium. For example, product washing
steps involving acids or bases other than sodium hydroxide are avoided. Second, the
process is designed to form the aluminosilicate in its most highly hydrated form.
Hence, high temperature heating and drying are avoided. Third, the process is designed
to form the aluminosilicate materials in a finely-divided state having a narrow range
of small particle sizes. Of course, additional grinding operations can be employed
to still further reduce the particle size. However, the need for such mechanical reduction
steps is substantially lessened by the process herein.
[0044] The aluminosilicates herein are prepared accoraing to the followin pocedung:
(a) dis colv undiam alcoipito (Na AlO2) in wator to fore hompose to polution
(b) add sulie hylopxide to the sudium aluminate nolution of step (a) at a weigbt ration
of

. Na A10, of 1:1.8 (proferred) and maintain the Lemperoture of the selution at about
BC°C untid all the NaOH dissolves and a homogeneous solution foams;
(c) add sodion silicate (RO2 SiO2 having a SiO2Na2O weight. into of 3.2 to 1) to the solution of step (h) to provide a solutier having
a weight ratio of Na2SiO32NaOH of 1.14:1 and a woight ratio of Na, SiO3 waAlO2 of 0.63:1;
(d) heat the vixture prepared in step (C) to about 90°C - 100°C and maintain at this
tonperature range for about one hour.
[0045] In a preferred embodiment, the mixture of step (c) is cooled to a temperature below
about 25°C, preferably in the range from 17°C to 23°C, and maintained at that temperature
for a period from about 25 hours to about 500 hours, preferably from about 75 hours
to about 200 hours.
[0046] The mixture resulting from step (d) is cooled to a temperature of about 50°C and
thereafter filtered to collect the desired aluminosilicate solids. If the low temperature
(<25°C) crystallization technique is used, then the precipitate is filtered without
additonal preparatory steps. The filter cake can optionally be washed free of excess
base (deionized water wash preferred to avoid cation contamination). The filter cake
is dried to a moisture content of 18% to 22% by weight using a temperature below about
150°C to avoid excessive dehydration. Preferably, the drying is performed at 100°C
- 105°C.
[0047] Following is a typical pilot-plant scale preparation of the aluminosilicates herein.
PREPARATION OF ALUMINOSILICATE BUILDER
[0048]

[0049] The sodium aluminate was dissolved in the water with stirring and the sodium hydroxide
added thereto. The temperature of the mixture was maintained at 50°C and the sodium
silicate was added thereto with stirring. The temperature of the mixture was raised
to 90°C - 100°C and maintained within this range for 1 hour with stirring to allow
formation of a sythetic aluminosilicate ion exchange material having the formula Na
12(AlO
2:SiO
2)
12.27 H
20. The mixture was cooled to 50°C, filtered, and the filter cake washed twice with
1001bs. of deionized water. The case was dried at a temperatureof 100°C - 105°C to
a moisture content of 18% - 22% by weight to provide the aluminosilicate builder material.
This synthetic aluminosilicate ion exchange material is known under the commercial
denomination ZEOLITE A; in the dehydrated form it can be used as a molecular sieve
and catalyst carrier. The sythetic aluminosilicate known commercially as ZEOLITE X
is also suitable for use in the present invention, as are the amorphous synthetic
aluminosilicates.
[0050] The aluminosilicates prepared in the foregoing manner arc charaederized by a cubic
crystal structure and may additionally be distinguished from other aluminosilicates
on the basis of the X-ray powder diffraction equipment. This included a nickel filtered
copper target tube at about 1100 watts of input power Scintillation detection with
a strip chart recorder was used to measure the diffraction from the spectrometer.
Calculation of the observed d-values was obtained directly from the spectrometer chart.
The relative intensities were calculated with Io as the intensity of the strongest
line or peak. The synthetic aluminosilicate ion exchange material having the formula

prepared as described hereinbefore had the following X-ray diffraction pattern:

[0051] The above diffraction pattern substantially corresponds to the pattern of ASTM powder
diffraction card file # 11-590. Water-insoluble aluminosilicates having a molar ratio
of (AlO
2): (SiO
2) smaller than 1, ie. in between 1.0 and about 0.5, preferably in between 1.0 and
about 0.8, can be prepared in a similar manner. These aluminosilicate ion exchange
materials (AlO
2:SiO
2 <1) are also capable of effectively reducing the free polyvalent hardness metal ion
content of aqueous washing liquor in a manner substantially similar to the aluminosilicate
ion exchange material having a molar ratio of A10
2:Si0
2 = 1 as described hereinbefore. Examples of aliminosilicates having a molar ratio:AlO
2:SiO
2<1, suitable for use in the instant compositions include:

