FIELD OF THE INVENTION
[0001] The present invention relates to the use of oleoyl sarcosinate in detergent compositions
built with zeolite and/or silicate builder materials to provide improved cleaning
benefits.
BACKGROUND OF THE INVENTION
[0002] The formulation of effective laundry detergent compositions which are sufficiently
robust to remove a wide variety of soils and stains from fabrics under a variety of
usage conditions remains a considerable challenge to the industry. This is especially
true since the advent of legislation which limits the use of effective phosphate builders
in many regions of the world.
[0003] Various laundry detergent compositions which are designed not only to clean fabrics,
but also to provide additional fabric care benefits, have been described in the literature
and have entered the marketplace with very substantial commercial success. While a
review of the literature would seem to suggest that a wide selection of surfactants
is available to the detergent manufacturer, the reality is that many such materials
are specialty chemicals which are not suitable for routine use in low unit cost items
such as home laundering compositions. The fact remains that most home-use detergents
still comprise one or more of the conventional ethoxylated nonionic and alkyl sulfate
or alkyl benzene sulfonate anionic surfactants, presumably due to the economic and
performance considerations.
[0004] By the present invention, oleoyl sarcosinate is employed as an anionic detersive
surfactant in granular laundry detergent compositions built with aluminosilicate and/or
silicate builder materials. The resulting formulations exhibit excellent solubility
even at cold water temperatures, excellent cleaning of both particulate soils and
greasy and oily soils, and provide excellent compatibility and cleaning benefits with
other detergent adjuncts, including enzymes. The compositions also provide excellent
color care for dyed fabrics and excellent skin mildness for handwash operations. These
and other advantages of the present invention will be seen from the disclosures hereinafter.
BACKGROUND ART
[0005] Oleoyl sarcosinate is described in the following patents and publications: U.S. 2,542,385;
U.S. 3,402,990; U.S. 3,639,568; U.S. 4,772,424, U.S. 5,186,855. European Patent Publication
505,129; British Patent Publication 1,211,545; Japanese Patent Publication 59/232194;
Japanese Patent Publication 62/295997; Japanese Patent Publication 02/180811, and
Chemical Abstracts Service abstracts Nos 61 : 3244q, 70 : 58865x, and 83 : 181020p.
SUMMARY OF THE INVENTION
[0006] The present invention encompasses detergent compositions comprising
(a) at least 0.1% by weight of oleoyl sarcosinate surfactant,
(b) at least 0.001% by weight of one or more detergency builders selected from the
group consisting of aluminosilicate, silicate builders and mixtures thereof; and
(c) the balance comprising detersive adjuncts and carrier materials.
[0007] Preferred compositions herein additionally comprise at least 0.001 %, by weight,
of an enzyme, especially an enzyme selected from the group consisting of proteases,
amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
[0008] Fully-formulated compositions herein may additionally comprise at least 1%, by weight,
of a non-oleoyl sarcosinate detersive surfactant, especially surfactants selected
from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, polyhydroxy fatty
acid amides, ethoxylated alcohols, and mixtures thereof.
[0009] Preferred granular laundry detergents provided by this invention comprise
(a) from 0.1% to 55%, by weight, of oleoyl sarcosinate surfactant;
(b) from 1% to 80%, by weight, of one or more detergency builders selected from the
group consist of aluminosilicate, silicate, and mixtures thereof;
(c) from 1% to 35%, by weight, of a non-oleoyl sarcosinate detersive surfactant;
(d) from 0.001% to 5%, by weight, of enzymes selected from the group consisting of
protease, cellulase, amylase, lipase, peroxidase, and mixtures thereof; and
(e) the balance of the composition comprising detersive adjunct ingredients.
[0010] The invention also encompasses a method for cleaning soiled fabrics, comprising contacting
said fabrics with an aqueous medium which contains at least 50 ppm, preferably from
100 ppm to 10,000 ppm, of a composition according to the above, preferably with agitation.
[0011] All percentages, ratios and proportions herein are by weight, unless otherwise specified.
DETAILED DESCRIPTION OF THE INVENTION
Oleoyl Sarcosinate:
[0012] The present invention compositions comprise oleoyl sarcosinate, in its acid and/or
salt form selected as desired for the compositions and uses herein, having the following
formula:
wherein M is hydrogen or a cationic moiety. Preferred M are hydrogen and alkali metal
salts, especially sodium and potassium. Oleoyl sarcosinate is commercially available,
for example as Hamposyl O supplied by W. R. Grace & Co. Compositions according to
the present invention typically comprise from 0.1% to 55%, preferably from 1% to 20%,
and most preferably from 3% to 15%, of oleoyl sarcosinate by weight of the composition.
[0013] In addition to the commercially-available oleoyl sarcosinate, oleoyl sarcosinate
useful herein can also preferably be prepared from the ester (preferably the methyl
ester) of oleic acid and a sarcosine salt (preferably the sodium salt) under anhydrous
reaction conditions in the presence of a base catalyst with a basicity equal to or
greater than alkoxide catalyst (preferably sodium methoxide). For example, the reaction
may be illustrated by the scheme:
[0014] This salt may optionally be neutralized to form the oleoyl sarcosinate in its acid
form.
[0015] The preferred method for preparing oleoyl sarcosinate is conducted at a temperature
from 80°C to 200°C, especially from 120°C to 200°C. It is preferred to conduct the
reaction without solvent although alcohol solvents which have a boiling point of at
least 100°C and are stable to the reaction conditions (ie. glycerol is not acceptable)
can be used. The reaction may proceed in 85% yield with a molar ratio of methyl ester
reactant to sarcosine salt reactant to basic catalyst of 1:1:0.05-0.2.
[0016] Methyl ester mixtures derived from high oleic content natural oils (preferably having
at least 60%, more preferably at least 75%, and most preferably at least 90% oleic
content) are especially preferred as starting materials. Examples include high-oleic
sunflower and rapeseed/canola oil. In addition, a high-oleic methyl ester fraction
derived from either palm kernel oil or tallow is acceptable. It is to be understood
that such oils typically will contain some levels of impurities, including some fatty
acid impurities that may be converted to sarcosinate compounds by this synthesis method.
For example, commodity canola/rapeseed oil may comprise a majority of oleic acid,
and a mixture of fatty acid impurities such as palmitic, stearic, linoleic, linolenic
and/or eicosenoic acid, some or all of which are converted to the sarcosinate by this
reaction method. If desired for formulation purposes, some or all of such impurity
materials may be excluded from the starting oil before preparing the oleoyl sarcosinate
to be used in the present compositions.
[0017] Finally, sarcosine remaining in the reaction mixture can be converted to an amide
by addition of maleic or acetic anhydride to the mixture, thereby minimizing the sarcosine
content and any potential for formation of undesired nitrogen-containing impurities.
[0018] The synthesis of oleoyl sarcosinate may be carried out as follows to prepare the
sodium oleoyl sarcosinate.
