Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~039608
In the production of powdered washlng and clean~lng
agent composltions, non-lonic ~urface-~ctive compounds (~on-
ionlc~) are ~requently u~ed in addition to or instead of the
anionic surface-active compounds. Accordlng to a technically
preferr~d productlon method, the aqueous mixture o~ the co~-
po~ents of the pr~paration 1~ trans~ormed lnto a pourable
powder by hot drying, partlcularly by atomization in a hot
gas. Since the Non-lonlcs are ~tea~-volatile~ a part thereo~
18 108t in the above hot dryin~. Thi~ 1~ undesirable for
economical ~nd ecological rea~ons. In order to a~oid tbese
lo~es, it i~ desirable to lncorporate the No~-ionlcs into
a preli~lnary m$xture by spray~ng them on powdered sub~trates,
~hich represent themselves conventlonal component~ Or solid
~ashing and cleanlng a6ent compo~itions, such a~ ~odium ~ri-
polypho~phate, sodium perborate or ~odlum sulfate. The~e
preliminary mlxture~ can then be admlxed wlth the remslnder
. .,
o~ the co~po~ente. However, the premixes obtained in this :
- m~nner have un~atis~actory po~der qualltie~ the Non-ionics
portlon in the pre~x e~ceeds 10% by weight of the total
premix. Iher~iore, wlth a premlx portion o~ about 50% by
weight in the total deterg¢nts, which 1~ conventional, only
5% by weight of Non-lonlcs can be l~corporated 1R the end
product.
It 18 also known to ~mprove the powder quallty of
the~e premixe~ by tbe addition o~ other 3ubstrates wlth a
large active surrace area, such a~ hlghly dlsper~ed slllca,
but in this matter, wash-lnactlve ball~t materlals ar~
;: introduced lnto the wa~hlng compo~ltion. In addition, sodlum
trlphosphate as a ~olid sub~trate ~h~uld be avoldsd, llkeNlse
ior ecologlcal rea~on~.
, ............................................................ . . .
.
,: . . . . ... . . ... .
`` ~039608
In cope~ding, commonly asslgned Canadlan Patent Application
Serial No. 197,628, filed April 16, 1974, an improvement in the
process of washing and ble.aching textiles is described wherein
the soiled textiles are immer~ed in an aqueous solltion containing
a water softening agent for a time sufficient to disperse or dis-
solve the soil from said soiled textiles into said aqueous solu-
tion, separating said aqueous solution and recovering said tex-
: tlles substantially soil-free. This improvement consists of
using at least one finely-dispersed water-insoluble silicate com-
10 pound containing at least some combined water and having a cal-
. cium binding power of at least 50 mg CaO/gm of anhydrous active
substance and the formula on the anhydrous basis
(M2jn)X Me23 (SiO2)y
. where M is a cation of the valence n, exchangeable with calcium .
. x is a member of from 0.7 to 1.5, Me is a member selected from
the group consisting of aluminum and boron, and y is a number
from 0.8 to 6, as said water softening agent.
The calcium binding power of the silicate compounds can
be as high as 200 mg CaOlgm of anhydrous active substance (AS) ~:
. 20 and preferably is in the range of 100 to 200 mg CaO/gm AS.
.: The cation ~ employed is preferably sodium. However, the
same can also be totally or partially replaced by other cations
:` exchangeable with calcium, such as hydrogen, lithium, potassium,
ammonium or magnesium, as well as by the cations of water-soluble
organic bases, for example, by those of primary, secondary or ter-
tiary alkylamines or alkylolamines with not more than 2 carbon
a~oms per alkyl radical, or not more than 3 carbon atoms per
alkylol radical.
2 :
.
;`
:
: db/n'~>,
~039608
An ob~ect of the present invention is to develop
- a preferably phosphate-free or low-pho~phats pourable deter-
gent containing non-ionl~ surface-active compounds, which do
not have the above-described disadvantages and where a 1088
o~ Non-ionics 1R avo~ded in the production.
Another bb~ect of the present inventlon i8 the
d~elop~ent o~ a pourable washing agent composltlon compri8ing
a premix powder component and optionally a ~econd powder -:
component obtained by hot drylng of an aqueous composltlon
containlng conventional heat-i~sen~itive washing agent
- component~, conslsting essentially Or
.~' (1) from 30~ to lO0~ by wsight o~ a prem~x powder component
con~ist~ng es~entially of
(A) at lea~t one rinely-dispersed, ~ater-in~olubl~ 8ill-
- cate compound containing at l~ast some comblned
; ~ater and ha~lng a calclum bindlng pow~ of ~t least
~; 50 mg cao/gm of anhydrous active substa~ce and the r~rmul~ o~ the anhydrQua ba~s
- (M2~)X ~e203 (S102)y
where M i~ a catlon of the val~nce n, exchangeable
with calcium, x ~ a number of from 0.7 to 1.5,
18 a ~ember ~elected from the group con~istl~g
Or alumi~um and boron, and y i~ a number from 0.8
to ,6., which sllicate compou~d can optional~y be
:'. '
partly replac~d with hi~hly disper~ed ~ilica in an
amount Or not more than ~% by weight of the ~eight
of t}~e premix,
(B) from 0 to 80% by weight oi the premix Or bleaching
oomponent~ ~elected :ero~ the eroup cQnsistlng of
inorganic peroxyhydrate co~pound~ eapable ~ ~upplylng
, ~
- 3 -
' ! ' , .
'
' " . ' ' .
22 in water, ~ 6Pc~ ated activators ~or per-
compounds, powdery stabil~zers for percompounds and
mlxtures thereof;~
(C) non-ionic surface-active compounds f~nely dlstrlbuted
. on and throughout component (A) or the mlxture o~ :
. components (A) and (B);
where ~,he mix ratlo of component (A) to component (C)
" i8 in the ratio of lO:l to 1:3 and at least 20~
: of said premix are component~ (A) and ~C) together,
the final mix ratio of the components being selected
whereby the premix i~ a pourable powder; and
(2) from O to 70% by weight of a ~econd powdery component
obtained by hot drying of an agueous composition eontaln-
ing conventional heat-~nsensltive washing agent component~.
