Note: Descriptions are shown in the official language in which they were submitted.
t7~7~
IR F1142C
PHOSPHATE-FREE, GEL-~IKE AUTO~TIC
DISHWASHER DET~RGENT COMPOSITIONS
BACKGROUND OF INVENTION
The present invention relates to gel-like aqueous liquid
automatic dishwasher detergent compo,sitions which are
phosphate-free with equivalent cleaning performance and
physical stability with improved characteristics as compared
to phosphate containing compositions.
Commercially available household-machine dishwasher
detergents pro~ided in powder form have several disadvantages,
e.g. non-uniform composition; costly operations necessary in
their manufacture; tendency to cake in storage at high
humidities resulting in the formation of lumps which are
difficult to disperse; dllstiness, a source of particular
irritation to users who suffer allergies; and tendency to cake
in the dishwasher machine dispenser. Liquid forms of such
compositions, however, generally cannot be used in automatic
dishwashers.
Recent research and development activity has focused on
the gel or "thixotropic" form of such compositions, e.g.
scouring cleansers and automatic-dishwasher products
characterized as thixotropic pastes. Dishwasher products so
provided are primarily objectionable in that they are
insufficiently viscous to remain ~'anchored" in the dispenser
cup of the dishwasher. Ideally, thixotropic cleaning
compositions should be highly viscous in a quiescent state,
~ t~ S) ~
~up of the dishwasher. Ideally, thixotropic cleaning
compositions should be highl~ viscous in a quiescent state,
singham plastic in nature, and have relatively high yield
values. When subjected to shear stresses, however, such as
~ein~ shaken in a container or squeezed through an orifice,
they should quickly fluidize and, upon cessation of th~
applied shear stress, quickly revert to the high viscosity or
Bingham plastic state. Stability is likewi~e of prim~ry
importance, i.e. there should be no signiEicant evidence of
10 phase separation or leaking after lollg standing.
The provision of automatic dishwasher compositions in gel
form having the afore-described properties has thus far proven
problematical, particularly with regard to compositions for
use in home dishwasher machines. For effective use, it i9
15 generally recommended that the automatic dishwashing
detergent, hereinafter also designated ADD, contain (1) sodium
tripolyphosphate (NaTPP) to soften or tie up hard water
minerals and to emulsify and/or peptide soi.1; (2) sodium
silicate to supply the alkalinity necessary for effective
20 detergency and to pro~ide protection for fine china glaze and
pattern; (3) sodium carbonate, generally considered to be
optional, to enhance alkalinity; (4) a chlorine-releasing
agent to aid in the elimination of soil specks which lead to
water spotting and filming; and (5) defoamer/surfactant to
25 reduce foam, thereby enhancing machine efficiency and
supplying requisite detergency. See, for example, SDA
Detergents in Depth, "Formulations Aspects of Machine
Dishwashing", Thomas Oberle (1974). Cleansers approximating
r3
~o the afore-described compositions are mostly liquids or
powders. Combining such ingredients in a gel form effective
for home-machine use has proved difficult. Generally, such
compositions omit hypochlorite bleach, since it tends to react
~ith other chemically active ingredients, particularly
surfactant. Thus, U.S. Patent 4,115,308 discloses thixotropic
automatic dishwasher pastes containing a suspending agent,
e.g. CMC, synthetic clays or the like; inorganic salts
including silicates, phosphates and polyphosphates; a small
amount of surfactant and a suds depressor. Bleach is not
disclosed. U.S. Patent 4,147,650 is somewhat similar,
optionally including Cl-(hypochlorite) bleach but no organic
surfactant or foam depressant. The product is described,
moreover, as a detergent slurry with no apparent thixotropic
properties.
U.S. Patent 3,g85,66~ describes abrasive scouring
cleaners of gel-like consistency containing (1) suspending
agent, preferably the smectite and attapulgite types of clay;
(2) abrasive, e.g. silica sand or perlite; and (3) filler
comprising light density powdered polymers, expanded perlite
and the like, which has a buoyancy and thus stabilizirlg effect
on the composition in addition to serving as a bulking agent,
thereby replacing water otherwise available for undesired
supernatant layer formation due to leaking and phase
destabilization. The foregoing are the essential ingredients.
Optional ingredients include hypochlorite bleach, bleach
stable surfactant and buffer, e.g. silicates, carbonates, and
monophosphates. Builders, such as NaTPP, can be included as
r~d) ~ r3
(h) sodlum hydroxide, AS necessary, to adjust pH; and
(i) water, balance.
~DD compositions so formulated are low-foaming; are
readily soluble in the washing medium and most effective at pH
~alues best conducive to improved cleaning performance, viz,
pH 10.5-14. The compositions are normally of gel consistency,
i.e. a highly viscous, opaque jelly-like material having
Bingham plastic character and thus relatively high yield
values. Accordingly, a definite shear force is necessary to
initiate or increase flow. Under such conditions, the
composition is quickly fluidized and easily dispersed. When
the shear force is discontinued, the fluid composition quickly
reverts to a hi~h viscosity, Bingham plastic state closely
approximating its prior con~istency.
U.S. Patent 4,511,~87, dated April 16, 1985, describes a
low-foaming detergent paste for dishwashers. The patented
thixotropic cleaning agent has a viscosity of at least 30 Pa.s
at 20C as determined with rotational viscometer at a spindle
speed of 5 revolutions per minute. The composition is based
on a mixture of finely divided hydrated sodium metasilicate,
an active chlorine compound and a thickening agent which is a
foliated silicate of the hectorite type. Small amounts of
nonionic tensides and alkali metal carbonates and/or
hydroxides may be used.
The compositions of the instant in~ention overcome many
of the aforementioned deficiencies, while providing
compositions which are phosphate-free and consequently
environmentally safe.
3'~J~7'~
further optional ingredients to supply or supplement building
function not provided by the buffer, the amount of such
builder not exceeding 5~ of the total composition, according
to the patent. Maintenance of the desired (greater than~ Ph
lo levels is achieved by the buffer/builder components. High
Ph is said to minimize decomposition of chlorine bleach and
undesired interaction between surfactant and blèach. When
present, NaTPP is limited to 5%, as stated. Foam killer is
not disclosed.
