[0001] This invention relates to a light duty detergent powder composition designed especially
for washing fine garments and synthetic fabrics.
[0002] Fine garments and synthetic and coloured fabrics require careful treatment and yet
need to be cleansed and washed like any other wash goods. The washing process, and
therefore any composition used in such a process, should not damage the fabric fibres,
should not bleach any dyes or pigments in the fabrics and should not cause loss of
brightness by the deposition of insoluble material onto the fabric surface. At the
same time effective soil removal is required. Furthermore a detergent powder that
feels soft and non-gritty in the hands would likely have a better consumer appeal
for being identified with mildness to fine garments.
[0003] French patent specification 2 237 960 (Unilever NV) describes a detergent composition
which in addition to a detergent active material contains an alkyl hydroxyalkyl cellulose
and a maleic acid copolymer. Compositions are disclosed therein which contain no bleach
and are thus suitable for the treatment of fine garments. European patent specification
EP 54 325-B (Unilever NV et al) describes compositions which contain a mixture of
sodium carboxymethyl cellulose, a linear polymer polycarboxylate and a cellulose ether.
The specifically exemplified compositions recommend the presence of 5% sodium silicate.
[0004] European patent specification 66 915 (Procter & Gamble) disclose a detergent composition
comprising carboxylic copolymers containing maleic acid and (meth)-acrylic acid monomers.
The examples teach that at least 5 wt % of sodium silicate should be present.
[0005] It is an object of this invention to provide a non-gritty, soft-feeling light duty
detergent powder composition especially designed for effective washing of fine garments
and synthetic fabrics and yet is exceptionally mild to colour and fabric caring.
[0006] According to the invention there is provided a bleach-free powdered detergent composition
for washing fine garments and synthetic and coloured fabrics, comprising:
(i) from 10% to 35% by weight of an organic surface active agent selected from anionic
surfactants, nonionic surfactants and mixtures thereof,
(ii) from 5% to 60% by weight of a detergency builder; and
(iii) from 1% to 15% by weight of a polymer mixture containing (a) an alkali metal
carboxymethyl cellulose having from 0.5 to 0.9 carboxymethyl ether groups per anhydrose
unit; (b) an alkylhydroxyalkyl cellulose derivative having a total number of substituent
groups per glucose unit of between 1.5 and 3.0; and (c) a polycarboxylate polymer
selected from compounds having the empirical formula:

wherein X is O or -CH₂-, Y is a comonomer or mixture of co-monomers, R¹ and R² are
bleach stable polymer end groups, R³ is H, OH or C₁ to C₄ alkyl, M is a water-soluble
cation, p is from 0 to 2 and n is at least 10, and mixtures thereof, characterised
in that the composition is essentially free of sodium silicate.
[0007] The compositions of the present invention are essentially free of sodium silicate.
Impurities in other ingredients may accidentally introduce this material. Such impurities
will generally only be present in small amounts in the overall composition, up to
about 0.5% by weight.
[0008] The individual components of the polymer mixture system are known in the art. However
the use of this particular mixture in a high active, non-bleaching and sodium silicate-free
detergent composition provides for the desired beneficial properties of an attractive
light duty detergent powder composition destined for the fine wash.
[0009] Polymer (a) - A well-known representative of this polymer is sodium carboxymethylcellulose
as available on the market, which has been used as soil-suspending and anti-redeposition
agent in fabric washing detergent compositions.
[0010] Polymer (b) - To be of use in accordance with the invention, the total number of
substituent groups per glucose unit of the cellulose derivative should be between
1.5 and 3.0, preferably between 2.0 and 3.0. There should be at least 1.0, preferably
from 1.0 to 2.5, and particularly preferably from 1.5 to 2.1, alkyl groups per glucose
unit; and at least 0.1, preferably from 0.2 to 1.5, and particularly preferably from
0.5 to 1.5, hydroxyalkyl groups per glucose unit. The alkyl groups should contain
from 1 to 4, and preferably from 1 to 3, carbon atoms, and the hydroxyalkyl groups
should contain from 2 to 4, preferably from 2 to 3, carbon atoms. Particularly preferred
alkyl groups are methyl and ethyl, and the preferred hydroxyalkyl groups are hydroxyethyl
and hydroxypropyl. Propyl, butyl and hydroxybutyl groups may also be used. When the
alkyl group is methyl it is preferred that the hydroxyalkyl group be hydroxypropyl,
and when the alkyl group is ethyl it is preferred that the hydroxyalkyl group be hydroxyethyl,
although it will be appreciated that other combinations of alkyl and hydroxyalkyl
groups may be used if desired. Particularly preferred cellulose derivatives for use
in accordance with the invention are methyl hydroxypropyl celluloses having from 1.7
to 2.1 methyl groups per glucose unit and from 0.8 to 1.0 hydroxypropyl groups per
glucose unit, and ethyl hydroxyethyl celluloses having from 1.5 to 1.6 ethyl groups
per glucose unit and from 0.5 to 0.6 hydroxyethyl groups per glucose unit.