~ Another ob~ect o~ the present invention i~ the
.- development of a pourable premix po~dery component for ad-
: m~xture in washlng agent compo~itions consisting essentially
of
(A) at least one finely-dispersed, ~ater-insoluble 8il~-
. cate compound containing at least some combined
water and having a calcium bindlng power of ~t least
50 Lg CaO/gm of anhydrou~ active ~u~stance and the
formula on the anhydrous ba~is
(M2/n)x M~203 (si2)y
~: where M is a cation o~ the valence n, exchangeable
wlth calcium, x $8 a number of from 0.7 to 1.5,
., - .
M~ i~ a member selected from the group consistlng
. . o~ alum~r~um and boron, and y i~ a number from 0.8
to 6, whlch ~ilicate comp~und can optionally be
3 partly replaced with highly disper~ed siLica in an
-- 4 --
. .
~` ~1039608
amount Or no~ more than ~ by weight of the ~elght
the premix;
(B) rrom 0 to 80% ~y weight o~ the premlx o~ bleaching :
components selected from the group consisting of
inorganlc peroxyhydrate compounds capable of supplylng
. .
H202 in ~ater, powdery acylated actlvators for per-
compounds, powdery stabil~zers ~or perc~mpounds and
;~ ~xture~ thereo~;
(C) non-ioDlc surface-active compounds finely distrlbuted
on and throughout component (A) or the mlxture o~
. components (A) and (B3;
where ~,he mix rat1o of component (A) to component (C) ~ -
; 1~ in the ratio of 10:1 to 1:3 and at le~st 20%
; o~ ssid premix are components (A) and (C) together,
: the ~inal ~ ratio o~ the component~ being selected :
. whereby the premix iB a pourable powder.
m ese and other ob~ects of the lnventlon will
~ . becom~ more apparent as the descriptlon thereo~ proceeds.
::: The above drawback~ have been overcome and the
above ob~ects hav~ been achieved by the pre~ent pourable
~a~hing agent compositions. The pourable .washing and clean-
.. iDg agent~ accordlng to the invention conslst Or ~rom 30% to
100% by w~ight o~ a prem~x composed of:
~A) Rt least one finely-dispersed, water-insolub~e silicate
compound contain$ng combined water in the given case,
.~ havlng a calcium blnding power o~ at least 50 mg CaO~gm .
oi' anhydrous acti-ve substance and the general for~ula
(on the anhydrou~ basig)
(M2/n)x Me2~3 (si2)y
... .
w~nere M i8 a catio~ o~ the valence n, exchangeable wlth ~ ~
.,'' , .
~ ,. ' -: ' '-' '
'" ~039608
calcium, x i~ a number from 0.7 to 1.5, pre~er~bly
rom 0.7 to 1.1, ~e i8 aluminum or boron, and y i8 a
number from 0.8 to 6, prererably ~ro~ 1.3 to 4, whore
. these compound~ can likewi~e be substituted partly by
highly d~sperEed silica ln amounts of not more tha~ 4%
by weight based on the entire premix;
(B) optionally, a bleachlng compollent o~ lnorganic percom-
:~ pounas whlch supply H22 in water, and/or activator~ for
the~e percompound~
~- 10 (C) Non-ionlc~ finely distrlbuted ~ver the component accord- -
lng to (A) or over the mixture o~ components (A) and (B);
ana from 0 to 70% by weight o~ a powder cQmponent
obta~n~d by hot drying of an aqueou~ co~po~ition with
~onventional heat-insensltive components Or washlng and
cleanin8 agents.
e premi~o~ mu~t, therefore, al~eady be con~idered
a8 wa~hlng and cleaning agent compQsltlon~ in the sen~e of
the inv~ntion.
The quantitative ratlo Or the cation-exchan~lng
20 component (A) and o~ the ~on-ionic~ (C) in the above-aerined
~ premix can b~ ln the range Or 10:1 to 3sl, ~epending o~
: ~hether the subetrates o~ co~po~ent (B) are alao pre~ent,
~hereby tne cation exchanging compoun~ accordln~ to (A) and
: the Non-ionics (C) r~present at lea~t 10% by ~eight o~ the
;. premlx.
, .
More particul~rly~ the present inve~tion res~de~
ln a pourable washing agent co~positlon co~prlsing a premix
. po~d~r compone~t and optionally a ~econd powder component
~' obtained by hot drylng o~ an aqueous composition containing
cQave~tional h~at-lnsensltlve wa~hlng age~t component~,
con~lsti~g es~ntlally of
, .
- 6 -
.
` 1039608
~` (1) from 30% to 100% by weight of a premix powder component
consisting essentially of
(A) at lea~t one finely-dispersed, ~ater-insoluble sili-
cate compound containlng at least some combined
water and bavlng a calclum binding power-of at least
50 mg Cao/gm of anhydrous active substance and the
formula on the anhydrou~ ba~i~
(M2/n)x ~ Me203 . (S102)y
where M is a cation of the valence n, exchangeable ~
wlth calcium, x is a number of from 0.7 to 1.5, -:
Me i8 a member selected from the group consistlng
of aluminum and boron, and y is a number from 0.8
to 6, which silicate compound can optionally be
partly replaced with hi8hly dispersed ~llica in an
amount of not more than ~% by ~Jeight of the weight
. of the premix;
. (B) from 0 to 80% by wei8ht of the premix of bleaching
components selected from the group con3i~ting of
inorganic peroxyhydrate compounds capable of ~upplying
20 H202 1n wster, powdery ac~lated activators for per-
compound6, powaery stabi~;zers ~or percompound~ and
~ixtures thereof;
;~ (C~ non-loDlc sur~ace-active compound~ ~inely distributed
. on and throughout component (A) or the mlxture o~
components (A) and (B);
: where ~he mix ratlo of component (A) to component (C)
i~ ln the ratio of 10:1 to 1:3 and at least 20~
o~ ~aid premix are components (A) and (C) together,
the fi~al mix ratlo of the component~ being selected
3 whereby the premix iB a pourable powder; and
,-
.
1039608
(2~ from 0 to 70~ by wei~lt of a second powdery component
obtained by hot dry~ng of ~n aqueou~ composltlon contaln-
lng conventional heat-lnsens1ti~e wsshing agent components.
