Technical Field
[0001] The present invention relates to the use of modified polymers known for their soil-release
properties, as cleaning agents for grease stain removal of fabrics in combination
with a non-ionic surfactant.
Background of the invention
[0002] Products used in laundering operation contain a number of ingredients which provide
certain basic benefits. For example, laundry cleaning products are formulated with
detergent surfactant systems to remove a variety of soils from clothes during washing.
These laundry products can also include ingredients which provide through-the-wash
fabric conditioning benefits such as softening and antistatic performance.
[0003] In addition to standard cleaning, softening and anti-static benefits, laundry detergent
can also impart other desirable properties. One is the ability to confer soil release
properties to fabrics woven from polyester fibers. The hydrophobic character of polyester
fabrics makes their laundering difficult, particularly as regards oily soil and oily
stains. The oily soil or stain preferentially "wets" the fabric. As a result, the
oily soil or stain is difficult to remove in an aqueous laundering process.
[0004] Certain polyesters have been found to be particularly useful as soil release compounds
in laundry detergent composition. During the laundering operation, these soil release
polyesters adsorb onto the surface of fabrics immersed in the wash solution. The adsorbed
polyesters then form a hydrophilic film which remains on the fabric after it is removed
from the wash solution and dried. This film can be renewed by subsequent washing of
the fabric with a detergent composition containing the soil release polyesters.
[0005] Such polyesters are disclosed in e.g. US Patent 4 116 885 and 4 711 730.
[0006] Continuous effort has been put against improving soil release polyesters; in e.g.
EPA 272 033 have been described such improved polyesters. More recently, EPA 311 342
has described further improved soil release agents consisting of sulfoaroyl end-capped
polyesters.
[0007] It has been found that certain modified polyesters described in EPA 311 342 not only
act as a soil release agents on polyester fabrics, but are also able to remove soils
from cotton-containing fabrics and to disperse such soils, during the main laundering
cycle of a laundry process as described in our co-pending application EP-A-641378
published on 8.3.95
[0008] A long-standing problem is the grease stain removal. With present detergent compositions
it is difficult to remove efficiently said grease from fabrics especially from polyester
fabrics.
[0009] It has now been surprisingly found that the modified polyesters as described in EPA
311.342 in combination with selected nonionic surfactants with a low ethoxylation
degree, shows an unexpected greasy stain removal of the fabrics.
[0010] The detergent composition according to the invention comprises a modified polyester
being a random copolymer of dimethyl terephtalate, dimethyl sulfoisophtalate ethylene
glycol and 1-2 propane diol, the end groups consisting primarily of sulfobenzate and
secondarily of mono esters of ethylene glycol and/or propane-diol and non-ionic surfactant,
being a C
12-15 primary alcohol ethoxylate containing about 3 moles of ethylene oxide per mole of
alcohol whereby the ratio of the nonionic surfactant to the modified polyester is
from 6:1 to 20:1 or 1:0.3 to 1:2.0, Present in the detergent composition in a ratio
1 : 0.3 to 1 : 2.0 provides a surprising thickening effect. This provides the formulator
with a potentially effective method by which said selected non-ionic surfactant can
be processed into granular dertergents.
[0011] It has further been found that the claimed modified polyester can have a thickening
effect on said selected non-ionic surfactant.
DETAILS DESCRIPTION OF THE INVENTION
The modified polyesters
[0012] The modified polyesters herein are random copolymers of dimethyl terephtalate, dimethyl
sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting
primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or
propane-diol. The target being to obtain is a polymer capped at both end by sulphobenzoate
groups, "primarily", in the present context most of said copolymers herein will be
end-capped by sulphobenzoate groups. However, some copolymers will be less than fully
capped, and therefore their end groups may consist of monoester of ethylene glycol
and/or propane 1-2 diol, thereof consist "secondarily" of such species.
[0013] The preferred selected polyesters herein contain about 46% by weight of dimethyl
terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene
glycol about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of
sulfoisophtalic acid, and have a molecular weight of about 3.000. The polyesters and
their method of preparation are described in detail in EPA 311 342.
