Method of making clear, stable prespotter laundry detergent

A method of making a heavy duty clear, single phase, solvated built aqueous liquid detergent composition. The composition consists essentially of at least one nonionic surfactant, at least one builder, an effective amount of a water soluble polymeric anionic hydrotrope to render the composition clear, stable and single phase which hydrotrope is a specific polymer of maleic anhydride and at least one alpha olefin, and water wherein the composition has a pH in the range of from 6 to 9. The novel hydrotrope used is a hydrolyzed (a) copolymer of maleic anhydride and a C.sub.6 to C.sub.24 alpha olefin or (b) ter- or higher polymer of maleic anhydride with two or more C.sub.6 to C.sub.30+ alpha olefins as long as one of the alpha olefins is a C.sub.2 to C.sub.18 alpha olefin and the ratio of alpha olefins present are such that the average alpha olefin carbon chain length in the ter- or higher polymer is greater than about 6 and less than about 18. Additionally, methods of making stable, one phase compositions of this type which further include a cationic fabric softening agent which are clear, stable and single phase.

TECHNICAL FIELD 
This invention relates to a clear stable single phase built liquid 
detergent composition which is nonionic in nature and contains a water 
soluble polymeric anionic hydrotrope which is a hydrolyzed alpha olefin 
maleic anhydride polymer. This polymer has at least one alpha olefin 
having a carbon content in the range of C.sub.6 to about C.sub.24 for 
copolymers and alpha olefins of C.sub.2 to C.sub.30+ carbon content for 
polymers containing two or more alpha olefins, more preferably from 
C.sub.6 to C.sub.18, and most preferably, C.sub.6 to C.sub.10 copolymers. 
The hydrolyzed alpha olefin maleic anhydride polymer acts as a coupling 
agent or hydrotrope between the separate phases normally inherent in built 
nonionic liquid detergents to provide the clear homogeneous detergent 
composition of the present invention. Moreover, it has been unexpectedly 
discovered that the use of this hydrotrope significantly increases the 
cleaning power and prespotting capabilities of the detergent composition 
such that the detergent, when used alone, performs at least equal to a 
liquid laundry detergent for detergency and better than a normal liquid 
laundry detergent as a prespotter. Moreover, it has been unexpectedly 
observed that this detergent composition, in spite of the use of the 
anionic alpha olefin maleic anhydride polymers, is stable to inclusion of 
cationic quaternary ammonium fabric softeners/disinfectants which normally 
would separate out of a detergent composition. 
BACKGROUND ART 
Normal powder detergents are a mixture of surfactants and inorganic 
builders in a ratio of about 1:1 to 1:2. When these components are 
concentrated into a liquid detergent form, there is a multiphase 
separation, particularly when nonionic surfactants are present since 
nonionic surfactants are not very tolerant of ionic inorganic builders. 
Historically, liquid detergents have recognized and struggled with this 
incompatibility. In the past, manufacturers formulated built liquid 
detergents that separated into two phases and simply instructed the 
consumer to shake the product well before using it. Currently, consumers 
are less likely to accept liquid detergent products which require shaking 
before use even though such products have good cleaning performance when 
properly shaken to combine the separate phases together. The result has 
been that current commercial liquid laundry detergents are almost all 
surfactants with very little or no inorganic builders present. The 
inorganic builders are desirable because they are the lowest cost cleaning 
components in detergents. 
Recent developments have partially solved this problem by using more 
expensive organic, polycarboxylate builders and by suspending inorganic 
builders in the liquid detergent system. Whereas these systems have been 
successful as a detergent, they have not provided good prespotter 
properties. One problem with the addition of a polymer to an aqueous 
liquid detergent composition, particularly to a built liquid detergent 
composition, is that the polymer sometimes tends to undesirably render the 
composition unstable and to cause phase separation. 
Good detergency and good prespotting properties have also historically been 
incompatible in a single liquid. The best cleaning detergents have been 
highly built, high alkaline systems. However, in a liquid detergent, high 
alkalinity will fix certain stains such as coffee, tea and red wine. 
Highly alkaline liquids can also cause skin irritations. 
This invention discloses a clear homogeneous built liquid system containing 
nonionic surfactants which is neutral to slightly alkaline and excellent 
for prespotter use. 
European Patent Application EP 0 000 224 A1 to Smith et al. teaches liquid 
and solid detergents for improved greasy soil removal. The improved greasy 
soil removal properties are the result of the presence of an essential 
ingredient which is a 3-component active system comprising anionic 
surfactants, alkoxylated nonionic surfactants and water soluble cationic 
surfactants. It is a further example of the use of conventional hydrotrope 
agents in liquid detergent formulations since it teaches that conventional 
hydrotropes such as sodium benzoate or sodium salts of toluene, xylene or 
cumene sulphonates can be included for insuring phase stability of the 
liquid compositions. Smith et al. teach the use of water soluble 
polycarboxylates as detergency builders. 
Furthermore, Smith et al. teach that 0.1% to about 3% of a further 
optional, but preferred, component can be included which is a polymeric 
material of molecular weight 2,000 to 2,000,000. They do not suggest using 
such materials as hydrotropes for built liquid detergent compositions of 
the type used in the present invention. That polymeric material includes a 
wide variety of possible polymers made by the polymerization of maleic 
acid or maleic anhydride with a polymerizable comonomer which includes 
alkyl esters of acrylic and methacrylic acid, styrene, N-vinyl pyrrolidone 
or monoolefins of the formula (iii) H(R.sub.4)C.dbd.C(R.sub.5)H where each 
of R.sub.4 and R.sub.5 is H or an alkyl group such that R.sub.4 and 
R.sub.5 together have 0 to 10 carbon atoms. Examples 7 and 8 of Smith et 
al. teach the use of GANTREZ AN119 which is a maleic anhydride/methyl 
vinylether copolymer. We have found that maleic anhydride/methyl 
vinylether copolymers do not act as hydrotropes in the present invention 
nor do copolymers of maleic anhydride and 1-butene. On page 30, lines 
22-35 of Smith et al., the applicants teach that in place of GANTREZ AN119 
in the working examples, various other maleic anhydride copolymers can be 
used such as an ethylene-maleic acid copolymer of molecular weight ("MW") 
4,000, a propylene-maleic acid copolymer of MW 30,000, a 1-hexene-maleic 
acid copolymer of MW 25,000 or MW 30,000, a vinyl pyrrolidone-maleic acid 
copolymer of MW 26,000, among others. We have found that although 
1-hexene/maleic anhydride copolymers are useful as hydrotropes in the 
present invention, that those copolymers containing alpha olefins with 
less than 6 carbon atoms as well as those made with methyl vinylether are 
not useful as hydrotropes. The built liquid detergent compositions of 
Smith et al. did not give clear, stable and single phase compositions. 
Thus Smith et al. does not suggest the method of the present invention and 
in fact specifically teaches that conventional hydrotropes should be used 
for insuring phase stability. 
British Patent Specification No. 1 596 756 is assigned to Procter & Gamble 
Limited, a subsidiary of Procter & Gamble Company to which the Smith et 
al. patent application is assigned. The disclosure of the '756 Patent is 
similar to and contains a broader teaching of maleic anhydride/acid 
copolymers than does the Smith et al. Patent. The '756 Patent teaches 
solid and liquid detergent compositions which require three components: an 
organic detergent, a phosphate builder based on orthophosphate, 
pyrophosphate and tripolyphosphate salts; and a builder auxiliary which is 
a mixture of (i) up to 4% of a polyphosphonic acid or salt thereof and 
(ii) up to 4% of a homo- or copolymeric polycarboxylic acid or salt 
thereof. The critical features of the ingredients used are described on 
page 1, lines 6-29 and on page 2, lines 44-51: small amounts of a mixture 
of polyacids improve the performance in whiteness retention (i.e., the 
antiredeposition properties) and ash deposition (i.e., precipitation of 
insoluble phosphate salts on clothing) of detergents containing the 
phosphate builders noted above. 
Thus, the '756 Patent requires phosphate builders which have fallen into 
environmental disfavor for use in detergents as well as two builder 
auxiliaries, one of which can be a copolymer of maleic anhydride with 
other polymerizable monomers. Examples 24-26 of the '756 Patent employ 1%, 
1%, and 0.5%, respectively, of GANTREZ AN139 which is a copolymer of 
maleic anhydride and methyl vinylether. Among the variety of monomers 
which are taught are those of the formula R.sub.4 R.sub.6 C.dbd.CR.sub.5 
R.sub.7 where each of R.sub.4 to R.sub.7 is --H or and alkyl group such 
that R.sub.4 to R.sub.7 together have from 1 to 20 carbon atoms, R.sub.4 
to R.sub.7 each optionally being hydroxy substituted. However these 
polymers are used in conjunction with a polyphosphonate for a purpose 
different from that of the method of the present invention. A further 
point of difference is that on page 10, the '756 Patent teaches that when 
the olefins of the previously described formula are used, the copolymers 
are preferably of high molecular weight and are preferably based on 
ethylene which is not operative in the method of the present invention. 
This teaching is present although page 16 of the '756 Patent contains the 
same language concerning substitution of other maleic acid copolymers such 
as those employing 1-hexene as is found on page 30 of Smith et al. 
Therefore neither Smith et al. nor the '756 Patent suggest the method of 
the present invention which requires certain specific hydrolyzed polymers 
of maleic anhydride and alpha olefins to serve as hydrotropes in certain 
built liquid detergent compositions which contain nonionic surfactants. 
Detergent compositions containing polymers as builders are old and well 
known in the art. A number of these patents can be seen by reviewing the 
literature. 
Erdy et al., in U.S. Pat. No. 3,691,107, disclose a novel detergent 
composition comprising a mixture of one or more surfactants with a unique 
builder which comprises a cross-linked, water-insoluble polymer of at 
least one C.sub.4 -C.sub.10 olefin and at least one polycarboxyl vinyl 
monomer. The cross-linked water insoluble polymer is a water-swellable gel 
forming material. This patent is of particular interest to the present art 
in examining Example 1, Table 1 as contained in column 11, lines 7-35. 
Specifically, alpha olefin maleic anhydride polymers disclosed, some of 
which are contemplated for use in the present invention, are disclosed as 
old and well known in the art. However, a reading of the Example indicates 
that they are being used in the Erdy patent Example as part of a powder 
detergent composition. No hydrotrope properties are described as being 
inherent in the alpha olefins of the Erdy composition and they further 
differ from the hydrotropes used in the present invention in that they are 
cross-linked with diamines and triamines and with diols and triols. The 
Erdy polymers are then hydrolyzed to make water insoluble swellable gels. 
All the examples are for powdered detergents and although they do mention 
an aqueous dispersion of the detergent composition, they are cloudy, 
two-phased liquids which do not possess the cleaning and anti-redeposition 
properties of the present invention. Moreover, the levels at which the 
alpha olefin maleic anhydride polymers are used at are a level of 40% by 
weight of the composition. It would appear that the use of the polymer is 
as a builder substitute, which is known in the art, and not as a 
hydrotrope or anti-redeposition agent which unexpectedly gives superior 
cleaning and prespotting capabilities to the detergent. 
Moreover, it has been unexpectedly found that the hydrolyzed alpha olefin 
maleic anhydride copolymers useful in the present invention are in a range 
of C.sub.6 to about C.sub.24 and specific polymers containing at least two 
different alpha olefins of C.sub.2 to C.sub.30+ carbon content, and most 
preferably, C.sub.6 to C.sub.10 copolymers, are able to bring together as 
a coupling agent the nonionic surfactants and the builders in such a 
manner as to present a clear, stable, single-phase liquid detergent 
composition which has the aforementioned prespotting and increased 
detergency. The prior art fails to teach the method of using the specific 
hydrolyzed maleic anhydride polymers of the present invention as 
hydrotropes to produce such clear and stable nonionic 
surfactant-containing built liquid detergent compositions. 
Rosnati, U.S. Pat. No. 3,208,949 discloses ethylene maleic anhydrides and 
polyvinyl methacrylate maleic anhydride interpolymers for use in a heavy 
duty or built liquid detergent system. The Rosnati patent discloses the 
use of a caprylic acid salt to function as a binary system to stabilize a 
built detergent into a substantially homogeneous pourable liquid 
detergent. The present invention does not contemplate the use of caprylic 
acid salts or any other type of binary agent for stability of the phases. 
Rather, the hydrolyzed alpha olefin maleic anhydride polymers by 
themselves are the stabilizing cleaning agents with the anti-redeposition 
properties for which Rosnati uses caprylic acid salts. Accordingly, the 
present invention differs from Rosnati. 
Tsukuni et al., U.S. Pat. No. 3,830,745 depicts a detergent composition 
which includes anionic or nonionic surface active agents, and as a 
builder, a novel water soluble salt of a copolymer of cyclopentene or its 
derivatives with maleic anhydrides. These cyclopentene maleic anhydride 
copolymers are hydrolyzed to form an alkali metal carboxylate salt to 
function as novel builders. The molecular weight of the copolymer is 
stated as 350 to 2000. It must be understood that this is a powder system 
and does not encompass the liquid detergent system of the present 
invention. Tsukuni does not contemplate a clear, stable, single phase 
built liquid detergent in which an alpha olefin maleic anhydride copolymer 
of a carbon range of C.sub.6 to about C.sub.24 and polymers containing at 
least two different alpha olefins of C.sub.2 to C.sub.30+ and most 
preferably, C.sub.6 to C.sub.10 copolymers, functions as a hydrotrope to 
bring two normally incompatible phases of a liquid detergent together into 
a clear homogeneous solution. Moreover, since only cyclopentene maleic 
anhydride copolymers are utilized, it is obvious that the hydrotropic 
anti-redeposition properties inherent in the hydrolyzed alpha olefin 
maleic anhydride polymer of the present invention would not be apparent 
because the families of cyclopentene maleic anhydride copolymers and the 
alpha olefin maleic anhydride polymers of the present invention are 
different. Accordingly, the present invention differs from and is an 
improvement over Tsukuni et al. 
Cooney, U.S. Pat. No. 3,852,213 discloses chelating compositions comprising 
90 to 70% of polyvinyl methacrylate maleic anhydride copolymer and 3 to 
30% borax, detergent dyeing, scouring and similar compositions containing 
the ingredients and a process for chelating varies Group II and Group III 
metal ions. The polyvinyl methacrylate maleic anhydride copolymer does not 
contemplate the hydrolyzed alpha olefin maleic anhydride polymers useful 
in the present invention. Accordingly, the present invention differs from 
Cooney. 
