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Patent 2026332 Summary

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(12) Patent: (11) CA 2026332
(54) English Title: STABLE THICKENED LIQUID CLEANING COMPOSITION CONTAINING BLEACH
(54) French Title: PRODUIT DE NETTOYAGE LIQUIDE, STABLE, EPAISSI RENFERMANT UN AGENT DE BLANCHIMENT
Status: Deemed expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 134/5.2
(51) International Patent Classification (IPC):
  • C11D 3/395 (2006.01)
  • C11D 3/37 (2006.01)
  • C11D 7/26 (2006.01)
(72) Inventors :
  • WISE, RODNEY MAHLON (United States of America)
(73) Owners :
  • THE PROCTER & GAMBLE COMPANY (United States of America)
(71) Applicants :
(74) Agent: KIRBY EADES GALE BAKER
(74) Associate agent:
(45) Issued: 1995-02-21
(22) Filed Date: 1990-09-27
(41) Open to Public Inspection: 1991-04-05
Examination requested: 1990-09-27
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
417,123 United States of America 1989-10-04

Abstracts

English Abstract




Liquid cleaning compositions displaying enhanced physical
stability in the presence of bleach are provided, comprising a
chlorine bleach ingredient, cross-linked polycarboxylate polymer, a
rheology stabilizing agent, and a buffering agent to maintain the
pH of the composition above about 10. Preferred liquid automatic
dishwashing detergent compositions containing builder and optional
surfactant and metalate, and displaying shear thinning behavior,
are disclosed.


Claims

Note: Claims are shown in the official language in which they were submitted.


- 29 -
CLAIMS:

1. A liquid cleaning composition comprising, by weight:
(a) a chlorine bleach ingredient providing from about 0.2% to
about 2.5% available chlorine;
(b) from about 0.1% to about 10% of a cross-linked
polycarboxylate polymer thickening agent;
(c) from about 0.05% to about 5% of a rheology stabilizing
agent having the formula


Image


wherein each X, Y, and Z is -H, -COO-M+, -Cl, -Br, -SO3-M+,
-NO2, -OCH3, or a C1 to C4 alkyl and M is H or an alkali
metal; or mixtures thereof; and
(d) sufficient alkalinity buffering agent to provide said
composition with a pH greater than about 10.

2. A liquid automatic dishwashing detergent composition of Claim 1
further comprising:
(a) from 0% to about 5%, of a detergent surfactant; and
(b) from about 5% to about 50% of a detergency builder
material.

3. The composition of Claim 2 further comprising from 0% to about
1% of an alkali metal salt of an amphoteric metal anion;
said composition having an apparent yield value of from about 40 to
about 800 dynes/cm2.

4. The composition of Claim 1 wherein the chlorine bleach
ingredient is selected from the group consisting of sodium
hypochlorite, potassium hypochlorite, and mixtures thereof.

- 30 -

5. The composition of Claim 1 comprising a chlorine bleach
ingredient providing from about 0.5% to about 1.5% available chlorine
based on the weight of the composition.

6. The composition of Claim 4 comprising a chlorine bleach
ingredient providing from about 0.5% to about 1.5% available
chlorine based on the weight of the composition.

7. The composition of Claim 1 wherein the molecular weight of the
polycarboxylate polymer thickening agent is from about 750,000 to
4,000,000.

8. The composition of Claim 1 comprising from about 0.25% to about
5% of the polycarboxylate polymer thickening agent.

9. The composition of Claim 7 comprising from about 0.5% to about
2% of the polycarboxylate polymer thickening agent.

10. The composition of Claim 8 comprising from about 0.5% to about
2% of the polycarboxylate polymer thickening agent.

11. The composition of Claim 1 wherein Z in the rheology stabilizing
agent is H.

12. The composition of Claim 11 wherein the rheology stabilizing
agent is benzoic acid, phthalic acid, toluic acid, or a salt, or a
mixture thereof.

13. The composition of Claim 1 comprising from about 0.1% to about
2% of the rheology stabilizing agent.

14. The composition of Claim 12 comprising from about 0.2% to about
1% of the rheology stabilizing agent.

- 31 -

15. The composition of Claim 13 comprising from about 0.2% to about
1% of the rheology stabilizing agent.

16. The composition of Claim 1 wherein the alkalinity buffering
agent is selected from the group consisting of alkali metal
silicates, alkali metal carbonates, alkali metal hydroxides, and
mixtures thereof.

17. The composition of Claim 1 comprising sufficient alkalinity
buffering agent to provide the composition with a pH greater than
about 11.5.

18. The composition of Claim 16 comprising sufficient alkalinity
buffering agent to provide the composition with a pH greater than
about 11.5.

19. The composition of Claim 2 wherein the surfactant is selected
from the group consisting of capped propylene oxide, ethylene oxide
block copolymers; condensation products of ethylene oxide and
propylene oxide with a mono-, di-, or poly-hydroxyl compound with
residual hydroxyls capped; alkali metal salts of mono- and/or
di-(C8-14) alkyl diphenyl oxide mono- and/or di-sulfonates; C8-18
alkyl sulfates; C8-18 alkyl sulfonates; and mixtures thereof.

20. The composition of Claim 2 comprising from about 0.1% to about
2.5% of a surfactant.

21. The composition of Claim 19 comprising from about 0.1% to about
2.5% of a surfactant.

22. The composition of Claim 2 wherein the builder is selected from
the group consisting of alkali metal tripolyphosphate, alkali metal
pyrophosphate, alkali metal silicates, alkali metal carbonates,
polycarboxylates, and mixtures thereof.

- 32 -

23. The composition of Claim 2 comprising from about 15% to about
40% of a builder.

24. The composition of Claim 22 comprising from about 15% to about
40% of a builder.

25. The composition of Claim 3 wherein the alkali metal salt of an
amphoteric metal anion is sodium or potassium aluminate, sodium or
potassium zincate, sodium or potassium stannate (IV), sodium or
potassium titanate (IV), or a mixture thereof.

26. The composition of Claim 3 comprising from about 0.01% to about
0.1% of an alkali metal salt of an amphoteric metal anion.

27. The composition of Claim 25 comprising from about 0.01% to about
0.1% of an alkali metal salt of an amphoteric metal anion.

28. The composition of Claim 19 wherein the builder is selected from
the group consisting of alkali metal tripolyphosphate, alkali metal
pyrophosphate, alkali metal silicates, alkali metal carbonates,
polycarboxylates, and mixtures thereof, and the chlorine bleach
ingredient is selected from the group consisting of sodium
hypochlorite, potassium hypochlorite, and mixtures thereof.

29. The composition of Claim 28 wherein the molecular weight of the
polycarboxylate polymer thickening agent is from about 750,000 to
4,000,000, and the rheology stabilizing agent is benzoic acid,
phthalic acid, toluic acid, or a salt, or a mixture thereof.

30. The composition of Claim 29 wherein the alkalinity buffering
agent is selected from the group consisting of alkali metal
silicates, alkali metal carbonates, alkali metal hydroxides, and
mixtures thereof, and the composition has a pH greater than about
11.5.

- 33 -

31. The composition of Claim 30 comprising, by weight:
(a) a chlorine bleach ingredient providing from about 0.5% to
about 1.5% available chlorine;
(b) from about 0.5% to about 2% of a cross-linked
polycarboxylate polymer thickening agent;
(c) from about 0.2% to about 1% of a rheology stabilizing
agent;
(d) from about 0.1% to about 2.5% of a surfactant; and
(e) from about 15% to about 40% of a builder.

