Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
ZC)~1~61
PATENT
Case S 3030
A PROCESS FOR PREPARING A DETERGENT SLURRY AND PARTICULATE
DETERGENT COMPOSITION
BACKGROUND OF THE INVENTION
I. Field of the Invention
The ~nvention relates to preparation of aqueous detergent
slurries w1th reduced viscosity. This invention also relates to
preparation of a particulate detergent and the novel detergent
compos~tion.
Particulate detergent composit10ns are generally prepared by
forming an aqueous slurry of the materlals which form the deter-
gent and drying the slurry. The slurry of the detergent fDrming
composition is generally formed in a apparatus called a crutcher.
IO Since the water present in the slurry must be removed to form a
particulate detergent, the slurry generally has as low a con-
centration of water as permitted by the required handling of the
slurry in the dry1ng operation.
Detergent cDmpositions generally compr~se at least one sur-
factant, detergent bu~lders such as phosphates, male~c acid/vinylether copolymers, silicates, carbonates, salts of nitrilotriacetic
acid, zeolites and the like, fillers such as sodium sulfate,
sodium chloride and various additlves which prevent redeposition,
.'" ~ '. ,.:, .' : . ' ,, -: , :'.
:'.. '.' " -, '' : - .: , - . ' :
.:''' ':'.;", ',.` ' ' ' ~
Z()~ .61
br1ghten the clothes, chelate metal 10ns and the 11ke.
2. Statement o~ Related Art
It 1s known that the 1nclus10n of a small amount of alkyl
glycos1des and part1cularly alkyl polyglycos1des 1n phosphate
bu11t detergent slurry compos1t10ns, reduces the slurry v1scos1ty
so that a h1gher concentrat10n of the non-aqueuous 1ngred1ents can
be 1n~1uded 1n the slurry. U.S. Patent 4,675,127, wh1ch 1s 1ncor-
porated here1n by reference, d~scloses phosphate bu~lt detergent
compos1t10ns conta1n1ng small amounts of alkyl polyglycosides to
reduce the v1scos1ty of the slurry and perm1t 1nclus10n of a
h1gher concentrat10n of the non-aqueous 1ngred1ents 1n the slurry.
U.S. patent 4,536,319 wh1ch 1s 1ncorporated here1n by reference
d1scloses detergent compos1t10ns conta1n1ng alkyl polyglycos~de
sur~actant and a co-surfactant.
W1th the advent of env1ronmental concerns, many locals
have banned the use of phosphates 1n detergent compos~t1ons or
severely 11m1ted the amount of phosphate wh1ch can be present.
One o~ the detergent bu11ders wh1ch has been substituted for the
now banned phosphates 1s sod1um carbonate. The 1nclus10n of alkyl
polyglycos1des alone 1n a carbonate bu11t detergent compos1t~on,
does not have the effect of substant1ally reduc1ng the v1scos1ty
of the slurry. Accord1ngly, slurr1es conta1n1ng h19her propor-
t10ns of water are requ1red so that the detergent slurry can be
handled and transported to the dry1ng apparatus. The 1ncluslon of
the add1t10nal water 1n the detergent slurry reduces the capac1ty
of the dry1ng apparatus and 1ncreases the cost of prepar1ng the
parS1culate detergent compos1t1on.
BRIEF DESCRIPTION OF THE INVENTION
Other than 1n the operat1ng examples, or where otherw1se
1nd1cated, all numbers express1ng quant1t1es of 1ngred1ents or
react10n cond1t10ns used here1n are to be understood as mod1f1ed
1n all 1nstances by the term "about".
It 1s been unexpectedly d1scovered that the v1scoslty of a
2~)(31t6~
carbonate conta1n1ng and partlcularly a carbonate bullt detergent
slurry can be substant1ally reduced by ~nclud~ng ln the detergent
slurry compos1tlon a v1scoslty reducing amount of an alkyl
polyglycos~de and an alkali metal chloride. The v~scos~ty of a
detergent slurry conta1nlng a zeollte can also be reduced by addl-
t10n of alkyl polyglycoslde and an alkall metal chlor1de to the
detergent slurry.
The process for preparlng a partlculate detergent composlt10n
of the present 1nventlon compr1ses formlng an aqueous slurry com-
pr~s1ng per 100 parts of total slurry welght:
1) from 15 to 50 parts by weight of water; and
2) from 50 to 85 parts by welght of a non-aqueous com-
pos1t10n, the non-aqueous composlt~on compr1ses:
a. from about 2% to 50% by weight of an an10n1c surfac-
tant, a nonlonlc surfactant or m1xture thereof;
b. from about 10% to about 70% by we1ght of an alkal1
metal carbonate bullder;
c. from about 0 to about 50~ by we1ght of at least one
supplemental bu11der;
d. from about 0 to about 60X by we1ght of at least one
f111er;
e. from about 0 to about 15X by welght of at least one
add1t1ve;
f. at least a v1scos1ty reduclng amount of at least one
alkyl glycos1de and an alkal1 metal chlor1de;
B. dry1ng the slurry to form the part1culate detergent
composlt10n.
The 1nvent10n also 1ncludes a slurry hav~ng the above com-
pos1t10n and a part1culate detergent formed from the dr1ed
slurry. The slurry 1s preferably dried by spray dry1ng.
Brief Descr1pt10n of the~Draw1ngs
F19. 1 1s a bar graph 111ustratlng a comparison of the
v1scos1ty of carbonate bu11t detergent slurries conta1n1ng alkal1 ~ ;
metal chlor1des, alkyl polyglycoside and a m1xture of alkal1 metal !; '''
chlor1de and alkyl polyglucos1de.
-3- ~ ;
., ' ' '
,
.
:, .' ' : . " ,- :- :, , , . ',:. .. - : ,
Z()~ 61
Flg. 2 1s a bar graph lllustratlng the effect of alkall metal
chlor1de and alkyl polyglucosldes of vary1ng compos1t10ns on the
vlscoslty of a carbonate bullt detergent slurry.
F1g. 3 1s bar graph 111ustrat1ng the effect1veness of alkall
metal chlor1de and alkyl polyglucos1de on the v1scos1ty of a car-
bonate bu11t detergent slurry contalnlng an anlonlc and non10n1c
surfactant.