Grifo et al., U.S. Pat. No. 3,328,309 depicts a liquid detergent 
composition having a surface active detergent ingredient in a liquid 
medium. The detergent may be any commonly used surfactants of the nonionic 
and anionic types and mixtures thereof. The Grifo et al. disclosure is 
important from the aspect that polymeric anhydrides having ethoxylated 
esters and anhydrides are similar but not the same as the hydrolyzed alpha 
olefin maleic anhydrides useful in the present invention. Indeed, the 
closest example between the alpha olefins of the present invention and 
those of the Grifo disclosure are propylene maleic anhydride copolymers. 
The copolymers of Grifo et al. are all partial esters made by heating the 
anhydrides with ethoxylated or hydroxy containing surfactants to make 
partial esters. The present invention does not utilize such anhydride 
compositions and so differs from Grifo et al. 
Renold, U.S. Pat. No. 3,509,059 depicts a stable, heavy duty liquid 
detergent composition which contains high electrolyte content as a builder 
which is produced in a stabilized form by polymerizing to a polymer a 
monomer in the presence of the detergent material. The polymer acts as a 
stabilizer for the compositions. The Renold composition differs from the 
present invention in that Renold is essentially a polymerization of an 
alpha, beta-unsaturated carboxylic acid to a surfactant. In other words, 
this is a polymer which is grafted onto a surfactant. The acid has to be 
converted to salt first in order to have a functioning system. Thus, it 
can be seen that this is not a polymer such as is used in the present 
invention but a grafted polymer. It follows that the stabilizing agent of 
Renold is chemically very different from the hydrotrope or stabilizing 
agent of the present invention. Accordingly, the present invention differs 
from Renold. 
Tuvell, U.S. Pat. No. 3,235,505 teaches a liquid detergent emulsion with 
excellent stability against phase separation even though they are built 
detergent compositions. The excellent emulsion stability is said to be due 
to the presence of maleic anhydride type polymers wherein the comonomer is 
an olefinically unsaturated compound having less than 5 carbon atoms such 
as ethylene, propylene, isobutylene, vinyl methyl ether and the like. The 
maleic anhydride polymers used in the Tuvell emulsions can further be 
cross-linked with a diamine or a diolefinic compound. The Tuvell 
compositions differ from the present invention in that emulsions rather 
than solvated compositions are to be made. Tuvell also describes the final 
liquid detergent product obtained by his process as being very fluid and 
very white in color (see Example I) while the compositions of the present 
invention are required to be clear which are not taught in the Tuvell 
Patent. 
Smith et al., U.S. Pat. No. 4,525,291 teaches built liquid detergent 
compositions which are single phase, clear and contain hydrogen peroxide 
along with stabilizers for that ingredient. However, it does not suggest 
the use of hydrolyzed polymers of maleic anhydride with certain alpha 
olefins as hydrotropes in such compositions. 
SUMMARY OF THE INVENTION 
The present invention is a method of making a clear, stable, solvated, 
single phase, built liquid laundry detergent utilizing an effective amount 
of a hydrolyzed alpha olefin maleic anhydride copolymer having a carbon 
range of C.sub.6 to about C.sub.24 and polymers containing at least two 
different alpha olefins of C.sub.2 to C.sub.30+, and more preferably from 
C.sub.6 to C.sub.18, and most preferably, C.sub.6 to C.sub.10 copolymers. 
The liquid laundry detergent is a heavy duty or built liquid detergent 
which is basically nonionic in nature and yet, is able to utilize borates, 
citrates, the nonphosphorus inorganic builders, the phosphates, the salts 
of nitrilotriacetic acid, salts of ethylenediamine tetraacetic acid, the 
nonphosphorus organic builders, and mixtures thereof as the main builders 
by the use of the hydrolyzed alpha olefin maleic anhydride polymers. 
Effective amounts, typically between about 1 to 10% by weight of the total 
built liquid detergent composition, of the hydrolyzed alpha olefin maleic 
anhydride polymers function as a hydrotrope to bring two different phases 
of a normally two phase system into a clear single phase liquid detergent 
which has remarkable cleaning and prespotting properties when compared to 
the prior art liquid detergents and powdered detergents. 
Liquid detergents as a rule contain no builders or much lower 
concentrations of builders than powdered detergents. These builders, which 
are common in the art, are normally ionic, and by raising the 
concentration of ionics in solution, the nonionic surfactants of liquid 
detergents tend to separate or phase out. In order to make up for the loss 
of detergency for lack of builders, liquid detergents must use higher 
surfactant levels. 
It has been discovered in the present invention that by using certain 
hydrolyzed water soluble polymeric anionic alpha olefin maleic anhydride 
polymers, the polymer acts as a hydrotrope to bring the builders in phase 
with the nonionic surfactants in an aqueous medium which forms a clear and 
stable single phase liquid detergent which is resistant to phase 
separation. 
Moreover, the hydrolyzed alpha olefin maleic anhydride polymers useful in 
the present invention have surprisingly been found to act as an excellent 
anti-redeposition agent as well as an additional builder which aids in the 
cleaning power of the aqueous detergent. Accordingly, detergents formed 
according to the present invention have excellent prespotting and cleaning 
properties when compared with other liquid detergents as known in the art. 
Further, it is another unexpected result of the use of the hydrolyzed alpha 
olefin maleic anhydride polymers that this built, single phase solvated 
liquid detergent is compatible with cationic quaternary ammonium fabric 
softeners which would normally separate out of solution in the presence of 
anionic detergents. Stable, one phase compositions which range from clear 
to translucent to opaque compositions containing cationic fabric softeners 
can be made and, in a more preferred embodiment, such compositions are 
clear in appearance. Accordingly, the use of the hydrolyzed alpha olefin 
maleic anhydride polymers function as hydrotropes to bring the nonionic 
surfactants and builder together in a solvated stable single phase liquid 
detergent and also allow the use of quaternary ammonium fabric softeners 
which are cationic in nature and would ordinarily separate out of a normal 
built liquid detergent. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
The present invention is concerned with a clear, stable, solvated, single 
phase built liquid detergent composition which is able to use surprisingly 
large amounts of ionic builders. This is achieved by the use of an 
effective amount of a hydrolyzed, water soluble alpha olefin maleic 
anhydride polymer to produce a clear, stable and single phase aqueous 
detergent composition containing nonionic surfactants. Aqueous detergent 
compositions based on anionic surfactants which are free of nonionic 
surfactants tend to be much easier to produce in a clear and phase stable 
state since the surfactants and the builders are more compatible due to 
their ionic nature. Generally, from about 1 to 10% by weight of the total 
aqueous built liquid detergent composition is composed of the alpha olefin 
maleic anhydride polymer hydrotrope. The alpha olefin polymers useful as a 
hydrotrope in this invention can be made by the bulk process disclosed by 
U.S. Pat. No. 4,358,573 and the solution process of U.S. Pat. No. 
4,522,992 incorporated herein by reference. 
For the purposes of the present invention, the term "clear" is intended to 
mean that the solution formed is substantially transparent to visible 
light although a slight amount of haze may be present as long as one can 
see through the composition. The term "solvated" is intended to mean that 
the composition is substantially in the form of an aqueous solution or 
extremely fine dispersion as opposed to an emulsion of two different 
phases which results in light scattering and thus, optically translucent 
or opaque compositions. The term "single phase" is intended to mean that 
the compositions are clear and do not separate into two phases at room 
temperature and do not separate into two phases after being stored at 
110.degree. F. for 24 hours. This is one advantage of the present 
invention over other compositions of the prior art such as those 
stabilized by sodium xylene sulfonate which tends to be sensitive to 
temperature changes in its effectiveness as a hydrotrope and can separate 
into two phases upon exposure to heat. 
The term "consisting essentially of" used in reference to the aqueous 
compositions is intended to exclude components such as waxes, hydrophobic 
silicone materials and other components which will render otherwise clear, 
stable and single phase aqueous compositions cloudy or unstable. The 
hydrolyzed alpha olefin maleic anhydride polymers useful in the present 
invention act as a coupling agent between nonionic surfactants and ionic 
builders to assist in producing clear, stable and single phase 
compositions, particularly those which retain such clarity and phase 
stability upon aging and exposure to heat, which would otherwise be cloudy 
or separate into two phases. The term "consisting essentially of" is also 
intended to mean that other conventional hydrotropes used to obtain 
clarity and phase stability in built liquid detergents are not necessary 
in the method of the present invention. 
The alpha olefin maleic anhydride polymers useful in the present invention 
are polymers of maleic anhydride and at least one 1-alkene which are 
copolymers of maleic anhydride with an alpha olefin having about 6-24 
carbon atoms and terpolymers or higher polymers with at least two 
different alpha olefins having from 2-30+ carbon atoms. Preferably, the 
polymers are comprised of from about 49 to 95 mole percent of maleic 
anhydride and from about 5 to 51 mole percent of alpha olefin. These 
polymers are partially disclosed in U.S. Pat. No. 4,358,573 (bulk 
processing) and U.S. Pat. No. 4,522,992 (solution processing) which 
patents are expressly incorporated by reference for their disclosure of 
suitable alpha olefin maleic anhydride polymers as well as in U.S. Pat. 
No. 4,871,823 entitled "1-Alkene/Excess Maleic Anhydride Polymers" issued 
on Oct. 3, 1989 in the names of Fred L. Billman, Lih-Bin Shih and Calvin 
J. Verbrugge and assigned to the same assignee as is the present invention 
which is likewise incorporated herein by reference. 
The anhydride included in the alpha olefin maleic anhydride polymers is 
most preferably maleic anhydride. However, other maleic anhydrides can be 
utilized in this formation of the polymers such as methylmaleic anhydride, 
dimethylmaleic anhydride, fluoromaleic anhydride, methylethyl maleic 
anhydride and the like. Accordingly, as employed herein the term "maleic 
anhydride" includes such anhydrides in whole or in part. It is preferred 
that the anhydride be substantially free of acid and the like before 
polymerization. 
The alpha olefins generally suitable in the formation of the polymers 
described herein have from 2 to 30+ carbon atoms and include the 
following: ethylene; propylene; 1-butene; 1-pentene; 1-hexene; 1-heptene; 
1-octene; 1-nonene; 1-decene; 1-dodecene; 1-tetradecene; 1-hexadecene; 
1-heptadecene; 1-octadecene; 2-methyl-1-butene; 3,3-dimethyl-1-pentene; 
2-methyl-1-heptene; 4,4-dimethyl-1-heptene; 3,3-dimethyl-1-hexene; 
4-methyl-1-pentene; 1-eicosene; 1-docosene; 1-tetracosene; 1-hexacosene; 
1-octacosene; 1-triacontene; 1-tetracontene; 1-octatriacontene; 
1-tetracontene; 1-octatetracontene; 1-pentacontene; 1-hexacontene; and 
mixtures thereof. The term "30+" or "C.sub.30+ " is used herein in its 
commonly accepted usage wherein a "C.sub.30+ " 1-alkene mixture is a 
mixture of high boiling 1-alkenes with carbon content between about 30 and 
60 carbon atoms per molecule. 
Mixtures of the above materials can be utilized. It is preferred to utilize 
straight chain 1-alkenes having from 6 to 18 carbon atoms, and 
accordingly, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 
1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 
mixtures thereof are preferred. These materials should be substantially 
free of diolefin as an impurity which causes gel formation and 
cross-linking. However, small amounts, i.e., less than 2 percent, can be 
present without causing undue gel formation and cross-linking in the 
resulting polymers. Also as noted above, either single materials, i.e., 
1-hexene, 1-decene, etc., can be used, or mixtures of these materials may 
be utilized. 
As is well known in the art, polymers containing equimolar ratios of alpha 
olefin maleic anhydride are essentially alternating polymers with maleic 
anhydride alternating between random comonomers. Accordingly, the alpha 
olefin maleic anhydride polymers may contain from about 49 to 95 mole 
percent of maleic anhydride and more preferably, from 49 to 70 mole 
percent of maleic anhydride. Under some conditions such as is described in 
the Billman et al. Patent noted above, it is possible to include an excess 
of maleic anhydride relative to the comonomer in these polymers. The 
amount of alpha olefin will correspondingly vary from about 51 down to 
about 5 mole percent. The optimum alpha olefin maleic anhydride polymers 
include about 50 mole % maleic anhydride and about 50 mole % alpha olefin, 
but this is dependent upon the alpha olefin selected. This is generally 
true for C.sub.18 and higher carbon content alpha olefins while for 
polymers containing C.sub.6 to C.sub.4 alpha olefins, it is believed that 
greater than an equimolar amount of maleic anhydride up to about 60 mole 
percent is better. 
Generally, it has been found that copolymers of maleic anhydride and a 
single alpha olefin having no less than 6 and no more than 24 carbon atoms 
are needed to obtain clear, single phase compositions, and more 
preferably, between 6 and 18 carbon atom alpha olefins Maleic anhydride 
polymers containing higher alpha olefins (i.e., more than 24 carbons per 
molecule) can be used in the compositions of the present invention in the 
form of ter- or higher polymers which also contain at least one C.sub.2 to 
C.sub.18 alpha olefin. Preferably, the ratio of C.sub.2 -C.sub.18 
:C.sub.18+ alpha olefins is such that the average alpha olefin carbon 
chain length in the polymer is greater than about 6 and less than about 18 
to obtain clear, single phase solvated compositions. 
For the best combination of anti-redeposition characteristics, detergency 
and oily stain removal, copolymers of maleic anhydride with a C.sub.6 
alpha olefin (i.e., 1-hexene) at about a 50:50 molar ratio are preferred. 
Alternatively, a copolymer of maleic anhydride with a C.sub.10 alpha 
olefin (i.e., 1-decene) at about a 60:40 molar ratio of maleic anhydride 
to alpha olefin can be used with comparable results. The latter can be 
used as the hydrotrope in the compositions of the present invention for 
economic reasons since the C.sub.6 alpha olefin polymers are more 
difficult to process. 
The alpha olefin maleic anhydride polymers may be prepared by any of a 
number of conventional polymerization processes including polymerization 
processes as set forth in U.S. Reissue Pat. No. Re. 28,475, U.S. Pat. Nos. 
3,553,177, 3,560,455, 3,560,456, 3,560,457, 3,488,311, 4,522,992 and 
4,358,573. Another method by which such polymers can be prepared is the 
preferred method of making the polymers described in the Billman et al. 
Patent noted above. That method is described in U.S. Pat. No. 4,859,752 
issued on Aug. 22, 1989 in the names of Thomas P. Bosanec, Kenneth R. 
Lukow and Calvin J. Verbrugge entitled "1-Alkene/Excess Maleic Anhydride 
Polymer Manufacture" and assigned to the same assignee as is the present 
invention. 
The polymers useful in the present invention are generally low molecular 
weight materials having a number average molecular weight within the range 
of from about 500 to 50,000. 