[0011] Many of these cellulose derivatives are available commercially, for example under
the Trade name of Modocoll
(R), supplied by the Mo och Domsjo Company, and others may readily be prepared by simple
chemical procedures. For instance, a methyl hydroxypropyl cellulose derivative may
be prepared by reacting the cellulose with dimethylsulphate and then with propylene
oxide (or viceversa: if one substituent is to be present in a greater amount than
the other, it is preferable that the major substituent is applied first), and an ethyl
hydroxyethyl cellulose may be prepared by reacting the cellulose with ethylene oxide
and then with ethyl chloride.
[0012] The polycarboxylate polymers (c) are disclosed and further characterised in EP-A-137
669, the most important members of which are:
(i) those belonging to the class of copolymeric polycarboxylates which, formally at
least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic
acid, itaconic acid and metaconic acid as first monomer, and an unsaturated monocarboxylic
acid such as acrylic acid or an alpha-C₁-C₄-alkyl acrylic acid as second monomer.
Preferred copolymers of this class are copolymers of maleic acid (anhydride) and (meth)acrylic
acid, as disclosed in EP-B-25 551 and GB Patent 1 596 756.
(ii) those belonging to the class of poly-(alpha-hydroxyacrylates);
(iii)those belonging to the class of polyacetal carboxylates or acetal polycarboxylates;
and
(iv) those belonging to the class of homopolymeric polyacrylates.
[0013] Any polymer of these classes can be chosen as polymer (c) in the polymer mixture,
either alone or as mixture, though preference is given to polymers of the classes
(i) and (iv).
[0014] These polymers should preferably be present in the composition at a total level of
from 1.5% to 10% by weight in proportions of 0.2-2% by weight of polymer (a), 0.1-3%
by weight of polymer (b) and 0.5-10%, most preferably 1-5% by weight of polymer (c).
[0015] The detergent composition of the invention contains at least one detergent-active
material, preferably at a level of 15% to 25% by weight. This material may be anionic
or nonionic in nature, but mixtures of anionic and nonionic materials are preferred.
[0016] The anionic detergent-active material can be a soap or a non-soap (synthetic) anionic
material. Anionic detergent-active materials are commercially available and are fully
described in the literature, for example in "Surface Active Agents and Detergents",
Volumes I and II, by Schwartz, Perry and Berch.
[0017] Synthetic anionic detergent-active materials useful in the present invention are
water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl
radicals containing from 8 to 22 carbon atoms, the term alkyl being used to include
the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic
detergent compounds are sodium and potassium alkyl sulphates, especially those obtained
by sulphating higher (C₈-C₁₈) alcohols produced for example from tallow or coconut
oil, sodium and potassium alkyl (C₉-C₂₀) benzene sulphonates, particularly sodium
linear secondary alkyl (C₁₀-C₁₅) benzene sulphonates; sodium alkyl glyceryl ether
sulphates, especially those ethers of the higher alcohols derived from tallow or coconut
oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride
sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of
higher (C₈-C₁₈) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction
products; the reaction products of fatty acids such as coconut fatty acids esterified
with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts
of fatty acid amines of methyl taurine; alkane monosulphonates such as those derived
by reacting alpha-olefines ((C₈-C₂₀) with sodium bisulphite and those derived from
reacting paraffins with SO₂ and Cl₂ and then hydrolysing with a base to produce a
random sulphonate; sodium and potassium salts of fatty acid ester sulphonates; water-soluble
salts of dialkyl esters of sulphosuccinic acid; and olefin sulphonates, which term
is used to describe the material made by reacting olefins, particularly C₁₀-C₂₀ alpha-olefins,
with SO₃ and then neutralising and hydrolysing the reaction product. The preferred
anionic detergent compounds are sodium (C₁₁-C₁₅) alkyl benzene sulphonates and sodium
(C₁₆-C₁₈) alkyl sulphates.