F1g. 4 1s a bar graph 111ustrating the effect of a1kal1 metal
chlor1de and alkyl polyglucoside on the v1scosity of a carbonate
bu11t detergent slurry conta1n1ng a nonion1c surfactant.
DETAILED DESCRIPTION OF THE INVENTION
All percentages shown are by weight unless otherw1se noted.
U.S. Patent 4,675,127 discloses that the add1t10n of alkyl
polyglycos1de to a detergent slurry conta1ning a phosphate bu11der
substant1ally reduces the v1scos1ty of the slurry. The amount of
water 1n the slurry can be reduced to form a slurry w1th a hlgher
concentratlon of act1ve 1ngredlents hav1ng a v1scos1ty wh1ch stlll
perm1ts handl1ng of the detergent slurry w1th normal handl1ng
equlpment. That 1s, the add1t10n of more non-aqueous mater1als to
the alkyl polyglycos1de conta1n1ng slurry produces a slurry wlth a
v1scos1ty and pumpab111ty not h1gher than a slurry of lower con-
centrat10n not conta1n1ng the alkyl polyglycos1de. However, alkyl
polyglucos1de alone does not substant1ally reduce the v1scos1ty of
carbonate conta1n1ng detergent slurr1es.
Appl1cants have unexpectedly d1scovered that the comblnat10n
o~ alkyl glycos1de and part1cularly an alkyl polyglycos~de and an
alkal1 metal chlor1de substant1ally reduces the v1scos1ty of car-
bonate conta1n1ng and particularly carbonate bu11t
detergent slurr1es. The d1scovery 1s unexpected s1nce the add1t10n ~9
of e1ther alkyl glycos1de or an alkal1 metal chlor1de salt alone
to a carbonate conta1n1ng detergent slurry does not substant1ally
reduce the v1scos1ty of the slurry and, 1n some cases, actually
1ncreases the v1scos1ty. The phrase "carbonate bu11t" detergent
' ,' ' ~''
-4- ~
20(~t6~
slurry refers to a slurry where1n a ma~or port10n sf the bu11der
15 an alkal1 metal carbonate, b1carbonate, sesqulcarbonate or m1x-
ture thereof. A carbonate conta1n1ng detergent slurry 1s one 1n
wh1ch the alkal1 metal carbonate, b1carbonate or sesqu1carbonate
1s present but does not compr1se more than 50% of the bu11der.
The 1nclus10n of alkyl glycos1de and the alkal1 metal
chlor1de 1n the carbonate bu11t or carbonate conta1n1ng detergent
slurry also stab111zes the slurry so that the v1scos1ty o~ the
slurry does not substant1ally 1ncrease over the per10d of t1me
between the detergent slurry preparat10n and transfer to the
dry1ng apparatus. Generally, the v1scos1ty of a detergent slurry
lncreases as the detergent slurry ages. Th1s 1s part1cularly cr1-
t1cal 1n low water slurr1es. Low water slurr1es as they age and
the 1ngred1ents hydrate tend to become granular and can set up as
a sol1d mater1al. The add1t10n of alkyl glycos1de and alkal1
metal chlor1de to the detergent slurr1es of the 1nvent10n perm1ts
the slurry to rema1n flu1d over long periods of t1me. Even when
the v1scos1ty of the carbonate conta1n1ng slurry does not requ1re
reduct10n, the add1t10n of alkyl glycos1de and preferably alkyl
polyglycos1de and alkal1 metal chlor1de 1mproves the texture and
handleab111ty o~ the slurry.
In the past, when 1t was necessary to hold the slurry ~n the
crutcher due to mal~unct10n1ng of plant equ1pment, the slurry had
to be d11uted to prevent sett1ng-up of the slurry as a sol1d
mater1al. The present 1nvent10n precludes such an occurrence.
The present 1nvent10n can be pract1ced as an emergency measure
where1n a m1xture of alkyl glycos1de and alkal1 metal chlor1de
can be 1ntroduced 1nto the slurry and m1xed therew1th to pre-
vent the slurry from sett1ng-up dur1ng a plant emergency.
The add1t10n of alkyl glycos1de and the alkal1 metal chlor1de
to a detergent compos1t10n conta1n1ng a non10n1c surfactant
can a1d 1n homogen1z1ng the/slurry and prevent1ng separat1ng out
or o111ng out of the non10n1c surfactant. Generally, detergent
slurr1es are prepared at an elevated temperature 1n a range of
about 130 to about 175F. The solub111ty of non10nic surfactants
Z~ fi~
generally decreases as the temperature 1ncreases. At the
detergent slurry preparat10n temperature, the non10n1c surfac-
tants, 1f present 1n substant1al quant1t1es, tend to separate from
the detergent slurry and form a d1scont1nuous or o11y phase. The
add1t10n of alkyl glycos1de and the alkal1 metal chlorlde a1d 1n
d1spers1ng the non10n1c surfactant throughout the detergent
slurry.
The non-aqueous port10n of the detergent slurry of the pre-
sent 1nvent10n compr1ses from 2 to 50'~ by welght of an an10n1c
surfactant, a non10n1c surfactant or a m1xture thereof. Prefer-
ably, the surfactant 1s present at from about 8 to about 25% by
we1ght and more preferably from about 10 to 20% by we1ght. Prefer-
ably, the detergent slurry compr1ses an an10n1c surfactant or a
m1xture of an anion1c surfactant and non10n1c surfactant 1n a
rat10 of from 5:1 to about 1:2 on a we1ght bas1s.
Typ1cal an10n1c surfactants wh1ch can be 1ncluded 1n the com-
pos1t~on of the present 1nvent10n 1nclude 11near or branched alkyl-
aryl sulfonates or der1vat1ves thereof (alky1benzenesulfonate,
alkyltoluenesulfonate, alkylpheno1sulfonates and the l~ke). Metal
(espec1ally alkal~ metal) salts of fatty ac1ds (comrnonly referred
to as "soaps"); alcohol sulfates; alcohol ether sulfates; alkane
sulfonates; alkene sulfonates; alpha sulfo methyl fatty esters;
and the 11ke. An1cn1c surfactants are well known 1n the art. The
preferred an10n1c surfactants are alkyl aryl sulfonate salts. ~ ;
The non10n1c surfactants useful ~n the compos~t~on of the
present 1nvent10n ~nclude alkoxylated (espec1ally ethoxylated and
m1xed ethoxylated, propoxylated adducts of pr1mary or secondary
fatty (Cg-C20) alcohols, alkoxylated alkylphenols, fatty alkanola-
m1des, and the 11ke. Non10n1c surfactants are well known 1n the
art and a deta11ed explanat10n of the1r structures and use w111
not be presented here.