[0019] Synthesis of Oleoyl Amide of Sarcosine Sodium Salt - A 2 L. 3-neck, round bottom flask is fitted with thermometer. Dean-Stark trap with
condenser, mechanical stirring, and a gas inlet adapter through which nitrogen is
passed over the reaction mixture. The reaction vessel is charged with sarcosine (43.3
g, 0.476 mol), sodium methoxide 25% in methanol (97.7 g, 0.452 mol), and methanol
(400 mL). The reaction is refluxed 15 min to neutralize the sarcosine and then methyl
ester derived from Cargill regular high-oleyl sunflower oil (148.25 g, 0.5 mol) is
added. After the methanol is removed with the Dean-Stark trap, reaction mixture is
heated to 170°C for 1 hr to drive off any water. The reaction is initiated by the
addition of sodium methoxide 25% in methanol (15.4 g, 0.0714 mol). Reaction is kept
at 170°C for 2.5 hr during which methanol is collected in the Dean-Stark trap. The
reaction is allowed to cool slightly and then methanol (200 g) is added. Maleic anhydride
(9.43 g, 0.095 mol) is added to the methanol solution and the reaction is stirred
at 60°C for 0.5 hr. Then most of the methanol is removed by rotary evaporation and
acetone (2 L) is added to precipitate the product. The product is collected by suction
filtration and allowed to air dry to give an off-white solid. Analysis of the reaction
mixture by GC indicates the majority of the product is oleoyl sarcosinate, with minor
amounts of the following impurities: sarcosine, oleic acid, and the sarcosinates derived
from palmitic acid, stearic acid, and linoleic acid.
[0020] Aluminosilicate and Silicate Builders: The level of aluminosilicate and silicate builder used in the present invention compositions
can vary widely depending upon the end use of the composition. The present granular
compositions will typically comprise at least 1% of such builder, more typically from
1% to 80%, and most typically from 5% to 50% by weight of the compositions. Lower
or higher levels of builder, however, are not meant to be excluded.
[0021] Examples of silicate builders are the alkali metal silicates, particularly those
having a SiO
2:Na
2O ratio in the range 1.0:1 to 3.2:1 and layered silicates, such as the layered sodium
silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly
abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder
does not contain aluminum. NaSKS-6 has the delta-Na
2SiO
5 morphology from of layered silicate. It can be prepared by methods such as those
described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred
layered silicate for use herein, but other such layered silicates, such as those having
the general formula NaMSi
xO
2x+1·yH
2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and
y is a number from 0 to 20, preferably 0 can be used herein. Various other layered
silicates from Hoechst include NaSKS-5, NaSKS-7 and NASKS-11, as the alpha, beta and
gamma forms. As noted above, the delta-Na
2SiO
5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful
such as for example magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds
control systems.
[0022] Aluminosilicate builders are also useful in the present invention Aluminosilicate
builders are of great importance in most currently marketed heavy duty granular detergent
compositions, and can also be a significant builder ingredient in liquid detergent
formulations. Aluminosilicate builders include those hawing the empirical formula
M
z/n[(AlO
2)
z(SiO
2)
y]·xH
2O
wherein z and y are integers usually of at least 6, the molar ratio of z to y is in
the range from 1.0 to 0, and x is an integer from 0 to 264, and M is a Group IA or
IIA element, e.g., Na, K, Mg, Ca with valence n.
[0023] Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates
can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates
or synthetically derived. A method for producing aluminosilicate ion exchange materials
is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred
synthetic crystalline aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an
especially preferred embodiment, the crystalline aluminosilicate ion exchange material
has the formula:
Na
12[(AlO
2)
12(SiO
2)
12]·xH
2O
wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated
zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has
a particle size of 0.1-10 microns in diameter.
[0024] Various other optional adjunct ingredients may also be used in combination with the
oleoyl sarcosinate and builders herein to provide fully-formulated granular detergent
compositions. The following ingredients are described for the convenience of the formulator,
but are not intended to be limiting thereof.
[0025] Detersive Surfactants - Nonlimiting examples of surfactants useful herein typically at levels from 1% to
55%, by weight, include the conventional C
11-C
18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C
10-C
20 alkyl sulphates ("AS"), the C
10-C
18 secondary (2,3) alkyl sulfates of the formula CH
3(CH
2)
x(CHOSO
3-M
+) CH
3 and CH
3 (CH
2)
y(CHOSO
3-M
+) CH
2CH
3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a
water-solubilizing cation, especially sodium, unsaturated alkyl sulfates such as oleyl
sulfate, the C
10-C
18 alkyl alkoxy sulfates ("AE
xS"; especially x up to about 7 EO ethoxy sulfates), C
10-C
18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C
10-18 glycerol ethers, the C
10-C
18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C
12-C
18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric
surfactants such as the C
12-C
18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates
and C
6-C
12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C
12-C
18 betaines and sulfobetaines ("sultaines"), C
10-C
18 amine oxides, and the like, can also be included in the overall compositions. The
C
10-C
18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include
the C
12-C
18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the
N-alkoxy polyhydroxy fatty acid amides, such as C
10-C
18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C
12-C
18 glucamides can be used for low sudsing. C
10-C
20 conventional soaps may also be used. If high sudsing is desired, the branched-chain
C
10-C
16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts.
[0026] Builders - Other detergent builders can optionally be included in the compositions herein
to also assist in controlling mineral hardness. Inorganic as well as organic builders
can be used. Builders are typically used in fabric laundering compositions to assist
in the removal of particulate soils.
[0027] Inorganic or P-containing detergent builders in addition to the present invention
silicate and zeolites include, but are not limited to, the alkali metal, ammonium
and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid,
carbonates (including bicarbonates and sesquicarbonates), and sulphates. However,
non-phosphate builders are required in some locales.
[0028] Examples of carbonate builders are the alkaline earth and alkali metal carbonates
as disclosed in German Patent Application No. 2,321,001 published on November 15,
1973.
[0029] Organic detergent builders suitable for the purposes of the present invention include,
but are not restricted to, a wide variety of polycarboxylate compounds. As used herein,
"polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably
at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition
in acid form, but can also be added in the form of a neutralized salt. When utilized
in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium
salts are preferred.
[0030] Included among the polycarboxylate builders are a variety of categories of useful
materials. One important category of polycarboxylate builders encompasses the ether
polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18,
1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al,
on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly
alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
[0031] Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers
of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2,
4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal,
ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic
acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic
acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
[0032] Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium
salt), are polycarboxylate builders may be used and are desirable due to their availability
from renewable resources and their biodegradability. Also, citrates can be used in
granular compositions in combination with zeolite and/or layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and combinations.
[0033] Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates
and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January
28, 1986. Useful succinic acid builders include the C
5-C
20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound
of this type is dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),
2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders
of this group, and are described in European Patent Application 0,200,263, published
November 5, 1986.
[0034] Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield
et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7,
1967. See also Diehl U.S. Patent 3,723,322.
[0035] Fatty acids, e.g., C
12-C
18 monocarboxylic acids such as oleic acid and/or its salts, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders, especially
citrate and/or the succinate builders, to provide additional builder activity. Such
use of fatty acids will generally result in a diminution of sudsing, which should
be taken into account by the formulator.
[0036] In situations where phosphorus-based builders can be used, and especially in the
formulation of bars used for hand-laundering operations, the various alkali metal
phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and
sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate
and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030;
3,422,021; 3,400,148 and 3,422,137) can also be used.