Therefore, the invention also resides in a pourable prealx
po~dery component for admi~ture in washlng a~ent composltions
conslsting essentlally of
(A) at least one finely-dispersed, water-insoluble 8ili-
. cate compound containing at least some combined
- water and having a calcium bindlng power of at lea~t
50 mg CaO/gm of anhydrous active substance and the
formula on the anhydrous basi~
(M2/n)x M~03 (sio2~y
where M is a cation of the valence n, exchangeable
with calcium, x is a number of from 0.7 to 1.5~
:~ Me i~ a member selected from the group consisting
~ of aluminum and boron, and y is a number from 0.8
; to 6, which silicate compound can optionally be
: partly replaced wlth highly dispersed silica in a~
amount o~ not more than ~ by weight o~ the ~elght
Or the premix,
(B) from 0 to 80% by welght of the premlx of bleachlng
component~ ~elected from the group consisting of
::~ inorganic peroxyhydrate compounds capable o~ ~upplylng
H202 ln ~ater, powdery acylated acti~ators for per-
compounds5 powdery stabi~1zers ror percompounds and m1 xture~ thereo~;
(C) non-lonic surface-active compounds ~nely distrlbuted
on and throughout component (A) or the mixture of
components (A) and (~);
~L0396Q8
~here the mix ratlo of co~ponent (A) to comp-gnent
(C) i8 in the ratio of 10:1 to 1:3 and at least 20%
o~ ~aid premix are co~ponent~ (A) and (C) together, ~; -
the flnal mix ratio of the comp~nent~ being ~electe~
~hereby the premix i8 a pourable po~der.
The synthet~c water-ln~oluble ~ilicate compoun~
~efined as component (A) will her~after b~ called "alumino-
silicates" iorsi~plicity'~ ~ake. Their Galcium bin~n~ :
.: power can attain ~alues ci 200 mg Cao/gm Or aDhydrous acti~e
substa~ce (AS) and i8 pre~erably in the range o~ 1~0 to 200
mg CaO/g~ AS.
Sodium ~ preferably used as a ~ation, but it can
al~o be replacea by hydroge~, lithiu~, potasffium~ ammoniu~ or
m~gne~um, a~ ~ell as by the c~tion~ o$ water-~oluble organlc
: ba~es, ~or exa~ple, by those Or pri~ry, seconaary or tertiary
.. alkylamines or alkylola~i~es Nith not more t~an two c~rbon
atoms per alkyl or not ~ore than three car~on atom~ per
- j alkylol. s
~,.. j
~th particular ad~antage alumino~ilicates are u~ed
. . 20 which CO~Bil3t of` at lea~t 80% by ~e~ght of p~rticles o~ a ~lz~
. . .
' ~ro~ 10 to 0~01 ~, pr~ferably ir~m 8 to 0.1 ~. The~ alu~ino~
. .
sllieate~ ~ontain pre~erably no prlmary or ~ecaldary parki~le~ : -
of a ~ize above 40,~.
m~ non-lo~lc ~urface-actlve co~pound~ (No~ lcs)
tG be utt-lized accordi~g to the lnventlon are the products
o~ addition o~ 8 to 20 mc~ls of ethylone oxlde to 1 ~ol of a
co~pound ha~ from 10 to 20 carbon ato~ d a labile
hydrog~n ato~ ~uch a~ ~atty alcdQls, alkklphenol~, ratty
aclas, ~atty amine~, fatty ac~d a~ide~ or alkan~ onamlaes.
E~pecially important are the purely aliphatic non-lonlc~
. . ~
,, .
` 1039608
derlved~ for example, from coconut or tallow ~atty alcohols,
fro~ oleyl alcohol or from secondary alkanol~-with 12 to
18 carbon atom~.
In addltion to the~e practically water-so~uble Non-
lonic~, the ~ater-lnsoluble or not readlly ~ater-soluble
ethoxylation product~ with 2 to 6 mol~ of ethylene oxide to
1 ~ol of the above compounds haring from 10 to 20 carbon
atoms and a labile bydrogen atom are Or i~ere~t becau~e of
thelr fat-di~solving and greying-inhibi~lng propertie~
these are used together wlth the water-~oluble Non-lonics
and/or other ~urfactants, a good cleanlag sifect i8 achie~ed,
partlcularly with hydrophobic 80il, ~f the quantitatiYe ratio
ln th~ iinisbed d~tergent iormulas of the low-etho~ylated
: Non-lonic~ to the hlgher ethoxylated Non-ionic~ 18 in the
range of 1:3 to 2:1, particularly 1:2 to 1:1.
Partlcularly preferred, be~ause of their good
cleaning actlon in co~bination wlth a ~ood biodegradability,
are the ethoxylatlo~ product~ of th~ prlmary, straight-
cha~ned C12 to C18 alkanols or alkenol~ ~ith an average degree
o~ ethoxylation ~f 3 to 5 or 10 to 15, respecti~ely, in the
.
above-indicated qua~tltati~e ratios.
,~ Al~o the product~ o~ additio~ o~ ethylene oxide to
- terminal or ~on-terminal vicln~l alkanediols having from 10
.~ to 20 carbon ato~ can be used as no~-ionic surrace-active
¢ompounde, with 2 to 4 or respectively 8 to 1~ ethyleneglycol
ether l~n~ts in the molecule being preferred.
Other ~uit~ble Non-lonlcs are those of the type of
the acid amlde~ which are obtained by reacting fatty acids,
ratty acid esters, fatty acid halides or alkane~ulfonic acid
hallde~ wlth mono- or dieth~nol~lne or by further ethoxylatlon
of the~e reaction products.
''
-- 10 --
` 3L0396()8
me invention thu~ concern~ substantlally the u~e
o~ tbe finely divided, cation-exchanglng alumlnoslllcates
according to (A) as solid ~ubstrates with good adsorptlon power
for the NQn-ionics. Thi8 mahes i8 not only posslble to provide
pourable ~ashlng and cle~ning agent eompo~ltions with a high
No~-lonics content, but lt make~ it unnec~s~ary to a ~reat
extent to use conventlonal water-soluble lnorganic or organic
sequester agents for calcium-ion~, because o~ the excellent
cation exchanger propertles of the alumino~illcate~. Pho8-
phoru~-containl~g calclum sequeskering agents3 partlcularly
sodium trlpolyphosphat~, can be completely eliminated ~rom the
prem$x acoording to the invention and thu~ from the washing
: and cleaDing age~ composttions made ~here~rom.
