Note: Descriptions are shown in the official language in which they were submitted.
S ~ 3
~IQUID DETERGENTS AND CLEANING SOLUTIONS:
BUILDER THEREFOR
Backqround of the Invention
This invention relates to cleaning solutions,
especially liquid laundry detergents. In particular, the
invention involves quaternary ammonium silicates as builders
or co-builders for liquid cleaners and laundry detergents.
Formulation problems primarily associated with laun-
dry detergents have changed over the years as a result of
the development and availability of raw materials, govern-
ment regulations, and public taste and acceptance of such
products. One of the most important problems associated
with laundering and laundry products is water hardness and
its geographic variability. Hard water contains calcium and
magnesium ions that inhibit the action of most surface
active agents included in the formulation to perform the
greatest portion of the cleaning job. The usual way of
combating hard water is to include a builder in the
formulation. Such builders function by reducing or elimi-
nating the activity of calcium and/or magnesium ions but do
not interfere with detersive action if said ions are not
present.
Initially these builders were precipitants--they
reduced the activity of calcium and magnesium ions by
precipitation from the washing bath. The activity of the
hard water ions was effectively reduced, but the precipi-
tated salts deposited onto fabrics, turning white fabrics
grayish. The complex phosphates essentially displaced the
earlier builders since they sequester the calcium and
magnesium and maintain the resulting inactive complex in
solution so that deposits do not form on clothes.
Phosphates remained the builder of choice for many
years, since they provided powder detergent with excellent
cleaning properties. Liquid detergents that were built
with phosphates were developed as taught in U.S. Patents
3,001,945; 3,066,104 and 3,208,947. These products could
not compete with phosphate built powders.
Recently many factors have changed washing practices
and detergent formulations. These include new fabrics, new
raw materials, higher energy costs, and government regula-
tions of phosphate discharge into the environment. In this
changing marketplace, liquid detergents have been competing
successfully with detergent powders.
The compositions of these liquid detergents are
limited, because producing relatively stable systems with a
number of components has proved difficult. In general,
these systems do not contain builders, or they contain ex-
pensive organic sequestering agents such as sodium citrate.
In addition, other ingredients known as hydrotropes may be
required to stabilize the liquids. These combinations are
expensive and increase to some degree the BOD load on water
treatment facilities.
In addition, the incorporation of silicate for corro-
sion control, for sequestration of magnesium ions, and as a
source of alkalinity has been very difficult because of
stability problems. U.S. Patents 3,935,192 and 4,388,205
teach the inclusion of silicates in liquid compositions of
either very high pH or very complex, expensive composition.
It is an object of this invention to provide organic
silicates that have not previously been used in detergents
and that provide stable liquid detergents and cleaning
solutions. It is another object of this invention to pro-
vide combinations of silicates that provide competitive
building and cleaning power for detergents. Further objec-
tives of this invention are to provide liquid detergents and
cleaning solutions that utilize these silicates in less com-
plex formulations and that provide corrosion protection.
3 2 ~
Su~mary of the Invention
We have found that certain quaternary ammonium
silicates have structures that differ from alkali metal
silicates sufficiently to allow formulation of less complex
liquid detergents and cleaning solutions. These silicates
that contain 0.8 to 5.0 moles of SiO2 per mole of Q2
(Q = quaternary ammonium ion) can be formulated with combi-
nations of surfactants and other detergent ingredients
without the need for expensive hydrotropes. If appropriate
hydrotropes are included in the composition, the ingredients
and amounts of ingredients can vary more widely. For
example, a higher level of silicate can be used in the
detergent. The silicates that provide such stable liquid
detergents have compositions wherein Q has a molecular
weight of less than 240. These silicates provide builder
properties by enhancing the performance of the surfactants.
They can be formulated with organic sequestering agents as
co-builders. A combination of sodium and/or potassium sili-
cate and the quaternary ammonium silicate also provides
excellent detergent properties.
The liquid detergents or cleaners of our invention
containing our limited number quaternary ammonium silicates
use water as the solvent and/or continuous phase. Some
undissolved materials may be suspended in the liquid, espe-
cially if the material is thickened. Non-aqueous liquids
can also be used as the solvent and/or continuous phase.
Liquid surfactants can be used, and our selected quaternary
ammonium silicates are compatible with such systems.
