Note: Descriptions are shown in the official language in which they were submitted.
:
U~ ' "t
~-~ Background of the Invention
,. , --
.
This invention broadly relates to an impxoved
surface active or cleaning composition which is
expecially useful for removing stains, soil and
foreiyn materials in general from a wide variety of
- substxates.
-A large number cf surface active agents have
been used heretofore in formulating surface active
compositions. Examples include the~lkali metal ~ -
¦ soaps of long chain fatty acids,~the alkali metal so~ps ~ ~
. .. - .. ..
of rosin acids and the derivatives of rosin acids,
l synthetic detergents of the anionic, cationic or-
1~ 15 nonloniF types,and mixtures of one or more of the
foregoing suxface active a~ents. It has also been
common practice to use inert diluents 5UCIl as~
sodium sulfate,~or builders such~as~polyphosphates,
po~lysilicates~or sodium~carboxymethylcellulose in
co~bination with one or more of the foregolng surface
actlvelagents.~ A numb~r o~ ni~rogen-contaLnlng
sequestering a~ents, anti~acterial a~ents, and
enzyme~s capable of remov~ny certain stains have also ;
b n ~dcd t- surfac~ ac~i~e ccn-o-itions ile~etorol-e.
1 0~4~
Many of the commercially available surface
active compositions presently reco~nended ~or general
household and industrial uses are not entirely satisfactory
for a number of reasons. The laundry detergents most widely
used at the present time usually include a phosphorus
or nitrogen-containin~ compound which eitl-ler directly
or indirectly results in a pollution ~roblem. The
phos~hates and nitrogen-cont~ining compounds promote
the ~rowth of microorganisms and alga in streams and
, 10 other bodies oE water into which sewage is introduced
;i and tbis results in an adverse change in the ecology.
~!;. . The presence of a high concentration of sodium sulfate
and other soluble fillers also is undes~rable ~hen the
~ater is to be reused downstream for purposes which
''' . :`
, 15 require a low sodium or solubles content. In instances
:1 . .
~ where laundry or dish washing detergents con~ain
, : :
l synthetic surfactants which are not destroyed by
: . :
~' microorganisms at a sufficient]y rapid rate, the -~ ~
.:
sur~actant concentration in streams tends to increase
2~ to an objectionable level. The enzymes presently
"~
added to~laundry deter~ents are not effective for
removing many stubborn stains and thus do not ~lways
produce the desired results. Also, all o~ the enzyme-
;,, ~ .
producing microor~anisms may~not be killed prior to aclding
the enzymc to the laundry detergent. It has been
reported that the live microorganisms are capable
~ , , ,
,. :
:.,, ~ ~ :. -,: . . ..
" "
of causing lung infections when finely divided particles of the
laundry detergent are inhaled,
i As a result of the above mentioned and other dis-
advantages, the art has long sought an entirely satisfactory
surface active composition for general household and industrial
use which does not re~uire the presence of phosphorus or nitro-
gen-containing compounds, inert fillers, enzymes and the likQ.
~owever, prior to the present invention an entirely satisfactory
heavy duty surface active composition was not available which
overcomes the pollution problems of:.the prior art..and yet is
i capa~le of removing stu~born stains, deeply embedded soil~ and :
other foreign materials from numerous types~of s.ubstrates.
. Thus, the present invention relates to a composition ~ .
of matter for use in removing stains and soil from su~strates
consisti~g essentially of as active ingredients :~
(A) A major proportion by weight of a surface active :~
; - :
agent effective in removlng stains and soil from substrate~ -
washed therewith in water, and :~:.
.
(B) A catalytically effective minor proportion by ~.
weight~of a catalyst,
the surface active agent being present in an ::~ .
;
amount effective to remove stains and soil from sub- I
:
strates washed in water containing the said compositin . ..
;~ and the catalyst being present in a catalytically
,:~ effective amount which promotes the ramoval of the
stains and soil from the substrates,
the catalyst being prepared by a process comprising
` admixing a water soluble alkali metal silicate with
an aqueous medium containing a diissolved substance which
is a source of calcium ion and a dissolved substance
which is a source of magnesium ion,
the aqueous medium containing said dissolved sub-
stances in amounts to provide between about 1 x 10 4
and 1 x 10~1 mole per liter each of calcium ion and magne
sium ion, . : -
. . .. .
^~ the a~ueGus medium containing said dissolved sub-
stances in amounts to provide a molar ratio of calcium
.' .. " :
ion to magnesium ion between about 2.0:1 and 1.0:2.0,
~`1 the alkali metal silicate having an alkali metal :
.
i~ oxide to silicon dioxide ratio between about 0.9:1.0 and
~i less than 2.0:1.0 and being admixed with the aqueo~s medium ~;
~I in an amount of about 0.05-2 moles per liter~ .
reacting the alkali metal silicate with said dis- :.
.I solved substances providing calcium ion and magnesium ion
in the aqueous medium in li~uid phase to produce an aqueous ;l
I suspension of finely divided particles of the reaction
.I product,
admixing a micelle-forming surfactant with the
aqueous medium in an amount to form catalyst micelles ~-.
compr~sing said finely divided particles of the reaction
produ~t upon agitating the aqueous medium, and
agitating the aqu~ous medium containing the finely
~
divided particles of the reaction product and surfactant
1 to ~orm said catalyst micelles.
:J
~
,,.
.
.
_ 4-q -
;, ~
. ~ . . .. . . . .. .. . ..