: The premixe~ suitable for the product~on of bleaehin~
: ~ashing agent compo~l~ions contaln a~ an additional solid
; sub~trate the bleaching component (B), ~hich con~i~ts o~ an
.~ lnorganic percompound or peroxyhydrate compound supplyi~g
H22 in water, partlcularly of sodlum perborate and/or a so~ia
actiYator for the percompound as ~ell as a atabilizer fo~ the
percompound, and ~hich can amount to ~rom 15% to 80% by weight .:
c. of the prem~x when th9 8a~e i8 pre~en~. But ~ompo~ent ~B) can
also con~ist exclusively of the actlvatox for percompounda
In the latter ca~e, three part~al mixtures are u~ed ~or the
production of the bleaching preparations, namely, the aeti- -
vator-containing premix, a hot-drled po~der, and the powdered
perco~pound. Ih premixes rOr non-bleaching ~reparatlQns, such
as prewashlng, fine wa~hing or ~ain wa~hing agent composltio~s,
compon~nt (B) 1~ naturally ~i9~ing.
- Tho pre~ixe~ accordlng to the ln~ention caa also
- 30 contain other co~v~ntl ~ 1 powdered comp~nents of washing and
clea~sing agent compo~ition~. m e~e include as a po~lb~e
:.
,
.: .
,
` ~l039608
constltuent of component (A) a hlghly dispersed silica with a
specl~ic ~ET-~urface of at least 250 m2/gm, wnl~h'should be
contain, however, only up to 4% by wei~ht of the premlx be-
cause Or its nature a~ a ballast sub~tance. The premixe~ con-
tai ~ a bleaching component (B) can also contain additlonally
a stabiLlzer, preferably ~agnesium ~ilicate to erih ~ce the
bles.chlng action. Optlonall~, and ln addition, the preml~ces
can contain the following water-soluble substrates: sodium
eul~ate, the alkali ~etal carbona~es, bicarbonate~, ~ilicat*~
10 or borate~, known as wash alkalls, or the water-~oluble
builder~ or se~uestering agent~ de3crlbed below; urea i~ also
..,
:~ ~u~table as a substrate.
Substances, such as enzymes, antl~lcrobial compounds
or per~umes, which are not ~ub~ected to hot drying bec~use o~
their instablllty relative to water and/or heat~ or becauso of
- their volatllity can al~o be added in ~mall Q~ounts to the
pre~lxes.
Tbe compositl~n of a pre~ix c~ntainlng percompounds
i8 generally llithin the follolring formula:
-. 20 10% to 60% by ~eight of the aluminosilicates according to (A),
20% to ~0% by weight o~ inor~anic percompound~ 8UpplylDg H22
in ~fater, particlllarly 80dium perborate,
10% to 30,~ by weight of Nor~-lonics,
O to 4% by weight oi highly di~persed silica,
O to 30% by lfeight Or ~ powdered activator ~d/or stabilizer
~or percompounds,
Premixe~ without percompounds ca~ ha~re the ~ollowing
comp~sltl0n:
60% to 90% by weight of the aluminosilicate~ aacordillg to (A),
10% to 40,~ by welght of llon-ionlcs,
: O to 4% by weight of hlghly disper~ed sllica,
o to 30~ by welght of a po-adered actlvator for-percompounds.
.: '
- 12 _
:lC~39608
The above-defined aluminosilicates can be produced syn-
thetically in a known, s~mple manner, or example, by reacting
wster-soluble s~licates with water-soluble aluminates in the
presence of water. To this end aqueous solutions of the start-
ing materials can be mixed with each other, or one component
which is present in solid form can be reacted with another com-
ponent which is present as an aqueous solution. The desired
aluminosilicates can also be obtained by mixing both solid com-
ponents in the presence of water. Aluminosilicates can also be
produced from Al(OH)3, Al203 or SiO2 by reaction with alkali -
metal silicate or alkali metal aluminate solutions. Finally,
such substances are also formed from the melt, but this method
seems of less economical interest because of the required high
melting temperature and the necessity of transforming the melt ~-
into finely-dispersed products. -
The cation-exchanging aluminosilicates to be used accord-
ing to the invention are only formed if special precipitation
. ~ .
conditions are maintained, otherwise products are formed which
have no, or an inadequate, calcium exchanging power. The cal-
cium exchanging power of at least 50 mg CaO/gm of anhydrous ~-
active substance (AS) is critical to the present process. If
aluminosilicates are employed with belo~ the critical limit of
calcium exchanging power, very little if any soil removal from
the soiled textiles is effected in the absence of other types of
calcium sequestering or precipitating agents. The production of -
useable alumlnosilicates according to the invention is described
in the experimental part.
The aluminosilicates in aqueous suspension produced by
precipitation or by transformation in finely-dispersed form
according tc other methods can be transformed from the
:
1 3 -
~.
db ~
. . .. . -, - ~ . , . - -
. .
1039608
amorphous into the aged or into the crystalline state by heating
the suspension to temperatures oP 50 to 200C. However, there
is hardly any difference between these two forms as far as the
calcium binding power is concerned. Aslde from the drying con-
dltions, the calcium binding power of the aluminosilicates is
proportional to the amount of aluminum contained therein with
reference to the amount of silicon.
The preferred calcium binding power, which is in the
range of 100 to 200 mg CaO/gm AS, is found primarily in com-
pounds of the composition:
0-7 to 1-1 Na2 A123 1-3 to 3-3 Si2
This summation formula comprises two types of different
crystal structures (or their non-crystalline initial products)
which also differ by their summation formulas.
* These are:
S a) 0-7 to 1~ a2O . A1203 . 1.3 to 2.4 SiO2
. ,
b) 0.7 to 1.1 Na2 A123 >2-4 to 3-3 Si2
The different crystal structures can be seen in the X-ray
~ diffraction diagram. In X-ray amorphous products, the crystal
; 20 structure can mostly still be recognized in an electron dif-
fraction diagram.