M1xtures of an~on1c and~non10n1c surfactants are part1cularly
preferred s1nce the detergents conta1n1ng such m1xtures ma1nta1n
the advantageous and des1rable properties of both the an10n1c and
the non10n1c surfactants.
--6--
., - ~ , : . . .
2S)~9~t61
The alkal1 metal carbonates are present ~n the non-aqueous
port10n of the compos1t10n at from about 15 to about 70% by
welght and preferably from about 30 to about 60~/. by we1ght and
more preferably from about 40 to about 55% by we1ght. The alkall
metal carbonates act as detergent bu11ders. Preferably, the alkal1
metal carbonate 1s sodlum carbonate. The phrase carbonate as used
here1n encompasses alkal1 metal carbonate, b1carbonate, and
sesqu1carbonate preferably the carbonate 1s sod1um carbonate or
b1carbonate.
The non-aqueous port10n of the detergent compos1t10n of the
present 1nvent10n can also contaln add1t10nal bu11ders wh1ch
1nclude the known bu11der mater1als convent10nally employed 1n the
manufacture of powder or granular detergent products. Examples of
such bu11der 1ngrsd1ents 1nclude alkal1 metal c1trates, alkal1
metal s111cates, alkal1 metal nltr110tr1acetates, carboxymethyl-
oxy-succ1nates, zeol1tes and the 11ke. Preferably addlt10nal
bu11ders are present at from 15-40'h by we1ght. The composit10n of
the present 1nventlon can conta1n m~nor amounts of phosphate
bu11ders. However, 1nclus10n of more than 20% by we19ht of the
2û non-aqueous port10n of the compos1tlon of a phosphate bu11der can
undu1y 1ncrease the v1scos1ty of the slurry. The present 1nven-
t10n 1s useful for reduc1ng the v1scos1ty of slurr1es conta1nlng a
ma~or port10n o- a zeol1te bu11der conta1n1ng a carbonate
bu~lder.
The detergent slurry of the present 1nvent10n can con-
ta1n f111er mater1als. F111er mater1als are generally water-
soluble mater1als wh1ch do not adversely affect the detergent
propert1es of the m1xture. F111er mater1als are generally neutral
water soluble compos1t10ns such as sod1um sulfate and sod1um
chlor1de. F111ers can be present up to 60X by we1ght of the non-
aqueous port10n of the detergent compos1t10n. Preferably the
f111ers are present at from 15 to 35X by we1ght and most pre-
ferably from 20 to 30X by we1ght of the non-aqueous port10n of the
detergent compos1t10n. The f111er mater1als are well known 1n the
art. Sod1um sulfate 1s a well known f111er.
ZS~3~Lt 6 ~
The detergent compos1t10n can conta1n up to 20X by we19ht of
at least one add1t1ve. Add1t1ves are mater1als such as ant1-
redepos1t10n agents, fragrances, chelat1ng agents, complex1ng
agents, colorants, foam stab111zers, organ1c solvents, whiten1ng
agents, br19hten1ng agents and the 11ke. Preferably add1t1ves are
present at from 0.5 to about 5%. The add1t1ve compos1t10ns
useful 1n detergent formulat10ns are well known to those skllled
1n the art and wlll not be set out 1n deta11 1n th1s appl1cat10n.
The compos1t10n of the present 1nvent10n must conta1n at
least a v1scos1ty reduc1ng amount of an alkylglycos1de and an
alkal1 metal chlor1de. Generally, from about 0.5 to about 10~ by
we1ght of the alkylglycos1de 1s sufflc1ent to reduce the v1scos1ty
of the detergent slurry compos1t10n when used w1th from about
0.5 to about 10% by we1ght of an alkal1 metal chlor1de. Both
the alkylglycos1de and the alkal1 metal chlor1de must be present
to ach1eve the substant1al v1scos1ty reduc1ng effects 1n the
detergent slurry compos1t10n of the present 1nvent10n.
The alkylglycos1de surfactants su1table for use 1n the prac-
t1ce of the present 1nvent10n 1nclude glycos1des of the formula:
RO-(R10)y~(G)xZb
where1n ; ;
R 1s a monovalent organ1c rad1cal conta1n1ng from about 6 to ~;
about 30 (pre~erably rom about 8 to about 18) carbon atoms; `;~ ,~
R1 1s a d1valent hydrocarbon rad1ca1 conta1n1ng rom about 2 to
about 4 carbon atoms;
0 1s an oxygen atom;
y 1s a number wh1ch has an average value from about O to about 1
and 1s preferably 0;
G 1s a mo1 ~y derived from a reduc1ng sacchar1de conta1n1ng 5 or 6
carbon atoms; and
x 1s a number hav1ng an average value from about 1 to 5 (prefer-
ably from 1.1 to 2).
~0
Z 1s 02M, O C-R2 O(CH2)pC02M, OS03M, O(CH2)pS03M;
R2 1s (CH2)2C02M or CHzCHCO2M; Z can be 02M only if Z 1s 1n place
2n~l~6~
of a pr1mary hydroxyl group 1n wh1ch the pr~mary hydroxyl-bear1ng
. '
carbon atom, -CH20H 1s ox1d1zed to form a - -OM group;
b 1s a number of from 1 to 3x+1 preferably an average of from 0.5
to 2 per glycosal group;
p 1s 1 to 10.
Alkyl glycos1des conta1n1ng Z subst1tuents and the1r method
of preparat10n are d1sclosed 1n Un1ted States Appl1cat10n Ser1al
No. 86,990 f11ed August 19, 1987, wh1ch 1s 1ncorporated here1n by
reference.
R 1s generally the res1due of a fatty alcohol hav1ng from
about 8-30 and preferably 8-18 carbon atoms.