and

Although completely hydrated aluminosilicate ion exchange materials are preferred
herein, it is recognised that the partially dehydrated aluminosilicates having the
general formula given hereinbefore are also excellently suitable for rapidly and effectively
reducing the water hardness during the laundering operation. Of course, in the process
of preparing the instant aluminosilicate ion exchange material, reaction-crystallization
parameter fluctuations can result in such partially hydrated materials. As pointed
out previously, aluminosilicates having about 6% or less water do not function effectively
for the intended purpose in laundering context.
[0052] The water-insol able, inorganic aluminosilicate ion exchange materials prepared in
the foregoing manner are characterized by a particle size diameter from about 0.1
micron to about 10 microns. Preferred ion exchange materials have a particle size
diameter from about 0.2 micron to about 10 microns. The term "partocle size diameter"
herein represents the number-average -particle size diameter of a given ion exchange
material as determined by conventional analytical technique such as, for example,
microscopic determination, scanning electron microscope (SEM).
[0053] Preferred detergent compositions of the present invention contain from 10% to 50%
of the aluminosilicate, more preferably from 15% to 25%.
Optional Components
[0054] It is to be understood that granular compositions of the invention can be supplemented
by all manner of detergent components, either by including such components in the
aqueous slurry for spray dring or by admixing such components with the compositions
of the invention after the drying step. Soil suspending agents at about 0.1% to 10%
by weight such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethylcellulose,
and polyethylene glycols having a molecular weight of about 400 to 10,000 are common
components of the present invetnion. Dyes, pigment optical brighteners, and perfumes
can be added in varying amounts as desired.
[0055] Other materials such as fluorescers, antiseption, germicides, enzymes in minor amounts,
anti-caking agents such as sodium sulfosuccinate, and sodium benzoate may also be
added. Enzymes suitable for use herein include those discussed in U.S. Patents 3,519,570
and 3,553,139 to McCarty and McCarty et al issued 7 July, 1970 and 5 January, 1971
respectively. Particularly preferred are proteolytic enzymes having maximum intrinsic
enzyme activity in the range from about pH 8 to about pH 9, especially preparations
derived from B. subtilis such as ALCALASE (Registered Trade Mark) manufactured by
Novo Industri A.S, Copenhagen, Denmark, and MAXATASE (Registered Trade Mark) manufactured
by GIST-BROCADES N.V. Delft. These can be used in levels from about 0.1 to about 2%
by weight of the composition.
[0056] Bleaches such as perborates and percarbonates and activators therefor can also be
added to the instant composition, although it is a feature of the invention that such
materials can be reduced in level or eliminated entirely. Suitably, therefore, per-bleaches
can be present in amounts up to about 15%, especially up to about 10% by weight of
the compositions.
[0057] An optional but highly desirable ingredient or the present compositions is from 0.1%
to 3% of a polymeric material having a molecular weight of from 2000 to 2,000,000
and which is a copolymer of maleic acid or anhydride and a polymerisable monomer selected
from compounds of formula:

wherein R
1 is CH
3 or a C
2 to C
12 alkyl group;

wherein R
2 is H or CH
3 and R
3 is H, or a C
1 to C
10 alkyl group;

wherein each of R
4 and R
5 is H or an alkyl group such that R
4 and R
5 together have 0 to 10 carbon atoms;

and (vi) mixtures of any two or more thereof, said copolymers being optionally wholly
or partly neutralised at the carboxyl groups by sodium or potassium.
[0058] Preferred examples of polycarboxylates in the above classes are polymaleic acid/acrylic
acid copolyer, 70:30 acrylic acid/hydroxy ethyl maleate copolymer, 1:1 styrane/ maleic
acid copolymer, propylene/maleic acid copolymer, isobutylene/maleic acid copolymer,
diisobutylene/maleic acid copolymer, methylvinylether/maleic acid copolymer, ethylvinylether/maleic
acid copolymer, ethylene/maleic acid copolymer and vinyl pyrrolidone/maleic acid copolymer.
The preferred material is a methylvinylether/maleic acid copolymer having an average
molecular weight from 12000 to 1,500,000.
[0059] Inorganic alkaline detergency builder salts can also be added, although high levels
of highly alkaline builder salts and of phosphorus containing builder salts should
be avoided. In particular, the phosphorus content of the compositions of the invention
is preferably less than about 6% by weight, and highly preferred compositions comprise
no more than about 1% by weight of phosphorus.
[0060] Inorganic builder salts include, for instance, alkali metal carbonates, tetraborates,
pentaborates, aluminates, sesquicarbonates, polyphosphates such as sodium tripolyphosphate
and pentapolyphosphate, and metaphosphates such as tetrametaphosphate, pentametaphosphate
and hexametaphosphate, as well as orthophosphates and pyrophosphates.
[0061] A further optional component of the present compositions is a suds depressant. Soap
is an effective suds depressent, especially C
16-22 soaps, for instance those derived by neutralisation of Hyfac (trade name) fatty acids.
These are hardened marine fatty acids of chain length predominantly C
18 to C
20. However, non-soap suds depressants are preferred. A preferred suds depressant comprises
silicones. In particular, there may be employed a particulate suds depressant comprising
silicone and silica releasably enclosed in a water soluble or water dispersable substantially
non-surface active detergent- impermeable carrier. Suds depressing agents of this
type are disclosed in British Patent Specification 1,407,997 incorporated herein by
reference.
[0062] A very suitable granular (prilled) suds depressant product comprises 7% siiica/silicone
(85% by weight sila- nated silica, 15% silicone obtained from Messrs. Dow Corning),
65% sodium tripolyphosphate, 25% tallow alcohol (EO) 25 (ie. condensed with 25 molar
proportions of ethylene oxide), and 3% moisture. Also suitable and preferred is a
combination of 0.02% to 5% by weight, especially about 0.3% of the composition; of
a substantially water insoluble wax or mixture of waxes, melting at from 35 C to 125°C,
and having saponification value less than 100, and a suds depressing amount, usually
about 2% of the composition, of particulate suds depressant mentioned above. Suds
depresant mixtures of this type are described in British patent application 10734/74,
incorporated herein by reference.
[0063] Another desirable component of the compositions of the invention is a water-soluble
cationic surfactant such as those described in European Application No. 78 200 050.9
incorporated herein by reference. The cationic surfactant, when used in combination
with anionic and nonionic surfactants in defined ratios and amounts, improves the
oil stain detergency performance of the formulation. Preferred cationic surfactants
have the general formula