[0037] Enzymes - Enzymes may be included in the formulations herein for a wide variety of fabric
laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based
stains, for example, and for the prevention of refugee dye transfer, and for fabric
restoration. The enzymes to be incorporated include proteases, amylases, lipases,
cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may
also be included. They may be of any suitable origin, such as vegetable, animal, bacterial,
fungal and yeast origin. However, their choice is governed by several factors such
as pH-activity and/or stability optima, thermostability, stability versus active detergents,
builders and so on. In this respect bacterial or fungal enzymes are preferred, such
as bacterial amylases and proteases, and fungal cellulases.
[0038] Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg
by weight, more typically 0.001 mg to 3 mg, of active enzyme per gram of the composition.
Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%,
preferably 0.01%-2% by weight of a commercial enzyme preparation. Protease enzymes
are usually present in such commercial preparations at levels sufficient 10 provide
from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
[0039] Suitable examples of proteases are the subtilisins which are obtained from particular
strains of B. subtilis and B. licheniforms. Another suitable protease is obtained
from a strain of Bacillus, having maximum activity throughout the pH range of 8-12,
developed and sold by Novo Industries A/S under the registered trade name ESPERASE.
The preparation of this enzyme and analogous enzymes is described in British Patent
Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based
stains that are commercially available include those sold under the tradenames ALCALASE
and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics.
Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application
130,756, published January 9, 1985) and Protease B (see European Patent Application
Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756,
Bott et al, published January 9, 1985). Other proteases include Protease A (see European
Patent Application 130,756, published January 9, 1985) and Protease B (see EP-A-0
251 446, and European Patent Application 130,756, Bott et al, published January 9,
1985). Most preferred is what is called herein "Protease C", which is a variant of
an alkaline serine protease from
Bacillus, particularly
Bacillus lentus, in which arginine replaced lysine at position 27, tyrosine replaced valine at position
104, serine replaced asparagine at position 123, and alanine replaced threonine at
position 274. Protease C is described in EP 90915958:4; U.S. Patent No. 5,185,250;
and U.S. Patent No. 5,204,015. Also preferred are protease which are described in
copending application U.S. Serial No. 08/136,797, entitled Protease-containing Cleaning
Compositions and copending Application U.S. Serial No. 08/136,626, entitled Bleaching
Compositions Comprising Protease Enzymes, which are incorporated herein by reference.
Genetically modified variants, particularly of Protease C, are also included herein.
[0040] Amylases include, for example, α-amylases described in British Patent Specification
No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo
industries.
[0041] The cellulase usable in the present invention include both bacterial or fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases
are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which
discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800
or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase
extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander),
suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Cellulases such as CAREZYME (Novo) are especially useful, since they provide additional
softening and appearance benefits to fabrics laundered in the present compositions.
[0042] Suitable lipase enzymes for detergent usage include those produced by microorganisms
of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in
British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487,
laid open to public inspection on February 24, 1978. This lipase is available from
Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"
hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES,
lipases ex Chromobacter viscosum. e.g. Chromobacter viscosum var. lipolyticum NRRLB
3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter
viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands,
and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa
and commercially available from Novo (see also EPO 341,947) is a preferred lipase
for use herein.
[0043] Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate,
perborate, persulfate and hydrogen peroxide. They are used for "solution bleaching,"
i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations
to other substrates in the wash solution Peroxidase enzymes are known in the art,
and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such
as chloro- and bromo-peroxidase Peroxidase-containing detergent compositions are disclosed,
for example, in PCT International Application WO 89/099813, published October 19,
1989, by O. Kirk, assigned to Novo Industries A/S. It may be desired to use, in combination
with these peroxidases, materials viewed as being peroxidase accelerators such as
phenolsulfonate and/or phenothiazine.
[0044] A wide range of enzyme materials and means for their incorporation into synthetic
detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January
5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457,
Place et al, issued July 18, 1978, in U.S. Patent 4,507,219. Hughes, issued March
26, 1985, and in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981.
[0045] Enzyme Stabilizers - A preferred optional ingredient for use in the present compositions comprising
enzymes is enzyme stabilizers. Enzyme stabilizers can be introduced at a level of
at least 0.5% by weight of the composition. Enzymes for use in detergents can be stabilized
by various techniques. Enzyme stabilization techniques are disclosed and exemplified
in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent
Application Publication No. 0 199 405, Application No. 86200586.5, published October
29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in
U.S. Patent 3,519,570. The enzymes employed herein can be stabilized by the presence
of water-soluble sources of calcium and/or magnesium ions in the finished compositions
which provide such ions to the enzymes. (Calcium ions are generally somewhat more
effective than magnesium ions and are preferred herein if only one type of cation
is being used.)
[0046] Additional stability can be provided by the presence of various other art-disclosed
stabilizers, especially borate species: see Severson, U.S. 4,537,706. Typical detergents
will comprise from 1 to 30, preferably from 2 to 20, more preferably from 5 to 15,
and most preferably from 8 to 12, millimoles of calcium ion per liter of finished
composition. This can vary somewhat, depending on the amount of enzyme present and
its response to the calcium or magnesium ions. The level of calcium or magnesium ions
should be selected so that there is always some minimum level available for the enzyme,
after allowing for complexation with builders, fatty acids, in the composition. Any
water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium
ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate,
calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the
corresponding magnesium salts. A small amount of calcium ion, generally from 0.05
to 0.4 millimoles per liter, is often also present in the composition due to calcium
in the enzyme slurry and formula water. In solid detergent compositions the formulation
may include a sufficient quantity of a water-soluble calcium ion source to provide
such amounts in the laundry liquor. In the alternative, natural water hardness may
suffice.
[0047] It is to be understood that the foregoing levels of calcium and/or magnesium ions
are sufficient to provide enzyme stability. More calcium and/or magnesium ions can
be added to the compositions to provide an additional measure of grease removal performance.
Accordingly, as a general proposition the compositions herein will typically comprise
from 0.05% to 2% by weight of a water-soluble source of calcium or magnesium ions,
or both. The amount can vary, of course, with the amount and type of enzyme employed
in the composition.
[0048] The compositions herein may also optionally, but preferably, contain various additional
stabilizers, especially borate-type stabilizers. Typically, such stabilizers will
be used at levels in the compositions from 0.25% to 10%, preferably from 0.5% to 5%,
more preferably from 0.75% to 3%, by weight of boric acid or other borate compound
capable of forming boric acid in the composition (calculated on the basis of boric
acid). Boric acid is preferred, although other compounds such as boric oxide, borax
and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium
pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butane
boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.
It is to be recognized that such materials may also be used in formulations as the
sole stabilizer as well as being used in combination with added calcium and/or magnesium
ions.
[0049] Finally, it may be desired to add chlorine scavengers, especially to protease-containing
compositions, to protect the enzymes from chlorine typically present in municipal
water supplies. Such materials are described, for example, in U.S. Patent 4,810,413
to Pancheri et al.
[0050] Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein may optionally contain bleaching agents or bleaching
compositions containing a bleaching agent and one or more bleach activators. When
present, bleaching agents will typically be at levels of from 1% to 30%, more typically
from 5% to 20%, of the detergent composition, especially for fabric laundering. If
present, the amount of bleach activators will typically be from 0.1% to 60%, more
typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach
activator.