In U.K. Yatent Application G~ 2,116,199A and G~
2,140,450A, both of which are assigned to Colgate-Palmolive,
liquid ADD compositions are disclosed which have properties
desirably characterizing thixotropic, gel-type structure and
which include each of the various ingredient~ necessaxy for
effective detergency within an automatic dishwasher. The
normally gel-like aqueous automatic dishwasher detergent
composition having thixotropic properties includes the
~ollowing ingredients, on a weight basis:
(a) 5 to 35~ alkali metal tripol~pho phate;
(b) 2.5 to 20~ sodium silicate;
(c) 0 to 9% alkali metal carbonate;
(d) 0.1 to 5~ chlorine bleach stable, water dispersible
organic detergent active material;
(e) 0 to 5% chlorine bleach stable foam depressant;
(f) chlorine bleach compound in an amount to provide
0.2 to 4~ of available chlorine;
(g) thixotropic thickener in an amount sufficient to
provide the composition with thixotropy index of 2.5 to 10;
;~3~ Jt ~!f~
Quite surprisingly, it was ~iscovered that the phosp~ate-
free compositions of the instant invention while providing
compositions which are environmentally safe also provide the
desired cleaning performance. They also provided remarkable
stabilization against change with time of the rheological
properties.
Accordingly, it is an object of the invention to provide
liquid ADD compositions having excellent cleaning performance,
improved physical stability and improved rheological
10 properties and having a density of 1.20 to 1.44 grams/li~er
while being phosphate-free and environmentally safe.
It i9 still another object of the instant invention to
provide compositions which have satisfactory chlorine levels
with satisfactory stability.
More specifically, it is an object of this invention to
provide excellent cleaning performance and improved physical
stability of aqueous liquid automatic dishwasher detergent
pastes or gels which are phosphate-free.
SUMMARY OF THE INVENTION
These and other objects of the invention, which will
become more readily understood from the following summary and
detailed description of the invention and preferred
embodiments thereof, are achieved by a phosphate-free built
25 aqueous liquid automatic dishwasher detergent composition
containing a stabilization system such that when the
composition is added to an aqueous wash bath, at a
~r~3J~7~
concentration of 10 grams per liter, the wa.sh bath has a pH of
at least 11.2.
In accordance with an especially preferred embodiment,
the present invention provides a gel-like viscoelastic aqueou.s
automatic dishwasher detergent composition which has a three-
dimensional structure and includes, on a weight basis:
(a) 1 to 20~ of at least one low molecular weight non
crosslinked polyacrylate;
(b) 0 to 20~ alkali metal sil:icate;
(c) 1 to 15~ of at least one phosphate free detergent
builder salt such as alkali metal carbonate;
(d) 0 to 8~ alkali metal hydroxide;
(e) 0 to 5~ chlorine bleach stable organic detergent
active material;
(f) 0 to 1.5~ stable foam depressant;
(g) chlorine bleach compound in an amount to provide
0.2 to 4~ of available chlorine;
(h) 0.1 to 5~ of a polymeric thickener having a
molecular weight of at least 500,000;
(i) 0 to 2~ of a metal salt of a long chain fatty acid
or a fatty acid in an amount effective to increase the
physical stability of the composition;
(j) 0 to a~ sodium sulfate;
(k) balance water, wherein the water is substantially
bound by hydration to the polymeric thickener so that the
composition is substantially free of unbound water and the
total amount of (b) alkali silicate, (c) alkali metal
carbonate and (d) alkali metal hydroxide provides a pH
sufficiently high such that when the composition is diluted in
an aqueous wash bath to provide a concentration of 10 grams
per liter the pH of the aqueous wash bath becomes at least
11.2 and the concentration of the alkali metal builder salt,
alkali metal hydroxide and alkali metal hydroxide is
preferably less than 25 wt.~, more preferably less than 22
wt.~, and most preferably less than 20 wt.~ and the residual
amount of the composition remaining in a poly olefinic
container after the poly olefinic composition is drained o~
the composition is less 5 wt.~ of the original amount of the
composition in the container and more preferably less than 2
wt.%.
The invention also provides a method for cleaning
dishware in an automatic dishwashing machine with an aqueous
wash bath containing an eEfective amount of th~ liquid
automatic dishwasher detergent ~LADD) composition as described
above. According to this aspect of the invention, the LADD
composition can be readily poured into the dispensing cup of
the automatic dishwashing machine and will be sufficiently
viscous to remain securely within the dispensing cup until
shear forces are again applied thereto, such as by the water
spray from the dishwashing machine.
It is known that LADD effectiveness i9 directly related
to (a) available chlorine levels; (b) alkalinity; (c)
solubility in washing medium; and (d) foam inhibition. In
accordance with the present invention, the types and amounts
of the alkaline components which are phosphate-free are chosen
so that when the composition is added to an aqueous wash bath
3~
to provide a concentration of 10 grams of composition per
liter of wash bath the pH of the wash bath becomes at least
11.2, preferably at least 11.5, such as from 11.5 to 13.5,
preferably 11.5 to 12.5.
~ENERAL DESCRIPTION OF THE INVENTION
The viscoelastic gel compositions of the in~tant
invention which have a three dimens:ional structure can be
generally descrlbed as follows:
Ingredient Amount (A._I.) Wt
Sodlum Sulfate 0 to 8
Alkali Metal Sllicate 0 to 20
Foam Depressant 0 to 1.5
Low Molecular Weight Polyacrylate ]. to 20~
Phosphate-free Bullder Salt 1 to 20%
Alkali Metal Hydroxide 0 to 8%
Metal Hypochlorite Solution (13~) 1 to 15%
Fatty Acid or Metal Salt of
Fatty Acid 0 to 2~
Polymeric Thickener 0.1 to 2.5%
Water Balance
Organic Detergent Active Material 0 to 5~
wherein the water of the composition is bound by hydration to
the polymeric thickener so that the composition has
substantially no free water.
Therefore, in accordance with an especially
preferred embodiment of this invention, the high alkalinity is
achieved in a phosphate-free, fatty acid salt stabilized,
chlorine-bleach containing li~uid automatic dishwasher
detergent composition, wherein the alkaline compounds include,
on an active basis, based on the total composition, from 0 to
20 weight alkali metal silicate, from 0 to 8 wt ~ alkali
metal hydroxide, from 1 to 20 wt ~ phosphate-free builder
salt, from 1 to 8~ of at least low molecular weight
noncrosslinked polyacrylate, from 0.1 to 5 weight percent
polymeric thickener and optionally a metal hypochlorite, a
foam depressant, and a detergent active material, wherein the
pH of 1 li.ter of aqueous wash bath containing 10 grams of the
composition being at least 11.2.