[0014] Furthermore, it has been found that the combined use of the present modified polyesters
with a cellulase enzyme and/or certain co-dispersing agents and the nonionic surfactant
provides superior cleaning benefits.
The non-ionic surfactants
[0015] The non-ionic surfactants according to the present invention are C
12-15 primary alcohol ethoxylates containing about 3 moles of ethylene oxide per mole of
alcohol
[0016] The modified polyesters herein are present in the detergent composition at a ratio
to the non-ionic surfactants of, from 1 : 6 to 1 : 20 or from 1;0,3 to 1:2,0.
DETERGENT COMPOSITION
[0017] The detergent compositions herein can be in a liquid or granular form and are preferably
delivered directly to the drum and not indirectly and via the outer casing of the
machine. This can most easily be achieved by incorporation of the composition in a
bag or container from which in can be released at the start of the wash cycle in response
to agitation, a rise in temperature or immersion in the wash water in the drum. Such
a container will be placed in the drum, together with the fabrics to be washed. Alternatively
the washing machine itself may be adapted to permit direct addition of the composition
to the drum e.g. by a dispensing arrangement in the access door.
[0018] When the compositions are in liquid form, a rigid container such as disclosed in
EPA 151 549 can be used the detergent composition herein are preferably in granular
form, and the container will be flexible, such as a bag or pouch. The bag may be of
fibrous construction coated with a water impermeable protective material so as to
retain the contents, such as is disclosed in EPA no. 0 018 678. Alternatively it may
be formed of a water insoluble synthetic polymeric material provided with an edge
seal or closure designed to rupture in aqueous media as disclosed in EPAs nos. 0 011
500, 0 011 501, 0 011 502, and 0 011 968. A convenient form of water frangible closure
comprises a water soluble adhesive disposed along and sealing one edge of a pouch
formed of a water impermeable polymeric film such as polyethylene or polypropylene.
[0019] In a variant of the bag or container product form, laminated sheet products can be
employed in which a central flexible layer is impregnated and/or coated with a composition
and then one or more outer layers are applied to produce a fabric-like aesthetic effect.
The layers may be sealed together so as to remain attached during use or may separate
on contact with water to facilitate the release of the coated or impregnated material.
[0020] An alternative laminate form comprises one layer embossed or deformed to provide
a series of pouch-like containers into each of which the detergent components are
deposited in measured amounts, with a second layer overlying the first layer and sealted
thereto in those areas between the pouch-like containers where the two layers are
in contact. The components may be deposited in particulate, paste or molten form and
the laminate layers should prevent egress of the contents of the pouch-like containers
prior to their addition to water. The layers may separate or may remain attached together
on contact with water, the only requirement being that the structure should permit
rapid release of the contents of the pouch-like containers into solution. The number
of pouch-like containers per unit area of substrata is a matter of choice but will
normally vary between 500 and 25,000 per square meter.
[0021] Suitable materials which can be used for the flexible laminate layers in this aspect
of the invention include, among others, sponges, paper and woven and non-woven fabrics.
[0022] However the preferred means of carrying out the washing process according to the
present invention includes the use of a reusable dispensing device having walls that
are permeable to liquid but impermeable to the solid composition.
[0023] Devices of this kind are disclosed in EPAs Nos. 0 343 069 and 0 344 070. The latter
Application discloses a device comprising a flexible sheet in the form of a bag extending
from a support ring defining an orifice, the orifice being adapted to admit to the
bag sufficient product for one washing cycle in a washing cycle. A portion of the
washing medium flows through the orifice into the bag, dissolves the product, and
the solution then passes outwardly through the orifice into the washing medium. The
support ring is provided with a masking arrangement to prevent regress of wetted,
undissolved, product, this arrangement typically comprising radially extending walls
extending from a central boss in a spooked wheel configuration, or a similar structure
in which the walls have a helical form.
[0024] The detergent compositions herein contain a surfactant.