A representative of type (A) above is ~he compound I of
the composition:
0.9 Na20 . A12O3 . 2.04 SiO2 ~ 4'3 ~2 (I)
A representative of type (B) above is compound II of the
composition:
0.8 Na2O . 1 A12O3 . 2.65 SiO2 . 5.2 ~2 (II)
The water content of compounds I and II was determined
after drying for 24 hours at 100C.
The amorphous or crystalline aluminosilicate contained
ln the aqueous suspension can be separated by filtration from
. ,
.,, ' , .
tb / ~
l03a60s
the remaining aqueous Aolution and be drled at temperatures of
50C to 800C, for example. Depending on the-drying conditions,
the product contains more or less combined water. Anhydrous pro-
ducts are obtained by drying at 800~C. If we want to remove the
water completely, this can be done by heating for 1 hour to 800C.
This is the way the AS contents of the aluminosilicates are also
tetermined.
:; .
Such high drying temperatures are not recommended for
the aluminosilicates to be used according to the invention, pre-
ferably the temperature should not exceed 400C. It is of par-
: ticular advantage that even products dried at substantially
- lower temperatures of 80 to 200C, for example, until the ad-
.... .. .
hering liquid water is removed, can be used for the purposes of
the invention. The aluminosilicates thus produced, ~hich con-
tain varying amounts of combined water, are obtained after the ~ -
disintegration of the dried filter cake, as fine powders whose ~
primary particle size does not exceed 0.1 mm, but is mostly lower - -
and ranges down to dust fineness, for example, to 0.1 ~. It must
be kept in mind that the primary particles can be agglomerated
to larger structures. In some production methods primary
particle sizes ranging from 50 to 1 ~ are obtained.
Of particular advantage are aluminosilicates having at -
least 80% by weight of particles of 10 to 0.01 ~, preferably 8
to 0.1 ~. These aluminosilicates preferably contain no primary
or secondary particles above 40 ~. As far as the products are
crystalline, they are "micro-crystalline."
~ ! '
The formation of smaller particle sizes can already be
enhanced by the precipitation contitions. For these smaller
particle sizes, the intermixed aluminate and silicate solutions,
. ,
.
, ~ .
db/~ ~
: - . . ~ - : : , . . . -
, - , . ~ . - ...
10;~96~)8
wnich can also be introduced ~lmultaneously into the reaction
vessel, are sub~ected to great shearlng forces. If crystalline
aluminum silicates are produced, which are preferred according to
the invention, the formation of larger or inter-penetrating
crystals is prevented by slowly stirring the orystallizing mass.
Nevertheless, undesired agglomeration of crystal particles
can occur during the drying, so that it is advisable to remove
these secondary particles in a suitable manner, for example, by
air sifting. Aluminosilicates obtained in coarser form, which
are ground to the desired particle size, can also be used.
Suitable for this purpose are, for example, mills and/or air
sifters or combinations thereof. The latter are described, for
example, in Ullmann, "Enzyklopadie der technischen Chemie" vol. 1,
1951, p. 632 to 634.
Prom the sodium aluminosilicates, aluminosilicates of
other cations, for example, those of potassium, magnesium or
water-soluble organic bases can be produced in 2 simple manner
by the exchange of bases.
In order to produce aluminosilicates I and II, the
following conditions are employed.
PROCESS CONDITIONS
The aluminate ~olution, diluted with deioni~ed water was
mixed in a vessel of 15 liter capacity, under vigorous stirring
with the silicate solution. Both solutions were at room tempera-
; ture. An X-ray amorphous sodium aluminosilicate was formed in
the exothermic reaction as a primary precipitation product.
After stirring for 10 minutes, the suspension of the precipita-
tion product was either separated as an amorphous product or trans-
ferred to a crystallization vessel where it remained for some
time at the elevated temperature given
.;'
'' '
db/ ~
,
:, :
1~39S08
to crystalllze. A~ter draining off the liquor from the cry~tals
and washing with deionized water untll the outflowing wash water
hat 8 pH-value of about 10, the fllter residue was dried. When
there iR any deviation from this general production procedure,
this is mentioned explicitly in the specific part. Thus, for
example, in some cases for the practical tests, the homogenized
uncrystallized suspension of the precipitation product or the
crystal sludge was used. The water content was determined by ~-
heating the product for one hour to 800C.
In the production of microcrystalline aluminosilicates,
indicated by the suffix "m", the aluminate solution diluted with
deionized water was mixet with the silicate solution and mixed in
a high-speed intensive stirrer (10,000 rpm, "Ultraturrax~", made
;, .
by Janke & Kunkel IKA-Werk, Stauffen/Breisgau/Federal Republic
; of Germany). ~fter vigorous stirring for 10 minutes, the sus- -
pension of the amorphous precipitation product was transferred
to a crystallization vessel where the formation of large crystals
was prevented by stirring the suspension. After draining off the
liquor and wa~hing with deionized water until the outflowing `-
20 water had a pH value of about 10, the filter residue was dried,
then ground in a ball mill and separated in a centrifugal sifter
("MicroplexG~" air sifter, made by Alpine, Augsburg, Federal
~ Republic of Germany) into two fractions, of which the finer
., fraction contained no portions above 10 ~. The particle size
distribution was determined by means of a sedimentation scale.
` The degree of crystallization of an aluminosilicate can
be determined from the intensity of the interference lines of an
~-ray diffraction diagram of the re~pective product, compared to
the correspond~ng diagrams of X-ray amorphous or fully crystal-
lized products.
'-' ' . '
:
.
db/~
... .. . . . . . . . .
" -~ , . . . .
:. ~ . ,
., , : ,. . .
S 039608
All data in % are ln percent by welght.