A part1cularly preferred group of glycos1de surfactants for
use 1n the pract1ce of the 1nvent10n 1nclude alkylpolyglycos1de
compos1t10ns 1n wh1ch R 1s a monovalent al1phat1c rad1cal (11near or
branched) conta1n1ng from 8 to 18 carbon atoms; y 1s zero; G 1s a
glucose mo1ety or a mo1ety der1ved therefrom; x 1s a number hav1ng
an average value of from about 1.0 to about 2Ø
The alkylpolyglycos1des can contaln a glycosal molety wh1ch
1s selected from group cons1st1ng of fructose, glucose, manose,
galactose, talose, gulose, allose, altose, 1tose, ar1banose,
xylose, luxose, r1bose and m1xtures thereof. Preferably the glyco-
sal mo1ety 1s a glucose mo1ety.
A v1scos1ty reduc1ng amount of the alkylglycos1de generally
ranges from 0.5 to 10X by we1ght of the non-aqueous port10n of the
detergent compos1t10n. However, detergent compos1t10ns contaln1ng
more than 10~ of the alkylglycos1de are also encompassed wlth~n
the present 1nvent10n. The alkylglycos1de 1s a surfactant per se
and can be ut111zed 1n h1gher amounts. However, su1table v1scos1ty
reduct10n can generally be obta1ned 1n the range from about 0.5 to
about 8X by we1ght. Preferably the alkylglycos1de 1s an alkyl
polyglycos1de and most preferably an alkyl polyglucoside.
The alkal1 metal chlor1de salts when used with the alkylgly-
cos1des 1n the practlce of the present 1nvent10n substant1ally
reduce the v1scos1ty of the aqueous detergent slurry compos1t10n
g
. , ,':
.. . ~, . . . .... . . .. ., .. ~.
Z~
of the present 1nventton. Generally, the alkall metal chlorldes
are present 1n from about 0.5 to about 10X by we1ght of the com-
pos1t10n. Greater amounts of alkal1 metal chlorlde can be present
1n the compos1t~on. Preferably the alkal~ metal chlor~de 1s
sod1um chlorlde, potass1um chlor1de or m~xtures thereof.
It has been d1scovered that ~nclus~on of the alkylglycos1de
and the alkal1 metal chlor1de salt ~n the detergent compos1t10n
can reduce the water content of the slurry up to 30% or more
w1thout a s1gn1ficant 1ncrease 1n the v1scos1ty of the slurry.
Reduct10n 1n the water content of the slurry results 1n a concom-
m1ttant 1ncrease 1n the throughput of the dry1ng apparatus s1nce a
substant1al port10n of the thermal load of a dry1ng apparatus 1s
ut111zed to prov~de the latent heat o- vapor~zat10n for the water
wh1ch 1s removed from the detergent slurry to form the part~culate
detergent compos~t10n. The preferred method of drying ~s spray
dry1ng wh1ch 1s well known 1n the art and w111 not be further
descr1bed here.
The h1gher sol1ds content also tends to produce a dr1ed
detergent hav1ng a h1gher bulk dens1ty. The h~gher bulk dens1ty
perm1ts packag1ng the detergent 1n smaller packages and, there-
fore, reduces packag~ng and sh1pp1ng costs.
The d1scovery of the present 1nventlon ~s unexpected s~nce
ne1ther the alkylglycos~de nor the alkal1 metal chlor1de
alone have a substant1al v1scos1ty reduc1ng effect on the
detergent slurry of the 1nvent10n. Only the comb1nat10n of the
alkylglycos1de and the alkal1 metal chlor1de substantially reduces
the v1scos1ty of the detergent slurry compos1t~on.
The detergent slurry compos1t~ons w~th the reduced v1scos1ty
are prepared by add~ng the surfactants, the alkylglycos1de, the
alkal1 metal chlor~de and any other l~qu~d or minor amounts of dry
lngred1ents to the water for form1ng the slurry. The water con-
ta1n~ng the mater1als 1s ag~tated, and the dry 1ngred1ents wh1ch
are to be added in ma~or proport~ons are m~xed w~th the aqueous
port10n. It takes a short per10d of m1x1ng, generally from 5 to 25
m1nutes, to form a slurry w~th a generally stable v~scosity.
-10-
Z0~1~6~
Dur1ng the 1n1t1al m1x1ng per10d, when the dr1ed 1nsred1ents are
belng hydrated w1th the water 1n the m1xture, the v1scoslty ot the
detergent slurry can vary. After a per10d of about 25 m1nutes of
m1x1ng the v1scos1ty of the slurry generally stab111zes. At th1s
po1nt, a compar1son of v1scos1t1es of slurr1es of substant1ally
the same compos1t1cn and sol1d content w1th and w1thout the alkyl-
~lycos1des and alkal1 metal chlor1de, shows that the v1scos1ty of
the detergent slurry of the 1nvent~on ~s substant1ally lower than
the equ1valent slurry not conta1n1ng the alkylglycos1de and the
alkal1 metal chloride.
In the examples wh1ch follow, the slurr1es were prepared 1n a
600 ml tall form beaker us1ng 420 to 470 9 of non-aqueous 1ngred1-
ents. A LIGHTNIN~ m1xer hav1ng a s1ngle, three blade st1rrer (2
1nches 1n d1ameter) pos1t10ned one half 1nch from the bottom of
the beaker was used for m1x1ng. The m1xer was attached to a
Var1ac~ power control un1t so that the m1x1ng could be done at the
h1ghest poss1ble speed w1thout entra1n1ng a1r 1nto the slurry. A1r
causes the slurry v1scos1ty to 1ncrease.
The beaker was placed 1n a constant temperature water c1r-
culat1ng bath ma1nta1ned at 160F. Water was 1ntroduced 1nto the
beaker, and the surfactants, s111cates, alkyl glycos1des and
alkal1 metal chlor1de along w1th any addit1ves were m1xed wlth the
water, The sod1um carbonate and any other bu11ders and f111ers
were then added to the aqueous m1xture 1n the beaker over a 10
m1nute per10d. The max1mum m1x1ng speed was atta1ned before all
the 1ngred1ents were added. The max1mum m1xer speed was about 2000
rpm as measured by a strobe 11ght.