_he Invention
~ 'he organic ammonium silicates useful in detergents
and cleaners, especially liquid detergents and/or cleaning
solutions, are of limited composition when considering the
class of such organic silicates. U.S. Patents 3,239,521;
3,301,853; 3,346,334 and 3,383,386 disclose a broad range of
organic ammonium silicates. These silicates have not been
formulated into stable liquid detergents and/or cleaning
4 ~ ~ -3~
solutions. Organic ammonium silicates that do form stable
liquid detergents that are effective cleaning materials
should contain 0.8 to 5.0 moles oE SiO2 for each mole of
Q2. The composition of Q is important in providing the
desired silicate. Its structure is as follows:
~ = Rn R'n~ (CH2CH2OH)4_(n + n-)N
When R and R' are methyl or ethyl, n + n' can be 0 to 4. If
R is propyl, isopropyl or butyl n is 1 and n' must be o. In
general, the molecular weight of Q is less than about 240.
The materials are available, as the hydroxides, as articles
of commerce, or can be prepared by numerous well known
syntheses such as the ethoxylation of amines. We do not
believe that Q2 exists in nature, but have adopted the
convention used in the silicate industry of expressing the
silicate compositions as oxides.
The silicate is formed by dissolving a source of
silica in the quaternary ammonium hydroxide. In general,
nearly pure silica sources with associated water that
dissolve in the hydroxide and equilibrate quickly are the
most desirable. Silica gels made by neutralizing or partly
neutralizing sodium or potassium silicate solution are very
useful. Sodium or potassium silicates that have been
partially or completely de-alkalized by methods such as ion
exchange ara also useful. we prefer to use a silica gel.
The quaternary ammonium silicates that conform to
these compositional requirements provide stable cleaning
solutions or liquid detergents when combined with surfactants
and other detergent ingredients. We consider a detergent
stable if it passes all the tests accepted by the manu-
facturers of such products. The detergent must be stable
under storage at room temperature for one year. It must be
stable for one month at 50C or two months at 40C and for a
minimum of 4 months at 1.7 to 4.4C. The liquid detergent
must also be stable for seven freeze/thaw cycles. Each cycle
involves 24 hours at -15C and 24 hours at room temperature.
Stability is evident if there is no phase separation, pre-
cipitation or haze formation.
.
.
We have found that sodium and potassium silicate
solutions do not pass these tests, and that quaternary
ammonium silicates that do not have the compositions des-
cribed hereinbefore do not form stable liquid detergents or
components thereof. In addition, we have found that certain
levels of Si~2 in the detergent are required for stability
when hydrotropes are not included in the formula-tion.
Essentially SiO2 levels of 2.0 to 4.5% by weight provide
the most stable liquids. At SiO2 levels less than about
2.0% the detergents failed at least one test. At SiO2
levels of more than about 4.5% the detergent is unstable.
If the liquid detergent does contain a hydrotrope to provide
additional stabillty, SiO2 levels up to about 10% can be
stable.
The quaternary ammonium silicates of our invention
provide builder properties in that they enhance the cleaning
surfactants in water that contains ions of calcium and
magnesium. The silicates of our invention provide such
enhancement even though they have not been found to seques-
ter calcium and/or magnesium ions. Indeed, the quaternary
ammonium silicates do not appear to reduce the activity of
calcium or magnesium ions in solutions in any way. Despite
this lack of sequestering power, combinations of nonionic
and anionic surfactants with the quaternary ammonium sili-
cate provide cleaning that is competitive with a combination
of the same surfactant system and sodium citrate, a known
sequestrant. We therefore define "builder" as, "any mate-
rial that provides enhancement of surfactant performance,"
and as such, we consider quaternary ammonium silicates to be
builders.
Combinations of the quaternary ammonium silicate and
other materials that do reduce the activity of hard water
ions such as calcium and magnesium in solution can be added
to liquid detergents with advantage. Any material that can
reduce these activities, and can be made stable with the
surfactants of choice, can be used. Since reduced amounts
of such co-builders can be used, some materials previously
thought to be unsuitable because of stability problems at
effective levels can be used. Inorganic phosphates that are
2i ~
stable alon~ with organic sequestering agents provide desir-
able combinations. Especially useful are the various salts
of ethylinediaminetetroacetic acid, nitrilotriacetic acid,
oxydisuccinic acid, mellitic acid, benzene polycarboxylic
acid, citric acid, tartrate succinates and polyacetyl
carboxylates. Aluminosilicate ion exchange materials are
also useful when they are maintained in suspension.