The calcium binding power of the aluminosilicates or
borosilicates was determined in the following manner. 1 liter
of an aqueous solution, containing 0.594 gm of CaCl2 (- 300 mg
CaO/1 = 30dH) and ad~usted to a pH of 10 with diluted NaOH, was
- mixed with 1 gm of the aluminosilicate or borosilicate (on the
anhydrous basis, AS). Then the suspension was stirred vigorously
for 15 minutes at a temperature of 22C (+ 2C). After filtering
off the aluminosilicate, the residual hardness x of the filtrate
was determined. From it, the calcium binding power was calculated
in mg CaO/gm. As according to the formula:
(30 - x) . 10
` If calcium binding power is determined at higher tempera-
ture, for example, at 60C, better values are obtained than at
22C. This fact distinguishes the aluminosilicates from most of
the soluble sequestering agents that have been suggested so far
for use in detergents and represents a particular technical pro-
gress in their use.
Production conditions for aluminosilicate I:
Precipitation: 2.985 kg of an aluminate solution of the composi-
tion 17-7% Na20, 15-8% Al203, 66.6% H20
0.15 kg of sodium hydroxide
9.420 kg of water
2.445 kg of a 25.8% sodium silicate solution of
the composition 1 Na20. 6.0 SiO2, prepared
freshly from commercial waterglass and easily
alkali-soluble silica
.~
Cry8tallization: 24 hours at 80C
Drying: 24 hours at 100C
~ , :
. - ' :
db¦~ -
- :. ~ : . . ~ .
` ` lC~39608
Composition: 0.9 Na20 . 1 A12O3 . 2.04 SiO2 . 4.3 H20
(e2 l ~ 6% H20 ) '
Degree of cry6tsl-
llzation: Fully crystalline
Calclum binding
power: 150 mg CaO/gm AS.
If the product obtained ~as dried for 1 hour at 400C, an
aluminum silicate Ia was obtained of the composition: ~ ;
0.9 Na20 . 1 A1203 . 2.04 SiO2. 2.0 H2O t= 11-4% H2O)
which is likewise suitable for the purposes of the invention.
Product conditions for aluminosilicate II:
Precipitation: 2.115 kg of an aluminate solution of the
composition: 17.7% Na2O 15.8% A12O3,
66.5% H20
0.585 kg of sodium hydroxide
9.615 kg of water
;. 2.685 kg of a 25.8% sodium silicate solution
of the composition: l Na20. 6 SiO2 (pre-
- pared as under I)
" 20 Crystallization: 24 hours at 80C
Drying: 24 hours at 100C and 20 torr.
Composition: 0.8 Na2O. 1 Al2O3. 2.655 SiO2. 5.2 H20
Degree of crystal-
lization: Fully crystalline
, :`
.~ Calcium binding
' power: 120 mg CaO/gm AS.
r
~ ' `
. ~ 9 ~
:: .
: ~ .
tb/~i!~
1039608
The aluminosl1icates I and II show in the x-ray dif-
fraction diagram the following interference lines.
d- values, recorded with Cu-K~- radiation in A
I II
_ 14.4
12.4
- 8.8
8.6
. 7.0
~ 4-4 (+)
4.1 (+)
- 3.8 (+)
3.68 ~+)
: 3.38 (+)
3.26 (+)
- 2.96 (+)
~ 2.88 (+)
.. ,~ .
~ 2.79 (+)
. 2.73 (+)
~,, .
:. 20 - 2.66 (+)
2.60 (+)
It is quite possible that not all these interference
.~lines will appear in the X-ray diffraction diagram, particularly
if the aluminosilicates are not futly crystallized. For this
~ .
. . .
:.~ reason, the d-v.alues which are the most important for the char-
aeterization of these types are identi$ied by a "~+)".
,':
s ,, . .-
."'' ~'.
O ~:
';.' :~'
., ~ .
. .
db~
. , . ., ~
1039608
The catldR-exchanglng aluml~oelllcates can partly
or complotely replace the phosphorus-containlng inorganic or
organlc cal¢iu~ sequèstering agenta Or the Nashlng and cleans-
lng agent compositlon~ especially aodlu~ trlpolypho~phate,
80 that tbe phosphoru~ concentratio~ in the sewage i~ con-
siderably redueed by U81ng the preparation according to the
lnventlon in~tead o~ the kno~n preparatlon~ wlth a hlgh sod~u~
: tripolypho~phate content.
Among the percompounds servine as bleaGhlng agentB
and releaslng H22 in ~a~er, sodlum perborate tetrahydrate
(NaB02 H2~ 3 H20) a~d the monohydrate (~aB02 ~22)
are o~ partlcular i~portance, but also other H202-releasing
borates can al~o be used, euch as p~rborax ~a2B4 ~ 4 H202.
The~ ¢ompounde can be roplaced partly or co~pletely by other
c~rrier~ of actl~e oxygen, particularly by peroxyhydrates,
~uch a~ poroxycarbo~tes, (Na2C ~ 1.5 H202) or peroxypyro-
pho~phate~.
It i8 reco~ended to incorpo~ate water-in~olubl~
. stabili3ers ~or the percompounds to~ether with the latter.
.. 20 Water-insoluble stabilizer~ are, ~r example, ~a~nesiu~ ~ilicatc
, . .
havlng a NgO:SiO2 ratio of 4:1 to 1:4, preferably 2:1 to 1:2,
: and particularly 1~ hlch are mostly obtained by precipita-
tlon from aqueou~ solutlon~. In thelr plaee, othsr alkallne --
e~rth mctal, cadmlu~ or tin sillcate~ o~ corresponding com-
position~ are also w able. A130 hydrous oxldo~ of tln are
`~ ~ultable a~ otabllizer~. The water-insoluble ~tablllzer~
and partlcularly m~gneslu~ sillcate can be i~corporated in
the wa~hing agent composition both in the pre~ix accordin~ -
: to the lnv~ntlon and in the atomlzation-drled powder~, addlng
lt ln such amounts that the portlon Or the ~ini~hod ~ashi~e
agent compositlonm 18 fro~ 1% to 4% by weight.
.
- 21 -
.. . ..
.