32. The composition of Claim 30 wherein the alkali metal salt of an
amphoteric metal anion is sodium or potassium aluminate, sodium or
potassium zincate, sodium or potassium stannate (IV), sodium or
potassium titanate (IV), or a mixture thereof.

33. The composition of Claim 32 comprising from about 0.01% to about
0.1% of an alkali metal salt of an amphoteric metal anion.

Description

Note: Descriptions are shown in the official language in which they were submitted.


- 2026332
STABLE THICKENED LIQUID CLEANING COMPOSITION CONTAINING BLEACH


Technical Field
This invention relates to liquid cleaning compositions
incorporating a chlorine bleach ingredient, cross-linked
polycarboxylate polymers, a rheology stabilizing agent, and a
buffering agent, and which display enhanced physical stability in
the presence of bleach. One particular application relates to a
liquid automatic dishwashing detergent composition additionally
1~ containing builder and optional surfactant and metalate, and
exhibiting shear thinning behavior, i.e., high viscosity at low
rates of shear and lower viscosities at high rates of shear.

Background of the Invention
Thickened aqueous cleaning compositions are known, having
been taught in U.S. Pat. Nos. 3,843,548; 3,558,496; 3,684,722;
4,005,027; and 4,116,851.
The use of bleaches in cleaning housewares is known, having
been taught in U.S. Pat. Nos. 3,928,065; 3,708,429; 3,058,917; and
3,671,440.
The use of polycarboxylate polymers in cleaning compositions
is known, as disclosed in U.S. Pat. Nos. 3,060,124; 3,671,440;
4,392,977; 4,147,650; and 4,836,948; U.K. Pat. No. 1527706; and
U.K. Pat. Application No. 2203163A , published October 12, 1988.
The use of benzoic acid or salt or derivative thereof in
cleaning compositions is known, as taught in U.S. Pat. Nos.
4,810,409; 4,810,413; 4,576,728; 3,932,316; and 4,333,862.
However, none of the above patents discloses applicant's
compositions containing a cross-linked polycarboxylate polymer, a
chlorine bleach ingredient, a rheology stabilizer, and a buffering
agent.
SummarY of the Invention
The compositions of this invention are liquid cleaning
compositions comprising, by weight:

21)~332


(a) a chlorine bleach ingredient providing from about 0.2%
to about 2.5% available chlorine;
(b) from about 0.1% to about 10% of a cross-linked
polycarboxylate polymer thickening agent;
(c) from about 0.05% to about 5% of a rheology stabilizing
agent having the formula
COO-M+
I~
X~
,~ ~.
Y Z
wherein each X, Y, and Z is -H, -COO-M+, -Cl, -Br,
-S03-M+, -N02, -OCH3, or a C1 to C4 alkyl and M is H or
an alkali metal; or mixtures thereof; and
(d) sufficient alkalinity buffering agent to provide said
composition with a pH greater than about 10.

A particularly preferred embodiment of this invention is a
liquid automatic dishwashing detergent composition further
comprising:
(a) from 0% to about 5% of a detergent surfactant;
(b) from about 5% to about 50% of a detergency builder
material; and
(c) from 0% to about 1% of an alkali metal salt of an
amphoteric metal anion.

Detailed Description of the Invention
The compositions of the present invention comprise four
essential ingredients: a chlorine bleach ingredient, a
cross-linked polycarboxylate polymer thickening agent, a rheology
stabilizing agent, and an alkalinity buffering agent.




2 ~ 2 ~ 3 3 2


Chlorine Bleach Ingredient
The instant compositions include a bleach ingredient which
yields a hypochlorite species in aqueous solution. The
hypochlorite ion is chemically represented by the formula OCl-.
The hypochlorite ion is a strong oxidizing agent, and materials
which yield this species are considered to be powerful bleaching
agents.
The strength of an aqueous solution containing hypochlorite
ion is measured in terms of available chlorine. This is the ox-
lo idizing power of the solution measured by the ability of the
solution to liberate iodine from an acidified iodide solution.
One hypochlorite ion has the oxidizing power of 2 atoms of
chlorine, i.e., one molecule of chlorine gas.
At lower pH levels, aqueous solutions formed by dissolving
S hypochlorite-yielding compounds contain active chlorine, partially
in the form of hypochlorous acid moieties and partially in the
form of hypochlorite ions. At pH levels above about 10, i.e., at
the pH levels of the instant compositions, essentially all
(greater than 99%) of the active chlorine is reported to be in the
form of hypochlorite ion.
Those bleaching agents which yield a hypochlorite species in
aqueous solution include alkali metal and alkaline earth metal
hypochlorites, hypochlorite addition products, chloramines,
chlorimines, chloramides, and chlorimides. Specific examples of
compounds of this type include sodium hypochlorite, potassium
hypochlorite, monobasic calcium hypochlorite, dibasic magnesium
hypochlorite, chlorinated trisodium phosphate dodecahydrate,
potassium dichloroisocyanurate, sodium dichloroisocyanurate,
sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid,
1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine
T, Dichloramine T, Chloramine B and Dichloramine B. A preferred
bleaching agent for use in the compositions of the instant
invention is sodium hypochlorite, potassium hypochlorite, or a
mixture thereof.
3s Most of the above-described hypochlorite-yielding bleachingagents are available in solid or concentrated form and are
dissolved in water during preparation of the compositions of the

2026332
instant invention. Some of the above materials are available as
aqueous solutions.
The above-described bleaching agents are dissolved in the
aqueous liquid component of the present composition. Bleaching
agents can provide from about 0.2% to about 2.5% available
chlorine by weight, preferably from about 0.5% to about 1.5%
available chlorine, by weight of the total composition.

Polymeric Thickening Aqent
The thickening agent in the compositions of the present
invention is a cross-linked polycarboxylate polymer thickening
agent. This polymer preferably has a molecular weight of from
about 500,000 to about 5,000,000, more preferably from about
750,000 to about 4,000,000.
The polycarboxylate polymer is preferably a carboxyvinyl polymer.
Such compounds are disclosed in U.S. Patent 2,798,053, issued on
July 2, 1957, to Brown. Methods for making carboxyvinyl polymers are
also disclosed in Brown.
A carboxyvinyl polymer is an interpolymer of a monomeric
mixture comprising a monomeric olefinically unsaturated carboxylic
acid, and from about 0.1% to about 10% by weight of the total
monomers of a polyether of a polyhydric alcohol, which polyhydric
alcohol contains at least four carbon atoms to which are attached
at least three hydroxyl groups, the polyether containing more than
one alkenyl group per molecule. Other monoolefinic monomeric
materials may be present in the monomeric mixture if desired, even
in predominant proportion. Carboxyvinyl polymers are substan-
tially insoluble in liquid, volatile organic hydrocarbons and are
dimensionally stable on exposure to air.
Preferred polyhydric alcohols used to produce carboxyvinyl
polymers include polyols selected from the class consisting of
oligosaccarides, reduced derivatives thereof in which the carbonyl
group is converted to an alcohol group, and pentaerythritol; most
preferred is sucrose or pentaerythritol. It is preferred that the
hydroxyl groups of the modified polyol be etherified with
e