The surfactants useful with the quaternary ammonium
silicate of our invention are any that form stable solutions
upon combination with our quaternary ammonium silicate,
remain stable in storage, and provide the desired cleaning
level. We have found nonionic, anionic and combinations
thereof to be useful. Zwitterionic and cationic surfactants
can be included. Useful nonionic surfactants can be
produced by condensing an alkylene oxide such as ethylene
oxide with aliphatic or alkyl aromatic compounds. The
important property is to balance the hydrophilic and hydro-
phobic properties to provide stability and cleaning. The
useful anionic surfactants include linear straight chain
alkyl benzene sulfonates which are often called LAS
materials, ether sulfates and alkyl benzene sulfonates that
may have branched carbon chains.
The quaternary ammonium silicates of our invention
also provide corrosion resistance that has not been avail-
able with most liquid detergents previously. Bleach
stability is also enhanced by the inclusion of our silicates
in such detergents. The relatively simple liquid detergent
formulations that include our quaternary ammoniurn silicate
can have lower pH values and allow the use of enzymes that
had not been possible in the prior art. Essentially, the
use of the quaternary ammonium silicate of our invention
allows full formulation of a heavy duty liquid laundry
detergent that had not been possible previously.
The liquid detergents containing the quaternary
ammonium silicate of our invention are about equal in laun-
dering performance to commercially marketed liquid
detergents.
Several of these quaternary ammonium silicates
crystallize to form solids at specific mole ratios. These
7 ~ 3
materials can be used as components of powdered or granular
detergents that are dry blended or agglomerated.
Exam~les
The following examples illustrate certain embodiments
of our invention. These examples are not provided to estab-
lish the scope of the invention, which is described in the
disclosure and recited in the claims. The proportions are
in parts by weight (pbw), percent by wei~ht (% wt/wt) or
parts per million (ppm) unless otherwise indicated.
The quaternary ammonium silicates used in the fol-
lowing examples were prepared by mixing silica hydrogel (34%
SiO2) with the various quaternary ammonium hydroxide
solutions at room temperature. The silica gel dissolved to
form water clear solutions. The compositions of these sili-
cate solutions were 2 to 8 moles of SiO2 for each mole of
Q2. They contained about 10 to 17% SiO2.
The stability tests were carried out by preparing a
skeleton detergent formulation of the components which are
most difficult to maintain in a stable liquid. We define a
stable liquid for cleaners and detergents as one that pro-
vides a clear solution upon synthesis and is stable (does
not exhibit phase separation, precipitation or haze) for at
least:
1 year at room temperature (1)
1 month at 50C or 2 months at 40C(2)
3 months at 3.0 1.5C (3)
7 freeze/thaw cycles of 24 hours at(4)
-15C and 24 hours at room temperature
Our skeletal detergent formulation comprises:
Anionic surfactant (linear alkyl sulfonate) 16.5%
Nonionic surfactant (Neodol 25-7 from Shell) 7.5%
Quaternary ammonium silicate (or sufficient ~20.0%
to provide the desired level of SiO2)
Water Balance to 100~0%
Example 1
De~ergents formulated with various ratios of tetra-
methylammonium silicate were tested for stability. The
results are as follows:
Table 1
Stability
(1) (2) (3) ~4)
Mole Ratio SiO2 as designated
(SiO2/Q2O) (%) hereinbefore
4.0 1.50 (1) (2) (3)
4.0 2.00 (2)
4.0 2.98 Pass
4.0 4.77 (4)
3.3 3.00 Pass
Pass means that all four stability requirements were met.
These results indicate that detergents formulated with
[(CH3)4N]2O silicate provide stability at about 3%
sio2 .