~1039608
In order to obtaln a satls~actory bleaching effect
wlth the washing agent composltlons eontaining pereompounds
at temperatures belo~ 80C, partieularly in th~ range of 40
to 60C, actlvator~ for the perco~pound~, particularly for
perborate, can be lneorporated in the preparatlon~ in the
pre~ix accordl~g to the i~vontlon. Preferred acti~ators are
those of the type of the N-acyl compounds whieh have a ~elting
: polnt Or at lea3t 70C, preferably at lOO~C~ for exa~ple, the
co~pounds N,N,N'~N'-tetraac~tylethylenediamlne, tetraa¢etyl-
glycoluril and tetrapropionylglycoluril. Particularly pre-
erred as an acylated aetlvator for percompounds i~ tetra-
aeetylglycolurll, melting point 233 to 240C, which 1~ al~o
suitabl~ as a ~olid substrate and whlch has a gOoa activatin~
efiect i~ amounts of 0.1 to 1 mol p~r ~ atom o~ activated
oxygen oi the p¢rcompound~. The premlxes according to the
inventlon can contaln pre~erably rrO~ 15% to 25% by welght
.. ~ of an activa~or a~ part of com~onent (B).
The inventlon also eoncerns a method for the pro-
ductlon Or the above-de~lned pre~i~es, whieh iB charaeterize~
i~ that the liguid ~o~-ionic~ are applied on a ~oving powder
the ~bove~defined eomponent~ according to (A) or on a
~; po~der ~ixture o~ the c~fflponent8 (A) and (B), a~d that the
`~ premix product 1~ mlxed likewi~e with a powder in the pourable
stat~, obtained by hot-drying of an aqueou co~po~ition con-
81~ting of heat-inaen~itive co~pon~nts Or ~shing and elean~lDg
~ a~e~t co~po~ition8.
~ Preferably the ll~uid Non-lo~lcs, ~r those llque-
fied by heati~g, are sprayed on the powder mlxture, ~hich
1~ done possibly in a closed ~essel. However, ~luld bed
method~ can also be used.
'''
.
_ 22 -
.
... ..
1~39608
Apart from the components of the premix, the
~inished wa~hine and cleanslng agent composltions can al80
contaln the follo~ing co~ponents: anionic and/or non-ionic
surface-actlv~ compound~ or tenslde~, ~urface-active or non-
sur~ace-actlve ~oam stabllizers or foam l~hibltors, textile
~o~tening agents, neutral or alkallne reactlng builder co~-
pounds, as well as auxiliary sub~bancea and additives ~hlch
sre pre~ent in s~all a~ouAt~, such as eorros1on lnhlbitor~, -
8011 8U8pen810n agent~, optical brlght~ners, dyes, etc.
The co~posltion Or a typlcal te~tlle ~ashlng agent
co~pQsltlo~ to be usQd in the washing temperature ranup o~
30~:C to 100C i8 ~lthln the follo~ng formula:
:: 5~ to 30~ by ~ight Or anionic and/or non-ionic or amphoterlc
~ur~ace-actl~e eo~pounds;
5% to 70% by welght of water-insoluble, but water_containing,
: ~ ~ ooili~ate~ of the defi~itiQn indieated under (A);
2% to 45% by ~ei~ht o~ water-soluble s-questering ~gent~ for
calcium 10~8;
O t~ 50% by ~lght o~ builder co~pound~ not capable of
se~u~toring calclu~ ions, particulaxly alkaline
builder ~alt~;
O to 40~ by welght Or A-bleachln~ co~ponent cQn~istln~ Or
percompou~ds, particul~rly 80diu~ p~rborate, and,
optlonally, ~tabilizers and/or activators;
O to 10~ by weight of other additlve~, which ar~ ~oatly
present in 8~11 a~ount~ in textile wa~hlng
compositions.
~ The pre-washlng and maln wa~hin~ agent co~po~itlon~
of this ~ormula contain no percompound~ tho full range
wa~hing agent compo~ition~ u~ed pre~rably at hlgh or co~klng
_ 23 -
~ 1~39608
temperature~, the content o~ the ~leachlng compo~ent 18 10%
to 40% by ~eight.
The quantitative data refer to the entire for~ula,
dlsregarding the fact. that lt con~ of both a premix and
a hot-dried poNder in ad~ixture. Indi~idual component~,
particularly the alumlnosllicate~, c~n be present both in
the premlxes and the hot-dried co~ponent.
The washing and clean~ing ~gent compo3itions
obtained accordlng to the invsntlon are used pre~erably ~or 10 wa~hing textiles, but they ca~ al~o be w ed ~or cle~ning
the ~urface~ Or non-textile obJect~, particularly ~arlous
household appliances.
Here follow~ a list o~ co~pound3 in ~ach of the
abov~ classlilcatlo~ ~hich are sultable ror u~ in the pre-
parQtions accoraing to the inventlon.
Tho anlonic or a~photerlc ~urface-acti~e compounds
or ten~lde~ contain ln the mol~cule at lea~t one hydrophobic
- organic molety and on~-water-~olubillzing, anionic or ampho-
~ terlc group. The hydrophobic molety i8 mo~tly an aliphatic
-~ 20 hydrocarbon radical ~ith 8 to 26, pre~erably 10 to 22 ana
particul~rly 12 to 18,carbon atoms or an alkyl aro~atic
radlcal, such as alkylphenyl, wlth 6 to 18, preferably 8 t0
16, aliphatic c~rbon atom~.
Among the anionic sur~ace-active compounda are,
~or exaE~le, 80~p8 of natural or synthetlc, pre~erably
- saturated, fatty aclds, optlonally al~o, ~oaps of reslnic
or n~phthonlc acid~. Suitablo 8ynthetic anionlc tenaides
are those of the type of the sulfonate~, 9ul~ate8 and
synthetic carboxylates~
_ 24 -
"` :10396Q8
Sultable anlon~c tensldes of the sulfonate type are alkyl-
benzene sulfonates (Cg 15 alkyl) mixtures of alkenesulfonates and
hydroxyalkanesulfonates, as well as alkanedisulfonates, as the~J
are obtained, for example, from monoolefins with terminal or
non-terminal double bonds by sulfonation with gaseous sulfur tri-
oxide and subsequent alkaline or acid hydrolysis of the sulfona-
: tion products. Also suitable are alkanesulfonates which are
obtained from alkanes by sulfochlorination or sulfoxidation and
subsequent hydrolysis or neutralization or by bisulfite addition
to olefins. Other suitable tensides of the sulfonate type arethe esters of ~-sulfofatty acids, for example, the ~-sulfonic
` acids of hydrogenated methyl or ethyl esters of coconut, palm-
kernel or tallow fatty acids.