[0051] The bleaching agents used herein can be any of the bleaching agents useful for detergent
compositions in textile cleaning or other cleaning purposes that are now known or
become known. These include oxygen bleaches as well as other bleaching agents. Perborate
bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
[0052] Another category of bleaching agent that can be used without restriction encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class
of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of
metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic
acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued
November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985,
European Patent Application 0,133,354, Banks et al, published February 20, 1985, and
U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching
agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent
4,634,551, issued January 6, 1987 to Burns et al.
[0053] Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds
include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach
(e.g., OXONE, manufactured commercially by DuPont) can also be used.
[0054] A preferred percarbonate bleach comprises dry particles having an average particle
size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by
weight of said particles being smaller than 200 micrometers and not more than 10%
by weight of said particles being larger than 1,250 micrometers. Optionally, the percarbonate
can be coated with silicate, borate or water-soluble surfactants. Percarbonate is
available from various commercial sources such as FMC, Solvay and Tokai Denka.
[0055] Mixtures of bleaching agents can also be used.
[0056] Peroxygen bleaching agents, the perborates, the percarbonates, 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. Various nonlimiting examples of activators
are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S.
Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can also be used. See
also U.S. 4,634,551 for other typical bleaches and activators useful herein.
[0057] Highly preferred amido-derived bleach activators are those of the formulae:
R
1N(R
5)C(O)R
2C(O)L or R
1C(O)N(R
5)R
2C(O)L
wherein R
1 is an alkyl group containing from 6 to 12 carbon atoms, R
2 is an alkylene containing from 1 to 6 carbon atoms, R
5 is H or alkyl, aryl, or alkaryl containing from about 1 to 10 carbon atoms, and L
is any suitable leaving group. A leaving group is any group that is displaced from
the bleach activator as a consequence of the nucleophilic attack on the bleach activator
by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
[0058] Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate,
and mixtures thereof as described in U.S. Patent 4,634,551.
[0059] Another class of bleach activators comprises the benzoxazin-type activators disclosed
by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990. A highly preferred
activator of the benzoxazin-type is:
[0060] Still another class of preferred bleach activators includes the acyl lactam activators,
especially acyl caprolactams and acyl valerolactams of the formulae:
wherein R
6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon
atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam,
3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl
caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl
valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures
thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which
discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
[0061] Bleaching agents other than oxygen bleaching agents are also known in the art and
can be utilized herein. One type of non-oxygen bleaching agent of particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum
phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al.
If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight,
of such bleaches, especially sulfonate zinc phthalocyanine.
[0062] If desired, the bleaching compounds can be catalyzed by means of a manganese compound.
Such compounds are well known in the art and include, for example, the manganese-based
catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416;
U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2,
and 544,490A1. Preferred examples of these catalysts include Mn
IV2(u-O)
3(1,4,7-trimethyl-1,4,7-triazacyclononane)
2(PF
6)
2, Mn
III2(u-O)
1(u-OAc)
2(1,4,7-trimethyl-1,4,7-triazacyclononane)
2-(ClO
4)
2, Mn
IV4(u-O)
6(1,4,7-triazacyclononane)
4(ClO
4)
4, Mn
IIIMn
IV4(u-O)
1(u-OAc)
2-(1,4,7-trimethyl-1,4,7-triazacyclononane)
2(ClO
4)
3, Mn
IV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH
3)
3(PF
6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed
in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various
complex ligands to enhance bleaching is also reported in the following United States
Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5.274,147; 5,153,161;
and 5,227,084.
[0063] As a practical matter, and not by way of limitation, the compositions and processes
herein can be adjusted to provide on the order of at least one part per ten million
of the active bleach catalyst species in the aqueous washing liquor, and will preferably
provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst
species in the laundry liquor.
[0064] Polymeric Soil Release Agent - Any polymeric soil release agent known to those skilled in the art can optionally
be employed in the compositions and processes of this invention. Polymeric soil release
agents are characterized by having both hydrophilic segments, to hydrophilize the
surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments,
to deposit upon hydrophobic fibers and remain adhered thereto through completion of
washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments.
This can enable stains occurring subsequent to treatment with the soil release agent
to be more easily cleaned in later washing procedures.
[0065] The polymeric soil release agents useful herein especially include those soil release
agents having: (a) one or more nonionic hydrophile components consisting essentially
of (i) polyoxyethylene segments with a degree of polymerization of at least 2; or
(ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of
from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene
unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii)
a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene
units wherein said mixture contains a sufficient amount of oxyethylene units such
that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity
of conventional polyester synthetic fiber surfaces upon deposit of the soil release
agent on such surface, said hydrophile segments preferably comprising at least 25%
oxyethylene units and more preferably, especially for such components having 20 to
30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobe
components comprising (i) C
3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise
oxyethylene terephthalate, the ratio of oxyethylene terephthalate C
3 oxyalkylene terephthalate units is 2:1 or lower, (ii) C
4-C
6 alkylene or oxy C
4-C
6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably
polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are
present in the form of C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose
derivatives are amphiphilic, whereby they have a sufficient level of C
1-C
4 alkyl ether and/or C
4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces
and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic
fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and
(b).
[0066] Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization
of from 200, although higher levels can be used, preferably from 3 to 150, more preferably
from 6 to 100. Suitable oxy C
4-C
6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric
soil release agents such as MO
3S(CH
2)
nOCH
2CH
2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580,
issued January 26, 1988 to Gosselink.
[0067] Polymeric soil release agents useful in the present invention also include cellulosic
derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene
terephthalate or propylene terephthalate with polyethylene oxide or polypropylene
oxide terephthalate. Such agents are commercially available and include hydroxyethers
of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein
also include those selected from the group consisting of C
1-C
4 alkyl and C
4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol,
et al.
[0068] Soil release agents characterized by poly(vinyl ester) hydrophobe segments include
graft copolymers of poly(vinyl ester), e.g., C
1-C
6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones,
such as polyethylene oxide backbones. See European Patent Application 0 219 048, published
April 22, 1987 by Kud, et al. Commercially available soil release agents of this kind
include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West
Germany).
[0069] One type of preferred soil release agent is a copolymer having random blocks of ethylene
terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of
this polymeric soil release agent is in the range of from about 25,000 to about 55,000.
See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to
Basadur issued July 8, 1975.
[0070] Another preferred polymeric soil release agent is a polyester with repeat units of
ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units
together with 90-80% by weight of polyoxyethylene terephthalate units, derived from
a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer
include the commercially available material ZELCON 5126 (from Dupont) and MILEASE
T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
[0071] Another preferred polymeric soil release agent is a sulfonated product of a substantially
linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
These soil release agents are described fully in U.S. Patent 4,968,451, issued November
6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release
agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December
8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric
compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
[0072] Preferred polymeric soil release agents also include the soil release agents of U.S.
Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic,
especially sulfoaroyl, end-capped terephthalate esters.