[0025] A wide range of surfactants can be used in the detergent compositions. A typical
listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of
these surfactants, is given in US Patent 3 664 961 issued to Norris on May 23, 1972.
[0026] Mixtures of anionic surfactants are particularly suitable herein, especially mixtures
of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably
from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred sulphonates include alkyl
benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl
radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is
derived from a C
12-C
18 fatty source preferably from a C
16-C
18 fatty source. In each instance the cation is an alkali metal, preferably sodium.
Preferred sulphate surfactants are alkyl sulphates having from 12 to 18 carbon atoms
in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10
to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree
of ethoxylation of 1 to 6. Examples of preferred alkyl sulphates herein are tallow
alkyl sulphate, coconut alkyl sulphate, and C
14-15 alkyl sulphates. An exemple of a preferred ethoxy sulphate is the so-called AE3S(C
12-15 alkyl 3 times ethoxylated sulphate). The cation in each instance is again an alkali
metal cation, preferably sodium.
[0027] One class of nonionic surfactants particularly useful in the present invention are
condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having
an average hydrophilic-lipophilic balance (HLB) in the range from 5 to 17, preferably
from 6 to 14, more preferably from 7 to 12. The hydrophobic (lipophilic) moiety may
be aliphatic or aromatic in nature and 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.
[0028] In addition to the selected non-ionic surfactants herein the present compositions
can also contain additional nonionic surfactants such as the C
9-C
15 primary alcohol ethoxylates containing 6-8 moles of ethylene oxide per mole of alcohol,
particularly the C
14-C
15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.
[0029] Another suitable class of additional nonionic surfactants comprises alkyl polyglucoside
compounds of general formula
RO (C
nH
2nO)
tZ
x
wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group
that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is
from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less
than 50% short chain alkyl polyglucosides. Compounds of this type and their use in
detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
[0030] Also suitable as additional nonionic surfactants are poly hydroxy fatty acid amide
surfactants of the formula
![](https://data.epo.org/publication-server/image?imagePath=1999/12/DOC/EPNWB1/EP93870127NWB1/imgb0001)
wherein R
1 is H,
or R
1 is C
1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R
2 is C
5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof. Preferably, R
1 is methyl, R
2 is a straight C
11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived
from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive
amination reaction.
[0031] A further class of surfactants are the semi-polar surfactants such as amine oxides.
Suitable amine oxides are selected from mono C
8-C
20, preferably C
10-C
14 N-alkyl or alkenyl amine oxides and propylene-1,3-diamine dioxides wherein the remaining
N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
[0032] Another class of surfactants are amphoteric surfactants, such as polyamine-based
species.
[0033] Cationic surfactants can also be used in the detergent compositions herein and suitable
quaternary ammonium surfactants are selected from mono C
8-C
16, preferably C
10-C
14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted
by methyl, hydroxyethyl or hydroxypropyl groups.
[0034] Mixtures of surfactant types are preferred, more especially anionic-nonionic and
also anionic-nonioniccationic mixtures. Particularly preferred mixtures are described
in British Patent No. 2 040 987 and European Published Application No. 0 087 914.
The detergent compositions can comprise from 1%-70% by weight of surfactant, but usually
the surfactant is present in the compositions herein an amount of from 1% to 30%,
more preferably from 10-25% by weight.
[0035] The detergent compositions herein also contain a builder
[0036] Builder materials will typically be present at from 5% to 80% of the detergent compositions
herein. The compositions herein should preferably be free or substantially free of
phosphate-containing builders (substantially free being herein defined to constitute
less than 1% of the total detergent builder system), and the builder system herein
consists of water-soluble builders, water-insoluble builders, or mixtures thereof.
[0037] Water insoluble builders can be an inorganic ion exchange material,commonly an inorganic
hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite
such as hydrated Zeolite A, X, B or HS.
[0038] Preferred aluminosilicate ion-exchange materials have the unit cell formula
M
Z [(A10
2)
z (siO
2)
y] xH
2O
wherein M is a calcium-exchange cation, z and y are at least 6; the molar ratio of
z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably
from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably
crystalline containing from 10% to 28%, more preferably from 18% to 22% water.