~ 5 ~ 2026332

allyl groups, the polyol having at least two allyl ether groups
per polyol molecule. When the polyol is sucrose, it is preferred
that the sucrose have at least about five allyl ether groups per
sucrose molecule. It is preferred that the polyether of the
polyol comprise from about 0.1% to about 4% of the total monomers,
more preferably from about 0.2% to about 2.5%.
Preferred monomeric olefinically unsaturated carboxylic acids
for use in producing carboxyvinyl polymers used herein include
monomeric, polymerizable, alpha-beta monoolefinically unsaturated
lower aliphatic carboxylic acids; more preferred are monomeric
monoolefinic acrylic acids of the structure
R
I




CH2 = C - COOH
where R is a substituent selected from the group consisting of
hydrogen and lower alkyl groups; most preferred is acrylic acid.
Various carboxyvinyl polymers are commercially available from
B. F. Goodrich Company, New York, N.Y., under the trade name
Carbopol~. These polymers are also known as carbomers or
polyacrylic acids. Carboxyvinyl polymers useful in formulations
of the present invention include Carbopol 910 having a molecular
weight of about 750,000, Carbopol 941 having a molecular weight of
about 1,250,000, and Carbopols 934 and 940 having molecular
weights of about 3,000,000 and 4,000,000, respectively.
Preferred polycarboxylate polymers of the present invention
are non-linear, water-dispersible, polyacrylic acid cross-linked
with a polyalkenyl polyether and having a molecular weight of from
about 750,000 to about 4,000,000.
Highly preferred examples of these polycarboxylate polymers
for use in the present invention are Sokalan PHC-25~, a
polyacrylic acid available from BASF Corporation, Polygel* DK
available from 3-V Chemical Corporation, and the Carbopol 600
series resins available from B. F. Goodrich, especially Carbopol
614, 616 and 617. It is believed that these are more highly
cross-linked than the 900 Carbopol series polymers and have
molecular weights between about 1,000,000 and 4,000,000.

*Trade mark

~2~3~2
6 -

Mixtures of polycarboxylate polymers as herein described may also
be used in the present invention.
The polycarboxylate polymer thickening agent is preferably
utilized with essentially no clay thickening agents since the
presence of clay usually results in a less desirable product
having phase instability. In other words, the polycarboxylate
polymer is preferably used instead of clay as a thickening agent
in the present compositions.
The polycarboxylate polymer thickening agent in the
compositions of the present invention is present at a level of
from about 0.1% to about 10%, preferably from about 0.25~o to about
5%, most preferably from about 0.5% to about 2%.
In the preferred liquid automatic dishwashing detergent
composition, the polycarboxylate polymer thickening agent provides
an apparent viscosity at high shear of greater than about S00
centipoise and an apparent yield value of from about 40 to about
800, and most preferably from about 60 to about 600, dynes/cm2 to
the composition.
The yield value is an indication of the shear stress at which
the gel strength is exceeded and flow is initiated. It is
measured herein with a Brookfield RVT model viscometer with a
T-bar B spindle at about 77F (25C) utilizing a ~elipath drive
during associated readings. The system is set to O.S rpm and a
torque reading is taken for the composition to be tested after 30
seconds or after the system is stable. The system is stopped and
the rpm is reset to 1.0 rpm. A torque reading is taken for the
same composition after 30 seconds or after the system is stable.
Apparent viscosities are calculated from the torque readings
using factors provided with the Brookfield viscometer. An
apparent or Brookfield yield value is then calculated as:
Brookfield Yield Value = (apparent viscosity at 0.5 rpm - apparent
viscosity at 1 rpm)/100. This is the common method of
calculation, published in Carbopol literature from the B. F.
Goodrich Company and in other published references. In the cases


~02633~


of most of the formulations quoted herein, this apparent yield
value is approximately four times higher than yield values
calculated from shear rate and stress measurements in more
rigorous rheological equipment.
Apparent viscosities at high shear are determined with a
Brookfield RVT viscometer with spindle #6 at 100 rpm, reading the
torque at 30 seconds.

RheoloqY Stabilizinq Agent
The rheology stabilizing agents useful in the present
invention have the formula:
COO-M+
~'1
X 5$

Y Z
wherein each X, Y, and Z is -H, -COO-M+, -Cl, -Br, -S03-M+, -N02,
-OCH3, or a Cl to C4 alkyl and M is H or an alkali metal.
Examples of this component include pyromellitic acid, i.e., where
X, Y, and Z are -COO-H+; hemimellitic acid and trimellitic acid,
i.e., where X and Y are -COO-H+ and Z is -H.
Preferred rheology stabilizing agents of the present
invention are sulfophthalic acid, i.e., where X is -S03-H+, Y is
-COO-H+, and Z is -H; other mono-substituted phthalic acids and
di-substituted benzoic acids; and alkyl-, chloro-, bromo-, sulfo-,
nitro-, and carboxy- benzoic acids, i.e., where Y and Z are -H and
X is a C2 to C4 alkyl, -Cl, -Br, -S03-H+, -N02, and -OCH3,
respectively.
Highly preferred examples of the rheology stabilizing agents
useful in the present invention are benzoic acid, i.e., where X,
Y, and Z are -H; phthalic acid, i.e., where X is -COO-H+, and Y
and Z are -H; and toluic acid, where X is -CH3 and Y and Z are -H;
and mixtures thereof.

2 ~ 3 3 2
_ 8 -

All the rheology stabilizing agents described above are the
acidic form of the species, i.e., M is H. It is intended that the
present invention also cover the salt derivatives of these
species, i.e., M is an alkali metal, preferably sodium or
potassium. In fact, since the pH of compositions of the present
invention are in the alkaline range, the rheology stabilizing
agents exist primarily as the ionized salt in the aqueous
composition herein. It is also intended the anhydrous derivatives
of certain species described above be included in this invention,
e.g., pyromellitic dianhydride, phthalic anhydride, sulfophthalic
anhydride, etc.
Mixtures of the rheology stabilizing agents as describèd
herein may also be used in the present invention.
This component is present in an amount of from about 0.05X to
about 2%, preferably from about 0.1% to about 1.5%, most
preferably from about 0.2% to about 1%, by weight, of the
composition.
Cross-linked polymers, especially those of high
molecular weight, as used in the present bleach-containing
composition, are vulnerable to bleach-initiated degradation and
result in a loss of rheology that can be unacceptable for some
applications. A certain small percentage of the chlorine bleach
ingredient is present in solution in the form of a free radical,
i.e., a molecular fragment having one or more unpaired electrons.
These radicals, although short lived, are highly reactive and may
initiate the degradation of certain other species in solution,
including the cross-linked polycarboxylate polymers, via
propagation mechanism. The polymers of this invention are
susceptible to this degradation because of the presumed oxidizable
sites present in the cross-linking structure.
A small addition of the rheology stabilizing agent
substantially increases the physical stability, i.e., rheological
stability, of the composition of the present invention when added.
Without wishing to be bound by theory, it is believed that the
rheology stabilizing agent functions as a free radical scavenger,
tying up the highly reactive species in the composition and
preventing them from attacking the degradation-susceptible
structure of the polycarboxylate polymers.