E~ample 2
Detergents formulated with trimethylethanol-ammonium
silicate, methyltriethanol-ammonium silicate and dimethyl-
diethyl-ammonium silicate were tested for stability with the
following results:
Table 2
Quaternary Mole RatioSiO2 Stability
Ammonium Ion (Sio2/Q2o) (~)(1) (2) (3) (4)
(cH3)3(cH2cH2oH)N 1.50 (1) (2)
~CH3)3(CH2CH2OH)N+ 4 3.30 Pass
CH3tcH2cH2oH)3N+ 4 1.25 (1) (2)
CH3(CH2CH2OH)3N+ 4 2.00 Pass
CH3(CH2CH2H)3N+ 4 4.00 (4)
(CH3)2(CH2CH3)2N+ 4 Pass
F.~ample 3
Detergents formulated with dimethyldiethanol-,
trimethylethyl- and methyltriethyl-ammonium silicate and
sodium silicates were tested for stability with the
following results:
Table 3
QuaternaryMole Ratio
Ammonium Ion (SiO2/Q2SiO2 Stability
or Sodium or Na20)(%)(1) (2) (3) (4)
(CH3)2(CH2CH20H)2N 4-00 1.5 (2)
(CH3)2(CH2CH20H)2N 4 00
( CH3 ) 3 ( CH2CH2 ) N
Na+ 2.75 l.S (2) (3) (4)
Na+ 3.30 1.5(1) (2) (3) (4)
These results indicate that silicates that do not have
structures conforming with that described hereinbefore do
not form stable detergents under the conditions tested.
E~ample 4
Detergents were formulated with tetramethylammonium
silicate solution and sodium or potassium silicate solution.
The results are as follows:
Table 4
Tetramethyl
ammoniumSodiumMole Ratio
SilicateSilicate~SiO2/Q2oSiO2 Stability
(%) (%) + Na2O (%)(1) (2) (3) (4)
15.1 1.6 3.88 2.98 Pass
12.4 3.1 3.72 2.98 Pass
9.8 4.7 3.69 2.98 (2) (4)
7.1 6.3 3.59 2.98(2) (3) (4)
Tetramethyl
ammonium Potassium Mole Ratio
SilicateSilicate(si2'Q2 SiO2 Stability
(%) (%) + K2O (%)(1) (2) (3) (4)
15.1 2.1 4.00 2.98 Pass
12.4 4.3 4.00 2.98 (3)
9.8 6.4 4.00 2.98 (3) (4)
7.1 8.6 4.00 2.98(2) (3) (4)
These results indicate that some mixtures of quaternary
ammonium silicates and alkali metal silicates provide stable
liquids, but that if the proportion of inorganic alkali metal
is too high instability results.
ExamPle 5
Several detergents formulated with silicates of our
invention and a commercial product were tested for launder-
ing efficiency using a Terg-o-tometer. The conditions were
as follows.
1. Hardness levels of 150 and 90 ppm were used for washing
and rinsing baths.
2. Washing and rinsing were carried out at 105F.
3. Three types of cloth were used: cotton, polyester and a
blend of cotton and polyester. These had standard soils
of clay and dust sebum. Clean cloths were used to test
redeposition.
4. One and one-half grams of each detergent were used in 1
liter of water for 15 swatches of cloth (2 swatches each
of 3 types of cloth and 2 types of soil with 1 clean
swatch of each type of cloth).
5. Washing time was 10 minutes and rinsing time was 5
minutes.
6. The cloth swatches were ironed on removal from the rinse
bath while being protected from contamination. They
were allowed to dry overnight while being protected from
contamination.
7. Reflectance numbers for the front and back of each
swatch of cloth (washed and unwashed) were obtained
using the tristimulus L. scale of a Hunter colorimeter.
The results, expressed as the average of the changes
in reflectance (~L) for identical soil-fabric combinations,
are summarized in Table 5. These results indicate that
liquid commercial detergents wherein the builder sodium
citrate has been omitted and a quaternary ammonium silicate
of our invention substituted provide satisfactory cleaning
when compared to said commercial detergent.