. DETAILErt DESCRIP~ION OF TI~E INVENTION
INCI.UDING PI~EF~RRE:D VI~IANTS Ti~EREOF
. ~ , .
: .
The improved surface active compositions of
the present invention compris~ ~ surface active
: . ,
s ayent and a catalytic amount of a novel catalyst
to be descrihed more fully hereinafter~ When
desired, the compositions may also contain a bleaching
agent and/or a water softening agent. ~.
~, .
5uitable surface active agents of the prio.r art
may be used in formulating the surface act-ve compositions
,
of the inven~ion. Examples of surface actlve agentsinclude ~.
:: the alkali Inetal soaps of long chain fatty aclds and :
, . . .
.especially the sodium and potassium soaps of fatty acids ~-
containing 14-25 carbon atoms and preferably about 16~
~; 15 carbon atoms. Oth~r surface active agen~ include deter~ents
~l which are not derived directly from fatty acids such as
; ~ synthe,ic anionic, cationic and nonlonic detergents. Speci~ic ~ -
examples of syntheti.c anionic detergents include the
alkali;metal salts of organic sulf~onates or organic
sulfates, and especialIy the al~ali metal salts of high
molecular weigllt alkyl or alk~rlaryl sulfonates such as
sod~um~or potassium dodccyl ben~ene~sulfonate,and the ` ~: :
sodium and potassium sulfatcs of sOraight chain primary ~ . :
alcohols such as sodium lauryl sulfate ar,d oth~r sodiu~
. 25 ~ and~-potassiuDl sulfates of.fatt~ alcohols or products : .
of t~e "Oxo" proccss. Specific: exarnplcs ~f cationic
detergents incluc1e ~he ~uatornary arNnollium ha].ides such
:, ' "~'`? ": ., ' , , '
as benzethonium chloride, and often members of this group
have outstanding germicidal activity as well as surface
active properties. SEecific examples of nonionic detergents
include compounds having a polyoxyethylene or other oxygenated
side chain and the remaindex of the molecule may be derived from ~,
fatty acids, alcohols, phenols, amides or amines.
Further examples of surface active agents are dis-
closed in the section on detergenc~ appearing in the Kirk-
cal Technolo~ (2nd E~ition),
Volume 6, pages 853-895, the disclosure of which is ~
' k~wn~l~n ~t~ls--ia;~t.~;Stil~ additional~-~specificsexampl~es of
$
detergent compositions for industrial or househ~ld use are
found in numerous United States patents, including the following
- ~ . ~ , .
3,031,510 3,119,848 3,222,287 3,382,177
3,043,780~) 3,140,261 3,223,647 3,382,285
3,048,548 3,144,412 3,282,852 3,422,021
3,053,771 3,156,655 3~314,891 3,424,689
3,061,551 3,173,877 3,320,172 3,429,a22
~ 30067,143 3,2~3,955 3,326,807 3,437,697 -
`I 20 3,082,172 3,208,949 3,337,463 3,444,242 ~-
3,095,381 3,101,374 3,349,03~ 3,499,841
~ 3,101~297 3,213,028 3,359,2Q5 3,507,~98
l 3,118,000 3,215,633 3,382,176 -
It is understood that the above surface active
agents are given ~y way of example only, and that o~her suit-
a~le surface active agents may be used. A mixture of one or
more of the a~ove surface activa agents may ~e used when desired.
It i~ also common practice to admix
~ .
'~ :
.~ ;, .
,~ - 6 - ,
~, ; .
. . - :, , : . : . .
' ' ' ~ `' . '
4~
tllerewith inert diluents such as sodlum sulfate, or
- builders such as polyphosphatcs, polysilicates and
sodium carboY~ymethyl cellulose.
.. . .
Water softening agents may be present in the
improved surface active composition. Examples of
water softening agents include washing soda, triscdium
phosphate, sodium metaphosphate, sodium tetraphosphate
and other substances effective to remove calcium and/or
.
magnesium ions from ~ater. Mixtures of water softening
agents may be used. The ~later softening a~ent may be
employed in the usual amount nece~sary to so~ten the
.~ ~ ' ' . .'.
water to be admixed with the surface active composition - ~
, . . , . .:
, at the time of use.
., ~ , .
'~ A bleaching agent also may be ~resent in the improved
~ 15 surface active ~omposition. Examples of hleaching agen-ts
!`' include hydrogen peroxide, sodium or potassium hypoch-
!
~i'! lorite, pero~ide, chlori~e and ~erborat~, calclum
hypochlorite, "Chlorinated lime" and other organic and
.. . ..
inorganic substances exhibiting a bleaching action.
Mixtures of bleaching agents may be used. The 'oleaching
agent may be employed in the usual amount necessary to
result in the desired degree oi bleaching action whell the
surface active agent is admixed with water at the time of use.
_
The active ingredlents of the surface active composi-
tion of the invan~ion, i.e~, the surface active agent a~ the
water softening agent and/or bleaching agent when used, may be
present in a major proportion by weight and the catalyst is
present in a catalytically e~fective minor amount by weight.
The proportions of surface active agents and other ingredients
present in the prior art surface active compositions, including
,,
those disclosed herein, may be used when desired and the cata-
lyst may be added thereto in a catalytically effective amount.