Nonionic surfactants are usually made by the condensation of an alkylene 
oxide (normally ethylene or propylene oxide) with an organic hydrophobic 
compound which is usually aliphatic or alkyl aromatic in nature. The 
degree of hydrophilic/hydrophobic balance of these nonionic surfactants is 
adjusted by shorter or longer chain lengths of the polyoxyalkylene 
constituent. The following are examples of suitable nonionic surfactants: 
polyethylene condensates of alkylphenols having an alkyl group containing 
from about C.sub.6 to C.sub.12 are useful. The ethylene oxide is present 
in an amount of about 5 to 25 moles of ethylene oxide per mole of 
alkylphenol. Commercial examples of these surfactants are Igepal CO-610 
marketed by GAF Corporation, Surfonic N95 marketed by Texaco and TRITON 
X-100 sold by Rohm and Haas Company. Other surfactants useful are the 
condensation products of long chain fatty aliphatic alcohols having a 
carbon content of about C.sub.8 to C.sub.22 when ethoxylated with about 1 
to 25 moles of ethylene oxide. Commercial examples of these surfactants 
are TERGITOL 15-S-9 from Union Carbide Corporation and NEODOL 25- 3, 25-7 
and 25-9 marketed by Shell Chemical Company. 
Condensation products of ethylene oxide with hydrophobic bases formed by 
the condensation of polypropylene oxide with polypropylene glycols are 
also useful as nonionic surfactants. The hydrophobic base which is reacted 
with polypropylene oxide and polypropylene glycol should have a molecular 
weight of about 1500 to 1800. Examples of these polypropylene condensates 
are the PLURONIC surfactants from BASF Wyandotte Corporation. Condensation 
products of ethylene oxide with a reaction product of propylene oxide and 
ethylene diamine are also useful. The hydrophobic base of propylene and 
ethylene oxide usually has a molecular weight from 2500 to about 3000. The 
final surfactant has a molecular weight of from about 5,000 to 11,000. 
Commercial examples of these condensates are the compounds sold by BASF 
Wyandotte Corporation under the trademark TETRONIC. 
Other examples are the semi-polar nonionic water soluble amine oxide 
surfactants having the formula: 
##STR1## 
wherein R.sup.1 is an alkyl, hydroxyl, or alkylphenol group having a 
carbon content of about C.sub.8 to C.sub.22, R.sup.2 is an alkylene or 
hydroxy alkylene group having a carbon content of about C.sub.2 to 
C.sub.3, x is a number of from 0 to 3 and preferably 2, and R.sup.3 and 
R.sup.4 can be an alkyl or hydroxyalkyl group having a carbon content of 
about C.sub.1 to C.sub.3 or a polyethylene oxide group containing from 
about 1 to 3 ethylene oxide groups. APG 23-3 from A. E. Staley 
Manufacturing Company is an example of an ethoxylated polysaccharide. 
Examples of commercial amine oxide surfactants are Ammonyx CDO or Ammonyx 
LO from Onyx Chemical Company. Other examples are tallow dimethyl amine 
oxide and coco alkoxyethyl dihydroxyethyl amine oxide. 
Other useful condensation products include alkyl polysaccharides having the 
formula: 
EQU R.sup.5 -O(C.sub.w H.sub.2w O).sub.z (Glycosyl).sub.q 
wherein R.sup.5 is an alkyl, alkylphenol, hydroxyalkyl or 
hydroxyalkylphenol group, said alkyl-containing groups having a carbon 
content of from about C.sub.10 to C.sub.18, w is a number from about 2 to 
3, z is a number from about 0 to 10, and q is a number of from about 1 to 
3. 
Fatty acid amines are also useful as nonionic surfactants in this 
invention. The fatty acid amines are those having the formula: 
##STR2## 
wherein R.sup.6 is an alkyl group having a carbon content of about C.sub.7 
to C.sub.21, R.sup.7 is hydrogen, a C.sub.1 to C.sub.4 alkyl group, a 
C.sub.1 to C.sub.4 hydroxyalkyl group and --(C.sub.2 H.sub.4 O).sub.p H 
where p varies from about 1 to 3, and mixtures of these surfactants. 
MAZAMIDE.RTM. C-2, PEG-3 cocomonoethanol amide, from Mazer Chemicals Inc. 
is an example of a fatty acid amide nonionic surfactant. 
More specifically, the surfactants which are especially useful in the 
present invention are the NEODOL surfactants available from Shell Chemical 
Company and identified as C.sub.9 to C.sub.15 linear primary alcohol 
ethoxylates. Other suitable surfactants include the TERGITOL surfactants 
available from Union Carbide Corporation and identified as polyethylene 
glycol ethers of secondary alcohols, polyethylene glycol ethers of primary 
alcohols, mixed polypropylene glycols of linear alcohols, nonylphenol 
polyethylene glycol ethers, trimethyl nonyl polyalkylene glycol ethers, 
and polyalkylene glycol ethers. 
Other nonionic surfactants which are especially useful in the present 
invention are ethoxylated nonylphenols and the ethoxylated octylphenols. 
Commercial examples of these chemicals are Surfonic N95 from Texaco, 
TRITON X100 from Rohm and Haas Company and Igepal CA620 from GAF 
Corporation. The ethoxylated secondary linear alcohols such as TERGITOL 
15-S-9 from Union Carbide Corporation are also especially useful. 
Ethoxylated nonylphenol surfactants result in the best oily stain removal. 
The C.sub.9 to C.sub.15 linear primary alcohol ethoxylates of the NEODOL 
surfactant type have the advantage of being easier to disperse in 
detergent compositions. The nonionic surfactants are present in a range of 
from 5 to 25 weight percent and for optimum detergency, at least 10% to 
25% by weight nonionic surfactant is present in the compositions of the 
present invention. 
At least one builder is present in an amount of from about 2 to 25% by 
weight of the composition and for better stain removal and water hardness 
control, from about 5% to 10% by weight of the composition. Detergency can 
be further improved by increasing the amount of builder present up to 25% 
by weight of the composition. Presumably, all effective ionic builders 
known in the art will prove effective in this system. However, those of 
special interest are the borates, citrates, the nonphosphorus inorganic 
builders, the phosphates, nitrilotriacetic acid or its salts, 
ethylenediamine tetraacetic acid or its salts, the nonphosphorus organic 
builders, and mixtures thereof. The presently preferred builder is 
selected from a salt of nitrilotriacetic acid such as trisodium 
nitrilotriacetate. Borates are useful to buffer the system and improve the 
whiteness and stain removal characteristics of the composition. 
The borates may be selected from the group consisting of sodium 
tetraborate, disodium octoborate tetrahydrate, sodium metaborate, the 
analogous potassium salts and mixtures thereof. Although more can be used, 
generally, no more than about 10% by weight borates are present in the 
compositions of the present invention. 
The phosphates, although currently in disfavor with ecologists, may also be 
useful in this invention. The phosphates may be selected from the group 
consisting of sodium tripolyphosphate, tetrapyropolyphosphate, tetrasodium 
pyrophosphate, disodium pyrophosphate, sodium metaphosphate, sodium 
hexametaphosphate, the analogous potassium salts of these compounds, and 
mixtures thereof. 
An example of a citrate builder is sodium citrate. 
The nonphosphorus inorganic builders are carbonates and particularly those 
selected from the group consisting of sodium carbonate, potassium 
carbonate, sodium bicarbonate, sodium sesquicarbonate, and mixtures 
thereof. 
The nonphosphorus organic builders useful in the present invention are 
those which are selected from the group consisting of alkali metal, 
ammonium, and C.sub.1 to C.sub.4 alkylammonium salts of polyacetates, 
carboxylates, polycarboxylates, and polyhydroxy sulfonates as well as 
mixtures thereof. 
This system also optionally further includes at least one additional 
builder and preferably two or more additional builders as an additional 
builder system which is present in an amount from about 2 to 10% by weight 
of the composition. The additional builder system may be selected from the 
group consisting of the salts of hexamethylenediamine tetraacetic acid, 
the salts of diethylenetriamine pentaacetic acids, alkali silicates, and 
mixtures thereof. 
Additionally, anionic surfactants are also useful in the present invention, 
but not in a preferred embodiment. The anionic surfactants are useful in a 
range of from about 2 to 25% by weight of the composition and preferably 
at about 5% by weight of the composition. The anionic surfactants include 
at least one anionic surfactant selected from the group consisting of 
alkali metal, ammonium, and C.sub.1 to C.sub.4 alkylammonium salts of 
fatty acids having a carbon content of from about C.sub.10 to C.sub.20, 
water soluble salts such as alkali metal, ammonium and C.sub.1 to C.sub.4 
alkylammonium salts of organic sulfuric reaction products having an alkyl 
group containing from about C.sub.10 to C.sub.20 carbon content, and a 
sulfonic or sulfuric acid ester group. 
Other useful anionics include the water soluble salts of the esters of 
alpha sulfonated fatty acids having a carbon content of about C.sub.6 to 
C.sub.20 in the fatty acid groups and from about C.sub.1 to C.sub.10 
carbon content in the ester groups. 
Other water soluble salts useful in the present invention include the water 
soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 
C.sub.2 to C.sub.9 carbon content in the acyl group and about C.sub.9 to 
C.sub.23 carbon content in the alkane alkyl ether sulfates containing from 
about C.sub.10 to C.sub.20 carbon atoms in the alkyl groups and from about 
1 to 30 moles of ethylene oxide, water soluble salts of olefin sulfonates 
containing from about C.sub.12 to C.sub.24 carbon content, 
beta-alkyloxyalkane sulfonates which contain from about C.sub.1 to C.sub.3 
carbon content in the alkyl group and from about C.sub.8 to C.sub.20 
carbon content in the alkane, anionic phosphate surfactants, N-alkyl 
substituted succinamates, and mixtures thereof. 
The composition may also optionally further include a pH adjuster to keep 
the liquid detergent near neutral or slightly alkaline in pH value. If the 
pH is over 9, then salting out of the builder may occur at higher builder 
levels such as at 10% or more by weight of the builder in the composition. 
The preferred pH ranges are from about 6 to 9, more preferably from about 
7 to 8.5, and most preferably at about 8. The pH adjusters may be selected 
from any compatible acid compound and citric acid is especially preferred 
because of its builder properties. The pH adjusters are present in a range 
of from about 0.1 to 5% by weight of the composition. 
Further, and surprisingly, the liquid laundry detergent composition may 
also further include at least one cationic quaternary ammonium fabric 
softener selected from the group consisting of: 
##STR3## 
Another example is the reaction product of about 2 moles of an acid having 
the formula R.sub.5 COOH and about 1 mole of an alkylene diamine having 
the formula H.sub.2 N--C.sub.2 H.sub.4 -NHR.sub.6, said reaction product 
being a mixture of amides, esters, imidazolines and mixtures thereof. 
In the foregoing formulas, R.sup.8 is an alkyl or alkenyl straight or 
branched chain hydrocarbon containing from 8 to 22, preferably from 11 to 
19 carbon atoms. R.sup.9 is an alkyl group containing from 1 to 3 carbon 
atoms. R.sup.10 represents R.sup.8 or R.sup.9. R.sup.11 is a divalent 
alkylene group containing from 1 to 2 carbon atoms. R.sup.12 is an 
aliphatic alkyl group containing from 15 to 19 carbon atoms. R.sup.13 is a 
hydroxyalkyl group containing from 1 to 3 carbon atoms. X is a suitable 
anion such as chloride, bromide, iodide, sulfate, alkylsulfate having 1 to 
3 carbon atoms in the alkyl group, acetate, etc. Also in the formulas, y 
is the valence of X and n represents an integer from 1 to 4. Mixtures of 
quaternary ammonium compounds may also be used to practice this invention. 
Cationic fabric softeners are basically, one, two or three alkyl chains 
emanating from a positively charged cation such as nitrogen or phosphorus. 
The alkyl groups are usually C.sub.10 -C.sub.22. These materials must be 
water soluble or water dispersible. The positively charged nitrogen can be 
a normal alkyl ammonium or in a cyclic ring such as imidazolinium or 
pyridinium salts. Examples of some of the more common commercial classes 
of cationic fabric softeners are monoalkyl trimethyl quaternary ammonium 
compounds, monomethyl trialkyl quaternary ammonium compounds, dimethyl 
dialkyl quaternary ammonium compounds, imidazolinium quaternary ammonium 
compounds, dimethyl alkyl benzyl quaternary ammonium compounds, complex 
diquaternary ammonium compounds, dimethyl dialkoxy alkyl quaternary 
ammonium compounds, diamidoamine based quaternary ammonium compounds, 
dialkyl methyl benzyl quaternary ammonium compounds, alkyl pyridinium 
salts, and amido alkoxylated ammonium. Usually these commercial quaternary 
ammonium compounds contain alkyl groups of C.sub.10 -C.sub.18 or a mixture 
thereof. To obtain clear solutions, use of an alcohol such as ethanol may 
improve the clarity of the composition if the composition is clear before 
addition of the cationic fabric softener compound. 
It has been surprisingly found that cationic quaternary fabric softeners 
may be tolerated in these detergent compositions to produce stable, one 
phase compositions. Some compositions are translucent to opaque in 
appearance depending upon the formulation employed. More preferred 
compositions are those which are found to be as clear in appearance as 
those which are free of such cationic fabric softeners. 
The composition may also include proteolytic enzymes in an amount of 0.01 
to 5% by weight of the composition, optical brighteners in an amounts of 
about 0.05 to 5% by weight of the composition as well as perfumes, dyes, 
disinfectants and other ingredients which are standard and well known in 
the art. 
Preferably, the composition is comprised of from about 10% to 25% by weight 
of at least one nonionic surfactant such as an ethoxylated nonylphenol 
surfactant, at least one builder which is preferably a salt of 
nitrilotriacetic acid along with a borate builder present in an amount of 
about 2 to 25% by weight of the composition and more preferably at about 
5% to 10% by weight of the composition, optionally, an additional builder 
system in an amount of about 2 to 10% by weight of the composition, a 
water soluble polymeric anionic hydrotrope anti-redeposition agent which 
is a hydrolyzed C.sub.6 to C.sub.10 alpha olefin and maleic anhydride 
copolymer which is present in an amount effective to render the built 
liquid detergent composition clear, stable and single phase, typically at 
about 1 to 10%, and more preferably from 2% to 5%, by weight of the 
composition, optionally a pH adjuster present in about 0.1 to 5% by weight 
of the composition as well as optionally effective amounts of proteolytic 
enzymes, optional cationic quaternary ammonium fabric softeners of the 
aforementioned type, and the balance of the composition being water. It is 
further contemplated that the composition have a pH in a range of about 6 
to 9, more preferably from about 7 to 8.5, and most preferably at about 8. 
The following Examples are offered to illustrate the invention and 
facilitate its understanding without limiting the scope or spirit of the 
invention. 