[0039] The above aluminosilicate ion exchange materials are further characterized by a particle
size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
The term "particle size diameter" herein represents the average particle size diameter
of a given ion exchange material as determined by conventional analytical techniques
such as, for example, microscopic determination utilizing a scanning electron microscope.
The aluminosilicate ion exchange materials are further characterized by their calcium
ion exchange capacity, which is at least 200 mg equivalent of CaCO
3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which
generally is in the range of from 300 mg eq./g to 352 mg eq./g. The aluminosilicate
ion exchange materials herein are still further characterized by their calcium ion
exchange rate which is described in detail in GB-1 429 143.
[0040] Aluminosilicate ion exchange materials useful in the practice of this invention are
commercially available and can be naturally occurring materials, but are preferably
synthetically derived. A method for producing aluminosilicate ion exchange materials
is discussed in US Patent No. 3 985 669. Preferred synthetic crystalline aluminosilicate
ion exchange materials useful herein are available under the designation Zeolite A,
Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In an especially preferred
embodiment, the crystalline aluminosilicate ion exchange material is Zeolite A and
has the formula
Na
12[(A10
2)
12 (SiO
2)
12] xH
2O
wherein x is from 20 to 30, especially 27. Zeolite X of formula Na
86 [(A10
2)
86(SiO
2)
106] - 10
.276H
2O is also suitable, as well as Zeolite HS of formula Na
6 [(A10
2)
6(SiO
2)
6] 7.5 H
2O).
[0041] Another suitable water-insoluble, inorganic builder material is layered silicate,
e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium
silicate (Na
2Si
2O
5). The high Ca
++/Mg
++ binding capacity is mainly a cation exchange mechanism. In hot water, the material
becomes more soluble.
[0042] The water-soluble builder can be a monomeric or oligomeric carboxylate chelating
agent.
[0043] Suitable carboxylates containing one carboxy group include lactic acid, glycollic
acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 368, 821
369 and 821 370. Polycarboxylates containing two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,
diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether
carboxylates described in German Offenlegenschrift 2 446 686, and 2 446 687 and U.S.
Patent No. 3 935 257 and the sulfinyl carboxylates described in Belgian Patent No.
840623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble
citrates, aconitrates and citraconates as well as succinate derivatives such as the
carbo-xymethyloxysuccinates described in British Patent 1 379 241, lactoxysuccinates
described in Netherlands Application 7205873, and the oxypolycarboxylate materials
such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1 387
447.
[0044] Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed
in British Patent No. 1 261 829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent
Nos. 1 398 421 and 1 398 422 and in U.S. Patent No. 3 936 448, and the sulfonated
pyrolysed citrates described in British Patent No. 1 082 179, while polycarboxylates
containing phosphone substituents are disclosed in British Patent No. 1 439 000.
[0045] Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates,
cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates,
2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates,
1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols
such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic
acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent
No. 1 425 343.
[0046] Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up
to three carboxy groups per molecule, more particularly citrates.
[0047] Preferred builder systems for use in the present compositions include a mixture of
a water-insoluble aluminosilicate builder such as zeolite A, or of a layered silicate
(SKS-6) and a water-soluble carboxylate chelating agent such as citric acid.
[0048] Other builder materials that can form part of the builder system for the purposes
of the invention include inorganic materials such as alkali metal carbonates, bicarbonates,
silicates.
[0049] Other suitable water-soluble organic salts are the homo- or co-polymeric acids or
their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals
separated from each other by not more than two carbon atoms.
[0050] Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are
polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers
having a molecular weight of from 20,000 to 70,000, especially about 40,000.
[0051] In a preferred embodiment of the present invention, the detergent compositions herein
will contain a cellulase enzyme such as described above, at levels of from 0.025%
to 10% of the composition.