For example, the cataly t may be added to commercially available
solid or liquid surface active compositions such as Ivory Snow*,
~ide* and Thrill*, or the compositions disclosed in the patents
I listed herein. ~he catalyst is present in a quantity to provide
a catalytic amount when the composition is admixed with water
in the recommended ratio to produce a washing or a cleaning
solution. Usually the catalyst is present in an amount to
provide about O~OOOOl-Ool weight percent, a~ preferably -
about 0.0004-0.001 weight percent in the water that is added
thareto at the time of use. Often the catalyst is present in
an amount o about 0.01-1 weight percent based upon the weight
of the concentrated surface active composition. Larger or ~-
smaller amounts may be
. ~
' ': ~. .'
..,. :,:
~; *~xademarks
8 - ~ ~
" ' '
l~, ' ,'' ,~ ,
J;,
:
present as it is only necessary to provide the catalyst
in catalytic amounts in the washing or cleaning solution
prepared by diluting the composition with water.
The surface active composition of the invention
may be used as a general purpose household cleanirlg agent for
removing stains, soil, grease, oil and fGreign materials
in general from textile materials, culinary articles,
walls,floors, furniture and other surfaces. The ~ -
preforMed composition may be admixed with water in the
usual ratios employed in the prior art in the absence
of the catalyst. Preferably, the preforme~ composition
is admixed wlth water under vigorous conditions of
~gitation so as to assure that a uniform aqueous
suspension of the catalyst is formed. Alternatively,the
lS surfàce active compositioll may be prepared a. the time
, ~ of use by admixing the surface active agent with the ~;
; catalyst, e.g., with the aqueous catalyst suspension
produced in the catalyst preparation step discussed
hereinafter. The aqueous catalyst~suspension as
prepared may be diluted with for e~:ample, 1,000 to
10,00~ volumes of water ~ither before, during or
after addin~ the surface active agent.
The surface active composiiion of the inventio
.
.
;4i~10~
may be d;Juted with water and used as an industrial
cleaner for removing hurned-on carbon and for removin3
, . .
oil, grease, dirt, stains and other deposits rom
industrial sl~rfaces in general. In some instances,
better results are obtained when an organic solvent is
present in an amount of approximately 1-30% by weiyht
and preferably about 10-20% by wei~ht of the di~uted
:'' '
aqueous composition. Examples o organic solvents include
normally liquid hydrocarbons,halogenated hydrocarbons,
~, . .
alcohols and ketones, and preferably those having about
6-20 carbon atoms. The solvent may be admixed ~ith the
.j ~ -
aqueous composition to form an emulsion-like mixture,
an~ it seems to have a synergistic effect as heavy
, : . . .
de~osi~s may be removed more qulc~ly and with`les~ ~
effort. Partially saponified fats and GilS such as
:: .
corn oil, soy bean oil, castor oil and cotton seed oil ~-
also aid in removing heavy deposits and may be admi~ed
Z ~ wIth the aqueous cGmposition in amounts approximating ~`
those set out above for the solvent. -~
;; 20~; ~ It is~understood that the surface active composition
Z~ of the invention, when used for a given specific purpose,
may contain the same surface active a~ent that is
recommended for use ~herefor by the prior art.
3 ~ ~ Ho~Jever, the novel catalyst increases the effeotiveness
3 ~ ~
~of a gi~en quantity of the surface~active a~ent and thus
3~
iess may be used, and/or the washing or cleaning time
; may be shortened, and/or the cleanlng or washing action
is enhanced mark~dlyO
When the surface active composition is used for a
specific purpose, then the usual prior art cleanin~ or
washing techniques therefor may be employed and it
,
is not nece~sary to use special equipment. The
sur~ace active comp~sition of the inven~ion may be
simply substituted for the surface active agent used
in the prior art without otherwise cllanging the washing
. or cleaning process e~:cept as noted herein.
,,
- PR~PARATION OF THE CATALYST
The catalyst used ln practicing the pres~nt
inven~ion may be prepared as described belo~7. In the
: . : . :. ,
presently preferred process for preparing an aqueous
suspen~ion of the catalyst, a water soluble alkali
.:
'I , . . . . .
' metal silicate is admixed and reacted with an aqueous
1' . : ;
i~ solution of a water soluble dissolved substance which
is a source of calcium ion and a water soluble dissolved
2a substance which is a source of magnesium ion to produce a
finely di~ided or colloidal suspension of the reaction product
The~aqueous solution contains the;dissolved substances
' I : ' ~ ' ~ ' , . . ~.
initially in amounts to provide between about 1 x 10
and 1 x 10 mo]e per liter each of calcium ion and
25~ ma~nesium ion; preferably between about 1 x 10 and
1 x 10 hlole per liter, and Ior s.till better results -
be w~;en about l x 10 and 6 x 10 mole per liter. Tlle
,; ~ . . .
~- ; dissolved subs~ances should ~lso be presen~ in amounts ~o ~ -
provide a Tn~lar ratio of c~lcium ion to ma~nesium ion
.. ,. - . . ., -. . ~
.~ . , ,., .. ,~} .---,
between about 2.0:1.0 and 1.0:2.0, and pre~erably
about 1.5:1.0 and 1.0:1.5O For best results, ~he
aqueous medium should contain the dissolved substances
in amounts to provide betwecn about 2.5 x 10-3
and 3.0 x 10 3 mole per liter each oE calcium ion
and magnesium ion, and the molar ratio of calcium i.on
to magnesium ion should be about 1.0:1.0, e.g., 2.9 x 10-3
mole per liter of calcium iOII and 2.7 x 10-3 mole per liter
of magnesium ion. The alkali me~a] silicate should have an
alkali metal oxide to silicon dio~ide ratio between about
0~9:1.0 and less than 2.0:100, and preferably between
; . . .: ~
~ about 0.9:1.0 and 1.2:1Ø The alkali m~tal silicat~
,
should be adinlxed with the aqueous medium in ar, amount of
about 0.0C-2 moles per liter, preferably ahout 0.'-1 mole
per llter, and for s~ill better results about 0.2-O.S mole
per liter. ~or bes-t results, the alkali metal silicate should
be an alkali metal meta-silicate having an alkali metal oxide
.1 . .