[0073] Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl
units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The
repeat units form the backbone of the oligomer and are preferably terminated with
modified isethionate end-caps. A particularly preferred soil release agent of this
type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy
and oxy-1,2-propyleneoxy units in a ratio of from 1,7 to 1,8, and two end-cap units
of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises
from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer,
preferably selected from the group consisting of xylene sulfonate, cumene sulfonate,
toluene sulfonate, and mixtures thereof.
[0074] If utilized, soil release agents will generally comprise from 0.01% to 10.0%, by
weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably
from 0.2% to 3.0%.
[0075] Dye Transfer Inhibiting Agents - The compositions of the present invention may also include one or more materials
effective for inhibiting the transfer of dyes from one fabric to another during tne
cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone
and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
If used, these agents typically comprise from about 0.01% to about 10% by weight of
the composition, preferably from about 0.01% to about 5%, and more preferably from
about 0.05% to about 2%.
[0076] More specifically, the polyamine N-oxide polymers preferred for use herein contain
units having the following structural formula: R-A
x-P; wherein P is a polymerizable unit to which an N-O group can be attached or the
N-O group can form part of the polymerizable unit or the N-O group can be attached
to both units. A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=;
x is 0 or 1, and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or
alicyclic groups or any combination thereof to which the nitrogen of the N-O group
can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides
are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole,
pyrrolidine, piperidine and derivatives thereof.
[0077] The N-O group can be represented by the following general structures:
wherein R
1, R
2, R
3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof,
x, y and z are 0 or 1, and the nitrogen of the N-O group can be attached or form part
of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides
has a pKa <10, preferably pKa <7, more preferred pKa <6.
[0078] Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble
and has dye transfer inhibiting properties. Examples of suitable polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates
and mixtures thereof. These polymers include random or block copolymers where one
monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine
N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the number of amine oxide groups present in the polyamine oxide polymer can
be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
The polyamine oxides can be obtained in almost any degree of polymerization. Typically,
the average molecular weight is within the range of 500 to 1,000,000; more preferred
1,100 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials
can be referred to as "PVNO."
[0079] The most preferred polyamine N-oxide useful in the detergent compositions herein
is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000
and an amine to amine N-oxide ratio of about 1.4.
[0080] Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a
class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average
molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most preferably from 10,000 to 20,000. (The average molecular weight range is
determined by light scattering as described in Barth. et al.,
Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which
are incorporated herein by reference.) The PVPVI copolymers typically have a molar
ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably
from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be
either linear or branched.
[0081] The present invention compositions also may employ a polyvinylpyrrolidone ("PVP")
having an average molecular weight of from 5,000 to 400,000, preferably from about
5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's
are known to persons skilled in the detergent field; see, for example, EP-A-262,897
and EP-A-256,696, incorporated herein by reference Compositions containing PVP can
also contain polyethylene glycol ("PEG") having an average molecular weight from 500
to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on
a ppm basis delivered in wash solutions is from 2.1 to 50:1, and more preferably from
3:1 to 10.1.
[0082] The detergent compositions herein may also optionally contain from 0.005% to 5% by
weight of certain types of hydrophilic optical brighteners which also provide a dye
transfer inhibition action. If used, the compositions herein will preferably comprise
from 0.01% to 1% by weight of such optical brighteners.
[0083] The hydrophilic optical brighteners useful in the present invention are those having
the structural formula:
wherein R
1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R
2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,
chloro and amino, and M is a salt-forming cation such as sodium or potassium.
[0084] When in the above formula, R
1 is anilino, R
2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic
acid and disodium salt. This particular brightener species is commercially marketed
under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred hydrophilic optical brightener useful in the detergent compositions
herein.
[0085] When in the above formula, R
1 is anilino, R
2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener
is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid disodium salt. This particular brightener species is commercially marketed under
tne tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
[0086] When in the above formula, R
1 is anilino, R
2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid, sodium salt. This particular brightener species is commercially marketed under
the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
[0087] The specific optical brightener species selected for use in the present invention
provide especially effective dye transfer inhibition performance benefits when used
in combination with the selected polymeric dye transfer inhibiting agents hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX
and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous
wash solutions than does either of these two detergent composition components when
used alone. Without being bound by theory, it is believed that such brighteners work
this way because they have high affinity for fabrics in the wash solution and therefore
deposit relatively quick on these fabrics. The extent to which brighteners deposit
on fabrics in the wash solution can be defined by a parameter called the "exhaustion
coefficient." The exhaustion coefficient is in general as the ratio of a) the brightener
material deposited on fabric to b) the initial brightener concentration in the wash
liquor. Brighteners with relatively high exhaustion coefficients are the most suitable
for inhibiting dye transfer in the context of the present invention.
[0088] Of course, it will be appreciated that other, conventional optical brightener types
of compounds can optionally be used in the present compositions to provide conventional
fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such
usage is conventional and well-known to detergent formulations.
[0089] Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from 0.1%
to 7%, by weight, in the compositions herein. Suitable polymeric dispersing agents
include polymeric polycarboxylates and polyethylene glycols, although others known
in the art can also be used.
[0090] Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric
acids that can be polymerized to form suitable polymeric polycarboxylates include
acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic
acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the
polymeric polycarboxylates herein or monomeric segments, containing no carboxylate
radicals such as vinylmethyl ether, styrene and ethylene is suitable provided that
such segments do not constitute more than 40% by weight.
[0091] Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble salts
of polymerized acrylic acid. The average molecular weight of such polymers in the
acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000
and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid
polymers can include, for example, the alkali metal, ammonium and substituted ammonium
salts. Soluble polymers of this type are known materials. Use of polyacrylates of
this type in detergent compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued March 7, 1967.
[0092] Acrylic/maleic-based copolymers may also be used as a preferred component of the
dispersing/anti-redeposition agent. Such materials include the water-soluble salts
of copolymers of acrylic acid and maleic acid. The average molecular weight of such
copolymers in the acid form preferably ranges from 2,000 to 100,000. A preferred copolymer
has an average molecular weight of 2,000 to 15,000, more preferably 6,000 to 13,000,
and most preferably 7,000 to 12,000. Other preferred copolymers have an average molecular
weight from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate
to maleate segments in such copolymers will generally range from 30:1 to 1:2, more
preferably from 10:1 to 1:1, and most preferably about 2.5:1 to 1:1. Water-soluble
salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali
metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers
of this type are known materials which are described in European Patent Application
No. 66915, published December 15, 1982, as well as in EP 193,360, published September
3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still
other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers.
Such materials are also disclosed in EP 193,360, including for example, the 45/45/10
terpolymer of acrylic/maleic/vinyl alcohol.
[0093] Particularly preferred dispersant polymers are low molecular weight modified polyacrylate
copolymers. Such copolymers contain as monomer units at from 90% to 10%, preferably
from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably
from 20% to 80% by weight of a substituted acrylic monomer or its salt and have the
general formula: -[(C(R
2)C(R
1)(C(O)OR
3)]- wherein the incomplete valencies inside the square braces are hydrogen and at
least one of the substituents R
1, R
2 or R
3, preferably R
1 or R
2, is a 1 to 4 carbon alkyl or hydroxyalkyl group, R
1 or R
2 can be a hydrogen and R
3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer
wherein R
1 is methyl, R
2 is hydrogen and R
3 is sodium.