The st1rr1ng at the max1mum m1x1ng speed was cont1nued for 5
m1nutes after all dry 1ngred1ents had been added. The v1scos1ty
was measured after the slurry had set for 10 m1nutes. The slurry
was then m1xed for an add1t10nal 20 m1nutes, and a second v1sco-
s1ty taken. Some slurries were m1xed for a second 20 m1nute per10d
and some were perm1tted to s1t for 16 hours at 160F, then st1rred
and the v1scos1ty measured. S1nce the v1scos1ty was relat1vely
stable and d1d not change s1gn1f1cantly after the f1rst 20 m1nute
, ", '.
-11- '", ' ,,
' ',':'
~ g 11L6 ~
mlx1ng per10d, the v1scos1t1es reported are shown as the 5 m1nute
and the 25 m1nute m~x1ng per10ds.
The v1scos1t1es of the slurry were measured by an RVT model
v1scos1meter mounted on a Brookf1eld Hel1path Stand. The
Brookf1eld Hel1path Stand slowly lowers the v1scos1meter 1nto the
slurry so that the rotat1ng shearlng sp1ndle descr1bes a hel~cal
path through the test sample. The read1ngs were taken ~n the bot-
tom halt of the slurry to m1n1m1ze the effect of m1xture lost or
crust format10n on the top of the slurry. A m~n~mum of ten
read1ngs were taken on average to get a representat1ve v1scos1ty,
The slurry compos1t10n and the results of the tests are shown
1n the examples and the F1gures.
EXAMPLES
Example 1
The exper1ment reported 1n F1g. 1 was done to determ1ne
the effect of sod1um chlor1de, potass1um chlor1de, alkyl polyglu-
cos1de and a m1xture of alkyl polyglucos1de and sod1um chlor1de
and alkyl polyglucos1de and potass1um chlor1de on the v1scos1ty of
a slurry. The slurry was prepared ut111z1ng an an10n1c surfactant
and sod1um carbonate. The slurry conta1ned 28% water and 72% by
we1ght of the follow1ng compos1t10ns:
Control APG
Percent Percent
NaLAS1 15 15
Na2C03 55 55
Na2S04 23 21-16
Sod1um S111cate3 7 7
APG~ 5002 0 2
KCl/NaCl 0 5
1. NaLAS 1s dodecylbenzene sulfonate sod1um salt sold under the
Tradename C-560 Slurry from V1sta Chemical Company.
12- ~ ~
. ~ .
'; .~''"
2~ fil
2. APG~ 500 1s an alkylpolyglucos1de w1th a 12-13 carbon alkyl
group and degree of polymer1zat10n (DP) of less than 1.4.
3. Sod1um S111cate was 47~ sol1ds with a 1:2.4 Na20/SiO2 rat10
sold under Tradename RU~ from Philadelph1a Quartz
Corporat10n. The sod1um s111cate was used 1n all of the
examples.
A slurry was prepared f1rst w1th no add1t1ves hav1ng the com-
pos1t1cn shown under Control. A second slurry was prepared
subst1tut1ng 5X of sod1um chlor1de for 5% of the sod1um sulfate 1n
the formulat10n. A second formulat10n where1n 5% of potass1um
chlor1de was subst1tuted for 5% of the sod1um sulfate 1n the for-
mulat10n. A fourth formulat10n was prepared 1n wh~ch 2% APG~ 500
was subst1tuted for 2% of the sod1um sulfate 1n the formulat10n.
A f1fth formulat10n was prepared in which 2X APG~ 500 and 5%
sod1um chlor1de were subst1tuted for 7% of the sod1um sulfate 1n
the compos1t10n. A s1xth formulat10n was prepared whereln 2% APG~
and 5% potass1um chloride was subst1tuted for 7% of the sod1um
sulfate. The slurr1es contained 28X water and 72% by we1ght of
the ~ormulat10n.
F1gure 1 clearly shows the unexpected reduct10n 1n the v1sco-
s1ty of the slurry when both APG~ 500 and alkal1 metal chlor1de
were present 1n the detergent slurry m1xture. The results are
completely unexpected s1nce ne1ther an alkal~ metal chlor1de nor
APG~ 500 alone substant1ally affected the v1scos1ty o~ the
detergent slurry.
The values for the v1scos1t1es shown on the bar graph of F19.
1 are as ~ollows:
Y1scos1ty
Bar (CPS)
Control 66,200
NaCl 65,000
KCl 61,000
2% APG 62,000
2% APG-5Z NaCl 8,000
2Z APG-5% KCl 5,000
-13-
Z0(~6~
Example 2
In th1s example, s1x slurr1es were prepared to determlne ~he
effect of alkyl cha1n length and degree of polymer1zatlon (DP) on
the v1scos1ty of a anionic detergent, carbonate bu11t system con-
ta1n1ng 28% water. The slurry 15 noted as conta1n1ng 72% sol1ds
by we1ght. The sol1ds are the port1On wh1ch remains
a~ter removal of water. Not all of the mater1als are necessarily
sol1ds but can be v1scous 11qu1ds.
The slurrles were prepared as descrlbed above and the v~sco-
s1t1es measured after 25 m1nutes of st1rr1ng at 2000 rpm.
The alkyl polyglycos1de was of the formula R0-(R10-)yGx
where1n y was equal to 0, Z was a glucose res1due and x is the
degree o~ polymer1zat1On and R 1s an alkyl group having from 8 to
13 carbon atoms.
APG~ R X
(Carbon
Atoms)
225 8-10 1.5-1.6
300 9-11 1.3-1.4
S00 12-13 1.4
550 12-13 1.7-2
The results o- the exper1ment are shown 1n F1g. 2. F1g. 2
clearly shows that alkyl polyglucos1des, over a broad compos1t1On
range, when comblned w1th an alkal1 metal chlor1de reduces the
v1scos1ty of a carbonate bu~lt detergent system.
The value o~ the v1scos1t1es shown on the bar graph were as
~ollows:
V1sccs1ty
Bar (CPS) ;
.