'3 ` .~ ~ f ~3
12
v ~ ~a, u
V V '~
R R o o o o o
V ~ V~
V V V V V V ~ ~
~ ~ ~ ;2 u ~ v ~ 3
O ~ ,s~ Un~ O
,~ ~a 0 ~ ,a tn v 3
u ~) 3
O o ~ ~0 ~ O . cr' ~U ,,~ 0 .~.~
~ o ~ ~ o ~-,~ o o-,~ 0
U ~ ~ ~,Z ~ Z .q
~1 Ul ~1 ~) G0 ~ O 0
~J O ~ ~ N U~
IU vO a~ o ~ o ~ 0
E~ u~ 0
.~ ~
o I ~ u. o ,~ ,~ r~ ~ ,1 a~
1~0 0 0 N N N N N N N N .r~ ,~
0~ 0
. I I ~1 ~ O U~ 0
~1 C~ ~ ~ ~ O~ N a~
0 0 ~ .~' N ~ '1 ~ N N (ll 0
C P. ~ ~1 I`J N N N N 1~ N C
I Sl ~ 00 CO ~ ~ V
V .~1 0 0 N O ~ ,~
~ vO ,~ 0 u~ 0 ~
~ I E n ~ N O U~ O O
E-l 0 N CO ~ ) ~ 0 O
~ Iq ~1 ~ N r~ ) 0
L O, A N N ~I N N ~1 ~1 ~
I n ~7 o c3 o Ir. ~ N O
~ ~.~ ~ 0
~1 o r- o ~ ~ o v
c ~ ~ ~n ~ ~ r~ ~ ~ ~ ~ ~ 0
~ I ~ .c In In o o o o U~ ~n 'I
Jl IU O C1~ N N 0 N a~ In ~ ~ o
N N~ N ~ ~ V
g
~ 00 ~1 o~ ~ ~ æ ~o O ~0 0 ~0
C~ ~ .~, V
O ~N
~_ N :2; o 8 ~
o ~ ~ +
~ O O N o , N
f~i ,, N N m ~r~ 2; N R 0
~ O ~; z N U ^'--
C~ V ~ N m ~ ~ q ~
~ ~rl IJ V ~) 'I ~ _ I_ ' C~ V~ V n~
c" u ~ m oN U
C~ ~U N N 1` ~ Ul N .. S~ 0 ,C~
. O ~ ~ O 0 h ~ v
O O O
U ~ 0 1~ 0
~aY~s'~ 3,
13
EsamPle 6
The corrosion protection afforded by a tetramethyl-
ammonium silicate was tested as follows. Aluminum coupons
were submerged in 1~ NaOH at room temperature. Gassing
developed in a short period of time. Then the silicate of
our invention that contained 3.9 moles of SiO2 per mole of
Q2 was added slowly until gassing stopped. The amount Gf
silicate required provided 2.7% SiO2 which is in the range
of silica required to provide stable liquid formulations.
Example 7
The laundering efficiency of various surfactants with
the silicates of our invention were tested using a Terg-o-
tometer as described in Example 5. The hardness level was
90 ppm. The level of surfactants used was 0.0393% of the
washing bath. The tetramethyl ammonium silicate (4SiO2/Q2o)
was added at 0.026% of the washing bath. The results for a
nonionic surfactant (octyl phenoxy polyethoxy ethanol) are
summarized in Table 6. These results show that the addition
of the silicate of our invention to the nonionic surfactant
provides improved cleaning in most categories. If an anti-
redisposition agent were added to this formulation, the
improvement provided by the quaternary ammonium silicate
would be even greater.
The results for an anionic surfactant (C12-C15-linear
primary alcohol ethoxy sulfate ammonium salt) are summarized
in Table 7. These results indicate that the addition of the
silicate of our invention to the anionic surfactant provides
improved cleaning in most categories. If an antiredisposi-
tion agent were added to this combination, the improvement
provided by the quaternary ammonium silicate would be even
greater.