'~ to silicon dio~i~e ratio of about 1:1, and it should be
; admixed with the aqueous medium in an amount to provide
20 about 0.2-0.3~mole per liter, e.g., about 0.25 mole
per~liter.
Examples of sources of calciwn ion and
magnesium ion for use in preparing the aqueous solution
nclude mineral acid salts such as the halides, sulfa~es,
25~ bisulfates, nitrites, and nitrates of calcium and
magnesium. ~The chlorides are usuall~ the prefcrred
-: .
~ 12
, ~ .
,
;
." . . . ~
~4~
halides, and both calcium al~d magneslum chloride are
soluble and ~ay be used. Magnesium sulfate and
bisulfate are soluble and often are the preferred
~ sources of magnesium ion. Calcium sulfate is only
; 5 slightly soluble in water and usually is not a preferred
- ~ source of calcium ion, but calcium bisulfate is somewhat
more soluble. While calcium and magnesium nitrite or-
nitrate are soluble in water and may be used, thfse
` substances are not preferred in most instances. The~ 10 sources of calcium ion and ~agnesium ion are dissolve~
!~ in the aqueous medium in a~ounts to provide calcium ion
and masnesium ion within the above ranges. Complete
ionization is assumed ~hen calculai:ing the quantities
to be dissolved ar.d any desired order of addition
! 15 iS satisfactory. For example, the source of calcium
. i . :
ion may be added to the aqueous medium before, durin~
or after the sou~ce of ~agnesium ion.
The alkali metal silicate to be admixed with
;the aqueous medium is preferably a water soluble sodium
`~ ~ : , ,.. -
2~ or potassiu.n silicate having an alkali metal oY.-~de
l20~ to silicon dioxide (SiO2) rlole~ratio hetween
about 0.9:1.0 and less than 2.0:1.0, and preferahly ~ -
between about 0.9:1.0 and 1.2:1Ø The best results are
usually; obtained with an alkali nletal metasilicate havins
~ 25 ~an alkali metal oxi-le to silicon dioxide ratio of about ~
.~i, - . ' : -
~ 1. Ilydr~ed alkali metal silicates dissolve ~aster
r: ~ ~ and-~should bc used for best results when the al~;ali
~,
.! ~; ~ '
':' ~ ~ " '. " ' " ' , . ' '. ;' "; ' ' ' . ' ' ' . . ' ' ' ' .
~ metal silicate is added in solid form. In instances
,
; where an anhy~rous alkali metal silicate is used, it
", . .
may be desirable to dissolve it in water and then add
the solution to the aqueous medium. Sodium metasilicate
is preferred and usually a hydrated sodium metasilicate
such as the pentahydrate gives thc best results.
Carbonate ion and/or bicarbonate ion should
~ , .
- not be present in the aqueous medium in suhstantial
concentrations as the calcium ion and magnesium ion are
precipitated in the form of their respective carbonates.
The free carbonate ion and/or bicarbonate ion corcentra~
' ~ tions in the aqueous medium should not exceed about 10
I parts per million by weight based upon the combined
l . weight of the watcr and the ingredients added thereto
;! .
l 15 and for this reason, the alkali metal silicates should
. ~ . . . . . ..
~ be substantially free of carbonate ion and hicarb~nate
~J - ~ :
~! ion. A small amount o~ preciptated calc.ium carbonate ~--
,1 , . .
and~or m~snesium carbon~te may be present in the - ~ :
: aqueous medium provided additional calcium ion and
. ~ . . .
magnesium ion are available to meet the above defined
concentrations.
Distilled water and/or deioni2e~ water are -~
usually pre~errcd over a natural or untreated water when
preparing the aqueous medium.~ In instances where water
25~ ~is~used which contains substant.ial ~nitial concentrations
of alkal.ine earth mctal ions, then this should be taken
:: .~ - .
~ 14 - ~
I
f '~
,,:; . - :
into consideration in calculating th~ amounts oE the
sources of calcium ion and magnesium ion ~hich arc
necessary to arrive at the final concentrations previously
discussed.
An electrolyte which aids in the preparation
, . . .
of colloidal suspensions may be present in the aqueous
,., , :, .
medium at the time of admixing the alkali metal silicate
th2rewith. Examples of electrolytes include those used
.~,; , .
, . . .
;; ~ in preparing prLor art colloidal suspensions such as
the a~kal~ metal halides, 5ul fates and bisulfates.
.. . . . .
Sodium chloride, sodium sulfate and sodium bisulfate are ~
;, . . : ~ .
usually preferred. The ele~trol~te should be added in -
small amounts such as, for example, about 0~00001-0.1 ~ ~;
mole per liter, but often Iarger or smaller amounts
may be present.
. ' . . ... ..