Control 66,200
KCl 61,000 -
APG~ 225 4,600
APG9 300 4 700
APG~ 500 6,400 ;
APG~ 550 5 400
' :,,. ':
-14-
, . ,
Z~ tfil
Example 3
The example was carr1ed out to show the reduct1On 1n v1sco-
s1ty of an an1Onic/non1On1c surfactant carbonate bu11t detergent
system by the ~ncorporat~on there~n of the APG~ alkyl polygluco-
s1de and an alkal1 metal chlor1de. A control formulat1On and ànequ1valent formulat1On conta1n1ng APG0 were prepared. The for-
mulat1Ons were as follows:
Control APG~
NaLAS1 12 12
LA~ 25 72 4 4
Na2C03 55 55
Na2S04 22 15
Sod1um S111cate 7 7
APG~ 325 0 2
KCl 5
The formulat1Ons were the same except for the subst1tut1Dn of
5% of KCL and 2% APG~ 325 for 7% for the Na2S04. F~g. 3 shows the
v1scos1ty of the control slurry conta1n1ng 37.5% water and an APG
and alkal1 metal chlorlde conta1n1ng slurry conta1n1ng 26% water.
Even though the slurry conta1n1ng APG0 and alkal1 metal chlor1de
conta1ned only 69X of the water 1n the control slurry the v1sco-
was only about 1/6 as h1gh.
The values for the v1scos1t1es shown 1n the bar graph were as
follows:
V1scos1ty
Bar (CPS)
Control 115 000
APG~ 15 500
. l .
The example 111ustrates that 1n a commerc1al operat1On a
slurry conta1n1ng a substant1ally h19her percentage of nonaqueous ;; ;;
mater1al could be processed w1th an 1ncrease 1n the eff1c~ency of the ;
., ~ :,'
-15-
: ''
' "" '
. .. .
Z~)~3~L1L6 1
drylng apparatus. The lower v1scosity would be advantageous 1n a
spray dry1ng process. In add~t10n, the APG~ 1n the formulat10n
alds ln prevent1ng the o111ng out of the non10n1c detergent.
1. NaLAS 1s sod1um dodecylbenzene sulfonate.
2. LAE 25-7 1s an ethoxylated pr1mary alcohol non~on1c surfac-
tant sold under Trademark Neodol 25-7 from Shell Chem kal
Company.
Example 4
The example ~llustrates the effect of APG~ and potass1um
chlor1de on the v~scosity of a non10n1c surfactant, carbonate bu11t
detergent system. The detergent slurr1es were prepared and v1sco-
slt1es determ1ned as descr1bed above. The results of the exper1-
ment are set forth 1n F1g. 4. The figure clearly shows that the
comb1nat10n of APG~ and potass1um chlor1de has a substant1al effect
on the v1scos1ty of the aqueous detergent slurry.
~he values for the v1scos1t1es shown 1n the bar graph were as
~ollows: ~
B (CPS)
Control72.5% Sol1ds 13,700
APG3 50072.5X Sol1ds 8,200
APG~ 50075~ Sol1ds 12,100
The add1tlon of the APG~ surtactant to the non10nlc detergent
slurry compos1t10n helps 1n prevent1ng the non10n1c detergent ~rom
o111ng out or separat1ng from the slurry at the elevated tem-
perature (160F) used for prepar1ng these slurr1es. -
The formulat10n ut111zed was as follows: ~;~
Control APG
LAE 25-7 12 12
Na2C03 55 55
Na2S04 26 19
Na S111cate 7 7 ;
APG~ 500 0 2
KCl 0 5
~''''"'
-16-
Z~)~11 fil
In the formulat10n, a port10n of the sodlum sulfate was
replaced by the APG~ and sod1um chlor1de. The amount of sod1um
sulfate was reduced and the amount of nonaqueous mater1al 1n the
slurry rema1ned constant. The example clearly shows that the
add1t10n of APG~ and an alkal1 metal chlor1de substant1ally redu-
ces the v1scos1ty of a non10n1c carbonate bu11t detergent system.
F1g. 4 clearly shows that a detergent slurry w1th a nonaqueous
content of 75~, had a lower v1scos1ty than the control w1th a
nonaqueous port10n of the slurry of 72.5X by we1ght.
Example 5
Twelve slurrles were prepared conta1n1ng d1fferent percen-
tages of nonaqueous 1ngred1ents and the v1scos1ty of the slurr1es
determ1ned after f1ve m1nutes of h1gh shear m1x1ng and after 25
m1nutes of hlgh shear m1x1ng. The nonaqueous port10n of the
aqueous detergent slurry 1s shown 1n Table I.
The results of the exper1ments are shown 1n Table I. APG~
225 refers to an alkylpolyglucos1de w1th a 9-11 carbon alkyl group
and x 1s 1.5-1.6. The other APG~ mater1als were as set forth 1n
example 2.
-1~7- ;
:' "'
,':
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, .........
zn~l~.fi~
TABLE I
Effect of APG Surfactants on V1scos1ty of Slurrles Contatn1ng
Anlon1c Surfactant and od1um arbonate
Tot~l % Slurry Viscos1ty (Cps)
5O11ds KCl % APG~In1tial* F1nal**
62.5 0 0 S,500 8,000
68.0 0 0 7,500 11,600
72.0 0 0 44,200 66,200
72.0 0 2 34,000 68,000
72.0 5 0 58,000 60,000
72.0 5 2 (225)4,800 4,600
72.0 5 2 (325)4,100 4,700
72.0 5 2 (500)5,~00 6,400
72.0 5 2 (550)5,1~0 5,400
74.0 0 0 63,000 98,000
74.0 5 2 (325)6,200 6,800
74.0 5 2 (500)6,200 13,200
* 5 M1n. H1gh Shear Mix1ng ** 25 M1n. H19h Shear M~x1ng
Compos1t1On of Slurry (Dry Sol1ds Bas1s)
Raw Materlal X :
An1on1c Surfactant (dodecylbenzenesulfonate
sod1um salt) 15
Sod1um Carbonate 55
Sod1um Sulfate 16-23
Sod1um S11~cate 7
Potass1um Chlor1de 0-5
APG~ 500 Surfactant 0-2
-18-
z(lnltfi~
Example 6
The etfect of APG~ and alkal1 metal chlor1de on the v1scos1ty
of slurr1es contalntng an an10n1c and non10n1c surfactant and
sod1um carbonate was determ1ned by preparlng s1x slurr1es hav1ng a
non-aqueous content of from 60.5 to 74~. Potass1um chlor1de and
APG~ were added to these slurr1es and the v~scos1ty of the
slurr1es determined. The slurr1es were prepared accord1ng to the
method set forth above. The compos1t10n of the slurry (dry sol1d)
1s shown 1n Table II.
1~ The results of the exper1ment are set forth 1n Table II.