[0018] Mixtures of anionic compounds may also be used, preferably mixtures of synthetic
anionic surfactants and alkalimetal soaps.
[0019] 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.
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 2 to 40 moles, preferably 2 to 9 moles of ethylene oxide per mole of alcohol.
Preferably, the aliphatic alcohol comprises between 9 and 18 carbon atoms and is ethoxylated
with between 2 and 9, desirably between 3 and 8 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 Lutensols, Dobanols and Neodols which have about 25% 2-methyl branching
(Lutensol being a Trade Name of BASF, 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 ICI) or the primary alcohols having more than 50% branched structure
sold under the Trade Name Lial by Liquichimica. Specific examples of nonionic surfactants
falling with the scope of the invention include "Dobanol 45-4", "Dobanol 45-7", "Dobanol
45-9", "Dobanol 91-2.5", "Dobanol 91-3", "Dobanol 91-4", "Dobanol 91-6", "Dobanol
91-8", "Dobanol 23-6.5", (all trademarks ex Shell) "Synperonic 6", "Synperonic 14",
(both trademarks ex ICI) 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 (Trademark ex Union Carbide) having from
9 to 15 carbon atoms in the alkyl group and up to 11, especially from 3 to 9, ethoxy
residues per molecule.
[0020] 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 1500 to 1800. Such synthetic
nonionic detergents are available on the market under the Trade Name of "Pluronic",
supplied by Wyandotte Chemicals Corporation.
[0021] The mixing ratio of anionic to nonionic materials is not very critical and can be
varied as desired by the skilled artisan. However, preference here is given to ratios
within the range of 6:1 to 1:2, preferably from 5:1 to 1:1.
[0022] The detergent compositions according to the invention also contain a detergency builder,
which can be an inorganic builder or an organic builder, in an amount within the range
of from 5% to 60%, preferably from 15% to 50% by weight.
[0023] Examples of phosphorus-containing inorganic detergency builders include the water-soluble
salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates.
Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates,
phosphates and hexametaphosphates.
[0024] Examples of non-phosphorus-containing inorganic detergency builders, when present,
include water-soluble alkali metal carbonate, bicarbonates, and crystalline and amorphous
alumino silicates. Specific examples include sodium carbonate (with or without calcite
seeds), potassium carbonate, sodium and potassium bicarbonates.
[0025] Examples of organic detergency builders, when present, include the alkali metal,
ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetal
carboxylates and polyhydroxysulphonates. Specific examples inlcude sodium, potassium,
lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid,
nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acid
and citric acid.
[0026] Sodium silicate is usually relied upon in detergent compositions to provide alkalinity.
In the compositions of this invention the desired alkalinity can be obtained by the
use of water-soluble alkaline builder materials. Alkali metal carbonates and their
mixtures with alkali metal phosphates are especially suitable.
[0027] In use, the detergent compositions according to the invention will preferably show
a pH of between 9.0 and 10.5.
[0028] It should be appreciated that the detergent composition according to the invention
may further contain any of the conventional additives in amounts in which such materials
are normally employed in fabric-washing detergent compositions and which serve to
further improve the laundering characteristics and/or add aesthetic appeal to the
compositions. Examples of these additives include lather boosters, anti-foaming agents,
non-silicate alkaline materials fabric-softening agents, corrosion inhibitors, inorganic
salts, sequestering agents, colouring agents and perfumes, so long as these additives
do not adversely influence the basic objective of the invention. Enzymes such as proteolytic,
lipolytic and amylolytic enzymes are preferably incorporated to effect stain removal
by bioaction.
[0029] Though in a preferred embodiment, the invention omits the use of fluorescent agents
or optical bleaching agents, as these additives could change the hue of the original
fabric colours, their presence in very small amounts up to 0.02% by weight is generally
desirable for aesthetic reasons in giving brightness to the powder appearance.
[0030] The detergent composition of the invention is generally manufactured and presented
in the form of a particulate powder, which includes the form of granules. Detergent
powder compositions according to the invention can be prepared using any of the conventional
manufacturing techniques commonly used or proposed for the preparation of fabric-washing
detergent powder compositions. These include slurry-making of the basic ingredients
followed by spray-drying or spray-cooling and subsequent dry-dosing of sensitive ingredients
not suitable for incorporation prior to the drying or heating step. Other conventional
techniques, such as noodling, granulation, dry-mixing, and mixing by fluidisation
in a fluidised bed, may be utilised as and when necessary and desired. Such techniques
are familiar to those skilled in the art of detergent powder composition manufacture
and require no further explanation as being essential to the invention.