- ~02~32
_ _ 9 _

Surprisingly though, other free radical scavengers are
ineffective as the rheology stabilizing agent in the present
invention because they react with chlorine bleach or are unable to
impede the interaction between the bleach ingredient and the
polymeric thickening agent. One of the preferred rheology
stabilizing agents herein is benzoic acid. Benzoates have been
characterized in the art as weak radical scavengers and nearly
ineffective in an alkaline medium. However, phthalic and toluic
acids, which have not been characterized as radical scavengers,
function effectively as a rheology stabilizing agent.
Buffering Aqent
In the instant compositions, it is generally desirable to
also include one or more buffering agents capable of maintaining
the pH of the compositions within the alkaline range, determined
as the pH of the undiluted composition ("as is") with a pH meter.
It is in this pH range that optimum performance and stability of
the bleach are realized, and it is also within this pH range
wherein optimum composition chemical and physical stability are
achieved.
Maintenance of the composition pH above about 10, preferably
above about 11.5, minimizes undesirable chemical decomposition of
the active chlorine, hypochlorite-yielding bleaching agents.
Maintenance of this particular pH range also minimizes the
chemical interaction between the strong hypochlorite bleach and
the surfactant compounds present in the instant compositions.
Finally, as noted, high pH values such as those maintained by an
optional buffering agent serve to enhance the soil and stain
removal properties during utilization of the present compositions.
Any compatible material or mixture of materials which has the
effect of maintaining the composition pH within the alkaline pH
range, and preferably within a 10 to about 13 range, can be
utilized as the buffering agent in the instant invention. Such
materials can include, for example, various water-soluble, inor-
ganic salts such as the carbonates, bicarbonates, sesquicar-
bonates, silicates, pyrophosphates, phosphates, tetraborates, and
mixtures thereof.

~ ~2~332

-- 10 --

Examples of materials which can be used either alone or in
combination as the buffering agent herein include sodium
carbonate, sodium bicarbonate, potassium carbonate, sodium
sesquicarbonate, sodium silicate, potassium silicate, sodium
pyrophosphate, tetrapotassium pyrophosphate, tripotassium
phosphate, trisodium phosphate, anhydrous sodium tetraborate,
sodium tetraborate pentahydrate, potassium hydroxide, sodium
hydroxide, and sodium tetraborate decahydrate. Combination of
these buffering agents, which include both the sodium and
potassium salts, may be used. This may include mixtures of
tetrapotassium pyrophosphate and trisodium phosphate in a
pyrophosphate/phosphate weight ratio of about 3:1, mixtures of
tetrapotassium pyrophosphate and tripotassium phosphate in a
pyrophosphate/phosphate weight ratio of about 3:1, and mixtures of
anhydrous sodium carbonate and sodium silicate in a
carbonate/silicate weight ratio of about 1:3 to about 3:1,
preferably from about 1:2 to about 2:1.
If present, the above-described buffering agent materials are
dissolved or suspended in the aqueous liquid component. Buffering
agents can generally comprise from 1% to about 25% by weight,
preferably from about 2.5% to about 20% by weight, of the total
composition.

Deterqent Surfactants
The compositions of this invention can contain from 0% to
about 5%, preferably from about 0. lYo to about 2.5%, of a
bleach-stable detergent surfactant.
Desirable detergent surfactants, in general, include nonionic
detergent surfactants, anionic detergent surfactants, amphoteric
and zwitterionic detergent surfactants, and mixtures thereof.
Examples of nonionic surfactants include:

2~332


(l) The condensation product of l mole of a saturated or
unsaturated, straight or branched chain, alcohol or fatty acid
containing from about 10 to about 20 carbon atoms with from about
4 to about 50 moles of ethylene oxide. Specific examples of such
compounds include a condensation product of 1 mole of coconut
fatty acid or tallow fatty acid with lO moles of ethylene oxide;
the condensation of 1 mole of oleic acid with 9 moles of ethylene
oxide; the condensation product of 1 mole of stearic acid with 25
moles of ethylene oxide; the condensation product of 1 mole of
tallow fatty alcohols with about 9 moles of ethylene oxide; the
condensation product of l mole of oleyl alcohol with 10 moles of
ethylene oxide; the condensation product of l mole of Clg alcohol
and 8 moles of ethylene oxide; and the condensation product of one
mole of Clg alcohol and 9 moles of ethylene oxide.
The condensation product of a fatty alcohol containing from
17 to 19 carbon atoms, with from about 6 to about 15 moles,
preferably 7 to 12 moles, most preferably 9 moles, of ethylene
oxide provides superior spotting and filming performance. More
particularly, it is desirable that the fatty alcohol contain 18
carbon atoms and be condensed with from about 7.5 to about 12,
preferably about 9, moles of ethylene oxide. These various
specific C17-Clg ethoxylates give extremely good performance even
at lower levels (e.g., 2.5%-3%) and at the higher levels (less
than SX) are sufficiently low sudsing, especially when capped with
a low molecular weight (Cl 5) acid or alcohol moiety, so as to
minimize or eliminate the need for a suds-suppressing agent.
Suds-suppressing agents in general tend to act as a load on the
composition and to hurt long term spotting and filming character-
istics.
(2) Polyethylene glycols or polypropylene glycols having
molecular weight of from about 1,400 to about 30,000, e.g.,
20,000i 9,500; 7,500; 6,000; 4,500; 3,400; and 1,450. All of
these materials are wax-like solids which melt between 110F(43C)
and 200F(93C).


_ - 12 - 2026332

(3) The condensation products of 1 mole of alkyl phenol
wherein the alkyl chain contains from about 8 to about 18 carbon
atoms and from about 4 to about 50 moles of ethylene oxide.
Specific examples of these nonionics are the condensation products
of 1 mole of decylphenol with 40 moles of ethylene oxide; the
condensation product of 1 mole of dodecyl phenol with 35 moles of
ethylene oxide; the condensation product of 1 mole of
tetradecylphenol with 25 moles of ethylene oxide; the condensation
product of 1 mole of hectadecylphenol with 30 moles of ethylene
oxide, etc.
(4) Polyoxypropylene, polyoxyethylene condensates having
the formula H0(C2H4O)X(C3H60)y(c2H4o)xH or HO(C3H60)y(C2H40)x
(C3H60)yH where total y equals at least 15 and total (C2H40)
equals 20% to 90% of the total weight of the compound and the
molecular weight is from about 2,000 to about 10,000, preferably
from about 3,000 to about 6,000. These materials are, for ex-
ample, the Pluronics which are well known in the art.
(5) The compounds of (1) or (4) which are capped with
propylene oxide, butylene oxide and/or short chain alcohols and/or
short chain fatty acids, e.g., those containing from 1 to about 5
2 carbon atoms, and mixtures thereof.
Useful surfactants in detergent compositions are those having
the formula R0-(C2H40)XR1 wherein R is an alkyl or alkylene group
containing from 17 to 19 carbon atoms, x is a number from about 6
to about 15, preferably from about 7 to about 12, and Rl is
selected from the group consisting of: preferably, hydrogen, C1 5
alkyl groups, C2 5 acyl groups and groups having the formula
-(CyH2yO)nH wherein y is 3 or 4 and n is a number from one to
about 4.
Particularly suitable surfactants are the low-sudsing com-
pounds of (4), the other compounds of (5), and the C17 19
materials of (1) which have a narrow ethoxy distribution.
In addition to the above mentioned surfactants, other suit-
able surfactants for detergent compositions can be found in the
disclosures of U.S. Patent Nos. 3,544,47l, 3,630,923, 3,888,781
and 4,001,132. l