In the Examples, the testing reported was done substantially in accordance 
with the American Association of Textile Chemists and Colorists (AATCC) 
method for measuring soil removal from artificially soiled fabrics (AATCC 
Method No. 153-1978) and for evaluating stain removal performance in home 
laundry (AATCC Method No. 130-1981). When reported, the formulations were 
tested according to the guidelines as set forth by the AATCC as these test 
methods relate to soil redeposition (AATCC Method No. 152-1980). 
In the following Examples, the ingredients listed were as follows unless 
otherwise indicated and the amounts and percentages used are by weight: 
ADOL.RTM. 42--Tallow alcohol, from Sherex Chemical Company. 
Ammonium Hydroxide--concentrated, 30% ammonia, 26.degree. Baume. 
EDTA--Ethylenediamine tetraacetic acid 
LAAS--Linear sodium alkyl aryl sulfonate, 60% in water. 
MILEZYME.RTM. APB--blend of protease and amylase in liquid form from Miles 
Biotech Products Division of Miles Laboratories, Inc. 
MYCON P200--Ethylenediamine tetra(methylene phosphonic acid) from Warwick 
International Ltd., free acid in cake form. 
MYCON P240--Hexapotassium salt of Ethylenediamine tetra(methylene 
phosphonic acid), from Warwick International Ltd., 27% in water. 
NEODOL.RTM. 25-7--Polyethylene glycol ether of a mixture of synthetic 
C.sub.12 -C.sub.15 fatty alcohols with an average of 7 moles of ethylene 
oxide from Shell Chemical Company. 
NEODOL.RTM. 25-9--Polyethylene glycol ether of a mixture of synthetic 
C.sub.12 -C.sub.15 fatty alcohols with an average of 9 moles of ethylene 
oxide from Union Carbide. 
NTA Salt--Trisodium salt of nitrilotriacetic acid ("NTA"), 40% in water. 
STPP--Sodium tripolyphosphate, anhydrous granules. 
SURFONIC.RTM. N-60--Ethoxylated alkylphenol of formula C.sub.9 H.sub.19 
C.sub.6 H.sub.4 -(OCH.sub.2 CH.sub.2).sub.b OH where b averages 6, from 
Texaco Chemical Corporation. 
SURFONIC.RTM. N-95--Same as SURFONIC N-60, but b averages 10 instead of 6. 
SXS--Sodium xylene sulfonate, 40% in water. 
TERGITOL.RTM. 15-S-9--Polyethylene glycol ether of a mixture of synthetic 
C.sub.11 -C.sub.15 fatty alcohols with an average of 9 moles of ethylene 
oxide, from Shell Chemical Co. 
TINO.RTM. CBS--Distyrylbiphenyl derivative from CIBA-GEIGY, optical 
brightener agent. 
TINO.RTM. PT--Benzenesulfonic acid, 2,2'-(1,2-ethandiyl) 
bis(5-(4-(bis(2- 
hydroxyethyl) amino)-6-((4-sulfophenyl) 
amino)1,3,5-triazin-2-yl)amino)-tetrasodium salt from CIBA-GEIGY, optical 
brightening agent. 
TKPP--Tetrapotassium pyrophosphate, 60% in water or 100% as indicated in 
the Examples. 
TRITON.RTM. QS30--Phosphonate surfactant in free acid form, from Rohm & 
Haas Co.

EXAMPLES 1-7 
In the following Table I, the formulations listed are given as parts by 
weight of nonvolatile ingredients. The alpha olefin/maleic anhydride 
polymers listed are to be added as 15% by weight solutions of the polymer 
hydrolyzed with sodium hydroxide (150% of stoichiometric amount) in water. 
TABLE I 
______________________________________ 
Ingredient 1 2 3 4 5 6 7 
______________________________________ 
1-hexene/maleic 
3.00 -- 4.00 4.00 -- 5.00 -- 
anhydride copoly- 
mer (1.0/1.0 molar 
ratio) 
1-hexene/1-decene/ 
-- 2.50 -- -- 6.00 -- -- 
maleic anhydride 
terpolymer (.5/.5/ 
1.0 molar ratio) 
1-decene/1-octa- 
-- -- -- -- -- -- 4.00 
decene/maleic anhy- 
dride terpolymer 
(.5/.5/1.0 molar 
ratio) 
Sodium hydroxide 
1.00 0.7 1.33 1.33 1.68 1.67 0.82 
Borate-sodium 
5.00 -- 3.00 5.00 20.00 
4.00 3.00 
tetraborate 
Tetrapotassium 
-- 5.00 -- -- -- 9.00 -- 
pyrophosphate 
(TKPP) 
Nitrilotriacetic acid 
4.00 -- 5.00 -- 2.50 -- -- 
(NTA), trisodium 
salt 
(NTA salt) 
Sodium citrate 
-- 2.50 -- -- -- -- 5.00 
Primary alcohol 
15.00 -- -- 9.00 -- 12.00 
15.00 
ethoxylate (9 mol) 
Secondary alcohol 
-- 12.00 -- 4.00 -- -- -- 
ethoxylate (7 mol) 
Ethoxylated (9.5 
-- -- 15.00 
-- 10.00 
-- -- 
mol) nonylphenol 
Citric acid 1.75 1.20 1.50 -- 2.50 2.00 1.20 
Optical brightener 
.20 .20 .20 .30 .15 .15 .30 
Methyl bis 2-hy- 
-- -- -- 3.20 -- -- -- 
droxyethyl 
ammonium sulfate 
Fragrance .20 .20 .20 .20 .20 .20 .20 
Dye .002 .002 .002 .002 .002 .002 .002 
Enzyme .50 -- -- -- -- -- .50 
Water (balance 
to 100%) 
______________________________________ 
Example 1 indicates the use of a C.sub.6 alpha olefin/maleic anhydride 
copolymer having a borax and an NTA salt builder system along with an 
enzyme for protein removal. The formula is expected to have excellent 
stain removal, especially grass and blood stain removal, on 100% cotton 
and blends of cotton and polyester when tested according to the test 
methods enumerated above. 
Example 2 demonstrates the use of a C.sub.6 -C.sub.10 alpha olefin/maleic 
anhydride terpolymer. The formulation of Example 2 does not contain a 
trisodium NTA salt/borax builder system. However, it does contain an 
optional builder system for use where use of NTA and/or its salts is not 
permitted by law. The system is expected to give good performance overall, 
however it is expected to have a slightly downscale detergency value 
relative to formulations using a 50:50 weight ratio of trisodium NTA salt 
and borax at the same total percentage in the formulation. 
Example 3 demonstrates the use of an ethoxylated nonylphenol surfactant 
because use of such a surfactant greatly increases oily stain and 
particulate soil removal. This formulation, using a C.sub.6 alpha 
olefin/maleic anhydride copolymer, is preferred when one desires to obtain 
a formulation giving optimum detergency, anti-redeposition properties and 
oily stain removal. 
Example 4 demonstrates the incorporation of a cationic quaternary ammonium 
fabric softener into compositions of the present invention. 
Example 5 indicates increasing the borax builder system to improve the 
whiteness readings of fabrics when they are washed with such a 
composition. 
Example 6 indicates a combination of borax along with tetrapotassium 
pyrophosphate as a builder system and a C.sub.6 alpha olefin/maleic 
anhydride copolymer in a detergent composition. The composition is 
expected to offer excellent anti-redeposition and stain removal 
properties. 
Example 7 indicates the use of a C.sub.10 -C.sub.18 alpha olefin/maleic 
anhydride terpolymer and is expected to demonstrate very good stain 
removal. Anti-redeposition properties are expected to be slightly 
downscale when compared with a similar formulation using, for example, a 
C.sub.6 alpha olefin/maleic anhydride copolymer substituted for the 
C.sub.10 -C.sub.18 alpha olefin/maleic anhydride polymer in Example 7, but 
is still expected to fall within the acceptable range for 
anti-redeposition properties. 
PROCESSING EXAMPLES 
The alpha olefin/maleic anhydride polymer used in this invention is 
hydrolyzed with sodium tetraborate, ammonium hydroxide, potassium 
hydroxide, or sodium hydroxide, and more preferably with sodium hydroxide. 
A concentrate is prepared with water, base, and polymer at a temperature 
of 40.degree. C.-95.degree. C. until a clear solution is formed. 
______________________________________ 
Processing Example A: 
Polymer Cut #1 % by Weight 
______________________________________ 
Water 70.0 
Sodium tetraborate 10.0 
1-hexene/maleic anhydride copolymer 
20.0 
100.0 
______________________________________ 
PROCESSING FOR EXAMPLE 1 
Charge 59.848 grams of water together with 3.5 grams of sodium tetraborate 
and 1.75 grams of citric acid. Agitate until dissolved. Add 15 grams of 
the polymer cut shown above. Add the rest of materials in the following 
order: 15.0 grams of primary alcohol ethoxylate, 0.020 grams of optical 
brightener, 0.50 grams of enzyme, 4.0 grams of trisodium NTA, 0.002 grams 
of dye, and 0.20 grams of fragrance. 
______________________________________ 
Processing Example B: 
Polymer Cut #2 % by Weight 
______________________________________ 
Water 70.0 
Ammonium Hydroxide 10.0 
1-hexene/maleic anhydride copolymer 
20.0 
100.0 
______________________________________ 
PROCESSING FOR EXAMPLE 4 
Charge 58.229 grams of water with 5.0 grams of sodium tetraborate. Add 20.0 
grams of Polymer Cut #2 shown above. Agitate until dissolved. Meanwhile, 
heat 9.0 grams of primary alcohol ethoxylate and 4.0 grams of secondary 
alcohol ethoxylate with 3.2 grams of methyl bis 2-hydroxyethyl ammonium 
sulfate to 100.degree. F. Slowly add the heated surfactants to the water, 
sodium tetraborate, and Polymer Cut #2 mixture until uniform. Add 0.30 
grams of optical brightener, 0.001 grams of dye, and 0.20 grams of 
fragrance. 
There is an amide formation up to 30% with a polymer or resin cut prepared 
with ammonium hydroxide. Performance is similar to cuts prepared with 
sodium hydroxide, potassium hydroxide, and sodium tetraborate. 
EXAMPLES 8-14 
In the following Examples, a polymer or "resin" cut was made by hydrolyzing 
the maleic anhydride/alpha-olefin polymers using sodium hydroxide and 
water. Unless otherwise noted, all amounts and percentages are by weight. 
Thus, 7.5 parts of sodium hydroxide was mixed with 77.5 or 72.5 parts of 
water and 15 or 20 parts, respectively, of maleic anhydride/alpha-olefin 
polymer and heated at 40.degree.-95.degree. C. until a clear solution was 
formed thereby providing a resin cut having 15% or 20% polymer content. 
The following abbreviations are used below when referring to the maleic 
anhydride copolymers or terpolymers used in the form of "resin cuts": 
MAH/C.sub.4 --1:1 molar ratio copolymer of maleic anhydride:1-butene, resin 
cut at 15% copolymer content. 
MAH/C.sub.4 /C.sub.10 --1:0.5:0.5 molar ratio terpolymer of maleic 
anhydride:1-butene:1-decene, resin cut at 15% terpolymer content. 
MAH/C.sub.6 --1:1 molar ratio copolymer of maleic anhydride: 1-hexene, 
resin cut at 20% copolymer content. 
MAH/C.sub.6 /C.sub.10 -1:0.5:0.5 molar ratio terpolymer of maleic 
anhydride:1-hexene:1-decene, resin cut at 15% terpolymer content. 
MAH/C.sub.10 1:1 molar ratio copolymer of maleic anhydride: 1-decene, resin 
cut at 15% copolymer content. 
Example 8 was a comparative Example prepared to reproduce Example 11 of the 
Smith et al. U.S. Pat. No. 4,525,291 containing sodium xylene sulfonate as 
a hydrotrope and to compare that composition with compositions 
substituting maleic anhydride/alpha-olefin copolymers as hydrotropes 
(Examples 9-12). Example 9 containing the MAH/C.sub.4 copolymer was a 
comparative Example based upon a combination of the teachings of the 
Tuvell U.S. Pat. No. 3,235,505 (which employs substantially equimolar 
copolymers of maleic anhydride with an olefinically unsaturated compound 
having less than 5 carbon atoms) in view of the Smith et al. patent's 
teachings even though the Tuvell Patent relates to an emulsion built 
liquid detergent composition reported to be "very white" in Tuvell's 
Example I rather than being clear. 
TABLE II 
______________________________________ 
Example No. 
8 9 10 11 12 13 14 
______________________________________ 
TERGITOL 15-S-9 
7.0 7.0 7.0 7.0 7.0 7.0 7.0 
SXS 12.50 -- -- -- -- 40.99 
-- 
MAH/C.sub.4 Resin 
-- 33.33 -- -- -- -- 60.32 
Cut 
MAH/C.sub.6 Resin 
-- -- 25.00 
-- -- -- -- 
Cut 
MAH/C.sub.10 Resin 
-- -- -- 33.33 
-- -- -- 
Cut 
MAH/C.sub.4 /C.sub.10 Resin 
-- -- -- -- 33.33 
-- -- 
Cut 
TRITON QS30 3.33 3.33 3.33 3.33 3.33 3.33 3.33 
TKPP.sup.1 25.00 25.00 25.00 
25.00 
25.00 
25.00 
15.00 
Deionized Water 
28.08 7.25 15.58 
7.25 7.25 -- -- 
MYCON P240 0.56 0.56 0.56 0.56 0.56 -- -- 
MYCON P200 -- -- -- -- -- 0.15 0.15 
Sodium Gluconate 
0.20 0.20 0.20 0.20 0.20 0.20 0.20 
H.sub.2 O.sub.2.sup.2 
23.33 23.33 23.33 
23.33 
23.33 
23.33 
14.00 
Appearance.sup.3 
S S C C C S S 
______________________________________ 
.sup.1 Tetrapotassium pyrophosphate, 60% in water for Examples 8-13 and 
100% for Example 14. 
.sup.2 Hydrogen Peroxide, 30% in water for Ex. 8-13 and 50% in water for 
Ex. 14. 
.sup.3 Composition at room temperature (about 23-25.degree. C.) within 
about 24 hours after formulation; S = separated into two phases; C = 
clear, one phase. 
As can be seen from Table II, comparative Examples 8 and 9 were unstable 
and separated into two phases shortly after they were made. Example 10, 
using an MAH/C.sub.6 copolymer resulted in a clear, solvated, single phase 
composition as did Example 11 having an MAH/C.sub.10 copolymer. Example 12 
shows that C.sub.4 alpha olefin can be employed to produce clear, 
solvated, single phase compositions of the present invention as long as 
another higher 1-alkene is also a significant part of the total alpha 
olefin content of the terpolymer. 