The conditions under which the alkali metal
.~ , . . .
silicate is admixed with the aqueous médium and reacted
with the sources of calcium ion and magnesium ion are
not eritical provided th~ reaction mlxture is maintained ~ ~
,~ ~n~ 20 in the liquid phase. The reaction temperature may be, ~ :
for example, between the freezing point and boiling poinS
;of water under the existing pressure conditions. At
atmospheric pressure, the temperature is usually about
10-90C and often a more~convenient temperature is about
~20-50C. In many instances, ambient or normal room
temperaturc i~ satisfactory.
The~degree of agita.ion is not critical, and ~ -
. ~ ~
~ 15
mild to vigorous agitation may be employed during addition
of the alkali metal silicateO For the best results, thc
aqueous medium should be agitatcd sufficiently to assure
rapid and uniform admixing of the alkali metal silicate.
S After completing the addition of the alkali metal silicate,
, .
when desired the agitation may be continued for a
sufficient period of time to assure complete reaction
.
and aging of the resulting collc,idal suspension, such
;l as for approximately 1-5 minutes to one hour or longer.
Upon admixing the alkali metal silicate with
the aqueous medium, it ta};es on a turbid appearance but ; ~-
in most ins*ances no significant amount of visible
precipitate is formed. The colloidal suspension of the
reaction product thus produced should be strongly
lS basic and may have a p}I value o, for example, appro~ima~ely
j 10-14 and preferably about 11-13, and for best results
,, . .
about 12. In view of this, the initial pH value OL the
aqueous medium containing the dissolved sources of c21ciu~
ion and magnesium ion is of importance and should ~e
.j ,
ao: about 6-9 and prefera~ly abo-lt 7-8.~ When necessary, i-t
is possible to adjust the pH~value of the aqueous mediu~
to~the for~going levels elther beforc,during or after ~ -
addition of t~le alkali metal silicate by adding bases
5 ~
~, ~ such as sodiuni or potassium hydroxide, or mineral acids
~: - . . . .
. ~ :
.. . . .. .. . . . .. .
- IL0~9LlQ~
;; ' ' . ', ' :
such as sulfuxic or hydrochloric acid.
The colloidal suspension may be stored for
several wee~s or longer while awaiting the further
treatment described hereinafter. In instances where
, .
~` 5 th~ colloidal suspension is to be stored over a substantial
period of time, the pH value should be maintained at the
a~ove descri~e~ level and the skorage vessel is preerably
~: .
~` a tightly capped pclyethylene bottle or other inert
plastic container which prevents the contents from
,Ij . ~ , .
absorbing carbon dioxide from the atmosphere.
:-,:
The colloidal suspension of the reaction product
,; - .
, is not suitable for use as a catalyst as prepared and it
,.j , " . . .
should b ag;tated sufficiently in the presence of a
micelle-forming surfactant to form-catalyst-containing
~j , . , - , ,
micelles. The degree of agitation, the length of
the agitation period, and the amount of the m1celle-
forming surfactant that is present in the colloidal
suspension are controlled at levels favorable to the
formation of micelles. For example, the surfactant may
. io: -be present in an amount of about 0.001-0.1 mole per liter
:
and preferably about 0O03-0.07 mole per lite- for most
surfactants. Smaller or lar~er amou~ts may be effective
with some surfactants such as 0.001 mole per liter or lcss, o~
0~2 mole per liter or more. About 0.05 mole per liter often
givcs the best results with many surfactants.
The minimum period of agit~tion and the mini~um
.~: . , . . , . - .. . .
:, . : ~ , ~. . , . - .
~ 17 - ~
,.~^, ~ , . : ,
degree of agitation that are requlred for micelle
formation va~ies somewhat with temperature and the type
and amount of surfactant. As is well understood in this
art, gradually increasing these variants in the presence
of an effective amount of the micelle-forming surfactant
'- will result in micelie formation when the proper lcvcls
are ~eached. As a general rule', longer periods of
agitat1on and/or more vigorous agitation are requ~red
to form micelles at lower températures approachir.g tne
freezing point of the colloidal suspension than at higher
:, .
te~peratures approaching the boiling point. ITI instances
where the aqueous suspension has a temperature OL
. ~ .
approXimately 50-90C., then mild agitation over a period
. . ~ .
of about 10-60 minutes is satisfactory. Often lon~er 03~ . .
.. , - , ~ , . .
'I 15 shorter periods of mild to vigorous agitation ~ay be
~ ~ ~ employed such as from about 1-5 minutes to several hours r ~j
'~ at temperatures varying, respectively, between the boiling
' ' point and the freezing point. When desired, the agitation
. . . . .
may be continued lonrJ after the catalyst-containing
~i ~ 20 ~ micelles~are formed as continued agitation does not see~ ~ ;
to have;an advorse affect.