[0052] In another preferred enbodiment of the present invention, the detergent compositions
or detergent additives herein will contain a soil anti redeposition or soil suspension
agent, in combination with the modified polyesters herein.
[0053] Antiredeposition and soil suspension agents suitable herein include cellulose derivatives
such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, homo- or
co-polymeric polycarboxylic acids or their salts and polyaminoacid compounds. Polymers
of this type include the polyacrylates and maleic anhydrideacrylic acid copolymers
previously mentioned as builders, as well as copolymers of maleic anydride with ethylene,
methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least
20 mole percent of the copolymer. Polyaminoaccid compounds such as those derived from
aspartic acid are for instance disclosed in WO-A-94 14 939 published on 7.7.94.
[0054] These materials are normally used at levels of from 0.5% to 10% by weight, more preferably
from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
[0055] The present detergent compositions are preferably in granular form and more preferably
in a "compact" form, i.e. having a density, which is higher than the density of conventional
detergent compositions. The preferred density of the compositions herein ranges from
550 to 950g/liter, preferably 650 to 850g/liter of composition, measured at 20°C.
[0056] The present "compact" form of the most preferred compositions herein is best reflected,
in terms of composition, by the amount of inorganic filler salt; inorganic filler
salts are conventional ingredients of detergent compositions in powder for, in conventional
detergent compositions, the filler salts are present in substantial amounts, typically
17-35% by weight of the total composition.
[0057] In the most preferred compositions herein, the filler salt is present in amounts
not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably
not exceeding 5% by weight of the composition.
[0058] Inorganic filler salts, such as meant in the present compositions are selected from
the alkali and alkaline-earth-metal salts of sulfates and chlorides.
[0059] A preferred filler salt is sodium sulphate.
[0060] The present compositions will typically include optional ingredients that normally
form part of detergent compositions. Enzymes, optical brighteners, bleaches, bleach
activators, suds suppressors, anticacking agents, dyes and pigments are examples of
such optional ingredients and can be added in varying amounts as desired.
[0061] Enzymes such as proteases, cellulase, lipases, or amylases are particularly desirable
ingredients of the compositions herein, in particular cellulase.
[0062] The cellulase usable in the combination with the modified polyesters herein may be
any bacterial or fungal cellulase, having a pH optimum of between 5 and 9.5.
[0063] Suitable cellulases are disclosed in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-24
47 832.
[0064] Examples of such cellulases are cellulase produced by a strain of Humicola insolens
(Humicola grisea var. thermoidea), particularly by the Humicola strain DSM 1800, and
cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted
from the hepatopancreas of a marine mullosc (Dolabella Auricula Solander).
[0065] The cellulase added to the composition of the invention may be in the form of a non-dusting
granulate, e.g. "marumes" or "prills", or in the form of a liquid in which the cellulase
is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or
dissolved in an aqueous medium.
[0066] Preferred cellulases for use herein are characterized in that said cellulase they
provide at least 10% removal of immobilized radioactive labelled carboxymethyl-cellulose
according to the C14CMC-method described in EPA 350 098 at 25x10
-6% by weight of cellulase protein in the laundry test solution.
[0067] Most preferred cellulases are those as described in International Patent Application
WO 91/17243. For example, a cellulase preparation useful in the compositions of the
invention can consist essentially of a homogeneous endoglucanase component, which
is immunoreactive with an antibody raised against a highly purified 43kD cellulase
derived from
Humicola insolens, DSM 1800, or which is homologous to said 43kD endoglucanase.
[0068] The modified polyesters herein typically achieve their cleaning benefits on cotton-containing
fabrics by being incorporated into a detergent composition including other detersive
ingredients, at a level of from 0.025% to 10% by weight of the composition.
[0069] Alternatively, the modified polyester herein can be added separately, to the laundry
cycle, in the form of a detergent additive; said additive posssibly containing other
selected detergent active materials, such as soil anti-redeposition agents and co-dispersing
agents, and/or cellulase enzyme; in particular, the modified polyesters herein can
be used to pre-treat cotton-containing fabrics, before the main wash cycle of a laundering
process.