wherein R
1 is selected from C
8-20 alkyl, alkenyl and alkaryl groups;
R2 is selected from C
I-4 alkyl and benzyl; A is an anion; and m is 1,2, or 3; provided that when m is 2, R
1 has less than 15 carbon atoms, and when m is 3, R
1 has less than 9 carbon atoms.
[0064] C
12 and C
14 alkyl trimethyl ammonium salts are highly preferred.
[0065] In preparing granular detergent compositions of the invention the components may
be mixed togather in any order and in powdery or in fluid form, eg. in an aqueous
dispersion. The composition may be sprayed dried, drum dried, freeze dried or dried
by other means, to provide a granular composition. Usually a moisture content of about
3% to about 10% is suitable to provide non-sticky free- flowing granules.
[0066] Liquid detergent compositions of the invention can contain, as optional ingredients,
organic carriers or solvents such as lower aliphatic alcohols having from 2 to 6 carbon
atoms and 1 to 3 hydroxyl groups; ethers of diethylene glycol and lower aliphatic
mono-alcohols having from 1 to 4 carbon atoms; and mixtures thereof. Liquid compositions
can also contain hydrotropes such as the water-soluble alkylaryl sulfonates having
up to 3 carbon atoms in an alkyl group such as sodium, potassium, ammonium and ethanolamine
salts of xylene-, toluene-, ethylbenzene- and isopropylbenzene sulfonic acids.
EXAMPLES 1-6
[0067] Built low-sudsing detergent compositions were prepared having the formulae given
below. To make the products a slurry was prepared containing all the components except
the bleach and enzyme and the slurry was then spray dried to form a granular intermediate.
Bleach and enzyme were dry mixed with the intermediate granules to form the stated
composition. All figures are given as % by weight.

[0068] The compositions of the above Examples all provide good detergency performance, particularly
on bleachable type soils and stains and at low wash temperatures compared with compositions
containing no polyphosphonate material, and compared with compositions containing
polyphosphonates but having pH in use outside the claimed range.
[0069] Similar results are achieved when the tripolyphosphate is replaced by a P
12 glassy phosphate. The anionic/ nonionic active systems of Examples 3-6 can be replaced
by all nonionic systems, for example, with Dobanol 45-E-7 and Dobanol 45-E-4. The
Zeolite A in Examples 1, 3, 5 and 6 can be replaced in whole or in part by an amorphous
sodium aluminosilicate. Enhanced performance is also obtained when myristyl trimethyl
ammonium chloride is replaced by lauryl trimethyl ammonium bromide, decyl trimethyl
ammonium chloride, dioctyl dimethyl ammonium bromide, lauryl dichlorobenzyl dimethyl
ammonium chloride, and cetyl trimethyl ammonium ethosulphate. Enhanced performance
is also obtained when sodium citrate is replaced by sodium succinate, sodium carboxymethyl-
oxysuccinate, sodium 2-oxa-1,1,3-propane-tricarboxylate, sodium lactate, sodium malonate,
or sodium diglycollate.
[0070] Products with enhanced performance are obtained when the sodium alkyl benzene sulphonate
is replaced by C
10-22 olefine sulphonates, C
10-20 paraffin sulphonates, and by zwitterionic detergents such as C
10-18 alkyl dimethyl ammonium propane sulphonate or hydroxypropane sulphonate.