~ ~ ~ A 9 ~ 53
14
s a
~ r-- ~ ~r ~ r--I a~ L~l Ul .5:
I co o ~
~a I . . ~ ~ . . 3
C o~ oU~
Ln ~ ~ E~u~Ln
s o
~ h
a ~ C ~ E~
o U~o~~1 o U:~ o~ U~
a) . . ~ a . . ~ u~
~) ~ I ~ ~ ~) . I O ~I G
o ~t~ ~ o ~
~2 ~,~ .,
ta 18
a) a .~ s
a~ I ~ ~ s~
U~ ~ ~ U ~ ~ o
aJ a o u,
~ o ~ ~
_ ~ ~ ~ _ ~
_
C ~ ~ D I ~
~ o ~ ~ ~ C o O
.,~ ~ . . l l . . ~ ~,
~) ~ O . ¦ ~~) ~ O h
ta O ~1.--1 rc C~1 ~ ~I Q
O t.) I ~.; t~
I U~ ~1
~ a~
a) Ell ~ c~ I Et`~~1 o c::
~: ~ :~1 o ~ I ~ I o co
~D lul ,~l. . I ul .c . . U\
l ~ a)l ,~ I ~ ~~D r~ ~
O ~ t`l l ~ U~l r~ ~ r ~ rl
r~ I ~ le~ O
r ~ I ` tR
~ ~ ~ ~ a
E~ a
K ~,- ~1 ~ E~ I ~ ~ Ln ~ u
t~l-, . . ~ t~-,l. . a
r~ C o~ o ~ o
I C~ ~ ~ I ~U~ ~ ~ o
l l O
_ ~ ~ O Ll r ~ r5 a
~ J~ ~ ~ Ia~
Ia) o . . a) c . . ~ a~
c ~ ~ ~ I ~, ~ s ~
0~ I I c ~ I I ~ O o
l , 3
a I u~
O ~ ,~ q ,, ~
r5 ~ cn
_ ~ _ ~ S
Ul ~ I
_ ~ I '' a) ~
a) O a O ~ u~ 3
.,~ v~ u~
~1 ~r rc G
(D ~ I t~ ~ a).r~
C C ~ .V Ul
G
(~ ~ ~c5
a~
O ~ t) o ~ ~ o la o
u~
a
s~
r5r5 Ir5 0
~~.q u~
E~ample 8
The laundering efficiency of another nonionic sur-
factant with the silicate of our invention and Zeolite A or
sodium citrate was tested with a Terg-o-tometer as described
in Example 7. The zeolite or citrate was present at
levels of .006% of the washing bath. The surfactant was a
C12-C15 linea. primary alcohol ethoxylate, and the re-
sults are summarized in Table 8. These results indicate that
the combination of the silicate of our invention and a small
amount of a sequestrant provides considerably improved
cleaning.
Example 9
The laundering efficiency of linear alkylsulfonate
(LAS), an anionic surfactant, with the silicate of our in-
vention and Zeolite A was tested using a Terg-o-tometer as
described in Example 8. The results are summarized in Table
9. These results indicate improved performance of a deter-
gent that would contain both the silicate of our invention
and Zeolite A.
~ V , ~
1~
O ~ ~ ~a ~ ~ o a)u,
. . . n5 ~ . . ~ O
O ~ ~ ~ O ~I t~
E~ In ~ ~ ~
~ a) ~ Q ~ In e
o ~ ~ ~ ~ o ~n o ~1 .,1
. . . ~ a:
I ~ ~ ~ a~
~ ~0 ~ O ~ ~ ~
~1 L Ll
a ~ ~ ", o
a ~ ~ ~ a o a~ ~
~ t~ IN ~
_ ~ ~ 1 ~:4 rl ~
co ~D D ~ co O ~ rl
O ~ ~ O~ O 00 ~) Ll
.~ ~ ~ ~ ~ . I ~ ~ ~
~ ~ ~ ~' a) I o ~u
a) a
c~ e~ , e O ~ ,~ ~O
~:: ~ ~1 ~ ~ ~ ~ ~o ~ ~
O~ I U~ Q~ 1~5 Ul Q . . _I
I ~ a)l ,, ",~, ~ ~ a) ~~) a)''
a I ~ ~ ~ ~ ~
E~ l u~ a o
~ O U~ U~ I ~.~1 o ~ O
I ,1 o O o ,_1 I ~ C CO ~r e~ .
I c~ ~n ~ r a c~ u~ ~ ~ ~ O
I I ~
I ~ ~ o ) ~ I ~ ~1 ~ o ,~~ o
~ ~ ~ ~ ~ ~ ~1 J~ O
I a~ o . . . I a) o . . ~a
N~ C ~1 ~1 00 0 U~ o C~
) I ll ~ ) ~1 ~~ L
I I ~
l O O l e ~ a
~ ~ ~
)~ O
~ ~ O .C
_ ~ , ~ C) 3
I ~_ ~ I Z a) rl
.. ~ -
a . a) ~
U~ rl
~) ~)
C, + + ~ C N ~ O~ ~1
~ ~ JJ ~ ,,~ a) t)
I_ ~ H U:~ ~¢ a) ~5~ a)
J ~ ~ a) ,~
U ~U ,l ~ - E~ 3~1
+
o ~ a
os~ ul m o ~
~ ~ ~ ~ ~ o
c~ r~~ + ~ ~ z; _