The alkali metal silicate such as sodium silicate, which
provides alkalinity and protection of hard surfaces, such as
fine china glaze and pattern, is employed in an amount ranging
from 1.0 to 20.0 weight percent, preferably 2.5 to 20 weight
percent, in the composition. The sodium silicate is generally
added in the form of an aqueous solution, preferab].y having
Na2O:SiO2 ratio of 1:1.3 to 1:2.~, especially preferably 1:2.0
to 1:2.6. At this point, it should be mentioned, especially
NaOH and sodium hypochlorite, are also o~ten added in the form
of a preliminary prepared aqueous dispersion or solution.
The liquid automatic dishwashing detergent composition
contains 1 to 20~ by weight of an akali metal phosphate free
detergency builder salt, more preferably 2 to 20~ by weight,
and most preferably 3 to 20~ by weight, wherein the
detergency builder is usually an alkali metal carbonate such
as sodium carbonate or potassium carbonate.
Other builder salts which can be mixed with the sodium
carbonate are gluconates and nitriloacetic acid salts. In
conjunction with the builder salts are optionally used a low
~ dJ ~r3
molecular weigh~ noncrosslinked polyacrylates having a
molecular weight of 1,000 to 100,000, more preferably 2,000
to 80,000. A preferred low molecular weight polyacrylate is
Sokalan~n PA30CL manufactured by BASF and having a molecular
weight of 8,000. Another preferred low molecular weight
sodium salt of a polyacrylate is Norasol LMW45~ which is also
know as Acusol 445N manufactured by Norsoshaas and having a
molecular weight of 4,500.
Other useful low molecular weight noncrosslinked polymers
are: Acusol~ 640D provided by Rohm & Haas; Norasol QR1014
from Norsohaas having a GPC molecular weiyht of 10,000.
Norasol A-l has a molecular weight of 60,000. SokalanPA30CL
from BASF is the most preferred because of its extremely high
bleach stability of at least six months as compared to the
other listed low molecular polymers which all have bleach
stabilities of less than six months. Sokalan PA30CL is a
polyacrylate of a chemical structure similar to Norasol LMW45
which has been modified to have increased bleach stability it
is believed by the elimination of heavy metals used in the
synthesis of the Sokalan PA30CL.
Acusol 445N is an excellent dispersant for calcium
carbonate which i9 formed during the washing process, wherein
the Acusol 445N controls crystal growth of the calcium
carbonate and helps suspends the calcium carbonate in the wash
bath. Another especially useful low molecular weight
polyacrylate polymer is Good-Rite3 K-7058N which is a 90 -
100~ neutralized sodium salt of a polyacrylate polymer having
a molecular weight of 5,800. K-70s8N is a good dispersant for
Jr~
calciu~l carbonate and excellent builder or sequestering agent
for heavy metal ions such as calcium or magnesium. A
combination of Acusol 445N and K-7058N provides maximum
enhancement for the alkali metal non phosphate builder salt
such as sodium carbonate. The chlorine stability of a
composition made with a combination of Acusol 445 and Good-
Rite3 K7058N is improved over compositions made with either
Acusol 445 or Good-Rite~ K7058N alone.
Another class of builders useful herein are the water
insoluble aluminosilicates, both of the crystalline and
amorphous type. Various crystalline zeolites (i.e. alumino-
silicates) are described in British Patent No. 1,504,168, U.S.
Patent No. 4,409,13~ and Canadian Patent Nos. 1,072,835 and
1,087,477. ~1 example of amorphous zeolites useful herein can
be found in Belgium Patent No. 835,351. The zeolites
generally have the formula:
(M2O)~(Al2O3~y(SiO2)~ wH~O
wherein x i9 1, y iS from 0.8 to 1.2 and preferably 1, z is
from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from
0 to 9, preferably 2.5 to ~ and M is preferably sodium. A
typical zeolite is type A or similar structure, with type 4A
particularly preferred. The preferred aluminosilicates have
calcium ion exchange capacities of 200 millie~uivalents per
gram or greater, e.g. 400 meq/g.
Foam inhibition is important to increase dishwasher
machine efficiency and minimize destabilizing effects which
might occur due to the presence of excess foam within the
washer during use. Foam may be sufficiently reduced by
suitable selection of the type and/or amount of detergent
actlve material, the main foam-producing component. The
degree of foam is also somewhat dependent on the hardness of
the wash water in the machine whereby suitable adjustment of
~he proportions of the inorganic or organic builder salt ~Ihich
has a water softening effect may aid in providing the desired
degree of foam inhibition. However, it is generally preferred
to include a chlorine bleach stable foam depressant ox
inhibitor. Particularly effective are the alkyl phosphoric
acid esters of the formula:
O
HO--P--R
OR
and especially the alkyl acid phosphate esters of the formula:
HO--P--R
OR
In the above formulas, one or both R groups in each type of
ester may represent independently a C,2-C20 alkyl or ethoxylated
alkyl group. The ethoxylated derivative of each type of
ester, for example, the condensation products of one mole of
ester with from 1 to 10 moles, preferably 2 to Ç moles, more
preferably 3 or 4 moles, ethylene oxide can also be used~
Some examples of the foregoing are commercially available,
such as the products SAP from Hooker and LPKN-158 from
Knapsack. Mixtures of the two types, or any other chlorine
bleach stable types, or mixtures of mono- and diesters of the
~ t~ ,J~
same type, may be employed. Especially preferred is a mixture
of mono- and di- Cl6-C~8 alkyl acid or ethoxylated alkyl
phosphate esters such as monostearyl/distearyl acid phosphate
1.2/1, and the 3 to 4 mole ethylene oxide condensates thereof.
~hen employed, proportions of O to 5 weight percent,
preferably 0.1 to 1.5 weight percent, of foam depressant in
the composition is typical. Other defoamers which may be used
include, for example, the known silicones, such as available
from Dow Chemicals. In addition, it is an advantageous
feature of this invention that many of the stabilizing salts,
such as the stearate salts, for example, sodium stearate, are
also effective as foam killers.
Although any chlorine bleach compound may be employed in
the compositions of this invention, such as
dichloroisocyanurate, dichloro-dimethyl handantoin, or
chlorinated TSP, alkali metal or alkaline earth metal, e.g.
potassium, lithium, magnesium and especially sodium,
hypochlorite is preferred. The composition should contain
sufficient chlorine bleach compound to provide 1.5 to 3.1
by weight of available chlorine, as determined, for example,
by acidification of 100 parts of the composition with excess
hydrochloric acid. A solution containing 0.2 to 4.0% by
weight of sodium hypochlorite (13~ of available chlorine)
contains or provides roughly the same percentage of available
chlorine. 0.8 to 1.6% by weight of available chlorine is
especially preferred.