~A i

202~32
- 13

Some of the aforementioned surfactants are bleach-stable but
some are not. When the composition contains a hypochlorite bleach
it is preferable that the detergent surfactant is bleach-stable.
Such surfactants desirably do not contain functions such as
unsaturation and some aromatic, amide, aldehydic, methyl keto or
hydroxyl groups which are susceptible to oxidation by the
hypochlorite.
Bleach-stable anionic surfactants which are especially
resistant to hypochlorite oxidation fall into two main groups.
One such class of bleach-stable anionic surfactants are the
water-soluble alkyl sulfates and/or sulfonates, containing from
about 8 to 18 carbon atoms in the alkyl group. Alkyl sulfates are
the water-soluble salts of sulfated fatty alcohols. They are
produced from natural or synthetic fatty alcohols containing from
about 8 to 18 carbon atoms. Natural fatty alcohols include those
produced by reducing the glycerides of naturally occurring fats
and oils. Fatty alcohols can be produced synthetically, for
example, by the Oxo process. Examples of suitable alcohols which
can be employed in alkyl sulfate manufacture include decyl,
lauryl, myristyl, palmityl and stearyl alcohols and the mixtures
of fatty alcohols derived by reducing the glycerides of tallow and
coconut oil.
Specific examples of alkyl sulfate salts which can be em-
ployed in the instant detergent compositions include sodium lauryl
alkyl sulfate, sodium stearyl alkyl sulfate, sodium palmityl alkyl
sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate,
potassium lauryl alkyl sulfate, potassium stearyl alkyl sulfate,
potassium decyl sulfate, potassium palmityl alkyl sulfate,
potassium myristyl alkyl sulfate, sodium dodecyl sulfate,
potassium dodecyl sulfate, potassium tallow alkyl sulfate, sodium
tallow alkyl sulfate, sodium coconut alkyl sulfate, magnesium
coconut alkyl sulfate, calcium coconut alkyl sulfate, potassium
coconut alkyl sulfate and mixtures of these surfactants. Highly
preferred alkyl sulfates are sodium coconut alkyl sulfate,
potassium coconut alkyl sulfate, potassium lauryl alkyl sulfate
and sodium lauryl alkyl sulfate.

2026332

A preferred sulfonated anionic surfactant is the alkali metal
salt of secondary alkane sulfonates, an example of which is the
Hostapur SAS from Hoechst Celanese.
A second class of bleach-stable surfactant materials operable
in the instant invention are the water-soluble betaine
surfactants. These materials have the general formula:
R2
I




Rl - N(+) - R4 - C00(-)
I




R3
wherein Rl is an alkyl group containing from about 8 to 18 carbon
atoms; R2 and R3 are each lower alkyl groups containing from about
1 to 4 carbon atoms, and R4 is an alkylene group selected from the
group consisting of methylene, propylene, butylene and pentylene.
(Propionate betaines decompose in aqueous solution and hence are

not included in the instant compositions).
Examples of suitable betaine compounds of this type include
dodecyldimethylammonium acetate, tetradecyldimethylammonium
acetate, hexadecyldimethylammonium acetate, alkyldimethylammonium
acetate wherein the alkyl group averages about 14.8 carbon atoms
in length, dodecyldimethylammonium butanoate, tetradecyldi-
methylammonium butanoate, hexadecyldimethylammonium butanoate,
dodecyldimethylammonium hexanoate, hexadecyldimethylammonium
hexanoate, tetradecyldiethylammonium pentanotate and tetradecyldi-
propyl ammonium pentanoate. Especially preferred betaine
surfactants include dodecyldimethylammonium acetate, dodecyldi-
methylammonium hexanoate, hexadecyldimethylammonium acetate, and
hexadecyldimethylammonium hexanoate.
Nonionic surfactants useful herein include ethoxylated and/or
propoxylated nonionic surfactants such as those available from
BASF Corp. of New Jersey. Examples of such compounds are
polyethylene oxide, polypropylene oxide block copolymers sold
under the trade names Pluronic~ and Tetronic~ available from BASF
Corp.
Preferred members of this class are capped oxyalkylene oxide
block copolymer surfactants of the following structure:

*Trade mark

~ - 15 ~ 2026332

(A1)X - (A2)y - (A03)z - R
/
I




((A1)x' - (A02)y~ - (A03)z~ - R )w
where I is the residue of a monohydroxyl, dihydroxyl, or a
polyhydroxyl compound; AO1, A02, and A03 are oxyalkyl groups and
one of AO1 and A02 is propylene oxide with the corresponding x or
y being greater than zero, and the other of AO1 and A02 is
ethylene oxide with the corresponding x or y being greater than
zero, and the molar ratio of propylene oxide to ethylene oxide is
from about 2:1 to about 8:1; R and R' are hydrogen, alkyl, aryl,
o alkyl aryl, aryl alkyl, carbamate, or butylene oxide; w is equal
to zero or one; and z, x', y', and z' are greater than or equal to
zero.
Other bleach-stable surfactants include amine oxides,
phosphine oxides, and sulfoxides. However, such surfactants are
usually high sudsing. A disclosure of bleach-stable surfactants
can be found in published British Patent Application 2,116,199A;
U.S. Patent 4,005,027, Hartman; U.S. Patent 4,116,851, Rupe et al;
U.S. Patent 3,985,668, Hartman; U.S. Patent 4,271,030, Brierley et
al; and U.S. Patent 4,116,849, Leikhim~
Other desirable bleach-stable surfactants are the alkyl
phosphonates, taught in U.S. Patent 4,105,573, to Jacobsen,
issued August 8, 1978.
Still other preferred bleach-stable anionic sur~actants
include the linear or branched alkali metal mono- and/or
di-(Cg 14) alkyl diphenyl oxide mono- and/or disulfonates, com-
mercially available under the trade ~arks Dowfax 3B-2 (sodium
n-decyl diphenyloxide disulfonate) and Oowfax 2A-1. These and
similar surfactants are disclosed in published U.K. Patent
3Q Applications 2,163,447A; 2,163,448A; and 2,164,350A.




r,~,

2~2~332
- 16 -
~,

OeterqencY Bui1der
Detergency builders are optional materials which reduce the
free calcium and/or magnesium ion concentration in a surfactant-
containing aqueous solution. In the preferred liquid automatic
dishwashing detergent compositions they are used at a level of
from about 5% to about 50%, preferably from about lS% to about
40%. Generally the detergency builder used in liquid automatic
dishwashing detergent compositions like those of the present
invention, is sodium tripolyphosphate in an amount from about 10%
to about 40YO~ preferably from about 15% to about 30%. Generally a
certain percentage of the sodium tripolyphosphate is in an
undissolved particulate form suspended in the rest of the
detergent composition. A phosphate ester, if present in the
composition, works to keep such solid particles suspended in the
aqueous solution.
The detergency builder material can be any of the detergent
builder materials known in the art which include trisodium
phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate,
sodium hexametaphosphate, potassium pyrophosphate, potassium
tripolyphosphate, potassium hexametaphosphate, sodium silicates
having SiO2:Na20 weight ratios of from about 1:1 to about 3.6:1,
sodium carbonate, sodium hydroxide, borax, sodium
nitrilotriacetate, sodium carboxymethyloxysuccinate, sodium
carboxymethyloxymalonate, polyphosphonates, salts of low molecular
weight carboxylic acids, and polycarboxylates, such as poly-
acrylates or polymaleates, copolymers and mixtures thereof.
Some of the above-described buffering agent materials addi-
tionally serve as builders. It is preferred that the buffering
agent contain at least one compound capable of additionally acting
as a builder.