Comparative Examples 13 and 14 were produced to determine if increasing the 
amount of hydrotrope in Examples 8 and 9 would produce clear, solvated, 
single phase compositions. MYCON P200 (free acid) was used instead of 
MYCON P240 in these Examples, 100% TKPP and 50% hydrogen peroxide solution 
was used in Examples 13 and 14. Example 13 contained 16.4% sodium xylene 
sulfonate and Examples 14 contained 9.05% MAH/C.sub.4 copolymer. Both 
samples separated into two phases upon standing at room temperature. 
Thus, to obtain clear, one phase, solvated built liquid detergent 
compositions, an MAH/C.sub.6 or higher 1-alkene copolymer appears to be 
necessary to act as a hydrotrope. However, polymers including a C.sub.4 
1-alkene can be employed as hydrotropes if there is further included a 
sufficient amount of higher 1-alkene such as a 1-decene, i.e., a 
MAH/C.sub.4 /C.sub.10 terpolymer. 
EXAMPLES 15-22 
In these Examples, polymers having substantially equimolar ratios of maleic 
anhydride to alpha olefins were evaluated as hydrotropes in built liquid 
detergent compositions. Examples 16-21 were clear, one phase solvated 
built liquid compositions while Example 15 was a comparative Example since 
it separated into two phases. 
In these Examples, the resin cuts used were: 
MAH/C.sub.4 /C.sub.6 --1:0.5:0.5 molar ratio terpolymer of maleic 
anhydride:1-butene:1-hexene; resin cut was 15% polymer, 5% sodium 
hydroxide and 80% tap water. 
MAH/C.sub.6 /C.sub.10 --1:0.5:0.5 molar ratio terpolymer of maleic 
anhydride:1-hexene:1-decene; resin cut was 20% polymer, 25% borax, and 
55.0% deionized water. 
MAH/C.sub.6 /C.sub.18 --1:0.9:0.1 molar ratio terpolymer of maleic 
anhydride:1-hexene:1-octadecene; resin cut was 15% polymer, 5% sodium 
hydroxide and 80% tap water. 
MAH/C.sub.10 /C.sub.18 --1:0.5:0.5 molar ratio terpolymer of maleic 
anhydride:1-decene:1-octadecene; resin cut was 25% polymer, 10.3% ammonium 
hydroxide, and 64.7% deionized water. 
MAH/C.sub.12 --1:1 molar ratio copolymer of maleic anhydride and 
1-dodecene; resin cut was 20% polymer, 9.13% Ammonium Hydroxide and 70.87% 
deionized water. 
MAH/C.sub.14 --1:1 molar ratio copolymer of maleic anhydride and 
1-tetradecene; resin cut was 20% polymer, 8.26% Ammonium Hydroxide and 
71.24% deionized water. 
MAH/C.sub.18 --1:1 molar ratio copolymer of maleic anhydride and 
1-octadecene; resin cut was 15% polymer, 5% sodium hydroxide and 80% tap 
water. 
The formulations employed are listed in Table III. Each composition was 
prepared by mixing the ingredients listed together sequentially and in the 
order listed in Table III with stirring. In Examples 19 and 20, the order 
of addition was deionized water, TINO CBS, polymer cut, borax, SURFONIC 
N-95, NTA salt, dye (as a 1% solution in water) and citric acid. 
The MAH/C.sub.4 /C.sub.6 polymer had an average of about 5 carbon atoms 
based on the total alpha olefin content. The result was a two phase 
composition. The remaining compositions were clear, single phase, solvated 
compositions. Examples 18, 19 and 20 were observed to be more viscous than 
the other compositions and Examples 19 and 20 were noted as being very 
viscous, i.e., very thick, but still pourable. 
TABLE III 
______________________________________ 
Example No. 
15 16 17 18 19 20 21 
______________________________________ 
Tap Water.sup.1 
53.33 58.9 52.83 
53.2 52.7 52.7 52.13 
Borax 2.0 -- 2.0 5.0 5.0 5.0 2.0 
Citric Acid -- 1.1 0.50 1.8 1.8 1.8 0.5 
MAH/C.sub.4 /C.sub.6 
26.67 -- -- -- -- -- -- 
Resin Cut 
MAH/C.sub.6 /C.sub.10 
-- 20.0 -- -- -- -- -- 
Resin Cut 
MAH/C.sub.6 /C.sub.18 
-- -- 26.67 
-- -- -- -- 
Resin Cut 
MAH/C.sub.10 /C.sub.18 
-- -- -- 20.0 -- -- -- 
Resin Cut 
MAH/C.sub.12 
-- -- -- -- 20.0 -- -- 
Resin Cut 
MAH/C.sub.14 
-- -- -- -- -- 20.0 -- 
Resin Cut 
MAH/C.sub.18 
-- -- -- -- -- -- 26.67 
Resin Cut 
SURFONIC N-60 
-- -- -- -- -- -- 6.0 
SURFONIC N-95 
12.0 -- 12.0 15.0 15.0 15.0 6.0 
ADOL 42 -- 15.0 -- -- -- -- -- 
NTA Salt 6.0 5.0 6.0 5.0 5.0 5.0 6.0 
TINO CBS -- -- -- -- 0.3 0.3 0.25 
C.I. Direct Blue 
-- -- -- -- 0.2 0.2 0.2 
86 Dye (1%) 
Fragrance -- -- -- -- -- -- 0.25 
Appearance.sup.2 
S C C C, V C, V C, V C 
______________________________________ 
.sup.1 Deionized water was used for Examples 19 and 20. 
.sup.2 Composition at room temperature within about 24 hours after 
formulation: S = Separated into two phases, C = clear, one phase; V = 
viscous. 
EXAMPLES 22-23 
In these comparative Examples, two built liquid detergent compositions were 
prepared without the use of an additional hydrotrope agent to show that 
certain formulations can be made which are stable and clear at room 
temperature. 
Example 22 was based on Example 55 of the Smith et al. '291 Patent. It is 
known that some formulations do provide clear, one phase built liquid 
detergent compositions without the addition of hydrotropes. In Example 22, 
the 6% of sodium xylene sulfonate and 7% of hydrogen peroxide solution 
listed in Example 55 of the Smith et al. '291 Patent was omitted and water 
was substituted in their place. Ethylene diamine tetraacetic acid ("EDTA") 
was used in place of hexapotassium ethylenediamine tetra(methylene 
phosphonate). The formulation for Example 22 is listed in TABLE IV. 
Example 22 was stable and clear at room temperature at the time the 
composition was prepared without the use of any additional hydrotrope 
agent. This formulation did contain ethanol which is a known cosolvent and 
6% of an anionic surfactant as well as a relatively low amount of nonionic 
surfactant. 
Example 23 did not contain any ethanol cosolvent or surfactants other than 
the one nonionic surfactant, SURFONIC N-95. This sample was clear and 
remained in a single phase after being prepared and remained so upon 
storage at room temperature. However, Example 23 immediately separated 
into two phases when its temperature reached 120.degree. F. after the 
sample was placed in an oven for stability testing. Another comparative 
Example was prepared using the formula of Example 23, but substituting 
1.0% MILEZYME APB in place of 1% of the water in the formulation and the 
same results were observed: the sample was clear and single phase at room 
temperature, but separated into two phases upon being heated to 
120.degree. F. 
Other compositions have also been prepared which are clear and stable 
without additional hydrotrope agent, the results are dependent upon the 
nature and amount of the builder salts and surfactants present. Stability 
upon heating which can occur during shipment and storage of such 
compositions can become a problem. The polymeric anionic hydrotropes of 
the present invention can help in reducing this temperature sensitivity. 
In any event, it is expected that when a polymeric anionic hydrotrope 
agent of the present invention is added to such a clear composition, it is 
expected that the anti-redeposition characteristics of the formulation 
will be improved. 
TABLE IV 
______________________________________ 
Example No. 
22 23 
______________________________________ 
Deionized Water -- 67.8 
TINO CBS -- 0.2 
Borax -- 5.0 
SURFONIC N-95 -- 20.0 
NEODOL 25-9 4.0 -- 
LAAS (60%) 10.0 -- 
NTA Salt 15.0 5.0 
Ethanol 10.0 -- 
Sodium Gluconate 0.2 -- 
EDTA 0.15 -- 
Deionized Water 60.65 -- 
Direct Blue 86 (1%) 
-- 0.2 
Citric Acid -- 1.8 
______________________________________ 
The compositions were prepared by mixing the ingredients listed in TABLE IV 
together in the order shown with stirring, allowing each ingredient to 
dissolve or disperse before the next ingredient was added. 
EXAMPLE 24-28 
These Examples use a base formulation containing reasonably high levels of 
both builder salts (TKPP and sodium citrate) and nonionic surfactants to 
demonstrate the differences in stain removal for compositions containing 
sodium xylene sulfonate as a hydrotrope (Example 24) and MAH/C.sub.4 
copolymer (Example 25) as hydrotropes versus MAH/C.sub.4 /C.sub.10 
terpolymer (Example 26), MAH/C.sub.6 copolymer (Example 27) and 
MAH/C.sub.6 C.sub.10 terpolymer (Example 28) as hydrotropes. The resin 
cuts used in these Examples were of the same type as those described for 
Examples 9-12 and 14. The formulations were listed in TABLE V. 
TABLE V 
______________________________________ 
Example 
24 25 26 27 28 
______________________________________ 
Tap Water 69.72 59.10 59.10 63.47 
59.30 
TKPP (60%) 8.33 8.33 8.33 8.33 8.33 
Citric Acid 1.20 1.20 1.20 1.20 1.20 
Sodium Citrate 
2.50 2.50 2.50 2.50 2.50 
NEODOL 25-7 12.00 12.00 12.00 12.00 
12.00 
SXS (40%) 6.25 -- -- -- -- 
MAH/C.sub.4 Resin Cut 
-- 16.67 -- -- -- 
MAH/C.sub.4 /C.sub.10 Resin Cut 
-- -- 16.67 -- -- 
MAH/C.sub.6 Resin Cut 
-- -- -- 12.50 
-- 
MAH/C.sub.6 /C.sub.10 
-- -- -- -- 16.67 
Resin Cut 
C.I. Direct Blue 86 
0.20 0.20 0.20 0.20 0.20 
Dye (1%) 
Appearance.sup.1 
S S C 0, C C 
______________________________________ 
.sup.1 Composition at room temperature within about 24 hours after 
formulation; S = separated into two phases; 0 = opaque; C = clear, one 
phase; SH = slight haze. 
The compositions were prepared by mixing the ingredients listed in TABLE V 
together in the order shown with stirring, allowing each ingredient to 
dissolve or disperse before the next was added. 
The compositions each contained 2.5% hydrotrope, 7.5% total builder salts, 
and 12% nonionic surfactant. Examples 24 and 25 containing sodium xylene 
sulfonate and the MAH/C.sub.4 copolymer both separated into two phases and 
are comparative Examples. The MAH/C.sub.6 copolymer compositions (Example 
27) was initially opaque, but appeared to be a one phase composition when 
it was prepared. After standing overnight, that composition became clear 
and remained a one phase composition. The terpolymer-containing 
compositions were both clear and one phase initially and remained so at 
room temperature. Thus, the MAH/C.sub.4 /C.sub.10 terpolymer was quite 
effective as a hydrotrope in this formulation while the MAH/C.sub.4 
copolymer was not. 
Each composition was vigorously shaken to insure that any separate phases 
were mixed together and the stain removal ability of each was tested 
according to standard test methods. A total of 11 agents were used to test 
each composition's ability to remove both water-borne and oil-borne stains 
from 65% polyester/35% cotton fabric swatches after one wash cycle: 
Columbian coffee, red lipstick, tea, chocolate, blood, Ragu' Spaghetti 
Sauce, clay, artificial sebum, grass, red wine and used motor oil. The 
test was done by having two persons separately evaluate the stain removal 
visually against a standard using a rating scale where 0=no stain removal 
to 5=complete stain removal. The two sets of individual ratings were 
averaged and the results are reported numerically in TABLE VI. 
TABLE VI 
______________________________________ 
Example No. 
24 25 26 27 28 
______________________________________ 
Columbian Coffee 
5.00 5.00 5.00 5.00 5.00 
Lipstick 1.50 2.00 2.00 2.25 2.00 
Tea 5.00 5.00 5.00 5.00 5.00 
Chocolate 5.00 5.00 5.00 5.00 5.00 
Blood 2.75 4.00 3.50 4.25 4.25 
Spaghetti Sauce 
2.75 3.25 3.25 3.25 3.25 
Clay 4.50 4.25 3.75 4.50 4.50 
Sebum 1.75 2.25 3.25 3.75 2.00 
Grass 3.00 3.75 3.75 3.75 4.00 
Red Wine 5.00 5.00 5.00 5.00 5.00 
Motor Oil (used) 
2.25 2.00 2.25 2.25 2.75 
AVERAGE 3.50 3.77 3.80 4.00 3.89 
______________________________________ 
Rating Scale: 
0 = No stain removal 
5 = Complete stain removal 
The sodium xylene sulfonate composition (Example 24) was fairly comparable 
in stain removing power to the other samples although it was less 
effective than the other samples for lipstick, blood, sebum and grass. The 
MAH/C.sub.4 copolymer composition (Example 25) was quite comparable in 
stain removal ability to the other compositions containing maleic 
anhydride/alpha-olefin polymers as hydrotropes. 
However, the sodium xylene sulfonate and MAH/C.sub.4 copolymer samples were 
vigorously shaken before using. If this was not done by a consumer and the 
product was allowed to separate into two phases before using, then 
cleaning ability might suffer if only part of the product was used. This 
result could occur if more of one phase was added than the other when the 
composition was added to the wash. 
One phase would be expected to have a better cleaning ability for certain 
stains than the other since the hydrophilic salts tend to stay in one 
phase and the surfactants, which have some hydrophobic character, tend to 
associate together. The maleic anhydride/alpha-olefin polymers of the 
present invention permit one phase compositions to be formed. 
The anti-redeposition characteristics of these compositions were also 
tested for gross differences between the samples by using a single washing 
cycle. Normally, multiple washing cycles are used, but significant 
differences in anti-redeposition behavior will often be evident after one 
wash cycle. Two different fabrics (cotton and DACRON.RTM. polyester) 
having one side predeposited with clay-type soil or artificial sebum were 
used and the other side of the cloth was left clean. Redeposition was 
measured using the clean or "white edge" of the sebum-soiled fabrics. The 
initial reflectance of the white edge (no soil present) was measured, each 
composition was vigorously shaken if it was not in one phase and was used 
to wash the cloth samples for one wash cycle. The reflectance of the white 
edge was again measured and the percentage difference between the two 
readings was calculated. Negative differences between readings would 
indicate that redeposition of the sebum soil was occurring. All of the 
compositions had positive readings and were fairly close together which 
indicated that the fabric sample became whiter after washing than it was 
before washing. Thus, no significant problem with soil redeposition for 
any of the compositions of Examples 24-28 tested was noted. 