~etergent active material which may be, useful herein
must be stable in the presence of chlorine bleach, especially
14
ypochlorite bleach, and those of the organic anionic, aMine
oxide, phosphine oxide, sulphoxide or betaine water.
Dispersible surfactant types are preferred; the first
mentioned anionics being most preferred. They are used in
amounts ranging from O to 5~, preferably 0.1 to 5.0%.
Particularly preferred surfactants herein are the linear or
branched alkali metal mono- and/or di-(C8-CI4) alkyl diphenyl
oxide mono- and/or disulphates, commercially available for
example as DOWE'~X~ 3B-2 and DOWFAX~ 2A-1. Alkyl ether
sulfates (Ct2-C~ 3EO-SO3-NaL) are suitable surfactants. In
addition, the surfactant should be compatible with the other
ingredients of the composition. Other suitable surfactants
include the primary alkylsulphates, alkylsulphonates,
alkylarylsulphonates and sec.-alkylsulphates. E~amples
include sodium ClO-Cl8 alkylsulphates such as sodium
dodecylsulphate and sodium tallow alcoholsulphate; sodium ClO-
Cl8 alkanesulphonates such as sodium hexadecyl-1-sulphonate and
sodium C12-C~8 alkylbenzenesulphonates such as sodium
dodecylbenzenesulphonates. The corresponding potassium salts
may also be employed.
As other suitable surfactants or detergents, the amine
oxide surfactants are typically of the structure R2RIN~O, in
which each R represents a lower alkyl group, for instance,
methyl, and Rl represents a long chain alkyl group having from
8 to 22 carbon atoms, for instance a lauryl, myristyl,
palmityl or cetyl group. Instead of an amine oxide, a
corresponding surfactant phosphine oxide R2RIPO or sulphoxide
RRISO can be employed. Betaine surfactants are typically of
t~J,~
~he structure R~RI~R''CO~-, in which each R represents a lower
alkylene group having from 1 to 5 carbon atoms. Specific
exa~lples of these surfactants include lauryl-dimethylamine
oxide, myristyl-dimethylamine oxide, the corresponding
~hosphine oxides and sulphoxides, and the corresponding
betaines, including dodecyldimethylammonium acetate,
tetradecyldiethylammonium pentanoate,
hexadecyldimethylammonium hexanoate and the like. For
biodegradability, the alkyl groups in these surfactants should
be linear, and such compounds are preferred.
Surfactants of the foregoing type, all well-known in the
art, are described, for example, in U.S. Patents 3,985,663 and
4,271,030.
Other useful surfactants are Akypos from Chemy which is a
nonionic. surfactant terminated by one functional carboxylate;
C-l230 3EO ether sulfates; and C, 12-18 alcohol sulEates.
Thixotropic thickeners, i.e. thickeners for suspending
agents which provide an aqueous medium with thixotropic
properties, are known in the art and may be organic or
inorganic water soluble, water dispersible or colloid-forming,
and monomeric or polymeric, and should, of course, be stable
in these compositions, e.g. stable to high alkalinity and
chlorine bleach compounds, such as sodium hypochlorite. These
materials are generally used in amounts of 0.1 to 4.0 percent
by weight, preferably 0.2 to 3.5 weight percent, more
preferably 0.3 to 3 welght percent, to confer the desired
thixotropic properties and Bingham plastic character.
However, in the presence of the metal salt fatty acid
i 3
stablllzers, the desired t~ixotropic properties and Bingham
plastic character can be obtained ln the presence of lesser
amounts of the thixotropic thickeners. Those especially
preferred generally comprise the inorganic, colloid-forming
~clays of smectite and/or attapulgite types.For example,
amounts of the inorganic colloid-forming clays of the smectite
and/or attapulgite types in the range of from 0.1 to 3~,
preferably 0.1 to 2.5~, especially 0.1 to 2~, are generally
sufficient to achieve the desired thixotropic properties and
Bingham plastic character when used in combination with the
physical stabilizer.
Smectite clays include montmorillonite (bentonite),
hectorite, attapulgite smectite, saponite and the like.
Montmorillonite clays are preferred and are available under
the tradenames such as Thixogel (registered trademark) No. 1
and Gelwhite (registered trademark) GP, H, etc., from Georgia
Kaolin Company; and ECCAGUM (registered trademark) GP, H,
etc., from Luthern Clay Products. Attapulgite clays include
the materials commercially available under the tradename
Attagel (registered trademar~), i.e. Attagel 40, Attagel 50
and Attagel 150 from Engelhard Minerals and Chemicals
Corporation. Mixtures of smectite and attapulgite types in
weight ratios of 4:1 to 1:5 are also useful herein. Abrasives
or polishing agents should be avoided in the LADD compositions
as they may mar the surface of fine dishware, crystal and the
like.
"~ 7~
The polymeric thixotropic thickeners are usually
polyacrylate resins such as Carbopol 614 or Carbopol 940 or
624.
Exemplary of the polycarboxylate type thickening agents
are cross-linked polyacrylic acid type thickening agents are
cross-linked polyacrylic acid-type thickening agents sold by
B.F. Goodrich under their Carbopol trademark, including both
the 900 series resins, especially Carbopol 941, which i9 the
most ion-insensitive of this class of polymers, and Carbopol
940 and Carbopol 934, and the 600 series resins, especially
Carbopol 614. The Carbopol 600 and 900 series resins are
hydrophilic high molecular weight, cross-linked linear acrylic
acid polymers having an average equivalent weight of 76, and
the general structure illustrated by the following formulas:
R
/ \\
OH O n.
wherein R can be hydrogen or an alkyl chain. Carbopol 941 has
a molecular weight of 1,250,000; Carbopol 940 has a molecular
weight of approximately 3,000,000. The Carbopol 900 series
resins are highly branched chained and highly cross-linked
with polyalkenyl polyether, e.g. 1~ of a polyalkyl ether of
sucrose having an average of 5.8 allyl groups for each
molecule of sucrose. The preparation of this class of cross-
linked carboxylic polymers is described in U.S. Patent
2,798,053, the disclosure of which is incorporated by
il2~ 3~
,eEerence. Further detailed information on the Carbopol 900
series resins is available from ~.F. Goodrich, see, for
example, the B.F. Goodrich cataloy GC-67, CarbopolR Water
Soluble Resins.