It can be seen from Table II that potass1um chlor1de alone has a
detr1mental effect on the v1scos1ty of the detergent s1urry.
Potass1um chlor1de alone w1thout APG~ 1ncreased the v~scosity of
the slurry.
In add1t10n, the APG prevented o111ng-out of the nonlon1c
surfactant from the slurry compos~t10n. The prevent10n of the
separat10n of nonlon1c surfactant from the detergent slurry 1s a
valuable attr1bute of 1ncorporat10n of the APG 1nto the slurry
compos1t1on.
' ' ',:
-19-
" ., ~"'' "
. . . ...
zn~l1 fi~
TABLE II
Effect o- APG Surfactants on V1scos1ty o~ Slurr1es Conta1n~ng
An~on1c and Non1On1c Surfactants and odlum arbonate
Total % Slurry V~scos~ty (Cp5)
So11ds KCl ~h APG~ In~t1al* F1nal**
60.5 0 0 34,500 42,000
62.5 0 0 141,000 115,000
74,0 0 0 >400,000
74.0 5 0 Set up sol~d
74 0 5 2 (325) I3,300 15,500 ;
74.0 5 2 (500) 82,000 84,000 - ~ ;
* 5 M1n. H1gh Shear M1x1ng ** 25 M~n H1gh Shear M1x1ng
Compos1t1On o~ Slurry (Dry Sol1ds Bas1s)
Raw Mater1a1 ~ ;
An1On1c Sur~actant (dodecylbenzenesulfonate) 12
sod1um sa1t
Non1On1c Sur-acant 4
Sod1um Carbonate 55
Sod1um Sul~ate 15-22
Sod1um 5~11cate 7
Potass1um Chlor1de 0-5
APG0 Sur~actant 0-2
-20-
,l ~ , " ",', ' -''"' ", ," ,--., ,'" "',' ',', `,,`. ~',~, ,~ ~ , ~ ,'~', "~
Z()O~l'lfi~
Example 7
The effect of a1kal1 metal chlor1de and APG~ on the v1scos1ty
of carbonate bu11t non1cn1c surfactant detergent slurr1es 1s shown
1n Table III. The compos1t10n of the slurr1es 1s shown 1n the
Table. The slurr1es were prepared as descr1bed above, and the
v1scos1t1es measured as descr1bed above.
The comblnat10n of alkal~ metal chlor1de and APG~ reduced the
v1scos1ty of the slurr1es.
-21-
'
: ~.
'
Z5~n~fi~:
TABLE III
E~fect of APG Surfactan
Total % Slurry Viscoslty (Cps)
Sol1ds KCl % APG~ In1t1al* F1nal**
72.5 û 0 lO,~iO0(1) 13,700
72,5 5 0 33,000(1) 29,400
72.5 5 2 7,000 8,200
75.0 5 2 13,000 12,100
77,0 5 2 64,000 43,700
* 5 M1n. H1gh Shear M1x1ng ** 25 M1n. H~gh Shear M1xlng
(1) Non10n1c sur~actant separated out.
Compos1t10n of Slurry (Dry 5011ds Bas1s)
Raw Mater1al %
Non10n1c Surfacant (Neodol 25-7) 12
Sod1um Carbonate 55
Sod1um Sul-ate 19-26
Sod1um S111cate 7
Potass1um Chlor1de 0-5
APG0 500 Surfactant 0-2
-22-
1 fi1.
Example 8
Slurr1es were prepared to determine the effect of degree of
ethoxylat10n of the APG polyglucos1de on the viscos1ty of an
aqueous detergent slurry. The compos1tion of the slurry 1s shown
1n Table IV.
The v1scos1t1es of the slurr1es prepared as descr1bed above
are set ~orth 1n Table IV.
It 1s clear from Table IV that up to about 1 mol of ethylene
ox1de per APG0 molecule can be used.
The examples clearly show that the add~tion of small amounts
of APG0 and an alkal1 metal chlor1de to a carbonate bu11t aqueous
detergent slurry substant1ally reduces the v1scos1ty of the
slurry. The reduct10n 1s 1mportant s1nce a slurry hav1ng a h19her
concentrat10n of non-aqueous mater~als can be prepared and dr1ed
wlth a lower 1nput of heat. Th1s perm1ts the capac~ty of the
dr1er to be 1ncreased or the part1culate detergent compos~t10n to
be prepared w1th a lower 1mput o~ energy per un1t we1ght.
The above examples are for 111ustrat~ve purposes only, and
are not 1ntended to 11m1t the scope of the 1nvent10n.
Typ1cal detergent formulat10ns wh1ch aqueous slurrys can be
1mproved by the add1t10n of small amounts of an alkal1 metal
ch10r1de and an APG0 are as follows:
An1cn1c sur~actant 5-30X by we1ght
Sod1um carbonate 15-70Z by we1ght
Sod1um sul~ate 0-60% by we1ght
Sod1um chlor1de 0-25% by we1ght
Sod1um s111cate 3-25X by weight
Alkyl polyglucosides 0.5-10% by we1ght
An10n1c surfactant-non10n1c surfactant conta1n1ng for-
mulat10ns are becom~ng more popular due to the attract~ve proper-
t1es of the an10n1c and non10n1c surfactants when they are
comb1ned 1n a detergent. A detergent conta1ning an an10n1c
and a non10n1c surfactant would be shown above with the add1t10n
of from about 3-lSX of the non10n1c surfactant. If an all-
non10n1c surfactant detergent 1s des1red, the anlon1c surfactant
-23-
tt1 fi~
can be replaced 1n the above formulat10n by about 3-15X o~ a
non10n1c surfactant. The add1t10n of APG~ and an alkal1 metal
chlor1de to the co~pos1t10n, 1~ the compos1t10n does not already
conta1n an alkal1 metal chlor~de w111 substantlally reduce the
vlscoslty o~ an aqueous slurry of the detergent.
A typlcal an1cn1c-non10n1c formulat10n would be as follows:
X Non-Aqueous
Component Compos1t1cn by We1ght
'
An10n1c Surfactant 8-lSX
Non10n1c Surfactant 2-1OX
Sodlum Carbonate 45-65%
Sod1um S111cate 3-10%
Soap 0- 5%
Carboxymethyl Cellulose 0.25-lX
(ant1redeposlt10n agent)
Opt1cal br1ghtener .25-1.0%
Sod1um chlor1de 2-1OX
APG~ l-lOZ
Na2S04 0-30Z
-24-
, . .