As~a~general rule, the micelle-~orming surfactants
known in the prior art may be used in practicing the prescnt
; invention. Micelle-forming surfactants used in the emulsion
as ~ polymerlzation~of monomeric organic compounds are disclosed ' -
.:~ . : ~
in the text SYnthetic Rubber, by G. S. whitby, et al, John ~:
Wiley & Sons, Incorporated, ~ew York (1954), and surface active
; agents in general are disclosed on Pages 418-424 o~ khe text
Orqanic Chemistry, Fieser and Fieser, 2nd Edition, Reinhold
Publishing Corporation, ~Tew York, ~ew Yor~ (1950), Examples
of surfactanks disclosêd-in-the abo~e ~exts lnclude ~he alkali :~
metal soaps of long chain fatty acids~ and especially the
sodium and potassium soaps of fatty acids containing about
14-25 carbon atoms and prefèrably about 16-18 carbon atoms,
' 10 and the sodium and potassium soaps of the rosin acids,
!' abietic acid and the derivatives thereof. Other micelle-
;l forming surfactants include fats and oils such as corn oil, ~
~ cotton seed oil, castor oil, soy bean oil and ~afflower oil :
3 which have been fully or partially saponified with alkali metal
;, bases to produce mixtures including saponified long chain fatty .;
¦ acids, the mono- or di-glycerides thereof, and glycerin.. i
I Examples of synthetic micelle-forming surfactants
j include the sulfonates of long chain alcohols prepared by
hydrogenation of naturally occurring fats and oils of the .
above types and especially sulfonated long chain alcohols
containing about 10-20 and preferably about 12-14 car~on atoms, ~ ~:
, the alkali metal salts of the-~,monosulf~nates;-of;monoglycerides
'~ such as sodium glyceryl monolaurata sulfonate, the sulfo- -
I nate~ oi succinic acid esters such as dioctyl
', ,
- 19 ~ "
.
j
0~ ,
sodium sulfosuccinate and the al~ylaryl alkali metal
sulfonatcs. SpeciLic examples of presently preferxed
micelle-orming surfactants include sodium and potassium
- sulforicinoleate, tetrahydronaphthalene sulfonatc,
octahydroanthracene sulfonic acid, butyl naph~halene sulfonic
; acid, sodium xylene sulfonate, alkyl benzene sulfonic acid
and potassium benzene sulfonate.
Sulfated long chain hydroxycarboxylic acids
containing about 14-25 carbon atoms and prefer~hly about
. . .
;~ 10 16-18 carbon atoms, and sulfated fats and oils containing
j hydroxycal-boxylic acids of this type produce eY.ceptiona]ly
` good micelle-forr.ing surfactants. At leas~ 25% of the
,.
hydroxyl groups and preferably at least 50% should be
. , .
sulfated, and up to 95-100% may be sulfated. It is usual]y
` 15 pre~erred that the sulfated oils and/or long chain
:~ . .
; hydroxycarbo~ylic acids be neutralized wi~h an alkali metal
base, and that the corresponding alkali metal salts be -
added to the colloidal suspension in tne form of an aqueous
solution. The aqueous solution may contain at le~st 25%
, .
of water and preferably at least 35-40% b~ weight. Much
larger percentages of water may ~e present when desired
such as 75-80% or more by weight.
A very active cata]yst is produced when using
.1 . .. .
~ sulfated castor oil as the micelle-forming surfactant
.~:1 , . .
J.:: ~ ' 25 ~Turk~y Red oil.~ Sulfated castor oil which has been ~
purified sufficiently to be of U.S.P. or medicinal grad~ ~ -
; :.
- ~ :
.
.
4~
.
produces an exceptionally active catalyst. For the best
results, the castor oil is reacted with about an ~qual
weight of concentrated sulfuric acid (e.g., 2~/o by weight)
at a temperature of approximately 25-3GC~ The mixture
may be xeacted for about two hours ~ith stirring and is
then neutralized with sodium hydroYide solutiorl. The reaction
mixture sep~rates into three layers, i.e., an upper layer
which is a water solution, an intermediate or oily layer,
, . . .
and a white curdy precipitate. The intermediate oily
.
layer is separated from the upper and lower layers, and
maybe added to the colloidal suspension as the micelle-
forming surfactant in an amount, for example, of 0.001-
~i 0.1 ~lole per liter, and preferably about 0.005 mole per liter.
The activity of the ca.alyst may be increased
~i~15 very markedly by cooling the aqueous catals~st suspension
to a temperature approaching the freezin~ point such as
iabout 0-10C., and then warmin~ over one or more cycles.
,,For best results, the aqueous catalyst suspension should
.. .. . . .
t be frozen and thawed over onc or mo-e cycles. The reason-
, : ,."., :,. .
ii~ 20 for the increased catalytic activity is not fully
understood at the present time but cooling and then
~ warmin~ the aqueous catalyst suspension seems to increas~
q~ ~ the concentration of th~ catalyst-containing micelles
and/or~increases the catalytic activity thereof,
The aqueous suspension o~ the catalyst contains
; ~ a relatively s~all percentac;e by ~eight of th~ active
~ - ; . ,
catalyst ~s produced. When desired, it n~ay be concentrated
by eval)oratin~ a portion oE the wate~ to produce
; .,, : ~, - ~ ,, :,
~ 21
LQ~ .
concentrated liquid catalyst suspension which may be
stored and used more conveniently. It is also possible to
prepare a dry catalyst concentrate by evaporating substantjally
all of the water. The preferred method of producing
the dry catalyst concentrate is by flash evaporation
using a technique analogous to that employed in preparin~
powdered milk. The catalyst concentrates produced
upon partial or complete evaporation of the water content
of the intially prepared aqueous suspension rnay ~e
reconstituted by addition of water wit'n little or no
.. . .
~ loss of catalytic activity. Preferably, the water is
,, .
added to the dry catalyst concentrate under sufficiently
~ ~igorous conditions of agitation to assure that the
f catalyst micelles are resuspended and uniformly distrihu~ed.
. .