[0070] Preferred optical brighteners are anionic in character, examples of which are disodium
4,4
1-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2,2
1-disulphonate, disodium 4,4
1-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2
1-disulphonate, disodium 4,4
1-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2,2
1-disulphonate, monosodium 4
1,4
11-bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,4
1 -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2
1-disulphonate, disodium 4,4
1 -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2
1disulphonate, disodium 4,4
1bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2
1disulphonate and sodium 2(stilbyl-4
11-(naphtho-1
1,2
1:4,5)-1,2,3-triazole-2
11-sulphonate.
[0071] Any particulate inorganic perhydrate bleach can be used, in an amount of from 3%
to 40% by weight, more preferably from 8% to 25% by weight and most preferably from
12% to 20% by weight of the compositions. Preferred examples of such bleaches are
sodium perborate monohydrate and tetrahydrate, percarbonate, and mixtures thereof.
[0072] Another preferred separately mixed ingredient is a peroxy carboxylic acid bleach
precursor, commonly referred to as a bleach activator, which is preferably added in
a prilled or agglomerated form in granular detergents. Peroxygen bleaching agents
are preferably combined with bleach activators, which lead to the in situ production
in aqueous solution (i.e. during the washing process of the peroxy acid corresponding
to the bleach activator). Examples of suitable compounds of this type are disclosed
in British Patent Nos. 1586769 and 2143231 and a method for their formation into a
prilled form is described in European Published Patent Application No. 0 062 523.
Preferred examples of such compounds are tetracetyl ethylene diamine and sodium 3,
5, 5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described
for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for
instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl
citrate (ATC) such as described in European patent application EP-A-624154.
[0073] Bleach activators are for instance normally employed at levels of from 0.5% to 10%
by weight, more frequently from 1% to 8% and preferably from 2% to 6% by weight of
the composition.
[0074] Optionally metallo-catalysts/MnPC can be used at a preferred about 0.2 part to the
total detergent composition according to the invention.
[0075] Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone
mixtures. Silicones can be generally represented by alkylated polysiloxane materials
while silica is normally used in finely divided forms exemplified by silica aerogels
and xerogels and hydrophobic silicas of various types. These materials can be incorporated
as particulates in which the suds suppressor is advantageously releasably incorporated
in a water-soluble or water-dispersible, substantially non-surface-active detergent
impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed
in a liquid carrier and applied by spraying on to one or more of the other components.
[0076] As mentioned above, useful silicone suds controlling agents can comprise a mixture
of an alkylated siloxane, of the type 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 trimethyl-silanated) silica having a particle size in the range from
10 millimicrons to 20 millimicrons and a specific surface area above 50 m
2/g intimately admixed with dimethyl silicone fluid having a molecular weight in the
range from about 500 to about 200000 at a weight ratio of silicone to silanated silica
of from about 1:1 to about 1:2.
[0077] A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S.
Patent 3 933 672. Other particularly useful suds suppressors are the self-emulsifying
silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published
April 28, 1977. An example of such a compound is DC-544, commercially availably from
Dow Corning, which is a siloxane/glycol copolymer.
[0078] The suds suppressors described above are normally employed at levels of from 0.001%
to 2% by weight of the composition, preferably from 0.01% to 1% by weight. The incorporation
of the suds mofidiers is preferably made as separate particulates, and this permits
the inclusion therein of other suds controlling materials such as C20-C24 fatty acids,
microcrystalline waxes and high MW 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. Patent No. 3 933 672.
[0079] Fabric softening agents can also be incorporated into detergent compositions in accordance
with the present invention. These agents may be inorganic or organic in type. Inorganic
softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898.
[0080] Organic fabric softening agents include the water-soluble tertiary amines as disclosed
in GB-A-1 400 898. Organic fabric softening agents include the water-insoluble tertiary
amines as disclosed in GB-A-1514276 and EP-B-O 011 340 and their combination with
mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-O
026 528 and di-long-chain amides as disclosed in EP-B-O 242 919. Other useful organic
ingredients of fabric softening systems include high molecular weight polyethylene
oxide materials as disclosed in EP-A-O 299 575 and 0 313 146.