[0031] The absence of silicate gives a snowy aspect of the powder and favours quick solubility
of the product without insolubles.
[0032] Whereas polymer (c), such as polyacrylates or acrylic acid/maleic acid copolymers,
aids in giving structure to the powder, the combined use thereof with polymer (a)
e.g. sodium carboxymethyl cellulose, and polymer (b) e.g. ethyl hydroxyethyl cellulose,
results in a further enhancement of the anti-redeposition properties of the composition;
with improved wettability of synthetic fibres being observed.
[0033] The invention will now be further described with reference to the following non-limiting
examples.
Example 1
[0034] The following detergent composition was prepared by spray-drying the basic ingredients
and dry-mixing the enzyme and anti-foaming agent.
| |
% by weight |
| C₁₂-alkyl benzene sulphonate |
12.5 |
| Nonionic fatty alcohol/7 ethoxylate |
3.5 |
| Sodium soap |
2.0 |
| Sodium triphosphate |
25.0 |
| Sodium carbonate |
5.0 |
| Sodium carboxymethylcellulose |
0.35 |
| Ethylhydroxyethylcellylose (ModocollR) |
0.35 |
| Acrylic/maleic acid copolymer (Sokalan CP5R) |
1.5 |
| Fluorescer |
0.01 |
| Sodium sulphate |
39.0 |
| Anti foaming agent |
1.5 |
| Proteolytic enzyme (Savinase 4.0T) |
0.65 |
| Water |
up to 100% |
| * Modocoll is a register Trade Mark (Mo och Domsjo) Sokalan CP5 is a registered Trade
Mark (BASF) Savinase 4.0T is a registered Trade Mark (Novo) |
[0035] The product obtained was a light powder of bulk density 0.40 g/cc having an appealing
white snowy appearance and a soft feel in the hands with very good solubility and
detergency properties.
[0036] When two similar products are compared, one containing 6.0% sodium silicate and one
in which the silicate was absent (the balance being made up by sodium sulphate), it
was found that the composition containing the silicate left a residue of insoluble
material when dissolved in water at 20°C, which residue was 3 times greater than that
left by the silicate-free composition.
1. A bleach-free powdered detergent composition for washing fine garments and synthetic
and coloured fabrics, comprising:
(i) from 10% to 35% by weight of an organic surface active agent selected from anionic
surfactants, nonionic surfactants and mixtures thereof;
(ii) from 5% to 60% by weight of a detergency builder; and
(iii) from 1% to 15% by weight of a polymer mixture containing (a) an alkali metal
carboxymethyl cellulose having from 0.5 to 0.9 carboxymethyl ether groups per anhydrose
unit; (b) an alkylhydroxyalkyl cellulose derivative having a total number of substituent
groups per glucose unit of between 1.5 and 3.0; and (c) a polycarboxylate polymer
selected from compounds having the empirical formula:

wherein X is 0 or -CH₂-, Y is a comonomer or mixture of comonomers, R¹ and R² are
bleach stable polymer end groups, R³ is H, OH or C₁ to C₄ alkyl, M is a water-soluble
cation, p is from 0 to 2 and n is at least 10, and mixtures thereof, characterised
in that the composition is essentially free of sodium silicate.
2. A composition according to Claim 1 in which polymer (c) is a copolymer of an unsaturated
polycarboxylic acid and an unsaturated monocarboxylic acid.
3. A composition according to Claim 1, in which the polymer (c) is a homopolymeric polyacrylate.
4. A composition according to Claim 1, in which the polymer mixture contains from 0.2
to 2% by weight of polymer (a), from 0.1 to 3% of polymer (b) and from 0.5 to 10%
of polymer (c).
5. A composition according to Claim 1, in which the detergency builder comprises an alkali
metal carbonate or a mixture thereof with an alkali metal phosphate.
6. A composition according to Claim 1, which is free of fluorescent agents and optical
bleaching agents.