' In general, these thickening resins are preferably water
dispersible copo].ymers of an alpha-beta monoethylenically
unsaturated lower aliphatic carboxylic acid cross-l.inked with
a polyether of a polyol selected from oligo saccharides,
reduced derivatives thereof in which the carbonyl group i9
converted to an alcohol group and pentaerythritol, the
hydroxyl groups of the polyol which are modified being
etherified with allyl groups, there being preferably at lease
two such allyl groups per molecule.
These water-dispersible cross-linked thickening resins as
described in the aforementioned U.S. Patent 2,798,053 and
which have been commercialized by B.F. Goodrich as the
Carbopol 900 series resins are prepared from essentially
linear copolymers. More recently, ~.F. Goodrich has
introduced the Carbopol 600 series resin. These are high
molecular weight, non-linear moderate branched chain
polyacrylic acid cross-linked with polyalkenyl ether. In
addition to the non-linear or branched nature of these re~ins,
they are also believed to he more highly cross-linked than the
900 series resins and have molecular weights between
1,000,000 and 4,000,000.
Most especially useful of the Carbopol 600 series resins
are Carbopol 614 and Carbopol 624 which are the most chlorine
bleach stable of this class of thickening resins. Carbopol
19
3~ r3
i
~14 and 624 are also highly stable in the high alkalinity
environment of the pxeferred liquid automatic dishwasher
detergent compositions and is also highly stable to any
anticipated storage temperature conditions from below freezing
~o elevated temperatures as high as 120F, preferably 1~0F,
and especially 160F, for periods of as long as several days to
several weeks or months or longer.
While the most favorable results have now been achieved
with Carbopol 614 moderate branched chain polyacrylic resin,
other branched cross-linked polycarboxylate-type thickening
agents can also be used in the compositions of this invention.
As used herein "polycarboxylate-type" refers to water-soluble
carboxyvinyl polymers of alpha, beta monoethylenically
unsaturated lower aliphatic carboxylic acids, which may be
linear or non-linear, and are exemplified by homopolymers of
acrylic acid or methacrylic acid or water-dispersible or
water-soluble salts, esters or amides thereof, or water-
soluble copolymers of these acids or their salts, esters or
amides with each other or with one or more other ethylenically
unsaturated monomers, such as, for example, styrene, maleic
acid, maleic anhydride, 2-hydroxethylacrylate, acrylonitrile,
vinyl acetate, ethylene, propylene, and the like, and which
have molecular weights of from 500,000 to 10,000,000 and are
cross-linked or interpolymerized with a multi-vinyl or multi-
allylic functionalized cross-linking agent, especially with a
polyhydric compound.
These homopolymers or copolymers are characterized by
their high molecular weight, in the range of from
f~'l~i~33~7'~
JOO ~ 0001000 ~ especially from 1,ooo,Ooo,000 to 4,000,000, and
by their water solubility, generally at least to an extent of
up to 5~ by weight, or more, in water at 25C.
The th;ckening agents are used in their cross-linked
~orm, wherein the cross-linking may be accomplished by means
known in the polymer arts, as by irradiation, or, preferably,
by the incorporation into the monomer mixture to be
polymerized of known chemical cross-linking monomer mixture to
be polymerized of known chemical cross-linking monomeric
agents, typically polyunsaturated (e.g. diethylenically
unsaturated) monomers, s~ch as, for example, divinylbenzene,
divinylether of diethylent glycol, N,N'-methylene
bisacrylamide, polyalkenylpolyethers (such as described
above), and the like. Typically, amounts of cross-linking
agent to be incorporated in the final polymer may range from
0.01 to 5 percent, preferably from 0.05 to 2 percent, and
especially, preferably form 0.1 to 1.5 percent, by weight of
cross-linking agent to weight of total polymer. Generally,
those skilled in the art will recognize that the degree of
cross-linking should be sufficient to impart some coiling of
the otherwise generally linear or non-linear polymeric
compound while maintaining the cross-linked polymer at least
water dispersible and highly water-swellable in an ionic
aqueous medium.
2~ The amount of the high molecular weight, branched chained
cross-linked polymeric acid or other high molecular weight,
hydrophilic cross-linked polycarboxylate thickening agent to
impart the desired rheological property of linear
7~
vlscoelasticity to the instarlt compositions will generally be
in the range of from 0.1 to 4.0~, based on the weight of the
composition, although the amount will depend on the particular
cross-linking agent, ionic strength of the composition,
~ydroxyl donors and the like, wherein mixtures of two or more
polymerlc thickening agents can be employed.
The bleach stability of the compositions can be improved
by employing in the composition a cross-linked linear
polyacrylate homopolymer type thickening agent which i9
substantially formed in non aromatic solvents in place oE the
Carbopol polymer which are branched chained, crosslinked
polyacrylic acid type thickening agents. These crosslinked
linear polyacrylate homopolymer type thickening agents are
sold by 3-V Chemical corporation under the names Polygel DB~,
Polygel DK~ and are manufactured by polymerization in a
trichloroethan non aromatic solvent such that they are free of
aromatic solvents. The Polygel DB~ and Polygel DK~ have an Mw
of 2,000,000 to 4,000,000.
The amount of the high molecular weight, cross-linked
polyacrylic acid or other high molecular weight, hydrophilic
cfross-linked polyacrylic acid-type thickening agent to impart
the desired rheological property of linear viscoelasticity
will generally be in the range of from 0.1 to 2~, preferably
from 0.2 to 1.4~ by weight, based on the weight of the
composition, although the amount will depend on the particular
cross-linking agent, ionic strength of the composition,
hydroxyl donors and the like.