'~i lS The aqueous catalyst suspension may be used as
1~ produced in practicin~ the inventlon, but preferably it
,~ is diluted witli approximately 100-10,000 parts by weig}lt
~ ~ of water and then used. For better results, the catalyst
`~ suspension should be diluted iYith about 250-2,000 parts
. ~ . . .. .
;by~weight of water before use, and for best results it ~ ~ -
~ should be diluted with about 500-1,000 parts by ~eiyht of
t~ water before use. The surface active agent may be add~d
thereto~when-desired as previously discussed. Alternatively
the~dry~Gatalyst or liquid catalyst concentrate may be
~admi~xed;with water an~/or the surface active a~ent to
j ~ ~ ~ . , . - .
~ 22 :~
. ~ . . : .
.~ .1 ~ ' ; : .
: :-:, :: :. ., :;: . :
-- provide an ef~ective catalyst concentration in the ~uantities
previously discussed. The weight of the catalyst is
calculated on a dry solids basis, i.e;, the weight of
the catalyst ingredients in the aqueous suspension as
produced after removal of the water.
:; . . .
The invention is further illustrated by kh.e
~ .
follo~Jing specific exam~les.
EXA~I.E I
'`'`` ' . ' ' ''
This example illustrates one present]y preferred
process for preparing the novel catalyst used in practicing
; the invention.
, Anhydrous calci~lm chloride in an amount of
0.66 ~ram and magnesium ~lfate heptabydrate in an amount
;l of 1.32 grams were dissolved in two liters of deionized - ;i
l 15 wa~er with stirring and ~;~arming until solution was complete.
: ~ .: . . .
Then 95 grams of sodium silicate pentahydrate having a
molecular ratio of sodiu~ oxide to siii.con dloxide of ~ `
1 were added to the ~olution wlth s~tirring and cont nued
warming to produce a white colloidal suspension of ~ne ~ -
l ~ 20 reaction product.
`" ~ After setting for 10 minutes, the colloidal
suspension was heated to 80C. and sulfated castor oil in
an amount of 50 grams was added with stirrir.g. The ~ ~;
~ . aver~e molecular weight of the sulfated castor oil was
,5 ' 25 940 and it contain~d 50~ o~ water. The turbidity
lessened somewllat as the co]loidal suspension was hea~ed
t 80-90C. for one hour with vi~orous stirrin~ ~o
- ~3
~: ~
~ - ~
.~a4~0~
.
produce catalyst micelles. The aqueous suspension
of catalyst micelles thus prepared had a viscosity
similar to that of water and it was used as the catalys~
in certain Examples as noted hereinafter.
A dry or solid catalyst concentrate ~as
prepared in a further run by evaporating water from the
~' .
initially prepared aqueous catalyst suspension. The
resulting dry catalyst concentrate was resuspended in
water and there was no substantial loss of cataly'ic
10 acti~ity. I~ still other runs, the ca~alytic activity
of *he aqueous suspension of catalyst as initially
,~:
prepared, the diluted aqueous suspension of catalys-t, ~
. .
and the reconstituted aqueous catalyst suspension was ~-
enhanced by freezing and thawing. ~-
,
EXAMPLE II. -~ -
This example illustrates the preparation ~
,~
~ of additional catalyst suspensions.
. :.
Five suspensions of-the catal~rst were prepared
~` from~the same ingredients as used in Example I and
following the general procedure~of Example I. The
ratlos of lngredients were varied~as follows:
Inqredient ~ mount o~ Ingredient
Run 1 - Run 2 Run 3 Run 4 Run 5
Deionized water 2 11.5 1 1.5 1 1.5 1 0.25
25 ` CaC12 0.66 g- 0.5 g 0.5 g 1.0 g 0.5 ~ -
, - ,.:
~ MgSO~.7~2O ~ 1.32 g~1.0 g 1.0 g 2.0 g 1.0 ~ ~
- . ~ . . .. . ,. ~
Na2SiO3 5H20 165 g 132 g 71 g 185 g 71 g
Sulfated Castor 100 ml 150 ml 150 ml 200 ml 15V ml
oil (approximately
50% by weight H20)
The catalyst suspensions prepared by the above ~ive
.
runs were used in certain examples as noted hereinafter.
Example III
This example illustrates the use o~ the catalyst pre~
pared in accordance with Example I in treating ~abrics.
A standard household automatic washer ~9 pounds
capacity) was used in obtaining the data for this example.
The recommended washing cycle for the stained ~abrics was
also used. ,
In one run, an attempt was made to remove chocolate
stains from a cotton shirt using commercially available
.j~ , . .
, laundry detergents (laundry detergents sold under the trademar~s ~ -
¦ Biz* and Tide-XK*) and an oxidizing agent (Chlorox*). The
chocolate stains were not removed by this treatment~ Howe~er,
chocolate stains were easily removed in a second run when
;'l , : ,
J 20 washing with a catalytic amount of the diluted catalyst
suspension ;~
, ~.,.
~i
. ; ;
'.'1! *Trademarks
.
' .
' '
n~
prepared in accordance with Example I.
In subsequent runs, six Eluid ounces of the cata-
lyst suspension prepared in accordance with Example I were
added to the washer along with the recommended amount of cold
water, laundry detergent and stained clothing. Blood, grape
juice, catsup, grease and grass stains were easily remo~ed.
It was not possible to ramove stains of this type whsn using
.~ ;
.
only a laundry detergent and Clorox*.