- 21~332
17 -

Alkali Metal Amphoteric Metalate
An optional component of the present invention is an alkali
metal salt of an amphoteric metal anion, hereinafter referred to
as a metalate. This component can provide additional structuring
to the polycarboxylate polymer thickening agent in the preferred
liquid automatic dishwashing detergent composition.
The metalate in the liquid automatic dishwashing detergent
compositions of the present invention is present at a level of
from 0% to about 1%, preferably from about 0.01% to about .lX.
The metalates of amphoteric metals, e.g., aluminum, zinc,
beryllium, tin, zirconium, titanium, etc., will act similarly in
the present invention to provide this polymer structuring benefit.
These alternative metalates are intended to be covered by the
present invention. A preferred metalate is potassium or sodium
aluminate, e.g., xM20-yA1203-zH20, where M is K or Na.
One method of incorporating the metalate into the preferred
liquid automatic dishwashing detergent composition is by
dissolving or colloidally dispersing an amphoteric metal oxide
into an aqueous alkali metal hydroxide in an amount equal to or
greater than one molar equivalent of the hydroxide. Some
metalates, such as sodium aluminate, are commercially available.
The metalate can be added into the composition at any point
when the pH of the mixture is above about 10, preferably above
about 11.5. A preferred method of incorporating the metalate into
the preferred liquid automatic dishwashing detergent composition
is by blending the metalate into an aqueous solution of an alkali
metal silicate and then incorporating the resultant colloid with
other components of the liquid automatic dishwashing detergent
composition. The preferred structuring benefit is seen when the
metalate is finely dispersed in the silicate such that very little
3 or no increased turbidity is visible in the mixture.
Formulation of these compositions with a metalate such as
aluminate assures that cationic metal ions such as Al+3 are not
present to precipitate silicate under such mixing conditions.


2~2~332
- 18 -

The lack of suspended or visible solids in this colloidal
silico-metalate, i.e., particle sizes smaller than about 1 micron,
allows for the finished composition to be a clear or translucent
gel when sufficient potassium salts are used to ensure dissolution
of other components, i.e., molar ratio of potassium to sodium ions
greater than about 1:1, preferably greater than about 3:2.
From about 0% to about 15%, preferably from about 3% to about
10%, on a solids basis, of the silico-metalate is added to the
polyacrylate polymer thickening agent to get the additional
structuring. The molar ratio of aluminum metal to SiO2 in the
preferred colloidal dispersion formed should be from about 0.01:1
to about 0.1:1, preferably from about 0.02:1 to about 0.06:1; to
get the best structuring benefits.
Other ODtional Materials
The compositions of the present invention may optionally
comprise certain esters of phosphoric acid (phosphate ester).
Phosphate esters are any materials of the general formula:
O O

RO - P - OH and HO - P - OH

OR' OR'

wherein R and R' are C6-C20 alkyl or ethoxylated alkyl groups.
Preferably R and R' are of the general formula: alkyl-(OCH2CH2)y
wherein the alkyl substituent is C12-C18 and Y is between O and
about 4. Most preferably the alkyl substituent of that formula is
C12-C18 and Y is between about 2 and about 4. Such compounds are
prepared by known methods from phosphorus pentoxide, phosphoric
acid, or phosphorus oxy halide and alcohols or ethoxylated
alcohols.
It will be appreciated that the formula depicted represent
mono- and di-esters, and commercial phosphate esters will
generally comprise mixtures of the mono- and di-esters, together
with some proportion of tri-ester. Typical commercial esters are
available under the trademarks ~Phospholan~ POB3 (Diamond
Shamrock), HServoxyl~ VPA~ (Servo), PCUK-PAE (BASF-~yandotte),


2026332
-- 19 --

SAPC (Hooker). Preferred for use in the present invention are
KN340N and KL340N (Hoescht) and monostearyl acid phosphate
(Oxidental Chemical Corp.). Most preferred for use in the present
invention is Hostophat-TP-2253 (Hoescht).
s The phosphate esters useful herein provide protection of
silver and silver-plated utensil surfaces. The phosphate ester
component also acts as a suds suppressor in the anionic
surfactant-containing detergent compositions disclosed herein.
If a phosphate ester component is used in the compositions of
0 the present invention, it is generally present from about 0.1% to
about 5%, preferably from about 0.15% to about 1.0% by weight of
the composition.
Metal salts of long chain hydroxy fatty acids have been found
to be useful in automatic dishwashing detergent compositions to
inhibit tarnishing caused by repeated exposure of sterling or
silver-plate flatware to bleach-containing automatic dishwashing
detergent compositions (U.S. Patent 4,859,358, Gabriel et al). By
"long chain hydroxy fatty acid" is meant the higher aliphatic
hydroxy fatty acids having from about 8 to about 22 carbon atoms,
preferably from about 10 to 20 carbon atoms, and most preferably
from about 12 to 18 carbon atoms, inclusive of the carbon atom of
carboxyl group of the fatty acid, e.g., hydroxy stearic acid. By
"metal salts" of the long chain hydroxy fatty acids is meant both
monovalent and polyvalent metal salts, particularly the sodium,
2s potassium, lithium, aluminum, and zinc salts, e.g., lithium salts
of the hydroxy fatty acids. Specific examples of this material
are potassium, sodium, and particularly lithium hydroxy stearate.
If the metal salts of long chain hydroxy fatty acids are
incorporated into the automatic dishwashing detergent compositions
of the present invention, this component generally comprises from
about 0.05% to about 0.3%, preferably from about 0.05% to about
0.2% by weight of the composition.
Conventional coloring agents and perfumes can also be added
to the instant compositions to enhance their aesthetic appeal
and/or consumer acceptability. These materials should, of course,
be those dye and perfume varieties which are especially stable
against degradation by high pH and/or strong active chlorine
bleaching agents.
*Trade mark

~ Q ~ 2
-- 20 --

If present, the above-described other optional materials
generally comprise no more than about 10% by weight of the total
composition and are dissolved, suspended, or emulsified in the
present compositions.
As used herein all percentages, parts, and ratios are by
weight unless otherwise stated.
The following Examples illustrate the invention and facili-
tate its understanding.
ExamPle I
o A liquid automatic dishwashing detergent composition of the present invention is as follows:
Ingredient % BY Weiqht
Sodium tripolyphosphate (STPP) 4.67
Tetrapotassium pyrophosphate (TKPP) 12.60
Sodium silicate, 2.4 ratio 3.27
Potassium carbonate (K2C03) 3.91
Sodium carbonate (Na2C03) 2.61
Available chlorine (added as NaOCl) 0.93
Potassium hydroxide (KOH) 0.84
Monostearyl acid phosphate (MSAP) 0.03
Polyacrylic acid (Sokalan PHC-25) 1.07
Al203 (added as sodium aluminate) 0.03
Rheology stabilizing agent (if added) 0.47
Trim KOH, to pH 12.2-12.3 0-0.3
Perfume, dye, water Balance to 100