22
~`~l,~,3 J
Another class of polymers useful in the instant
composition are based on methyl vinyl either/maleic anhydride
copolymers and terpolymers. Examples of useful polymers are:
methyl vinyl ether, maleic anhydride, acrylic acid, cross-
linked; methyl vinyl ether, maleic anhydride, vinyl
pyrrolidone, cross-linked; and methyl vinyl ether, maleic
anhydride, isobutene, cross-linked. The cross-linking agent
is essential to establish the kind of polymer network useful
in this invention. The cross-linking agent can be any
hydrocarbon with a chain length of four or more carbon atoms
containing at least two carbon-carbon double bonds. The
cross-linking ayent is mainly a hydrocarbon with optional
halogen and oxygen-containing substituents and linkages such
as ester, ether and OH groups. These cross-linking agents can
vary in amount from 0.01 to 30% by weight of the total
~uantity of polymer used. examples of cross-linking agents
are 1,7-Octadiene, 1,9 Decadiene, non-terminal dienes, Divinyl
Glycol, Butane Divinylether, polyallyl pentaerythritol and
polyally sucrose. Cross-linking can also be achieved through
the maleic anhydride after the polymer is formed, via ester or
amide formation using polyols and polyamines such as 1,4
butane diol and polyethylene glycols.
The most useful polymers of these inventions are the
Gantrez AN cross-]inked with aliphatic dienes such as 1,7
oc~adiene and 1,9 decadiene.
Gantrez AN polymers cross-linked from .01 to 10~ by
weight of 1,7 octadiene were shaken overnight in order to
23
~r3~7~
nydrolyze the maleic anhydride ring. The polymer solutions
were neutralized to pH 7 to fully ionize the carboxyl yroup~.
The results show that 5~ by weight of cross-linking agent is
necessary before a gel is formed. If Gantrez AN is cross-
Iinked with 1,0 decadiene then a gel is formed at 3-4~ cross-
linking.
The cross-linking causes the formation of a polymer that
disperses in water to form a gel with a yield point. Table II
gives typical yield points for the polymer cross-linked with
1,9 decadiene.
Table II. Yield Point~ as a Function of Polymer
Concentration in Water for Cross-linked
Gantrez (Gantrez ACV-4006 Cross-linked with
1,9 Decadiene).
Polymer Concentration PH Yield Point, Pa
_ (Weight_-O) __
0.125 7 37
0.250 7 64
0 500 7 176
~easurements were made using the Haake Rotoviscometer RV12
with MV IP sensor system. Shear rate was varied from 0 to 10
sec~~.
srookfield viscosity measurements were made using cross-
linked Gantrez polymers, and results are summarized in ~able
III. Results show that even at very low concentrations,
cross-linked Gantrez yield highly viscous polymer solutions.
These viscosities characterize the degree of polymerization of
the polymers.
Table III. Brookfield Viscosityn of 0.5~ Cross-linked
Gantrez (ACV-4006) in water at pH 7.
1 0 .. ---~
Spindle #RPMBrookfield Viscosity
~,cps l
T-C 1 376 X 103
T-C 2.5 180 X 103
T-C 5 105 X 103
T-C 10 59 X 103
~The measurements were taken with a Brookfield Model DV II.
__
The copolymer of methyl vinyl ether/maleic anhydride is
illustrated by the following formula:
--(C~ ~(C~ C)y
1 ~
j O===C\ ; ~O
Me
wherein x is 50 mole~.
$~
The copolymer is cross-linked with 0.5 to 20.0 wt~ of a
diene monomer having 6 to 20 carbon atoms, more preferably
7 to 16 and most preferably 8 to 12, wherein preferred diene
monomers are 1,7 Octadiene and 1,9 decadiene. These water-
~dispersible, cross-linked thickening resins were obtained from
the GAF corporation. The amount of the cross-linked polymeric
thickening agent or other high molecular weight, hydrophilic
cross-linked polycarboxylate thickening agent to impart the
desired rheological property of linear viscoelasticity will
generally be in the range of from 1.5 to 5~, preferably from
.5 to 2.5, by weight, based on the weight of the composition,
although the amount will depend on the particular cross-
linking a~ent, ionic strength of the composition, hydroxyl
donors and the like.
The preferred long chain fatty acids are the higher
aliphatic fatty acids having from 8 to 22 carbon atoms, more
preferably from 10 to 20 carbon atoms, and especially
preferably from 12 to 18 carbon atoms, inclusive of the
carbon atom of the carbox~l group of the fatty acid. The
aliphatic radical may be saturated or unsaturated and may be
straight or branched. Straight chain saturated fatty acids
are preferred. Mixtures of fatty acids may be used, such as
those derived from natural sources such as tallow fatty acid,
coco fatty acid, soya fatty acid, etc., or from synthetic
sources available from industrial manufacturing processes.
Thus, examples of the fatty acids from which the
polyvalent metal salt stabilizers can be formed include, for
example, decanoic acid, dodecanoic acid, palmitic acid,
26
2~
myristic acid, stearic acid, oleic acid, eicosanoi.c acid,
tallow acid, coco fatty acid, soya fatty acid, mixtures of
these acids, etc. Stearic acid and mixed fatty acids are
preferred.
~ The polyvalent metals of Groups IA, IIA, IIB, and IIIB,
and Groups IIIA, IVA, VA, IB, IIB, IVB, VB, VIIB and VIII of
the Periodic Table of the Elements can also be used. A key
requirement is that the metal salt of the fatty acid must be
dispersible in the aqueous medium containing the Carbopol
within the composition. The most preferred metal cations are
selected from Group lA. Naturally, for ~ADD compositions, as
well as any other applications where the invention composition
will or may come into contact with articles used for the
handling, storage or serving of food products or which
otherwise may come into contact with or be consumed by people
or animals, the metal salt should be selected by taking into
consideration the toxicity of the metal. For this purpose,
the calcium and magne3ium and sodium salts are especially
higher preferred as generally safe food additives. Sodium
stearate i9 the most preferred species of the instant
invention.
The amount of the fatty acid salt stabilizer to achieve
the desired enhancement of physical stability and viscosity
enhancement will depend on such factors as the nature of the
fatty acid salt, the nature and amount oE the thixotropic
agent, detergent active compound, inorganic salts, other LADD
ingredients, as well as the anticipated storage and shipping
conditions.
Generally, however, amounts of the metal fatty acid salt
or fatty acid stabilizing agents in the range of from 0 to
0.4 wt.~, preferably from 0.005 to 0.6 wt.~, especially
preferably from 0.04 to 0.50 wt.~, and most preferably 0.02
~o 0.4 wt.~, provide a long-te~ stability and absence of
phase separation upon standing or during transport at both low
and elevated temperatures as are required for a commercially
acceptable product. To obtain the ~laximum benefit of the
fatty acid or the metal salt of the fatty acid it is critical
that they must be properly dispersed in the medium containing
the polymeric thickener.