[0094] The low molecular weight polyacrylate dispersant polymer preferably has a molecular
weight of less than 15,000, preferably from 500 to 10,000, most preferably from 1,000
to 5,000. The most preferred polyacrylate copolymer for use herein has a molecular
weight of 3500 and is the fully neutralized form of the polymer comprising 70% by
weight acrylic acid and 30% by weight methacrylic acid.
[0095] Other suitable modified polyacrylate copolymers include the low molecular weight
copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766,
and 5,084,535.
[0096] Agglomerated forms of the present invention may employ aqueous solutions of polymer
dispersants as liquid binders for making the agglomerate (particularly when the composition
consists of a mixture of sodium citrate and sodium carbonate). Especially preferred
are polyacrylates with an average molecular weight of from 1,000 to 10,000, and acrylate/maleate
or acrylate/fumarate copolymers with an average molecular weight of from 2,000 to
80,000 and a ratio of acrylate to maleate or fumarate segments of from 30:1 to 1:2.
Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate
monomers are disclosed in European Patent Application No. 66,915, published December
15, 1982.
[0097] Other dispersant polymers useful herein include the polyethylene glycols and polypropylene
glycols having a molecular weight of from about 950 to about 30,000 which can be obtained
from the Dow Chemical Company of Midland, Michigan. Such compounds for example, having
a melting point within the range of from about 30° to about 100°C can be obtained
at molecular weight of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000. Such compounds
are formed by the polymerization of ethylene glycol or propylene glycol with the requisite
number of moles of ethylene or propylene oxide to provide the desired molecular weight
and melting point of the respective polyethylene glycol and polypropylene glycol.
The polyethylene, polypropylene and mixed glycols are referred to using the formula
HO(CH
2CH
2O)
m(CH
2CH(CH
3)O)
n(CH(CH
3)CH
2O)
oH wherein m, n, and o are integers satisfying the molecular weight and temperature
requirements given above.
[0098] Yet other dispersant polymers useful herein include the cellulose sulfate esters
such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate,
methylcellulose sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate
is the most preferred polymer of this group.
[0099] Other suitable dispersant polymers are the carboxylated polysaccharides, particularly
starches, celluloses and alginates, described in U.S. Pat. No. 3,723,322, Diehl, issued
Mar. 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No.
3,929,107, Thompson, issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch
esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat.
No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated starches described in
U.S. Pat. No. 3,629,121, Eldib. issued Dec. 21, 1971, and the dextrin starches described
in U.S. Pat. No. 4,141,841, McDanald, issued Feb. 27, 1979, all incorporated herein
by reference. Preferred cellulose-derived dispersant polymers are the carboxymethyl
celluloses.
[0100] Yet another group of acceptable dispersants are the organic dispersant polymers,
such as polyaspartate.
[0101] Another polymeric material which can be included is polyethylene glycol (PEG), PEG
can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition
agent. Typical molecular weight ranges for these purposes range from 500 to 100,000,
preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
[0102] Polyaspartate and polyglutamate dispersing agents may also be used, especially in
conjunction with zeolite builders. In compositions containing detergent builders,
it is believed, though it is not intended to be limited by theory, that polymeric
dispersing agents enhance overall detergent builder performance, especially zeolite
and/or silicate builders, when used in combination with other builders (including
lower molecular weight polycarboxylates) by crystal growth inhibition, particulate
soil release peptization, and anti-redeposition. Dispersing agents such as polyaspartate
preferably have a molecular weight (avg.) of about 10,000.
[0103] Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated
into the compositions of the present invention. Suds suppression can be of particular
importance in the so-called "high concentration cleaning process" as disclosed in
U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
[0104] A wide variety of materials may be used as suds suppressors, and suds suppressors
are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia
of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons,
Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic
fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September
27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used
as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms,
preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such
as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
[0105] The detergent compositions herein may also contain non-surfactant suds suppressors.
These include, for example; high molecular weight hydrocarbons such as paraffin, fatty
acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols,
aliphatic C
18-C
40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines
such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed
as products of cyanuric chloride with two or three moles of a primary or secondary
amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates
such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g.,
K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin
and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid
at room temperature and atmospheric pressure, and will have a pour point in the range
of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure).
It is also known to utilize waxy hydrocarbons, preferably having a melting point below
about 100°C. The hydrocarbons constitute a preferred category of suds suppressor for
detergent compositions. Hydrocarbon suds suppressors are described, for example, in
U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus,
include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated
hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used in this
suds suppressor discussion, is intended to include mixtures of true paraffins and
cyclic hydrocarbons.
[0106] Another preferred category of non-surfactant suds suppressors comprises silicone
suds suppressors. This category includes the use of polyorganosiloxane oils, such
as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins,
and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane
is chemisorbed or fused onto the silica. Silicone suds suppressors are well known
in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5,
1981 to Gandolfo et al. and European Patent Application No. 89307851.9, published
February 7, 1990, by Starch, M. S.
[0107] Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates
to compositions and processes for defoaming aqueous solutions by incorporating therein
small amounts of polydimethylsiloxane fluids.
[0108] Mixtures of silicone and silanated silica are described, for instance, in German
Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in
granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta
et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
[0109] An exemplary silicone based suds suppressor for use herein is a suds suppressing
amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from 2.0 x 10-3 to 1.5 Pascal seconds (20 cs to 1.500 cs.) at 25°C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin composed
of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 units of from 0.6:1 to 1.2:1, and
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid silica gel.
[0110] In the preferred silicone suds suppressor used herein, the solvent for a continuous
phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol
copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone
suds suppressor is branched/crosslinked and preferably not linear.
[0111] To illustrate this point further, typical liquid laundry detergent compositions with
controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to
0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor,
which comprises (l) a nonaqueous emulsion of a primary antifoam agent which is a mixture
of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing
silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote
the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least
one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene
glycol having a solubility in water at room temperature of more than 2 weight %; and
without polypropylene glycol. Similar amounts can be used in granular compositions,
gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and
4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February
22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line
46 through column 4, line 35.
[0112] The silicone suds suppressor herein preferably comprises polyethylene glycol and
a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular
weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol
and polyethylene/polypropylene copolymers herein have a solubility in water at room
temperature of more than 2 weight %, preferably more than 5 weight %.
[0113] The preferred solvent herein is polyethylene glycol having an average molecular weight
of less than 1,000, more preferably between 100 and 800, most preferably between 200
and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG
200/PEG 300. Preferred is a weight ratio of between 1:1 and 1:10, most preferably
between 1:3 and 1:6, of polyethylene glycol copolymer of polyethylene-polypropylene
glycol.
[0114] The preferred silicone suds suppressors used herein do not contain polypropylene
glycol, particularly of 4,000 molecular weight. They also preferably do not contain
block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
[0115] Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl
alkanols) and mixtures of such alcohols with silicone oils, such as the silicones
disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include
the C
6-C
16 alkyl alcohols having a C
1-C
16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under
the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark
ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol
- silicone at a weight ratio of 1:5 to 5:1.