The polyacrylic acid is slurried into demineralized water at
3.4Z by weight. All other ingredients are added in the following
order while stirring with a paddle blade mixer: additional
available trim water, TKPP as a 40Z aqueous solution, sodium
aluminate (nominally 46.8% Al203) about SZ in water, and KOH (45%
in water added before, or premixed with, the colloidal aluminate
dispersion), silicate as 47.3% solids in water, sodium and potassi-
um carbonates and STPP as dry powders (essentially dissolved
within five minutes), a heated 2.6% aqueous dispersion of


Z~"g-3-3`~
_ - 21 -

MSAP suds suppressant, the rheology stabilizing agent. The acids
or anhydrides are neutralized by the excess caustic already
present in the composition. Heat is added during mixing up to
this point so that the mixture temperature is above about 130F
(54C). This temperature is maintained at least five minutes to
aid in sample equilibration. After the composition has cooled to
about 90F (32C) or below, the aqueous sodium hypochlorite is
added as approximately 13% available chlorine. Optional perfume
and colorants are added last. The composition is clear or
translucent, with no visible particles or turbidity. Balance
1 water is added, along with sufficient KOH trim to adjust the pH of
the composition "as is" to 12.2-12.3, and further KOH trim is used
if needed after overnight equilibration.
After about one to three days of equilibration, samples of
the above composition exhibit an apparent Brookfield yield value
of about 250 to 450 dynes/cm2, an apparent viscosity at high shear
(100 rpm, Brookfield RVT #6) of about 1300 to 2000 cps, and an
apparent viscosity at moderate shear (20 rpm, Brookfield RVT #6)
of about 4000 to 7000 cps.
Physical properties are recorded, and light-shielded bottled
samples are placed in 100F (38C) and 120F (49C) and at ambient
conditions. Brookfield apparent viscosities are determined with a
Brookfield RVT model with #6 spindle at 100 RPM. In the rapid
aging condition of 120F (49C), the following viscosity readings
are taken at one-week intervals. The day following the making of
the composition is the initial day.

% of Initial ViscositY After:
Rheology Stabilizing Initial 1 2 3 4 6
Agent ViscositY Week Weeks Weeks Weeks Weeks
(Centipoise)
None 1900 112% 14% --
Benzoic acid 1760 114% 111% 122% 101% 69%
Phthalic anhydride 1380 1807. 178~. 152% 107% 22%
Pyromellitic anhydride 1750 94% 74% 32% --
Mellitic anhydride 1600 153% 41% --


~`2~3~i2
-- 22 --

It is seen that a benzene ring with one or two carboxylic
acid groups can more than double the rheological life of the above
composition under such storage conditions. Apparently four
carboxyl functions on the ring exhibit reduced benefit, and more
than four carboxyls result in essentially no stability benefit.
Note that viscosity usually increases in the early weeks and is
believed to be due to continuing polymer swelling by caustic and
bleach.
The addition of benzoic acid or substituted benzoic acids
usually results in an initial lower viscosity compared to the no
1 additive formula, but a dramatically improved storage stable
formula is achieved.
ExamDle II
Benzoic acid and the benzoate salts are identified in
published literature as potential free radical scavengers. Other
liquid automatic dishwashing detergent compositions using known
free radical scavengers are prepared approximately according to
the method described in the preceding Example. With the addition
of benzoic acid or benzoate salt, the available chlorine decays at
about the same rate or slower, compared to the no-additive
control. Most other free radical scavengers degrade the activity
of the hypochlorite bleach when placed in storage tests in the
formula context of the previous example.


% of Initial Value Remaining
Rheology Stabilizing ViscositY Av. Chlorine
Agent Level 2 Weeks 3 Weeks 2 Weeks 3 ~eeks
None -- 14% -- 4g% --
Benzoic acid 0.47X 111% 122% 65% 487.
Sodium benzoate 0.56X 131% 122% 56% 46%
Phytic acid 0.47% 14% -- 45% --
Ascorbic acid 0.47% not read -- 0% --
Dilauryl thiodi- 0.47% 5% -- 0% --
propionate


~2~?32
_ - 23 -

As seen from the above examples, most free radical scavengers
either are reducing agents (reactive to available chlorine) or
have chemical structures reactive to hypochlorite. Even phytic
acid, said to be a hydroxyl radical scavenger in the same sense as
benzoic acid, is not readily reactive with the hypochlorite, but
it does not exhibit the rheology stabilization of the benzoic acid
or sodium benzoate.
Example III
Various levels of benzoic acid (prospective rheology
stabilizing agent) are tested following the method of preparation
in Example I. Also, these samples are screened in the rapid aging
stability test as described above. Viscosity stability as a
function of storage time is shown:
% of Initial Viscosity After:
Initial 1 2 3 4 6
Benzoic Acid Level ViscositY Week Weeks Weeks Weeks Weeks
(Centipoise)
None 1900 112% 14% **
0.1% 3540* 108~o 92% 14% **
0.2% 1830 107% 113% 91% 66% **
0.5% 1760 114% 111% 122% 101% 69%
0.7% 1300 145% 101% 84% 68% 94%
1.0% 1430 130% 134% 158 122% 105%
*This sample only at 1.21% polyacrylic acid vs. 1.07% in other
25samples.
**Measured below 10Z of initial viscosity, or approaching
water-thin by appearance.
The degree of increased rheological stability desired in a
composition can be achieved by adjustment of the level of benzoate
compound added to the formulation, realizing that higher levels
can adversely affect initial composition viscosity.

2~2~`3:32
-- 24 --

Example IV
The following liquid automatic dishwashing detergent
compositions are as follows:
% BY Weiqht
Inqredient Composition --- A-l A-2 B-l B-2
Sodium tripolyphosphate (STPP) 4.67 4.67 4.67 4.67
Tetrapotassium pyrophohphate (TKPP)12.60 12.60 12.60 12.60
Sodium silicate, 2.4 ratio 6.54 6.54 3.27 3.27
Potassium carbonate (K2C03) 4.92 4.92 3.91 3.91
Sodium carbonate (Na2C03) 1.84 1.84 2.61 2.61
lo Available chlorine (added as NaOCl)0.93 0.93 0.93 0.93
Potassium hydroxide (KOH) 0.84 0.84 0.84 0.84
Polyacrylic acid (Sokalan PHC-25) 1.07 1.07 1.31 1.31
Zn2 (added as potassium zincate) 0.03 0.03 0 0
Benzoic acid 0 0.47 0 0 47
Trim KOH, to pH below O-O.B 0 O.B 0 0.3 0 0.3
Perfume, dye, trim water to 100%Balance to lOO~o
A B
Neat pH of Compositions --- 12.5-12.6 12.2-12.3
A storage test as described in Example I is set up with the
formulations. Viscosity stability as a function of time in 120F
(49C) is summarized.
% of Initial ViscositY After:
Initial 1 2 3 4
Com w sition ViscositY Week Weeks Weeks Weeks
2s (Centipoise)
A-1 1380 130% 36% * *
A-2 1480 121% 105% 95% 100%
B-1 2960 90% *
B-2 4320 114% 87% 88% 72%
*Measured viscosity below 10% of initial, or approaching
water-thin by appearance.
The addition of benzoic acid to the A-1 and B-1 compositions
results in dramatic increase in rheological stability of the A-2
and B-2 compositions under the stress test conditions.