Depending on the amounts, proportions and types of
physical stabilizers and thixotropic agents, the addition of
the fatty acid salt or fatty acid not only increases physical
stability, but alRo provides a simultaneous increase in
apparent viscosityO Ratios of fatty acid salt or fatty acid
to thixotropic agent in the range of from 0.02-0.4 weight
percent fatty acid salt and from 0.1 - 2.5 wei~ht percent
thixotropic agent are usually sufficient to provide these
simultaneous benefits and, therefore, the use of these
ingredients in these ratios is most preferred.
Other conventional ingredients may be included in these
compositions in small amounts, generally less than 3 weight
percent, such as perfume, preservatives, dyestuffs and
pigments and the like, all of course being stable to chlorine
bleach compound and high alkalinity (properties of all
components). Especially preferred for coloring are the
chlorinated phthalocyanines and polysulphides of
28
7 ~
~luminosllicate which provide, respectively, pleasing green
and blue tints. Tio~ may be employed for whitening or
neutralizing off-shades.
The liquid ADD compositions of this invention are readily
employed in known manner for washing dishes, other kitchen
utensils and the like in an automatic dishwasher, provided
with a suitable detergent dispenser, in an aqueous wash bath
containing an effective amount of the composition, generally
sufficient to fill or partially fill the automatic dispenser
cup of the particular machine being used.
DETAILED DESCRIPTION OF THE_INVENTION
The invention may be put into practice in various ways
and a number of specific embodiments will be described to
illustrate the invention with reference to the accompanying
examples.
All amounts of proportions referred to herein are by
weight of the composition unless otherwise indicated.
29
2~ 3~ 3
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. - . .
{.~'r.3~JJ~
62301-1767
The procedure ~o~ ~4rm~ng ~o~ulation~ (A~O)
comprise~ ~onming a ~ir~t a~ueou~ ~olution A' by ~ddin~ a~
room temperatur~ urder mixin~ conditio~ fir~t the di~per~ion
o~ the Nora~ol LMW-45~ into tha wa~er, seco~dly, th~ Carbopol
S 614 and thirdly, a sufficlent amount of caustic ~oda to j~st
neutrali7e ~he ~olyc~rboxylate pol~mer. A 3econd agueou~
solutio~ (B') i~ ~ormed by ~ddin~ at room tempex~ture under
conditions of mixing to the water, ~ir~t the builde~ ~lt,
secondly, the ~oqium eulfate, thir~ly, the ~odium ~l~ilicate
an~ lastly, the bala~c~ o~ the cau~tic ~oda. A third a~ou8
~olution (C') whlch is s~titled the premi~ i~ ~ormed ~t 60-70C
by adding to wate~ (3 ~arka~ fi~st ~e did~cyldiphenyl ethe~
disulfonate (0.4~ part~) and secondly, the ætearic acld (O.lS
part~). Solution ~ a~ded under condiCiong o~ mixins a~
room tem~erature to Solutio~ A'~ The mixed ~olu~ion~ o~ A' ~
B' a~ room ~emperature under conditions o~ mixin~ i~ a~ded the
third solution (C'). The combined solutions of A', B' and C'
are added to the 13% hypochlorite solution to form the final
formulations A-O.
~am~lçLII
Formulatio~ 0 we~e te~to~ ~or ~oil removal on
di~he~ in a ~tandard multl-~oil ~e~e u~ing a Bo~ch SMS5~1
(di~hw~ah~r) at 65C wherein 3 ml. of Galax~ ~in~e ald ~old ~y
Colya~e Palmoli~e Co. wa~ u~ed. A rating ~y~tem of l-10 wa~
~5 u~ed with lO rep~e~en~ln~ maximum ~oil removal.
~1
~ $i'3i~
,~
N 11
o ~o r c
01
t ~1
æl
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..
~o u~ In
Ul ~ CO N t~
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O O
~1
U~ In
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U)
.t,
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Lr\
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ar.... ",~ _~
~` Ll JJ ~ ~o 4.1 ta
U U ,U-~ .~3.~
;
~G971~ ~ 62301-1767
~ULTI-$0IL TEST
This method allows to evaluate the removal of critical soils
on several representative items of dishes as well the
performance on soiled glasses.
ETHODOLOGY:
. Dishwasher: Bosch SMS 5021
. Rinse Aid: 3 ml Galaxy
. Recommended Dosage: Gel emerald 55 g
Galaxy 55 g
. Dishwasher Load:
Lower Basket: . 6 Plates with Porridge Soils
. A Stainless Steel Plate with Rice
Soils
. A Stainless Steel Plate with White
Sauce
(mixture made from milk, flour,
butter)
. Cutleries in the Cutlery Basket:
with Rice (2 spoons, 2 knives, 2
forks)
with Porridge (2 spoons ~ 2 knives)
Upper Basket: . 8 Glasses Soiled with Tomato Juice
. 8 Glasses Soiled with Cocoa Beverage
. 8 Glasses Soiled with Milk
4 products are ~ested simultaneously in 4 dishwashers
according to the statistical procedure made in "Latin Square".
A wash cycle with 4 replicates per product.
. pH value is measured during wash cycle
. Washing Program: .Prewash
.Main Wash at 65 C
.Rin~qe Cycle
.Drying
~ 62301-1767
Water hardness during wash: 100-150 ppm CaCoz.
EVALUATION:
. Each piece of dishes is evaluated according to a scale
from 0 (no removal) to 10 (complete soil removal).
' . The glasses are evaluated in a viewing box in
. overall performance (from 0 to 10)
. p~r item of performance as
.Filming (on a scale from 0 to 4 (no
filming)
.Spotting (0 to 4 (no spotting)
.Soil Redeposition (0 to 4)
Example of Results shown in the preceeding Table.
- 34 -
$~
~D
r~ VX
~ Ol o
o
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Vx
~1 0
' o ~ E
v vv 1-~
Ul ~ U 0 ~.C ~` V
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Hl ~ ~ U ' ~ 8
0 8 ~ ~
C~l ~) ~ O , O U ~
U ~V U U
L ~
U ~ ~ O ~ ~ ~
u~ tn A~ O O r l
~ r ' ~ X
~:1 ul ~ ~1 -- ~o O _ ~ O ta
~`
~ ~ ~ .C A~
. O i~ ~
~ ~ H .C tJ) 1:~ 8 ~
~ û~ ~! c" vv 1:1 ~1
~ ~ E~ .~ ~ ~ ~ ù
~ _ _ ~ ~ ~ ~ qV~ U
~o c~ ~ x æ
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2~ 62301-1767
RHEOLOGICAL DETERMINATION
CARRIMED (model:_ CSL 100): This apparatus is equipped to
operate in oscillating mode ln order to fully assess the
viscoelastic behavior of Carbopol-based No P gels. This
~e~hod is attractive for its "in depth" characterization of
gel structures because several experiments can be carried out
to test completely one sample.