EXAMPLE 29 
This Example shows a formulation which is preferred when one desires a 
built liquid laundry detergent composition made by method of the present 
invention which possesses a very good combination of pre-spotting 
characteristics, anti-redeposition characteristics and ability to remove 
oily stains from fabrics. The formula was as follows: 
______________________________________ 
Tap water 67.848 
MAH/C6 Copolymer 4.00 
Ammonium Hydroxide 
0.80 
TINO CBS 0.25 
Borax 5.00 
SURFONIC N-95 15.00 
NTA Salt 5.00 
C.I. Direct Blue 86 Dye 
0.002 
Citric Acid 1.80 
Fragrance 0.30 
100.000% 
______________________________________ 
The MAH/C.sub.6 Copolymer is a 1:1 molar ratio copolymer of maleic 
anhydride and 1-hexene. The resulting composition is clear, is dyed blue, 
and has a pH in the range of about 7.5-8.5. Typically, such a composition 
is slightly viscous and the viscosity is generally between 100 and 200 
centipoise at room temperature. A resin cut was prepared using the water, 
copolymer and ammonia solution listed before the other ingredients are 
added in the order listed. Sodium hydroxide can be substituted on a 
stoichiometric basis for the ammonium hydroxide. 
EXAMPLE 30 
This Example shows a formulation using a relatively economical blend of 
ingredients while still giving good pre-spotting, detergency and 
anti-redeposition characteristics. properties. The formulation was as 
follows: 
______________________________________ 
Tap Water 53.88 
Borax 2.0 
MAH/C.sub.10X50 Resin Cut 
26.67 
SURFONIC N-60 6.0 
SURFONIC N-95 6.0 
TINO CBS 0.25 
STPP 5.0 
Direct Blue 86 Dye (1%) 
0.2 
Fragrance 0.25 
100.00% 
______________________________________ 
The resin cut used in Example 34 was composed of 15% of the 
MAH/C.sub.10.times.50 copolymer, 7.5% sodium hydroxide, and 77.5% water 
tap. The MAH/C.sub.10.times.50 copolymer used in this Example and those 
referred to in other Examples were about 1:5:1.0 molar ratio copolymers of 
maleic anhydride and 1-decene containing an excess of maleic anhydride 
relative to the amount of 1-decene and were of the type described in the 
Billman et al. Patent previously incorporated by reference. 
This formulation was found to be a clear, one phase solvated liquid 
detergent composition which remained in one phase even after it was stored 
at 110.degree. F. for 1 week as part of an accelerated stability test. 
EXAMPLE 31-32 
These Examples show formulations containing increased levels of NTA salts 
as builders along with relatively high levels of nonionic surfactants and 
the effect of pH on the stain removal and soil removal from artificially 
soiled fabric. The formulations used were as follows: 
______________________________________ 
Example No. 
31 32 
______________________________________ 
Tap Water 41.18 41.58 
Borax 2.0 2.0 
MAH/C.sub.10X50 Resin Cut.sup.1 
26.67 26.67 
SURFONIC N-60 6.0 6.0 
SURFONIC N-95 10.0 10.0 
TINO CBS 0.25 0.25 
NTA salt 12.0 12.0 
Direct Blue 86 Dye (1%) 
0.20 0.20 
Citric Acid -- 1.30 
Sodium Hydroxide 1.70 -- 
100.00% 100.00% 
______________________________________ 
.sup.1 Polymer cut, 15% in water using sodium hydroxide as alkali. 
Example 31 had a pH of 10.0 and was rather alkaline. Example 32 had a pH of 
7.5. Both compositions were found to be clear, one phase, solvated built 
liquid detergent compositions at room temperature. 
The stain removal ability of each composition was evaluated after 3 wash 
cycles versus a commercially available built liquid detergent sold by 
Unilever in Canada under the tradename WISK. The commercially-obtained 
detergent had a pH of 12 ("CAN WISK-12") which is highly alkaline and, for 
test purposes, the pH of a portion of that detergent was adjusted to a pH 
of 7.5 ("CAN WISK-7.5"). The stain removal tests were done as described in 
Examples 24-28 using swatches of two different types of fabrics: 100% 
cotton and 65% polyester/35% cotton. The results are reported in TABLE 
VII. Example 31 was found to be better than Example 32 in removing blood 
and lipstick stains while Example 32 was found to be better than Example 
31 in removing tea and red wind stains. Overall, Examples 31 and 32 were, 
on average, as good as the commercial WISK detergent and were better than 
the Canadian WISK detergent against stains on 100% cotton fabrics and were 
both better, on average, than either of the commercial products against 
stains on 65% polyester/35% cotton fabrics. 
TABLE VII 
______________________________________ 
CAN CAN 
Example No. 31 32 WISK-7.5 
WISK-12 
______________________________________ 
A) 100% Cotton Fabric: 
Columbian Coffee 
5.0 5.0 5.0 4.0 
Lipstick 2.5 2.0 2.0 2.5 
Tea 4.0 5.0 5.0 4.5 
Chocolate 3.5 4.0 4.5 4.5 
Blood 4.0 3.0 4.0 4.5 
Spaghetti Sauce 
3.5 3.5 3.5 3.0 
Clay/Dirt 3.5 3.5 3.0 3.0 
Sebum 3.0 3.0 2.5 2.0 
Grass 3.5 3.5 2.5 3.0 
Red Wine 3.0 4.0 4.5 2.0 
Motor Oil (used) 
2.5 2.5 1.5 2.0 
AVERAGE 3.45 3.55 3.45 3.18 
B) 65% Polyester/35% Cotton Fabric: 
Columbian Coffee 
4.5 5.0 5.0 4.0 
Lipstick 2.5 2.0 2.5 2.5 
Tea 4.5 5.0 5.0 4.0 
Chocolate 5.0 5.0 5.0 5.0 
Blood 5.0 4.0 5.0 5.0 
Spaghetti Sauce 
4.5 4.5 4.0 4.0 
Clay/Dirt 4.5 4.0 3.5 4.0 
Sebum 3.5 4.0 3.0 3.5 
Grass 3.5 3.5 3.0 3.5 
Red Wine 3.5 4.5 4.5 3.0 
Motor Oil (used) 
3.5 3.0 2.0 2.0 
AVERAGE 4.05 4.05 3.86 3.68 
______________________________________ 
Rating Scale: 
0 = No stain removal 
5 = Complete stain removal 
The detergency and anti-redeposition characteristics of each formulation 
were tested using 3 washing cycles following the standard testing 
procedure. Eight different fabric swatches for particulate soil removal 
testing were used. Cotton ("COTTON"), Dacron.RTM. polyester ("POLY") and 
65% polyester/35% cotton ("BLEND") were purchased from Testfabrics, Inc. 
which were rolled on one side of the swatch with roller containing a 
standard oily carbon black soil. The WFK fabrics had one side deposited 
with clay-type soil and were purchased from Testfabrics, Inc. 
(WFK-COT=cotton, WFK-BLEND=BLEND and WFK-POLY=POLY). Likewise, POLY AND 
BLEND fabrics deposited with an artificial sebum mixture on one side were 
purchased from Testfabrics, Inc. for use herein (SEB/POLY=POLY and 
SEB/BLEND=BLEND). The whiteness index values for fabrics containing 
clay-type soils and were thus more effective in removing such soil than 
the WISK detergent. Examples 31 and 32 had significantly better clay-type 
soil removal than did the CAN WISK-12 detergent on the BLEND and POLY 
fabrics. 
Redeposition was measured using the clean or "white edge" of the 
oily-soiled fabrics. The initial reflectance of the white edge (no soil 
present) was measured. The swatch was then washed using the composition to 
be tested for 3 wash cycles. The reflectance of the white edge was again 
measured and the percentage difference obtained between the two readings 
is reported in TABLE VIII. EDGE/COT is the anti-redeposition value for 
cotton, "EDGE/BLEND" is the value for the BLEND fabric and "EDGE/POLY" is 
the value for the DACRON polyester fabric. Negative anti-redeposition 
values would indicate that redeposition of the oily soil was occurring. 
Higher anti-redeposition values indicate that the fabric appeared whiter 
after washing (i.e., higher reflectance values were measured) than before 
washing. All anti-redeposition values were positive and the readings for 
the BLEND and the POLY fabrics were fairly close together, indicating each 
formulation was comparable to the others. Examples 31 and 32 were 
significantly better in anti-redeposition characteristics than the CAN 
WISK-7.5 and CAN WISK-12 detergents on cotton fabric. 
TABLE VIII 
______________________________________ 
CAN CAN 
Example No. 31 32 WISK-7.5 
WISK-12 
______________________________________ 
WFK/COT 24.76 22.78 13.14 20.51 
WFK/BLEND 28.38 27.61 10.69 17.30 
WFK/POLY 23.62 19.54 7.71 7.46 
SEB/POLY 37.36 34.36 31.00 34.03 
SEB/BLEND 26.35 19.33 17.24 33.07 
COTTON 26.31 22.67 34.11 32.95 
BLEND 19.19 18.28 18.93 16.29 
DACRON 19.59 18.60 18.85 14.30 
EDGE/COT 23.13 22.32 18.47 19.73 
EDGE/BLEND 3.03 3.01 3.11 2.40 
EDGE/POLY 1.50 1.74 1.86 1.59 
______________________________________ 
EXAMPLE 33 
This Example illustrates a composition of the present invention employing a 
MAH/C.sub.8 copolymer along with an enzyme additive. The MAH/C.sub.8 resin 
cut was composed of 20.0% MAH/C.sub.8 copolymer, 12.2% Ammonium Hydroxide 
and 67.8% deionized water where the MAH/C.sub.8 copolymer was a 1:1 molar 
ratio copolymer of maleic anhydride and 1-octene. The composition was 
prepared by mixing the following in the order listed: tap water 51.4%, 
borax 5.0%, citric acid 1.8%, MAH/C.sub.8 resin cut 20.0%, SURFONIC N-95 
15.0%, TINO CBS 0.3%, MILEZYME.RTM.APB 1.0%, NTA Salt 5.0%, C.I. Direct 
Blue 86 Dye (1%) 0.2% and fragrance 0.3%. 
The resulting composition had a pH of 8.2 and was a clear, solvated, one 
phase composition which remained in one phase upon storage at room 
temperature and also upon storage at 110.degree. F. for at least 1 week. 
EXAMPLE 34 
In this Example, a composition of the present invention was prepared using 
an MAH/C.sub.10.times.50 copolymer resin cut containing a fabric softening 
agent (VARISOFT.RTM. 222LT). 
The MAH/C.sub.10.times.50 resin cut was composed of 20% 
MAH/C.sub.10.times.50 polymer, 5% sodium hydroxide and 75% deionized 
water. The composition was prepared by mixing the following in the order 
listed: tap water 43.13%, borax 2%, citric acid 0.5%, 
MAH/C.sub.10.times.50 resin cut 26.67%, SURFONIC N-60 6.0%, SURFONIC N-95 
12.0%, TINO CBS 0.25%, VARISOFT 222LT 3.0%, NTA salt 6.0%, C.I. Direct 
Blue 86 (1%) 0.2% and fragrance 0.25%. 
The resulting composition was observed to be a clear, one phase, solvated 
composition which remained one phase and very uniform upon storage at room 
temperature. This composition exhibited good detergency. This composition 
was evaluated for stain removal characteristics against several 
commercially available liquid detergent products for comparative purposes: 
BOLD 3 and SOLO, both of which are sold in the United States by Procter & 
Gamble, neither of which were believed to contain builder salts since the 
addition of builder salts is generally known to cause phase separation in 
the products when cationic fabric softeners are included in the 
formulation. As an additional comparison, Example 34 was also tested 
against two commercially available built liquid detergent products 
although neither product contained a fabric softener: the CAN WISK--12 
noted in Examples 31-32 and LIQUID TIDE sold in the United States by 
Procter & Gamble. The results obtained after one wash cycle with each 
composition are reported in TABLE IX. Example 34 was found to compare very 
favorably with the two commercial built liquid detergent products on stain 
removal and was significantly better than the BOLD 3 product containing 
cationic fabric softeners on stain removal. 
TABLE IX 
______________________________________ 
LIQUID CAN 
Example 34 BOLD 3 SOLO TIDE WISK-12 
______________________________________ 
A) 100% Cotton Fabric: 
Colombian Coffee 
4.5 2.0 4.0 3.5 3.5 
Lipstick 2.0 3.0 2.5 3.5 3.5 
Tea 5.0 4.0 5.0 4.5 4.5 
Chocolate 4.5 2.5 4.0 3.5 3.5 
Blood 3.0 2.0 3.5 3.5 3.5 
Spaghetti Sauce 
3.0 3.0 3.0 3.0 3.0 
Clay/Dirt 4.0 3.5 4.0 3.5 3.5 
Sebum 3.0 2.0 3.0 3.0 2.0 
Grass 3.0 3.5 4.0 5.0 3.0 
Red Wine 5.0 4.5 5.0 5.0 5.0 
Motor Oil (used) 
3.5 1.0 3.0 2.0 2.5 
AVERAGE 3.68 2.82 3.73 3.64 3.41 
B) 65% POLY/35% COTTON FABRIC: 
Colombian Coffee 
5.0 3.5 4.5 4.5 4.5 
Lipstick 2.0 3.5 2.5 2.5 3.0 
Tea 5.0 4.5 5.0 5.0 5.0 
Chocolate 5.0 3.0 5.0 5.0 5.0 
Blood 4.5 3.0 5.0 5.0 5.0 
Spaghetti Sauce 
4.0 3.5 3.5 4.0 3.5 
Clay/Dirt 5.0 4.0 5.0 5.0 5.0 
Sebum 3.0 2.5 2.5 2.0 2.5 
Grass 3.5 4.0 4.5 5.0 4.0 
Red Wine 5.0 5.0 5.0 5.0 5.0 
Motor Oil (used) 
3.0 2.0 3.0 2.5 3.5 
AVERAGE 4.09 3.50 4.14 4.14 4.18 
______________________________________ 
Rating Scale: 
0 = No stain removal 
5 = Complete stain removal 
All five compositions were then tested for anti-redeposition and 
particulate soil removal as was described in Examples 31-32, but only 
using the C.I.E. Hunter "L" readings (i.e., which does not take yellowing 
into account). The results are reported in Part A of TABLE X. The number 
of wash cycles used was 3 cycles. "CLAY COT" indicates artificial clay 
mixture applied to 100% cotton fabric and "CLAY BLEND" indicates 
artificial clay mixture applied to 65% polyester/35% cotton fabric. 