1. Bleichmittelfreies pulverförmiges Waschmittel zum Waschen von Feinwäsche und synthetischer
und Buntwäsche, umfassend:
(i) 10 bis 35 Gew.-% eines organischen Tensids, ausgewählt aus anionischen Tensiden,
nichtionischen Tensiden und Gemischen davon;
(ii) 5 bis 60 Gew.-% eines Detergenzbuilders; und
(iii) 1 bis 15 Gew.-% eines Polymergemisches, enthaltend (a) eine Alkalimetall-Carboxymethylcellulose
mit 0,5 bis 0,9 Carboxymethylethergruppen pro Anhydroseeinheit; (b) ein Alkylhydroxyalkylcellulosederivat
mit einer Gesamtzahl von Substituentengruppen pro Glucoseeinheit zwischen 1,5 und
3,0; und (c) ein polycarboxyliertes Polymer, ausgewählt aus Verbindungen der empirischen
Formel:

worin X 0 oder -CH₂- bedeutet, Y ein Comonomer oder ein Gemisch von Comonomeren
darstellt, R¹ und R² bleichmittelstabile Polymerendgruppen darstellen, R³ H, OH oder
C₁ bis C₄-Alkyl bedeutet, M ein wasserlösliches Kation darstellt, p 0 bis 2 bedeutet
und n mindestens 10 bedeutet und Gemische davon,
dadurch gekennzeichnet, daß das Mittel im wesentlichen natriumsilicatfrei ist.
2. Mittel nach Anspruch 1, wobei das Polymer (c) ein Copolymer einer ungesättigten Polycarbonsäure
und einer ungesättigten Monocarbonsäure ist.
3. Mittel nach Anspruch 1, wobei das Polymer (c) ein homopolymeres Polyacrylat ist.
4. Mittel nach Anspruch 1, wobei das Polymergemisch 0,2 bis 2 Gew.-% des Polymers (a),
0,1 bis 3 % des Polymers (b) und 0,5 bis 10 % des Polymers (c) enthält.
5. Mittel nach Anspruch 1, wobei der Detergenzbuilder ein Alkalimetallcarbonat oder ein
Gemisch davon mit einem Alkalimetallphosphat umfaßt.
6. Mittel nach Anspruch 1 ohne Fluoreszenzmittel und optische Bleichmittel.
1. Une composition détergente en poudre ne contenant pas d'agent de blanchiment pour
laver des vêtements délicats et des tissus synthétiques et couleurs, comprenant :
(i) de 10 % à 35 % en masse d'un agent tensioactif organique sélectionné à partir
des agents tensioactifs anioniques, des agents tensioactifs non ioniques et des mélanges
de ceux-ci ;
(ii) de 5 % à 60 % en masse d'un édificateur de détergence ; et
(iii) de 1 % à 15 % en masse d'un mélange polymère contenant (a) une carboxyméthyl
cellulose de métal alcalin ayant de 0,5 à 0,9 groupe éther carboxyméthylique par unité
anhydrose ; (b) un dérivé d'alkylhydroxyalkyl cellulose ayant un nombre total de groupes
de remplacement par unité glucose compris entre 1,5 et 3,0 ; et (c) un polymère polycarboxylate
sélectionné à partir des composés ayant la formule empirique suivante :

où X est 0 ou -CH₂-, Y est un comonomère ou un mélange de comonomères, R¹ et R² sont
des groupes terminaux polymères stables à l'agent de blanchiment, R³ est H, OH ou
un alkyle en C₁ à C₄, M est un cation soluble dans l'eau, p est un entier de 0 à 2
et n est au moins égal à 10, et des mélanges de ceux-ci, caractérisée en ce que la
composition ne comprend essentiellement pas de silicate de sodium.
2. Une composition selon la Revendication 1, dans laquelle le polymère (c) est un copolymère
d'un acide polycarboxylique insaturé et d'un acide monocarboxylique insaturé.
3. Une composition selon la Revendication 1, dans laquelle le polymère (c) est un polyacrylate
homopolymère.
4. Une composition selon la Revendication 1, dans laquelle le mélange polymère contient
de 0,2 à 2 % en masse de polymère (a), de 0,1 à 3 % de polymère (b) et de 0,5 à 10
% de polymère (c).
5. Une composition selon la Revendication 1, dans laquelle l'édificateur de détergence
comprend un carbonate de métal alcalin ou un mélange de celui-ci avec un phosphate
de métal alcalin.
6. Une composition selon la revendication 1, ne contenant pas d'agents de fluorescence
ni d'agents optiques de blanchiment.