The fabrics washed in water containing the catalyst
suspension were softer and brighter. Thus, the catalyst sus-
~ension is useful as a fabric softener and brightner as well
as a stain remover.
^1 Example IV
The general procedure of Example III was repeated in a
series of runs with the exception of reducing the amount of -~
laundry detergent to between one half and one eighth of the
recommended amount employed in Example III. It was found that
only one-fourth as much laundry detergent was required when
washing clothing in the presence of a catalytic amount of the
catalyst.
~;,1 Example V
The general pror~eduras of Examples III and IV were
repea~ed in a series of runs with the~exception~of u~sing the
catalysts prepared in accordance with Example II. The
atalysts o~ Example II wera found to be active and produced
comparable results.
, ~ ' . ''
*~rademarks ~ ~ ;
26 -
o~
Example VI
A catalyst suspension was prepared in accordance
with the procedure of Example I. The water content was removed
by evaporation to produce a dried catalyst concentrate.
The dried catalyst concentrate and commercially avail-
able laundry deterg~nt (Tide~XK~) are admixed in proportions to
pro~ide 1 weight percent of the catalyst in the resulting
catalyzed surface active composition. A portion of the ad-
mixture is tested following the general washing procedure of
Example III. The admixture is as effective in washing soiled
clothing as separate additions of catalystJandidet~er~ent.
Exam~le VII -
. , ., - _ , ~ :, -
A second portion of the admixture of Tida-XK*
and dried catalyst prepared in Example VI is stirred in water to
produce a soap solution. The seap solution is tested as a
general household detergent to remove stains, dirt and grease
from woodwork, linoleum, painted surfaces and procelain enamel.
The catalyst is omitted in a second run which was ~ -;
1 otherwise identical for the purpose of obtaining comparative
i data. The catalyzed soap solution is much more effective and
removes the stains, dirt, grease and other foreign materials
faster and with 1 2SS effort than the soap solution which does
not contain the catalyst.
'~
- 27 -
*Trademarks
.
~xample VIII
A catalyst suspensi~n was prepared following
~he general procedure of Example I and then diluted
with 1,000 volumes of water.
White c~oth was treated in accordance with
. .
prior art practiccs to prepare a standard stained and
- soiled cloth for use in testirlg the eEfectiveness o~
7 ' laundry de~ergents. The clotll was saturated with an
admixture of soiI, mustard, catsup, milk, grape juice,
~t
vege~able oil, mineral oil and bacon grease. The
,~ . .
admixture was dried and the initially white cloth too~
on a dark brown color. ~ -
~; :
`. ~ A portion of the stained and soiled cloth was
~ -
.; . wash~d in the diIuted catalyst suspension prepared above
using the recon~lended ~nount of~ordinary laundry soap.
A standard household automatic washer and ~he recommende~ -
;~j ; washing cycle were used.
A secund portion of the stained and soiled
~;~ cloth~was washed in so~t tap water to which had been add~ -~ the reconunended amount of a com~lercially available heavy
duty~laundry detergent. The~manufacturer considered the~
laundry~detergent~to be the best ~ormula available. The
wàsher,~washing cyclej/ and other variables were the same
in ~he two runs with the cxception o~ using laundry soap
25 ~ and cataiyst in;tl-e ~irst run, and the heavy auty
laun~ry~deteryent without catalyst in the secoJId run.
28 -
Following washing, the two test cloths were
dried and examined in daylight. The cloth washed in the
first run with ordillary laundry soap and dilut~d catalyst
suspension was substantially the same color as the
original white cloth. The cloth washed in the second
run with heavy duty detergen~ without catalyst was
somewhat lighter in color than the stained and soiled
cloth, but markedly darker in color than the washed cloth
from the first run. It was obvious that the stains and
, 10 soil were not removed effectively from the cloth washed
; in the second run, whereas they were in .he cloth washed
;i~ in the first xun. - ;
~i Example IX -
`~ A catalyst suspension wa-i prepared in accordance
il . . . .
l; ~ 15 with Example I and the water content was evaporated to
,
`l produce a dried catalyst concentrate. ,
The dried catalyst concentrate is a~nixed with
~J
a commercially available dish washing detergent in an
1~
amount of 1% by weight.
20 ~ The resulting a~nixture of catalyst and detergent
is used in one series of runs to wash soiled~dishes wi~h
`drled food partlcles thereon in~a standard automatic
dishwasher. In a second series of runs which were
otherwisie identical, the ca~alyst was omitted and only
f ~ 5 the original det~rgent formulation is used. The
,~: ,~ ~ , . . .
recommended amount of detergent and the recommended ~ ~ -
washing cycle was used in each series Qf runs.
- 29
.: :
. . .
: ~ . ~ ~ .: . ,
:. : ;~ ,
: .
The dishes washed in the serics o runs
. . ..
~ using the catalyst were much clcaner and were free of
: food particles. The dishes from these runs also dried
without leaving behind a noticeable soap film.
The dishes ~lashed in the absence of the
catalyst had dried food particles still adhering tG
the surfaces. The dried dishes also had a noticeable
film thereon.
. .: . . ' ' ' ' ~
,` : ' . : '
- ' ' . ~ . ~
:~ .
.' ' ' , ,' . . . .
. .
'~ ` ; ' :' '
1, ' ' . ' . , ~`' ' ' . . '
1,: . . ' ~.::
' '. ',
~ 30
, . . . :
.