. . ,~ .;,
. ., - .
-
' .' ~ ,~
: ~:
~ABLE IV
'
Effect o~ Ethoxylated APG Surfactants on Vlscos1ty of Slurr1es
Conta1n~ng Anionlc Surfactants and Sodium Carbonate
Total Z Slurry V1scos1ty (Cps)
Sollds KCl X APG (500) Moles E0~nlt1al* F1nal**
72 0 0 0 44,200 66,200
72 5 3 0 12,300 14,000
72 5 3 0.5 1~3,000 22,500
72 5 3 2.0 400,000 --
* 5 M1n. H1gh Shear Mlx1ng ** 25 M1n. H19h Shear M1x1ng
Composltlon of Slurry (Dry Sol1ds Bas1s) ~;
Raw Mater1al %
.
An1cn1c Sur~acant 15
Sod1um Carbonate 55
Sod1um Sul~ate 16-23
Sod1um S111cate 7
Potass1um Chlor1de 0-5
APG0 500 Surfactant 0-3
znn~.1 f;1.
Example 9
Four sod1um carbonate bu11t detergent slurr1es were prepared
contaln1ng sod~um tr1polyphosphate. The slurr1es were prepared as
descr1bed above and the vlscos1t1es measured as descr1bed.
S The comb1nat~on of alkal1 metal chlor1de and an alkyl
polyglucos1de were effect1ve 1n reduc1ng the viscos1ty of the
slurr1es. The addlt10n of potass1um chlorlde alone substantlally
1ncreased the v1scos1ty of the slurry.
The results of the exper1ments are shown 1n Table V.
-26-
: ' '"','',~''
,' ' ~ ,, ,",
'.""' ''~",''"'
. .,, ,;
:
, :, ~.,,, ., ~
:
zn~ fi~
TABLE V
V1scos1ty Reduct~on of Crutcher Slurr1es Conta1n1ng Carbonate,
Sulfate and Phosphate
Compos~t1On (Dry Sol1ds Bas~s)
1 _ 2 3 4
% NaLAS 15 15 15 15
% Na2C3 25 25 23 25
X Na2S04 33 30 30 31
% STP* 20 20 20 20
% S111cate 7 7 7 7
% KCl 3 3
% APG0 500 0 0 2 2
V1scos1ty (72.5% Sol1ds100,000 230,000 23,000 30,000
25 M1nutes)
* L1ght Dens1ty Granular Sod1um Tr1polyphosphate from FMC Corp.
-27-
.", ~"'',,',
,," ~,"',,'
zn(-l1.fil
Example 10
Four slurr1es were prepared conta1n1ng a large proport10n of
zeol1te A. Two of the slurr1es conta1ned sod~um tr~polyphosphate.
All of the slurr1es conta1ned sod1um carbonate. The add1t10n of
alkal1 metal chlor1de and APG~ to the slurr1es reduced the v1sco-
s1ty of the slurr1es.
The results of the exper~ments are shown ln Table VI.
.. . . .
-28- ~ ~ ~
, . . .
:
.. . . .
, .;~ ~ ;
, ' ,",
'. ~ '
. . . - .
. . .
.. .. :,
' ',' ~ "" ~'
~,. ,, . "
" , .: '~"
ZS)~l~fil
TABLE Vl
1scos1ty Reductlon of Crutcher S1urr1es Conta~n1ng Carbonates,
Su1~ates, Zeol~tes and/or Phosphate
ompos1tlon (Dry Sol~ds Bas~s)
''' ;,:., ''
1 2 3 4
NaLAS 15 15 15 15
% Na2co3 25 23 12 10
% Na2so4 28 25 16 13
% Zeol1te A 25 25 25 25
% STP* 0 0 25 25
% S111cate 7 7 7 7
% KCl o 3 o 3
% APG~ 500 0 2 0 2
Vlscos1ty (72.5% Sol1ds 47,000 42,000 280,000 82,000
25 M1nutes)
* L1ght Dens1ty Granular Sod1um Tr1polyphosphate from FMC Corp.
~''
-29- ~:
. ' ' . .'':
:; '' ,' ';"
";' ''''"''"'''
.,, ,,",;,,
,: ' ' ,~"
,, ," ,
",
', ~.~;''.'",'
ZOOl'l.fil
Example 11
Slurr1es were prepared ut111z1ng sulfated and carboxylated
alkyl polyglucos1de der1vat1ves as descr1bed above. The v1scos1-
t1es were determ1ned as descr1bed.
The results of the exper1ments are shown 1n Table VII. The
add1t10n of small amounts of alkal1 metal chlor1de and the alkyl
polyglucos1de to the slurry substantlally reduced the v1scos1ty of
the slurr1es.
The 1nvent10n has been descr1bed by way of spec1f1c embod1-
ments. The spec1f1c embod1ments d1sclosed are not 1ntended to
11m1t the 1nvent10n.
-30- ~
, ' ~;, :;,
";,
:: ' ' '
'".:';'': :.,
', ' '' ,"'
zonlt6l
TABLE VII .
V1scos1ty Reduct1On of Crutcher Slurr1es Us1ng APG~ Der1vat1ves
Compos~t1On (Dry Sol~ds Bas1s)
1 2 3 4 5
% NaLAS 15 15 15 15 15
% Na2C03 55 53 53 53 53
% Na2so4 23 20 20 20 20
% Sl11cate 7 7 7 7 7
% KCL 3 3 3 3
% APG0 83VV-137D* 0 2
26XX-18 2
2VV-88-2 2
XP8E-A96 2
V1scos1ty (72.5% Sol1ds) 92,000 44,500 31,000 53,000 21,000
*83VV-137D APG~ 500 Sul~ated w1th 0.25 equ1valent per APG0 molecule.
26XX-18 APG~ 500 Sul~ated w1th 2.0 equ1valent per APG~ molecule.
2VV-88-2 APG0 500 Carboxylated with 1.0 equ1valent per APG~
molecule. ;
XP8E-A96 APG~ 500 made w1th C12-C13 alcohol (Neodol 23) and has an average DP of 1!3 - 1.4
-31- - ;
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