Example 34, BOLD 3 AND SOLO were tested for anti-redeposition and 
particulate soil removal taking yellowing into account using whiteness 
index readings (include C.I.E. Hunter "L", "a" and "b" readings) and this 
testing is reported in Part B of TABLE X. 
TABLE X 
______________________________________ 
Part A: LIQUID CAN 
Example 34 BOLD 3 SOLO TIDE WISK-12 
______________________________________ 
WFK/COT 13.8 10.5 16.3 14.2 14.9 
WFK/BLEND 25.0 9.5 16.7 14.5 22.8 
WFK/POLY 13.6 7.9 15.3 8.6 8.8 
SEBUM/BLEND 
8.7 7.5 10.4 12.5 9.9 
SEBUM/POLY 8.7 11.3 12.5 9.0 12.2 
SEBUM/COT 21.3 20.8 22.4 20.2 21.7 
CLAY COT 7.5 8.6 9.3 7.0 9.6 
COTTON 19.0 31.9 29.9 16.1 23.6 
BLEND/POLY 16.4 18.4 19.8 17.2 17.1 
POLY 24.2 21.3 19.7 15.4 22.8 
EDGE/COT 0.2 1.0 0.8 0.6 0.6 
EDGE/BLEND 1.8 1.6 1.8 1.7 1.9 
EDGE/POLY 1.7 1.7 1.6 1.7 1.7 
______________________________________ 
Part B: 
Example 34 BOLD 3 SOLO 
______________________________________ 
CLAY BLEND 20.36 23.95 13.81 
SEBUM/POLY 38.58 25.50 22.70 
SEBUM/COT 27.41 25.83 18.25 
SEBUM/BLEND 
18.47 15.38 12.61 
WFK/COT 23.97 19.20 14.48 
WFK/BLEND 29.12 13.87 12.84 
WFK/POLY 22.22 7.43 9.66 
COTTON 22.19 17.62 15.51 
POLY 21.26 17.00 12.29 
EDGE/COT 20.17 12.17 10.74 
EDGE/POLY 0.63 0.43 0.26 
______________________________________ 
In TABLE X, Part A, except for the COTTON and CLAY COTTON entries, the 
composition of Example 34 was comparable to the two commercial built 
liquid detergent products that did not contain fabric softener (LIQUID 
TIDE and CAN WISK-12) in particulate soil removal and anti-redeposition 
characteristics and significantly better than those two commercial 
products on particulate soil removal from clay-soiled BLEND fabrics. In 
TABLE X, Part A, the composition of Example 34 was comparable to the two 
commercial built liquid detergent products that did contain fabric 
softener (BOLD 3 AND SOLO) in particulate soil removal and 
anti-redeposition characteristics. In the more demanding testing regimen 
used reported in TABLE X, Part B, except for the BOLD 3 CLAY BLEND entry, 
the composition of Example 34 was better than the two commercial products 
containing fabric softening agents in particulate soil removal and 
anti-redeposition characteristics. 
EXAMPLES 35-37 
These Examples demonstrate the effect of varying the builder salt and 
surfactant system of enzyme-containing compositions of the present 
invention on stain removal ability. Example 36 further provides an example 
of a composition containing an anionic surfactant in addition to nonionic 
surfactants. 
The MAH/C.sub.6 /C.sub.10 resin cut was composed of 20% MAH/C.sub.6 
/C.sub.10 polymer, 12.2% Ammonium Hydroxide and 67.8% deionized water 
wherein the MAH/C.sub.6 /C.sub.10 polymer was a 1:0.5:0.5 polymer of 
maleic anhydride, 1-hexene and 1-decene. The formulations are listed in 
TABLE XI. The stain removal results obtained after 1 wash cycle for each 
composition are listed in TABLE XII. TABLE XII shows that all three 
compositions tested had relatively the same amount of stain removal 
ability. 
TABLE XI 
______________________________________ 
Example No. 
35 36 37 
______________________________________ 
Tap water 51.8 47.8 54.8 
Borax 5.0 5.0 5.0 
Citric Acid 2.0 2.0 2.0 
MAH/C.sub.6 /C.sub.10 Resin Cut 
20.0 20.0 20.0 
LAAS (60%) -- 7.0 -- 
SURFONIC N-95 15.0 17.0 12.0 
TINO CBS 0.3 0.3 0.3 
MILEZYME APB 0.5 0.5 0.5 
NTA Salt 5.0 -- -- 
STPP -- -- 5.0 
C.I. DIrect Blue 86 (1%) 
0.2 0.2 0.2 
Fragrance 0.2 0.2 0.2 
______________________________________ 
TABLE XII 
______________________________________ 
65% POLY/ 
100% Cotton Fabric 
35% Cotton Fabric 
Example No. 
35 36 37 35 36 37 
______________________________________ 
Colombian Coffee 
5.0 5.0 5.0 5.0 5.0 5.0 
Lipstick 2.5 2.0 2.0 3.5 3.5 3.5 
Tea 5.0 5.0 5.0 5.0 5.0 5.0 
Chocolate 4.5 4.0 4.5 5.0 4.0 4.5 
Blood 4.5 4.0 4.0 5.0 5.0 5.0 
Spaghetti Sauce 
2.5 2.5 3.0 4.0 4.0 3.5 
Clay/Dirt 4.0 3.5 4.5 5.0 4.5 5.0 
Sebum 3.0 3.5 3.5 4.0 3.5 4.0 
Grass 4.5 4.0 4.5 4.5 4.5 5.0 
Red Wine 5.0 4.5 5.0 5.0 5.0 5.0 
Motor Oil (used) 
2.0 2.0 2.0 3.0 2.0 3.0 
AVERAGE 3.86 3.64 3.91 4.45 4.18 4.41 
______________________________________ 
EXAMPLES 38-39 
Example 38 demonstrates a composition of the present invention which 
contains a cationic fabric softening agent and employs 
MAH/C.sub.10.times.50 copolymer. Example 39 is a comparative Example that 
substitutes sodium xylene sulfonate as a hydrotrope in place of the 
MAH/C.sub.10.times.50 copolymer. 
The resin cut used in Example 38 was composed of 15% of the 
MAH/C.sub.10.times.50 copolymer, 7.5% sodium hydroxide, and 77.5% water. 
Example 38 was prepared by mixing the following together with stirring in 
the following order: tap water 42.78%, borax 5.0%, citric acid 1.75%, 
NEODOL 25-9 9.0%, NEODOL 25-7 4.0%, VARISOFT 222LT 3.20%, C.I. Direct Blue 
Dye 86 (1%) 0.10%, NTA Salt 7.50%, and MAH/C.sub.10.times.50 resin cut 
26.67%. The resulting composition was found to remain in one phase at room 
temperature, but was observed to be opaque rather than crystal clear in 
appearance. 
Example 39 had the same formula as Example 38 but used 59.4% tap water and 
1.8% citric acid. Ten percent of a sodium xylene sulfonate solution (40% 
in water) was substituted for the 26.67% amount of MAH/C.sub.10.times.50 
resin cut used in Example 38. The resulting composition separated into two 
phases at room temperature indicating that the sodium xylene sulfonate was 
not effective as a hydrotrope in this formulation while the 
MAH/C.sub.10.times.50 copolymer was effective to form a single phase 
composition. 
EXAMPLE 40-41 
These Examples provide more examples of compositions of the present 
invention which contain cationic fabric softening agents. These 
formulations were evaluated against commercially available liquid 
detergent compositions for stain removal characteristics. Example 40 was 
found to have very good pre-spotting ability and remained one phase at 
room temperature although it was opaque in appearance rather than clear. 
Example 41 was found to be opaque, but stable at both room temperature and 
upon storage for at least one week at 110.degree. F. 
The resin cut used to prepare Example 40 was composed of 10.2% Ammonium 
Hydroxide, 69.8% water and 20% of a 1:1 copolymer of maleic anhydride and 
1-decene ("Resin Cut 40"). Example 40 was prepared by mixing the following 
together, with agitation, in order listed: deionized water 62.25%, Resin 
Cut 40 20.00%, VARISOFT 222LM 6.00%, SURFONIC N-95 10.00%, citric acid 
1.00% and sodium hydroxide 0.75%. 
The resin cut used to prepare Example 41 was composed of 10.2% Ammonium 
Hydroxide, 69.8% water and 20% of a 1:1 copolymer of maleic anhydride and 
1-decene (hereinafter "Resin Cut 41"). Example 41 was prepared by mixing 
the following together, with agitation, in the order listed: deionized 
water 49.4%, Resin Cut 41 20.0%, borax 5.0%, C.I. Direct Blue Dye 86 (1%) 
0.2%, TINO PT 6.0%, SURFONIC N-95 10.0%, VARISOFT 222LT 3.0%, NEODOL 
91-8 5.0% and citric acid 1.4%. In preparing Example 41, the SURFONIC 
N-95, VARISOFT 222LT and NEODOL 91-8 were blended together and heated to 
100.degree. F. before being added to the other ingredients. 
Example 40 was evaluated for stain removal ability versus a built liquid 
laundry detergent sold in the United States by Procter & Gamble under the 
brand name "SOLO". One half cup of the composition was poured onto the 
fabrics containing the stains and these fabrics were placed in a washing 
machine along with 4 clean towels using a "medium" washing cycle with a 
90.degree. F. water temperature. Example 40 outperformed the commercial 
laundry detergent product in most categories of stain removal as can be 
seen from the data in TABLE XIII. The dry fabrics were also observed for 
resistance to static cling. Fabrics washed with the commercial product had 
good static control while fabrics washed with Example 40 had very little 
static control, i.e., the fabrics tended to stick together due to a 
buildup of static charges. 
TABLE XIV 
______________________________________ 
100% Cotton 
65% POLY/35% Cotton 
Fabric Fabric 
Example 40 SOLO 40 SOLO 
______________________________________ 
Colombian coffee 
2.5 2.0 3.5 2.5 
Tea 2.5 2.5 4.0 3.0 
Chocolate 4.0 2.0 5.0 3.0 
Blood 3.0 2.0 3.0 2.0 
Spaghetti Sauce 
4.0 4.0 4.5 4.0 
Clay/Dirt 3.5 3.0 4.0 3.5 
Sebum 3.5 3.0 4.0 3.0 
Grass 3.0 3.0 4.0 4.0 
Rose' Wine 5.0 5.0 5.0 5.0 
Motor Oil (used) 
2.5 2.5 3.0 2.0 
AVERAGE 3.35 2.90 4.00 3.20 
______________________________________ 
Example 41 was evaluated for stain removal ability versus the SOLO 
detergent noted above and two other commercial built liquid detergents 
sold commercially in the United States: AURA detergent that was sold by 
Samuel Taylor in Australia and YES detergent that was sold in the United 
States by Texize. One half cup of the composition was poured onto the 
fabrics containing the stains and these fabrics were placed in a washing 
machine along with 4 clean towels using a "medium" washing cycle with an 
85.degree. F. water temperature. Example 41 outperformed the commercial 
laundry detergent products as can be seen from the data in TABLE XIV. The 
dry fabrics were also observed for resistance to static cling. SOLO 
detergent had the most resistance to static cling followed by AURA and, 
lastly, by Example 41. For fabrics dried in a dryer, Example 41 gave the 
softest feeling to the touch while for clothesline dried fabrics, AURA 
detergent gave the softest feeling to the touch. 
TABLE XIV 
______________________________________ 
Examples SOLO AURA YES 41 
______________________________________ 
A) 100% Cotton Fabrics 
Colombian Coffee 
3.5 2.5 3.0 4.5 
Lipstick 2.0 2.0 2.0 2.5 
Tea 3.5 3.5 3.5 4.5 
Chocolate 2.0 3.5 3.0 3.5 
Blood 2.0 3.5 3.0 3.5 
Spaghetti Sauce 
4.5 3.5 3.0 3.5 
Clay 2.5 3.0 3.5 3.5 
Sebum 2.0 3.0 2.5 3.0 
Grass 4.5 3.0 3.5 3.5 
Red wine 2.5 1.0 2.5 4.5 
Motor Oil (used) 
1.0 2.0 1.5 2.0 
AVERAGE 2.73 2.77 2.82 3.50 
______________________________________ 
B) 65% POLY/35% COTTON Fabrics 
Colombian Coffee 
4.5 4.0 4.5 5.0 
Lipstick 3.0 2.0 3.0 2.5 
Tea 3.5 3.5 4.0 4.5 
Chocolate 3.0 4.5 4.0 4.5 
Blood 3.0 4.0 4.0 4.0 
Spaghetti Sauce 
5.0 4.5 4.5 4.5 
Clay 3.0 4.5 4.0 4.0 
Sebum 3.0 3.5 2.0 3.5 
Grass 4.5 4.0 4.0 4.0 
Red wine 3.0 3.0 4.5 5.0 
Motor oil (used) 
2.0 2.5 1.5 3.0 
AVERAGE 3.41 3.64 3.64 4.05 
______________________________________ 
EXAMPLES 42-47 
In these Examples, the stain removal, particulate soil removal and 
anti-redeposition characteristics of formulations made using copolymers of 
maleic anhydride and various 1-alkenes having an excess of maleic 
anhydride were evaluated. 
The following copolymers were made according to the method described in the 
Bosanec et al. Patent previously incorporated by reference and the 
polymers used in these Examples, having the approximate molar ratios based 
on the reactants initially charged (a slight excess of the stated molar 
ratio is often found), are listed below: 
MAH/C.sub.10.times.50 --1.5:1 molar ratio copolymer of maleic 
anhydride:1-decene. 
MAH/C.sub.10.times.100 --2:1 molar ratio copolymer of maleic 
anhydride:1-decene. 
MAH/C.sub.14.times.50 --1.5:1 molar ratio copolymer of maleic 
anhydride:1-tetradecene. 
MAH/C.sub.14.times.100 --2:1 molar ratio copolymer of maleic 
anhydride:1-tetradecene. 
MAH/C.sub.18.times.50 --1.5:1 ratio copolymer of maleic anhydride and 
1-octadecene. 
MAH/C.sub.18.times.100 --2:1 molar ratio copolymer of maleic anhydride and 
1-octadecene. 
The base formulation employed was as follows: tap water 42.63%; borax 2.00; 
Polymer Resin Cut 26.67%; SURFONIC N-60 6.00%; SURFONIC N-95 10.00%; 
TINO CBS 0.25%; NTA Salt 12.00%; Direct Blue 86 (1%) 0.20% and 
fragrance 0.25%. Resin Cuts containing the following polymers were used in 
the base formulation to produce the indicated Example No.: 
______________________________________ 
Polymer Example No. 