[0116] For any detergent compositions to be used in automatic laundry washing machines,
suds should not form to the extent that they overflow the washing machine. Suds suppressors,
when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing
amount" is meant that the formulator of tne composition can select an amount of this
suds controlling agent that will sufficiently control the suds to result in a low-sudsing
laundry detergent for use in automatic laundry washing machines.
[0117] The compositions herein will generally comprise from 0% to 5% of suds suppressor.
When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein,
will be present typically in amounts up to 5%, by weight, of the detergent composition.
Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight,
of the detergent composition, although higher amounts may be used. This upper limit
is practical in nature, due primarily to concern with keeping costs minimized and
effectiveness of lower amounts for effectively controlling sudsing. Preferably from
0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
As used herein, these weight percentage values include any silica that may be utilized
in combination with polyorganosiloxane, as well as any adjunct materials that may
be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts
ranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon suds suppressors
are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels
can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight
of the finished compositions.
[0118] Brightener - Any optical brighteners or other brightening or whitening agents known in the art
can be incorporated at levels typically from 0.05% to 1.2%, by weight, into the detergent
compositions herein. Commercial optical brighteners which may be useful in the present
invention can be classified into subgroups, which include, but are not necessarily
limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines,
dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other
miscellaneous agents. Examples of such brighteners are disclosed in "The Production
and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John
Wiley & Sons, New York (1982).
[0119] Specific examples of optical brighteners which are useful in the present compositions
are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988.
These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners
disclosed in this reference include Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available
from Ciba-Geigy, Artic White CC and Artic White CWD, available from Hilton-Davis,
located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stil-
benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these
brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene,
1,3-diphenyl-phrazolines, 2,5-bis(benzoxazol-2-yl)thiophene, 2-strylnapth-[1,2-d]oxazole;
and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Patent 3,646,015,
issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
[0120] Chelating Agents - The detergent compositions herein may also optionally contain one or more iron
and/or manganese chelating agents. Such chelating agents can be selected from the
group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted
aromatic chelating agents and mixtures therein, all as hereinafter defined. Without
intending to be bound by theory, it is believed that the benefit of these materials
is due in part to their exceptional ability to remove iron and manganese ions from
washing solutions by formation of soluble chelates.
[0121] Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates,
N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
[0122] Amino phosphonates are also suitable for use as chelating agents in the compositions
of the invention when at lease low levels of total phosphorus are permitted in detergent
compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more
than about 6 carbon atoms.
[0123] Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions
herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
[0124] A preferred biodegradable chelator for use herein is ethylenediamine disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November
3, 1987, to Hartman and Perkins.
[0125] If utilized, these chelating agents will generally comprise from 0.1% to 10% by weight
of the detergent compositions herein. More preferably, if utilized, the chelating
agents will comprise from 0.1% to 3.0% by weight of such compositions.
Fabric Softening Clay:
[0126] Various clay through-the-wash fabric softeners, especially the impalpable smectite
clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well
as other softener clays known in the art, can optionally be used typically at levels
of from 0.5% to 10% by weight in the present compositions to provide fabric softener
benefits concurrently with fabric cleaning. Clay softeners can be used in combination
with amine and cationic anti-static agents, as disclosed, for example, in U.S. Patent
4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued
September 22, 1981.
[0127] The clay softening system herein will typically comprise a fabric softening clay
present in an amount of at least 0.5%, preferably from 4% to 30% by weight of the
detergent composition. The preferred clays are of the smectite type, although other
types of softening clays are known and may be used herein. The following describes
non-limiting examples of softening clays.
[0128] Smectite type clays are widely used as fabric softening ingredients in detergent
compositions. Most of these clays have a cation exchange capacity of at least 50 meq./100
g.
[0129] Smectite clays can be described as three-layer expandable materials, consisting of
alumino-silicates or magnesium silicates.
[0130] There are two distinct classes of smectite-type clays, in the first, aluminum oxide
is present in the silicate crystal lattice, in the second class of smectites, magnesium
oxide is present in the silicate crystal lattice.
[0131] The general formulas of these smectites are Al
2(Si
2O
5)
2(OH)
2 and Mg
3(Si
2O
5)(OH)
2, for the aluminum and magnesium oxide type clay, respectively. The range of the water
of hydration can vary with the processing to which the clay has been subjected. Furthermore,
atom substitution by iron and magnesium can occur within the crystal lattice of the
smectites, while metal cations such as Na
-, Ca
2-, as well as H
- can be co-present in the water of hydration to provide electrical neutrality.
[0132] It is customary to distinguish between clays on the basis of one cation predominantly
or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation
is predominantly sodium. Such absorbed cations can become involved in equilibrium
exchange reactions with cations present in aqueous solutions. In such equilibrium
reactions, one equivalent weight of solution cation replaces an equivalent of sodium,
for example, and it is customary to measure clay cation exchange capacity in terms
of milliequivalents per 100 g of clay (meq/100 g).
[0133] The cation exchange capacity of clays can be measured in several ways, including
electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene
blue procedure, as set forth in Grimshaw. The Chemistry of Physics of Clays, Interscience
Publishers, Inc. pp. 264-265 (1971). The cation exchange capacity of a clay mineral
relates to such factors as the expandable properties of the clay, the charge of the
clay, which in turn, is determined at least in part by the lattice structure, and
the like. The ion exchange capacity of clays varies widely in the range from 2 meq/100
g for kaolinites to 150 meq/100 g, and greater for certain clays of the montmorillonite
variety. Illite clays have an ion exchange capacity somewhere in the lower portion
of the range, ca. 26 meq/100 g for an average illite clay.
[0134] It has been determined that illite and kaolinite clays, with their relatively low
ion exchange capacities, are not useful in the instant compositions. Indeed such illite
and kaolinite clays constitute a major component of clay soils. However, smectites,
such as nontronite having an ion exchange capacity of approximately 50 meq/100 g,
saponite, which has an ionexchange capacity greater than 70 meq/100 g, have been found
to be useful fabric softeners.
[0135] The smectite clays commonly used for this purpose herein are all commercially available.
Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite,
saponite, sauconite, and vermiculite. The clays herein are available under commercial
names such as "fooler clay" (clay found in a relatively thin vein above the main bentonite
or montmorillonite veins in the Black Hills) and various tradenames such as Thixogel
#1 (also, "Thixo-Jell") and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey;
Volclay BC and Volcay #325, from American Colloid Co., Skokie, Illinois; Black Hills
Bentonite BH 450, from International Minerals and Chemicals; and Veegum Pro and Veegum
F, from R. T. Vanderbilt. It is to be recognized that such smectite-type minerals
obtained under the foregoing commercial and trade names can comprise mixtures of the
various discrete mineral entities. Such mixtures of the smectite minerals are suitable
for use herein.
[0136] Preferred for use herein are the montmorillonite clays having an ion capacity of
50 to 100 meq/100 g which corresponds to ca. 0.2 to 0.6 layer charge.
[0137] Quite suitable are hectorites of natural origin, in the form of particles having
the general formula
wherein Me
III is Al, Fe, or B; or y=O; M
n+ is a monovalent (n=1) or divalent (n=2) metal ion, for example, selected from Na,
K, Mg, Ca or Sr.