[0081] In the preferred granular detergent compositions herein, levels of smectite clay
are normally in the range from 5% to 20%, more preferably from 8% to 15% by weight
with the material being added as a dry mixed component to the remainder of the formulation.
Organic fabric softening agents such as the water-insoluble tertiary amines or di-long-chain
amide materials are incorporated at levels of from 0.5% to 5% by weight, normally
from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials
and the water-soluble cationic materials are added at levels of from 0.1% to 2%, normally
from 0.15% to 1.5% by weight. These materials are normally added to the spray dried
portion of the composition, although in some instances it may be more convenient to
add them as a dry mixed particulate, or spray them as a molten liquid on to other
solid components of the composition.
[0082] The compositions herein may also contain dye-transfer inhibiting agents such as polyvinylpyrrolidones
having a molecular weight from 5 000 to 2 200, typically present in the preferred
granular detergent compositions herein, at level such as to deliver from 5 to 500
mg/l of said polyvinyl pyrrolidones in the wash solution. Also PVPVI could be used
as dye-transfer inhibiting agent in detergent compositions.
[0083] The compositions of the invention may fully contain from 0.05% to 5% by weight of
the composition, prefereably from 0.05% to 1% by weight, most preferably from 0.1%
tot 0.5% by weight of a chelant (heavy metal sequestrant).
[0084] A suitable chelant for inclusion in the detergent compositions in accordance with
the invention is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal,
alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures
thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium
salt thereof. Examples of such preferred sodium salts of EDDS include Na
2EDDS and Na
4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg
2EDDS . The magnesium salts are the most preferred for inclusion in compositions in
accordance with the invention.
[0085] Other chelants include the organic phosphonates, including amino alkylene poly (alkylene
phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates,
ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene
phosphonates. The phosphonate compounds may be present either in their acid form or
as a complex of either an alkali or alkaline metal ion, the molar ratio of said metal
ion to said phosphonate compound being at least 1:1. Such complexes are described
in US-A-4,259,200. Preferably, the organic phosphonate compounds where present are
in the form of their magnesium salt. The level of phosphorus containing chelants in
the compositions of the invention is preferably minimised, with their complete exclusion
from the compositions being most preferred. Other chelants suitable for inclusion
herein include amino polycarboxylate chelants such as EDTA and HEDTA.
Making process
[0086] Compositions according to the present invention can be made via a variety of methods
including dry mixing, spray drying, agglomeration and granulation and combinations
of any of these techniques. The compositions according to the present invention can
be prepared with different bulk densities, from conventional granular products to
so-called "concentrated" products (i.e. with a bulk density above 600g/l).
EXAMPLES
[0087] The following examples illustrate the invention and facilitate its understanding.
[0088] The abbreviations for the individual ingredients have the following meaning:
- LAS:
- sodium salt of linear dodecyl benzene sulfonate
- AS:
- sodium salt or C14-15 alkyl sulfate
- TAS:
- sodium salt of tallow alcohol sulfate
- FA45E7:
- fatty alcohol (C14-C15) ethoxylated with about 7 moles of ethylene oxide
- FA25E3:
- fatty alcohol (C12-15) ethoxylated with about 3 moles of ethylene oxide
- CAT:
- C12 alkyl trimethyl ammonium chloride
- Clay:
- smectite clay
- Zeolite A4:
- sodium salt of zeolite 4A with average particle size between 1 - 10 micrometer
- SKS-6:
- crystalline layered silicate (Hoechst)
- Copolymer AA/MA:
- copolymer of acrylic acid and maleic acid
- PAA:
- Polyacrylate polymer
- CMC:
- carboxymethylcellulose
- Phosphonate:
- sodium salt of ethylenediamine tetramethylene phosphonic acid
- EDTA:
- sodium salt of ethylenediamine tetra acetate
- PB1:
- NaBO2.H2O2
- TAED:
- tetra acetyl ethylene diamine
- PVP:
- Polyvinylpyrrolidone
- Silicate (R=n):
- SiO2/Na2O=n
- Cellulase:
- 43kD species according to the description herein above
- Amylase:
- Termamyl® 60T (Novo-Nordisk)
- Lipase:
- Lipolase® 100T (Novo-Nordisk)
- Protease:
- Savinase® 4T (Novo-Nordisk)
- SSS:
- Suds Suppressing System (silica/silicone mixture)
The modified polyester used throughout the following examples correspond to the species
described in claim 2 herein.