One experiment usually done on gels is "The Structure
Recovery~': This one allows to characterize how the gel
structure is recovered after breakage by an high steady
stress:
STRUCI~RE RECOVERY MEASURING CON ITIONS:
. The samples are studied Eirst after 1 week aging (i.e. when
the structure is obtained) and on aging. (1 month, 2 months,
3 months) at different storage temperatures.
The Carbopol NOP Gels are observed to be rheologically
stabilized within 2 weeks - 1 month period.
. Cell for measuring: Cone-Plate (gap: 53 Mm - cone angle: 4
degrees - (cone diameter: 2 cm)
. The gel structure is broken, first by a steady stress of
400N/m2 during 1'. After an equilibrium time of 10 sec,
storage modulus (G'~ representative of ~he alastic component
and loss modulus ~G") representative of the viscous component
are determined versus recovery time. In oscillating mode:
Measuring Conditions: Torque: 100 micro N.m
Oscillation Frequency: 1 Hz
Thermostatisation Temp.: 20 C
36 -
~ 31 J~ 3 ~ 2301-1767
The moduli are observed to be stabilized around 20' (1200
sec).
RHEOM~T 30 (CONTR~VES~: This apparatus observes the
~otational viscometer principle operating in steady mode to
determine the apparent viscosities on a large range of shear
rates (30-32 values).
PRINCIPLE:
The concentric measuring cell i8 based on a measuring head and
measuring tube rigidly coupled together, the measuring bob
being driven by a DC motor. The braking torque exerted by the
sample results in a change in the motor's armature current.
Translated in viscosity, shear stress and shear rate from
measuring conditions. The data are then analyzed in terms of
Casson Law ( ~ (Pa) = Go
or
Bingham Law ( G = Go +~ ~ )
G = shear stress ~ = shear rate gradient ~ = Viscosity
(Type of Cello Setting B)
Measurement Temp.: 25 C).
RHEOMAT 108 (CONTRAVES): Uses the ~ame principle as Rheomat
30. But only operates at selected shear rate appropriate to
conditions and tested sample.
Viscosity measurement is done after perturbation 30 sec.
SETT NG FOR CARBOPOL-BASED FORMULAE:
Cell: 2 Rate: 1 ( ~= 17.7 sec~)
(Minimum value detectable: 0.3 Po sec)
SETTING FOR_EMERALD SOLUTIONS.
~ 37 -
~ 62301-1767
Cell: 2 Rate: 4 ( ~ = 64 sec-l)
tMinimum value detectable: 0.2 Po sec).
CEL~ 2: Measuring cup diameter: 32.54 mm
Measuring bob: 24 mm.
PHYSICAL STABILITY. The samples are stored in small
glasswares (brown to avoid W influence) and the physical
stability is visually determined on aging at 3 te~lperatures of
storage 4C, 35C, RT.
The sample is considered a~ physically stable when no
presence of syneresis is observed on ageing ~syneresis: liquid
separation from gel in bottom of gla~sware for emerald
structures.)
- 38 -
7~
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o a~ ~ ~ o I
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3xample IV 62301-1767
Forrnulas F-I were formulated according to the following
procedure.
F G H
, _ _ I
ICarbopol 1.0 1.0 1.0 1.0 l
... 1614 l
¦Polygel DX b 0 0 0
I ._ ._ _,
IGantrez O 0 0 0
¦Sodïum ~~~~ 25-.b-- 25.025.0 25.0
¦Silicate
1~47.S%)
¦NaOH (S0%) 4.s 4.5 4.5 ~
¦Good-Rite_~ ___ 7.75 7 75i--75 1¦
¦K-
¦7058N(45%)
.. .. _ _I
Acusol 445N 9.25 7.75 7.75 7.75
. . _ _ ~
l Sodlurn 0 5 5 5
~ Carbonate
Sodium -~ o --- - 6 -- 6 -- ~
Fluoride
Dowfax 3B2 0.8 0.8 0.8 0 8 ------
(45O
_... ... _ ...... _ .. ___
- 42 -
~ 62301-1767
Fatty Acid' ~ 0.1 - 0.1
NaOCï (12%) 10.0 9.2 9.2 10.0
Colorant -- .0-0-3 .00-3 .b0:1 .003 ~-
Fragrance .03 ~ 03 .03 .03
Sodium- 0.i 0 0.1 0
Stearate
_ ._ _ _ _~_
Water Balance ~alance Balance BalanCe
Sodium _ _ 1.5 ~
l Ben~oate
Density1.23 1.32 1.32 _
Spottin-g-~-- 1 0~~--- 1-`---- ~ --- 2 _
Filming~ 2.6 2.0 2 _
Viscosity~ ~800 ~- 3980 3620----- 6500 --
C1 Avg~ 1.04 0.93 0.94 1.05
- _ -
~Fatty acid is a mixture of stearic acid and palmatic acid -
ratio 1:1
2Te~ted according to ASTMD-3566 79
3Tested according to ASTM2-3566-79
~Brookfield HATD Model Spindle #4 20 rpms, R.T. reading taken
after 90 seconds of shear on example.
- 43 -
~r~q 5~ 3~7~
62301-1767
- The above formulas were made by first making an
aqueous solution of the cro~s-linked polymer such as Carbopol
614 at room temperature amd subsequently neutralizing the
polymer under mild agitation at room temperature first with
~he sodium silicate and then the sodium hydroxide. The 7058
polymer was then added with ~lurring followed by the 44 SN
polymer. To the resultant solution was added with slurring
the sodium carbonate then an aqueous solution of the NaF (if
present), then an emulsion of the Dowfax 3~2 and the fatty
acid or sodium st~arate, then the bleach was added with
slutting and finally the fragrance was added with slurring if
A~203 or so~ium benzoate were added, they were post added to
the composition with ~tirring.
The emulsion of the Dowfax 3B2 and fatty acid or
sodium stearate was formed by fir~t heating the Dowfax 3~2 to
a temperature of 70-80C and the powdered fatty acid or sodium
stearate was added to the heated Dowfax 3B2 with stirring.
The formed heated emul~ion was then added to the batch.
- 44 -