-- 25 --
20263~2
Example V
Various cross-linked polyacrylate polymers from several
sources are incorporated into the approximate composition of
Example I. Samples of the compositions are placed into the 120F
(49C) storage test described above, with the following results:
Benzoic
Cross-Linked Acid % of Initial ViscositY Remaining At:
Polyacrvlic Acid Level 2 Weeks 3 Weeks 4 Weeks
0.93% Carbopol 6141None 80% 31% **
lo 1.21% Carbopol 614 0.47% 97% 71% 50%
0.93% Carbopol 6171None 60% **
1.21% Carbopol 617 0.47% 89% 21% **
0.93% Carbopol 6271None **
1.21% Carbopol 627 0.47% 18% **
0.93% Thixol 602 None **
1.21% Thixol 60 0.47% 97% 98% 42%
**Measured viscosity below about 10% of initial, or approaching
water-thin by appearance.
1Carbopol polyacrylates are from B. F. Goodrich Co.
2Thixol 60 (trade mark) (otherwise TX 60) is from Coatex (France) or
Polyacryl (U.S.).

The degree of stabilization benefit achieved with the
addition of benzoic acid depends on the type of polymer used in
the composition. Both the degree of benefit and the rate of
2s degradation of viscosity without the benzoate additive are thought
to be dependent on the amount or type of cross-linking component
and/or presence of other minor components in the particular
polymer stock. Nevertheless, there is some degree of improvement
in rheological stability seen with all polymer stocks tested.
Example VI
Substituted benzoic acids are placed into the compositions of
Example I (less the MSAP) as candidate rheology stabilizers and
are subjected to the same stress stability testing in
light-shielded bottles at 120F (49C).

~2~32
- 26 -

% of Initial R maininq
Rheology Stabilizing ViscositY ~v. Chlorine
Aqent Level 2 Weeks 3 Weeks 2 ~eeks 3 ~eeks
Salicyclic acid 0.47% Not read * 07O *
5-sulfosalicylic acid 0.47% Not read * OYO *
m-hydroxybenzoic acid 0.47% Not read * 0% *
o-chlorobenzoic acid 0.47% 210% 108% 60% 49%
m-chlorobenzoic acid 0.47% 80Y. 96% 56% 467,
p-chlorobenzoic acid 0.47% 154% 107% 6~% 55%
m-sulfobenzoic acid, 0.47% 162% 33% 59% 47%
monosodium salt
m-toluic acid 0.47% 887. 109% 58% 47%
p-toluic acid 0.47% 124X 134% 61% 53%
p-nitrobenzoic acid 0.47% 117% <40% 52% 44%
4-sulfophthalic acid 0.47% 175% <40% 54% 45%
*Denotes a sample no longer monitored, due to very low previous
readings.
All the above mono-substituted benzoic acids (except ones
with a hydroxyl substituent) are effective at increasing the
rheological stability of the composition substantially beyond that
given by compositions with no rheology stabilizing agent (see
Examples I-III). Readings below about 80% of initial viscosity
can be considered to reflect a noteworthy drop in viscosity for
purposes of this test (since Brookfield viscosity values with
thick compositions of this type have considerable variability).
The hydroxybenzoic samples lose all available chlorine by day
one, so no viscosity readings are considered relevant beyond that
point.
The successful viscosity stabilization with the
4-sulfophthalic acid and failure by the 5-sulfosalicylic acid
indicate that the di-substituted benzoic acids, or
mono-substituted phthalic acids, follow the same pattern.

2026332
- 27 -

Of the above compositions, only those containing toluic acids
and m-chlorobenzoic are above 80% of initial viscosity at four
weeks, and only the one with m-toluic acid is still above 80% at
six weeks. Thus, toluic acid is a preferred rheology stabilizer,
and it appears that a meta isomer may be a preferred positional
configuration.
ExamPle VII
Liquid cleaning compositions of the present invention are as
follows:
Formula Parts, % of Active Ingredient
Inqredient A-l A-2 B-l B-2 C-l C-2
Sodium silicate solids,
2.4 ratio 2.50 2.50 2.50 2.50 2.50 2.50
Available chlorine
(added as NaOCl) 1.00 1.00 1.00 1.00 1.00 1.00
KOH trim to pH shown below 0-2 0-2 0-2 0-2 0-2 0-2
Acetic acid, glacial 0 0 0 0 0.50 0.50
Polyacrylic acid
(Sokalan*PH25) 1.30 1.30 1.25 1.25 1.00 1.00
Benzoic acid
(stabilizing agent) 0 0.50 0 0.50 0 0.50
Water -----------Balance to 100-------------

Composition pH,
measured as-is 12.0 12.0 11.0 11.0 10.3 10.3

Initial apparent
viscosity, cps 1410 1070 1400 1220 4290 5680

Initial apparent yield
value, dynes/cm2 72 88 108 88 * *
*Note: The C-1 and C-2 compositions are so highly structured due
to the reduced pH that syneresis (clear phase separation)
prevents accurate measurement of yield value.

*Trade mark

3 ~
- 28 -

All of the above compositions are clear to translucent gels and
are useful for hard surface cleaning and similar applications. The
compositions containing benzoic acid as a rheology stabilizing agent
are able to retain viscosity and yield value (80% of initial values
or higher) for a longer time under stress storage than the
compositions without the stabilizing agent. Benzoic acid and other
rheology stabilizing agents of the invention result in a lower
initia~ viscosity as indicated above, but the stabilization effect
over time more than compensates for a lower initial viscosity.



Representative Drawing

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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 1995-02-21
(22) Filed 1990-09-27
Examination Requested 1990-09-27
(41) Open to Public Inspection 1991-04-05
(45) Issued 1995-02-21
Deemed Expired 2004-09-27

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1990-09-27
Registration of a document - section 124 $0.00 1991-02-20
Maintenance Fee - Application - New Act 2 1992-09-28 $100.00 1992-08-21
Maintenance Fee - Application - New Act 3 1993-09-27 $100.00 1993-06-09
Maintenance Fee - Application - New Act 4 1994-09-27 $100.00 1994-07-26
Maintenance Fee - Patent - New Act 5 1995-09-27 $150.00 1995-08-17
Maintenance Fee - Patent - New Act 6 1996-09-27 $150.00 1996-08-19
Maintenance Fee - Patent - New Act 7 1997-09-29 $150.00 1997-08-20
Maintenance Fee - Patent - New Act 8 1998-09-28 $150.00 1998-08-04
Maintenance Fee - Patent - New Act 9 1999-09-27 $150.00 1999-08-09
Maintenance Fee - Patent - New Act 10 2000-09-27 $200.00 2000-08-08
Maintenance Fee - Patent - New Act 11 2001-09-27 $200.00 2001-08-07
Maintenance Fee - Patent - New Act 12 2002-09-27 $200.00 2002-08-08
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
THE PROCTER & GAMBLE COMPANY
Past Owners on Record
WISE, RODNEY MAHLON
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
Documents

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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Description 1995-02-21 28 1,091
Cover Page 1995-02-21 1 18
Abstract 1995-02-21 1 14
Abstract 1995-02-21 1 14
Claims 1995-02-21 5 141
Office Letter 1991-03-18 1 20
Examiner Requisition 1993-01-15 2 85
PCT Correspondence 1994-12-14 1 49
Prosecution Correspondence 1993-07-08 4 115
Fees 1996-08-19 1 73
Fees 1995-08-17 1 73
Fees 1994-07-26 1 65
Fees 1993-06-09 1 59
Fees 1992-08-21 1 40