______________________________________ 
MAH/C.sub.10X50 
42 
MAH/C.sub.10X100 
43 
MAH/C.sub.14X50 
44 
MAH/C.sub.14X100 
45 
MAH/C.sub.18X50 
46 
MAH/C.sub.18X100 
47 
______________________________________ 
Examples 42-45 were found to be clear, single phase compositions while 
Examples 46-47 were found to separate into two phases at room temperature. 
This is in contrast to the results of Example 21 above wherein an 
MAH/C.sub.18 copolymer having a 1:1 molar ratio of maleic anhydride to 
1-octadecene was found to give a clear, stable phase composition in a 
formulation which was similar to the one used herein except that Example 
21 contained about one-half the level of NTA Salt as the present formula 
and citric acid to adjust the pH of the composition. 
Each formulation was tested for stain removal as in the previous Examples 
where such testing as done using two wash cycles. The results are reported 
in TABLE XV. Examples 46-47 were vigorously shaken before adding to the 
wash so that the phases would be mixed together as well as possible. 
TABLE XV 
______________________________________ 
Example 
42 43 44 45 46 47 
______________________________________ 
A) 100% Cotton Fabric: 
Colombian Coffee 
4.25 4.25 3.75 4.25 3.75 3.75 
Lipstick 2.50 2.25 2.00 2.75 3.25 2.75 
Tea 3.75 5.00 4.00 3.00 3.75 2.75 
Chocolate 4.00 4.50 4.50 4.25 3.00 3.75 
Blood 4.25 4.25 3.25 4.50 4.00 3.50 
Spaghetti Sauce 
2.75 3.00 3.00 3.00 2.50 2.50 
Clay/Dirt 2.50 3.25 3.25 3.25 2.50 2.50 
Sebum 2.50 3.00 3.25 2.50 2.50 2.50 
Grass 2.75 3.00 3.25 2.75 2.75 2.75 
Red Wine 3.50 3.25 3.25 3.25 3.00 3.00 
Motor Oil (used) 
2.75 2.00 2.00 3.00 2.25 2.50 
AVERAGE 3.23 3.43 3.23 3.32 3.02 2.91 
B) 65% POLY/35% Cotton Fabric: 
Colombian Coffee 
5.00 5.00 5.00 5.00 5.00 5.00 
Lipstick 1.25 3.25 2.25 1.25 3.25 2.25 
Tea 4.75 5.00 5.00 5.00 4.75 4.75 
Chocolate 4.50 5.00 5.00 5.00 5.00 4.75 
Blood 4.75 5.00 4.25 4.50 5.00 4.50 
Spaghetti Sauce 
3.50 3.25 3.00 3.50 3.00 3.00 
Clay/Dirt 3.75 4.00 4.00 3.00 2.75 3.50 
Sebum 2.00 3.25 3.25 2.00 2.00 2.00 
Grass 4.00 4.50 4.50 3.50 4.00 4.25 
Red Wine 4.50 4.50 4.50 4.50 2.75 3.75 
Motor Oil (used) 
2.75 2.75 2.50 2.75 2.75 2.75 
AVERAGE 3.70 4.14 3.93 3.64 3.75 3.68 
______________________________________ 
As can be seen from TABLE XV, stain removal efficiency decreased as the 
carbon length of the 1-alkene present in the maleic anhydride copolymer 
increased. Generally, lower amounts of excess maleic anhydride gave better 
stain removal efficiency as the carbon length of the alpha olefin was 
decreased. The polymers containing 1-octadecene were the poorest of the 
group tested for stain removal from 100% cotton and similar to Examples 42 
and 45 on the BLEND fabric. 
The particulate soil removal and anti-redeposition characteristics of 
Examples 42-47 were also evaluated as was done in the previous Examples 
including such testing using two washing cycles. The results obtained are 
reported in TABLE XVI below. 
TABLE XVI 
______________________________________ 
Example 
42 43 44 45 46 47 
______________________________________ 
CLAY BLEND 21.4 20.0 18.8 19.2 20.5 21.1 
WFK/COT 21.5 22.1 19.9 20.2 19.1 20.0 
WFK/BLEND 14.2 16.4 15.8 17.1 16.0 15.4 
WFK/POLY 17.0 17.3 14.1 14.9 14.2 13.7 
COTTON 21.1 25.6 25.0 22.9 24.3 20.6 
BLEND 9.6 10.2 9.5 9.8 8.9 10.0 
POLY 17.9 18.9 18.3 17.4 16.7 17.9 
EDGE/COT 10.8 13.1 12.7 11.4 13.2 12.2 
EDGE/BLEND 5.7 5.4 5.3 5.5 4.2 5.7 
EDGE/POLY 2.4 2.4 2.4 2.1 2.1 2.0 
______________________________________ 
As can be seen from TABLE XVl, Examples 42-47 were fairly comparable to 
each other in particulate soil removal and in anti-redeposition 
characteristics for the fabrics and materials tested. 
EXAMPLES 48-50 
These Examples describe the attempt to reproduce Example 5 of the Smith et 
al. European Patent Application No. EP 0 000 224. Example 48 was to 
reproduce Example 5. Examples 49 and 50 were intended to follow the 
instructions found on page 30 of the '224 Patent Application to substitute 
a 1-hexene-maleic acid copolymer for the GANTREZ.RTM. AN119. 
The maleic anhydride polymers used were GANTREZ AN119 from GAF Corporation 
having a measured molecular weight of M.sub.w 24,775 and M.sub.n 2,413, an 
MAH/C.sub.6 polymer of maleic anhydride and 1-hexene having a molecular 
weight of M.sub.w 8,190 and M.sub.n 3,450 (hereinafter "MAH/C.sub.6 -1"), 
and an MAH/C.sub.6 polymer of maleic anhydride and 1-hexene having a 
molecular weight of M.sub.w 2,382 and M.sub.n 1,075 (hereinafter 
"MAH/C.sub.6 -2"). The molecular weights were determined using gel 
permeation chromatography, polystyrene standards. On page 26, the '224 
Patent states that the GANTREZ AN119 polymer has a molecular weight of 
240,000, but our analysis gave a molecular weight of one-tenth of that 
number. The '224 Patent calls for the use of a 1-hexene-maleic acid 
copolymer of 25,000 or 30,000 molecular weight and in view of the 
differences noted with respect to the GANTREZ AN119 molecular weight, it 
was felt that the polymers used in this experiment were comparable to what 
was called for by the '224 Patent. 
The 15% resin cuts used had the following formulation: 15 parts of the 
polymer, 7.5 parts of 50% aqueous sodium hydroxide solution and 77.5 parts 
of tap water. 
The base formulation used for Examples 48-50 was: 13.33% of linear sodium 
alkylate sulfonate (60% actives) from Stepan Company, 6.00% of lauryl 
trimethyl ammonium chloride (50% actives) from Sherex Chemical Company, 
4.00% DOBANOL 45-7 which was a C.sub.14 -C.sub.15 linear primary alcohol 
ethoxylate having an average of 7 moles of ethylene oxide per molecule 
from Shell Chemicals, UK, 4.00% DOBANOL 45-4 which was a C.sub.14 
-C.sub.15 linear primary alcohol ethoxylate having an average of 4 moles 
of ethylene oxide per molecule from Shell Chemicals, UK, 18.00% disodium 
pyrophosphate, 6.67% of one of the 15% polymer resin cuts (Example 48 used 
the 15% GANTREZ AN119 resin cut; Example 49 used the 15% MAH/C.sub.6 -1 
resin cut; and Example 50 used the 15% MAH/C.sub.6 -2 resin cut), 1.00% of 
DEQUEST.RTM. 2060 which was diethylene triamine penta(methylene phosphonic 
acid) from Monsanto Company, 10.00% sodium benzoate from Monsanto Company, 
2.00% SAG.RTM. Silicone Antifoam 10 from Union Carbide Corporation, 0.30% 
microcrystalline wax sold by Witco-Netherlands under the name WITCODOR.TM. 
272 having a melting point of 35.degree.-115.degree. C., 0.15% of a 
brightener sold by Ciba-Geigy Corporation under the name TINO CBS-X 
which is a distyrylbiphenyl derivative, and 34.55% tap water. 
Examples 48-50 had pH values of 6.0, 6.2 and 6.0 after preparation. All 
three compositions had an opaque appearance and separated into layers upon 
standing and were thus not stable, single phase compositions. Thus, the 
'224 Patent does not suggest the method of the present invention since the 
compositions obtained were not clear or single phase compositions. 
EXAMPLES 51-53 
In these Examples, Example 25 of British Patent No. 1,596,756 containing 
GANTREZ AN139 was repeated as Example 51 and Examples 52-53 show the 
effect of substituting a 1-hexene-maleic anhydride copolymer for the 
GANTREZ AN139. 
The maleic anhydride polymers used were GANTREZ AN139 from GAF Corporation 
(molecular weight was not measured), the MAH/C.sub.6 -1 used in Example 
49, and an MAH/C.sub.6 polymer of maleic anhydride and 1-hexene having a 
molecular weight of M.sub.w 9,289 and M.sub.n 3,460 (hereinafter 
"MAH/C.sub.6 -3"). The molecular weights were determined using gel 
permeation chromatography, polystyrene standards. 
The GANTREZ AN139 was not used as a resin cut since the '756 Patent did not 
call for such use. The 15% MAH/C.sub.6 resin cuts used had the following 
formulation: 15 parts of the MAH/C.sub.6 polymer, 7.5 parts of 50% aqueous 
sodium hydroxide solution and 77.5 parts of tap water. Since the final pH 
of the Example 51 composition was 8.0, the GANTREZ AN139 was assumed to 
have been hydrolyzed. 
The composition of Example 51 was as follows: 33.33% of triethanolammonium 
dodecyl benzene sulfonate (60% actives) from Continental Chemical, 20.00% 
DOBANOL 45-7, 14.00% tetrapotassium pyrophosphate, 5.00% sodium silicate, 
1.00% GANTREZ AN139, 1.00% DEQUEST 2041 from Monsanto Company which was 
ethylene diamine tetra(methylene phosphonic acid) at 90% actives in the 
form of a white, wet cake material (used, at the recommendation of 
Monsanto Company, in place of DEQUEST 2040 which was no longer 
manufactured or available), 15.00% of sodium toluene sulfonate (40% 
actives) from Texaco Chemical Company, 10.00% SDA-3A denatured 95% ethyl 
alcohol from U.S. Industrial, and 0.67% tap water. 
The composition of Examples 52-53 was as follows: 33.33% of 
triethanolammonium dodecyl benzene sulfonate (60% actives) from 
Continental Chemical, 20.00% DOBANOL 45-7, 14.00% tetrapotassium 
pyrophosphate, 5.00% sodium silicate, 6.67% of the 15% polymer cut 
(Example 52 used MAH/C.sub.6 -1 and Example 53 used MAH/C.sub.6 -3), 1.00% 
DEQUEST 2041, 6.45% of sodium toluene sulfonate (93% actives) from Texaco 
Chemical Company, 10.00% SDA-3A denatured 95% ethyl alcohol from U.S. 
Industrial, and 3.55% tap water. 
Examples 51-53 had pH values of 8.0, 8.7 and 8.7 after preparation. All 
three compositions had an opaque appearance and separated into layers upon 
standing and were thus not stable, single phase compositions. Thus, the 
'756 Patent does not suggest the method of the present invention since the 
compositions obtained were not clear or single phase compositions. 
EXAMPLES 54-58 
These Examples demonstrate the lack of hydrotrope properties possessed by 
GANTREZ AN119 in comparison with an MAH/C.sub.10 copolymer useful as a 
hydrotrope in the method of the present invention. 
The GANTREZ AN119 was used as a 10% resin cut having the following 
formulation: 10 parts of the GANTREZ AN119, 2 molar equivalents of 50% 
aqueous sodium hydroxide solution and the balance was tap water. The 
MAH/C.sub.10 resin was used as a 20% resin cut used having the following 
formulation: 20 parts of the MAH/C.sub.10 polymer, 10.2 parts of 
concentrated aqueous ammonium hydroxide solution and 69.8 parts of tap 
water. 
The formulation of comparative Example 54 was 38.4% tap water, 5.0% borax, 
40.0% GANTREZ AN119 10% resin cut, 15.0% SURFONIC N-95, and 1.6% aqueous 
50% sodium hydroxide solution. The resulting composition had a pH of 7.5, 
was clear and single phase, but very viscous. 
Since Example 54 appeared to indicate that the GANTREZ AN119 was acting as 
a hydrotrope, comparative Example 55 was prepared which did not contain 
any GANTREZ AN119 to see if the detergent composition would become cloudy 
or two phase. Example 55 had the following formulation: 78.4% tap water, 
5.0% borax, 15.0% SURFONIC N-95, and 1.6% aqueous 50% sodium hydroxide 
solution. The resulting composition had a pH of 9.8, was clear and single 
phase, but viscous. Thus this detergent composition did not appear to 
require a hydrotrope to become clear and single phase. 
Since Example 55 was much more alkaline than Example 54, comparative 
Example 56 was made which used the same composition as Example 55, but 
contained 1.5% citric acid and correspondingly less tap water (76.9%) to 
reduce the pH of the composition. Example 56 had a pH of 7.5 and was 
clear, single phase and viscous. Thus the amount of ionic borax builder 
was not enough to cause instability and phase separation in this detergent 
composition. 
To test the hydrotrope properties of GANTREZ AN119, comparative Example 57 
was prepared which was similar to Example 54, but further contained 5.0% 
of another builder, nitrilotriacetic acid. Thus the formulation of Example 
57 was: 31.69% tap water, 5.0% borax, 1.00% citric acid, 40.0% GANTREZ 
AN119 10% resin cut, 15.0% SURFONIC N-95, 5.00% nitrilotriacetic acid and 
2.31% aqueous 50% sodium hydroxide solution. The resulting composition had 
a pH of 7.5, was cloudy and separated into two phases upon standing. 
Apparently the increased level of builder caused the formerly clear and 
stable composition to become cloudy and unstable. The GANTREZ AN119 did 
not help to retain that clarity and stability. 
In Example 58, the MAH/C.sub.10 copolymer was substituted for the same 
amount of GANTREZ AN119 in the formulation of Example 57. More citric acid 
was needed in Example 58 than in Example 57 to obtain a pH of 7.5. Thus, 
the formulation of Example 58 was: 52.5% tap water, 5.0% borax, 2.2% 
citric acid, 20.0% MAH/C.sub.10 20% resin cut, 15.0% SURFONIC N-95, 5.00% 
nitrilotriacetic acid and sufficient aqueous 50% sodium hydroxide solution 
to obtain a pH of 7.5. The resulting composition had a pH of 7.5, was 
clear and remained single phase upon standing. Thus, the MAH/C.sub.10 
copolymer functioned as a hydrotrope while the GANTREZ AN119 did not.