[0138] In the above formula, the value of (x+y) is the layer charge of the hectorite clay.
[0139] Such hectorite clays are preferably selected on the basis of their layer charge properties,
i.e., at least 50% is in the range of from 0.23 to 0.31.
[0140] More suitable are hectorite clays of natural origin having a layer charge distribution
such that at least 65% is in the range of from 0.23 to 0.31.
[0141] The hectorite clays suitable in the present composition should preferably be sodium
clays, for better softening activity.
[0142] Sodium clays are either naturally occurring, or are naturally-occurring calcium-clays
which have been treated so as to convert them to sodium-clays. If calcium-clays are
used in the present compositions, a salt of sodium can be added to the compositions
in order to convert the calcium clay to a sodium clay. Preferably, such a salt is
sodium carbonate, typically added at levels of up to 5% of the total amount of clay.
[0143] Examples of hectorite clays suitable for the present compositions include Bentone
EW and Macaloid, from NL Chemicals, N.J., U.S.A., and hectorites from Industrial Mineral
Ventures.
[0144] Other softening clays of varoius types and classes are disclosed in the literature
and may also be used herein.
[0145] Anti-Static Agents - Consumers who use fabric softeners have come to expect that fabrics treated therewith
will also be provided with an anti-static benefit. Since softener clays are rather
poor anti-stats, the formulator may wish to add an anti-static agent to such compositions.
Various anti-static agents are known in the art and may be used herein, so long as
they do not disadvantageously interact with the other ingredients of the compositions.
Quite suitable water-soluble antistatic agents herein include the well-known cationic
and quaternary ammonium salts such as C
10-C
18 trimethyl ammonium chloride, the acid salts of the C
10-C
14 dimethyl amines, the hydroxy-substituted quats, such as the C
10-C
18 dimethyl(hydroxyethyl)ammonium chloride, C
10-C
18(dihydroxyethyl)methylammonium chloride, lauryl trimethylammonium chloride or bromide,
and the like. Such optional anti-stats are preferably used at levels from 0.15% to
2.5% of the compositions.
[0146] Other Ingredients - A wide variety of other ingredients useful in detergent compositions can be included
in the compositions herein, including other active ingredients, carriers, hydrotropes,
processing aids, dyes or pigments, solvents for liquid formulations, solid fillers
for bar compositions, etc. If high sudsing is desired, suds boosters such as the C
10-C
16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
The C
10-C
14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
Use of such suds boosters with high sudsing adjunct surfactants such as the amine
oxides, betaines and sultaines noted above is also advantageous. If desired, soluble
magnesium salts such as MgCl
2, MgSO
4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional
suds and to enhance grease removal performance.
[0147] Various detersive ingredients employed in the present compositions optionally can
be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate,
then coating said substrate with a hydrophobic coating. Preferably, the detersive
ingredient is admixed with a surfactant before being absorbed into the porous substrate.
In use, the detersive ingredient is released from the substrate into the aqueous washing
liquor, where it performs its intended detersive function.
[0148] To illustrate this technique in more detail, a porous hydrophobic silica (trademark
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5%
of C
13-15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant
solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring
in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be
used). The resulting silicone oil dispersion is emulsified or otherwise added to the
final detergent matrix. By this means, ingredients such as the aforementioned enzymes,
bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers,
fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents.
[0149] The detergent compositions herein will preferably be formulated such that, during
use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and
11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques
for controlling pH at recommended usage levels include the use of buffers, alkalis,
acids, etc., and are well known to those skilled in the art.
[0150] Granular detergents can be prepared, for example, by spray-drying (final product
density about 520 g/l) or agglomerating (final product density above about 600 g/l)
the Base Granule. The remaining dry ingredients can then be admixed in granular or
powder form with the Base Granule, for example in a rotary mixing drum, and the liquid
ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
[0151] The following examples illustrate the detergent compositions of this invention, but
are not intended to be limiting thereof.
EXAMPLE I
[0152] A granular detergent composition comprising a non-phosphorus builder system is as
follows:
Ingredient |
% (wt.) |
Oleoyl Sarcosinate, Na |
8.0 |
Tallowalkyl Sulfate, Na |
2.5 |
C12-14 N-methylglucamide |
5.0 |
C12-14 Trimethylammonium Chloride |
1.2 |
Zeolite A (1-10 micrometer) |
23 |
Maleic/Acrylic Copolymer |
5.0 |
Sodium Percarbonate |
12 |
TAED |
4.0 |
Sodium Carbonate |
10.6 |
Sodium Silicate (2.0) |
5.0 |
Glycerol |
0.5 |
Savinase (enzyme) |
1.6 |
Silicone (suds suppressor) |
0.5 |
Water, Perfume, Minors |
Balance |
EXAMPLE II
[0153] The composition of Example I is modified by replacing the sodium percarbonate with
an equivalent amount of sodium perborate and deleting the N-methylglucamide. In an
alternate mode, all or part of the TAED bleach activator can be replaced by NOBS bleach
activator.
EXAMPLE III
[0154] A granular detergent composition comprising a mixed, non-phosphorus builder system
is as follows:
Ingredient |
% (wt.) |
Oleoyl Sarcosinate, Na |
8.0 |
C14-15 Alkyl Sulfate, Na |
3.0 |
Sodium Citrate |
5.0 |
Zeolite A (1-10 micrometer) |
20.0 |
Sodium Percarbonate |
18.0 |
TAED/NOBS (1:1) |
5.0 |
Sodium Sulfate |
12.0 |
Sodium Silicate |
5.0 |
C12-14 Dimethyl (Hydroxyethyl) Ammonium Chloride |
1.5 |
Polyacrylate (mw 4000-5000) |
3.0 |
Hydrogen Tallow Fatty Acid |
0.5 |
CAREZYME |
0.9 |
SAVINASE |
0.75 |
TERMAMYL |
0.75 |
Optical Brightener |
0.2 |
Moisture, Minors |
Balance |
EXAMPLE IV
[0155] In the composition of Example III, the Zeolite A may be replaced by an equivalent
amount of SKS-6. In an alternate mode, the alkyl sulfate can be replaced by a C
11-14 alkyl benzene sulfonate surfactant.
EXAMPLE V
[0156] A granular composition comprises the following ingredients.
Ingredient |
% (wt.) |
Oleoyl Sarcosinate, Na |
19.0 |
Zeolite A (1-10 microns) |
25.0 |
Sodium Citrate |
3.0 |
Sodium Percarbonate |
12.0 |
Polyaspartate |
5.0 |
EDDS |
3.0 |
Protease |
1.0 |
Lipase |
1.0 |
TAED |
5.0 |
Sodium Carbonate |
10.0 |
Sodium Silicate |
3.0 |
Water and Minors |
Balance |
EXAMPLE VI
[0157] The composition of Example V is modified by reducing the oleoyl sarcosinate to 17%
of the composition and adding 2% by weight of coconutalkyl ethoxylate (1-5 avg. ethoxylate)
as NEODOL.
EXAMPLE VII
[0158] A detergent bar is prepared by compacting and extruding a composition generally according
to Example V.