The method of preparation was as follow:
The process of preparation of the selected polyester herein includes mixing all the
monomers in a round bottomed flask, stirring at 180°C, until a clear solution results,
and continue stirring for 24 hours. Then transferring the contents of the round bottomed
flask to a further single necked round bottomed flask (typically 1 litre), heating
under vacuum for 45 minutes at 200°C, removing from flask and cooling. A clear glass
solid is obtained, which is then crushed gently to be used.
COMPACT DETERGENT COMPOSITIONS (all levels in % by weight) |
Examples: |
I |
II |
III |
LAS |
-- |
-- |
-- |
TAS |
-- |
-- |
-- |
AS |
6.00 |
6.50 |
6.50 |
FA45E7 |
3.00 |
-- |
-- |
FA25E3 |
6.00 |
7.00 |
7.00 |
CAT |
-- |
-- |
-- |
Tallow glucose amide |
-- |
-- |
-- |
Na citrate/citric |
4.00 |
4.00 |
4.00 |
Zeolite 4A |
13.00 |
13.00 |
12.50 |
SKS-6 |
12.00 |
12.00 |
12.00 |
Copolymer AA/MA |
5.00 |
3.00 |
3.00 |
Polypeptide |
-- |
2.00 |
2.00 |
Phosphonate |
-- |
-- |
-- |
EDTA |
-- |
-- |
-- |
Na carbonate/bicarbonate |
9.00 |
10.00 |
10.00 |
Silicate (R2) |
3.50 |
3.50 |
3.50 |
CMC |
0.30 |
-- |
-- |
Clay |
--- |
-- |
-- |
PB1 |
-- |
12.00 |
12.00 |
Percarbonate |
23.00 |
-- |
-- |
TAED |
6.00 |
4.00 |
4.00 |
Protease |
1.40 |
1.40 |
1.40 |
Cellulase |
0.10 |
0.10 |
0.10 |
Lipase |
0.30 |
0.30 |
0.30 |
Amylase |
-- |
-- |
-- |
Na Sulfate |
3.50 |
4.00 |
4.00 |
PVP |
-- |
-- |
-- |
PVNO |
-- |
-- |
0.50 |
SSS |
0.50 |
0.50 |
0.50 |
Modified polyester |
0.50 |
0.50 |
0.50 |
Minors + water Balance to 100% |
|
|
|
Example IV
[0089] Numerous attemps have been made to thicken C25E3 (being FA
25E3) with various different detergent ingredients with limited success. The use of
modified soil release polymers according to this invention provides a method of thickening
C25E3.
[0090] By mixing C25E3 with soil release polymer solution in the ratio of one part C25E3
to 0.3 parts soil release polymer at room temperature with mild stirring one forms
a thick white viscous paste which does not separate upon standing.
- Different soil release polymers may provide the same thickening effect.
- Higher levels of soil release polymers produce a thicker paste.
Ratio |
C25E3 |
Soil release polymer |
Thickening effect |
3 |
0.3 |
None |
2 |
0.3 |
Slightly thicker but separates on standing |
1 |
0.3 |
Thick stable white paste |
1 |
2.0 |
Thick stable white paste |
Conditions
Room tempature, mild stirring
[0091] This above shows the thickening of nonionic surfactant C25E3 by the addition of a
soil release polymer solution as described in this application. This provides the
formulator with a potentially effective method by which C25E3 can be processed into
granular detergents.