` Suitable tensides of the sulfate type are the sulfuric ;
acid monoesters of primary alcohols (e.g. from coconut fatty al-
cohols, tallow fatty alcohols or oleyl alcohol) and those of
~` secondary alcohols. Also suitable are sulfated fatty acid -
alkanolamides, sulfated fatty acid monoglycerides or sulfated
resction products of 1 to 4 mols of ethylene oxide with primary
; 20 or secondary fatty alcohols or alkylphenols.
Other suitable anionic tensides are the fatty acid esters
or amides of hydroxy- or amino-carboxylic acids or sulfonic acids,
. .r .
such as the fatty acid sarcosides, fatty acid glycolates, fatty
.; acid lactates, fatty acid taurides or fatty acid isoethionates.
.,"~,, .
~ The anionic tensides can be present in the form of their
",,. ~
~ alkali metal salts, ~uch as the sodium or potassium salts, the
~ . ~
ammonium salts, as well as soluble salts of organic bases, such
as the lower alkylolamines, for example, mono-, di- or
triethanol am~ne.
2 ~ ~
~ ,.
tb/~
.~ .. . . .
,
. .. .
1039608
The foamlng power of the tenside can be lncreased or
reduced by combination of suitable tenside types. A reduction
can also be achieved by additions of non-surface-active organic
substances.
A reduced foaming power, that is desirable ~or the use in
washing machines, is often attained by combination of different
tenside types, such as of sulfates and/or sulfonates with the
- nonionics, and/or with soaps. In soaps, the foam inhibition in-
creases with the degree of saturation and the number of carbons
in the fatty acid residue. Soaps derived from saturated C20 24
fatty acids have been proven good as foam inhibitors.
The amphoteric surface-active compounds or tensides which
can be employed are particularly betaines containing a quadruple
substituted, that is, quaternary ammonium group and a covalently-
bound acid group, whose positive and negative charges are ba-
lanced intramolecularly. The betaines have on the nitrogen at ~
most two, but generally only one higher-molecular-weight ali- ~ -
phatic hydrocarbon radical of a hydrophobic nature, and at least
one, but gene~ally two, lower alkyl radicals with 1 to 3 carbon
a~oms, which can be substituted by hydroxyl groups or connected
with each other directly or over a hetero atom. The anionic,
water-solubilizing acid group is connected with the ammonium
nitrogen over the fourth substituent, which consists mostly of
. . . - ::.
a short-chained aliphatic radical having, optionally, a double
bond or a hydroxyl group, such as an alkylene, hydroxyalkylene or
alkenylene, all having from 1 to 3 carbon atoms. Typical re-
presentatives are, for example, the compounds:
3-(N-hexadecyl-N,N-dimethylammonio~-propane sulfonates,
.' '. ,
2 B :
.
:
.:
db/~
- : . ,,
~039608
3-(N-tallow-alXyl-N,N-dimethyl~mmonio)-2-hydroxypropane
8~ onate3,
: 3-(N-hexadecyl-N,N-bis-~2-hydroxyethyl3-ammonio)-2-hydroxy-
- pro wl sulfate, and
N-tetradecyl-N,N-di~ethyl-a~onio-acetate.
Compound~ can al30 be used for the purpo e3 of the
inventi~n es seq~eeterlng agent~ ~or calcium with such a
se~uester~ng capacity that they were not considered heretofore
aæ typical ~eque~tering age~ts for calclum, but ~uch eompounds
. 10 are frequently capable of delaying the precipitation of cal-
: cium carbonate from aqueou~ solutlon.
Amon8 the ~e~uestcrlng agents are thos~ of an
inorganlc nature, such a~ the alkali ~etal pyrophosphate~,
tripolyphosph~tes, hlgher polypho~phate~ and ~taphosphat~.
Org~nlc co~pounds which are u~ed as ~equestering
agents are found, as known, among the polycarboxylic acid~,
hydroxyearboxylic acids, amlnoearboxyl~e acids, ~arboxyalkyl
ether~, poly~n~ onie polym0r~, and particularly the polymeric
~ earboxylic acids a~d the phosphonic a¢ids, these coalpound~ ~
:~ 20 being u~ed mo~tly in the form o~ their water-~oluble salts~
.~ ~uch as their aIkali metal ~alts.
W~akly acid, ~Rutral or alkaline-reacting i~organic
- or organic salt~ ca~ b~ used a~ bullder -3alt8 as ladicated
above.
Sultable ~akly acid, neutral or alkaline-reacting
~alts ~or use according to the inventio~ are, for exa~ple,
the bicarbonate~, carbo~t~, bora~s or silicatea of thc
alkali ~etal~, alkali metal sul~ates, as well a~ the alkali
metal ~alts or organic, non~urf~ce-actlve ~ul~onic acids,
carboxylic acld~ and ~ulfocarboxylic acid~ c~ntaining from
- 27 _
,. .
. -.. , . ~ . .. .
r ~ ~L039608
to 9 carbon atoms. The~e include, ~or example, water-soluble
salts of benzenesulfonic acid, toluene~ulfonic acit or xylene-
sulfonic acid, water-soluble salt6 of sulfoacetic acld, sulfo-
benzoic acid or of sulfodicarboxylic acids, as well as the salts
of acetic acid, lactlc acid, citric acid and tartaric acid.
The preparations according to the invention can further-
more contain soil suspension agents or dirt carriers, which keep
the dirt released from the fibers in suspension in the liquor
and so prevent graying. Suitable compounds are water-soluble ~`
colloids, mostly of an organic nature, such as the water-soluble
salts of polymeric carboxylic acids, glue, gelatin, salts of
ether carboxylic acids or ether sulfonic acids of starch or cellu-
; lose, or salts of acid sulfuric acid esters of cellulose or
starch. Water-soluble polyamides containing acid groups are also
suitable for this purpose. ~urthermore, soluble starch prepara-
tions and other than the above-mentioned starch products can be ~;
` used, for example, degraded starches aldehyde starches etc.
Polyvinyl pyrrolidone can also be used. `~
The enzyme preparations to be used are mostly a mixture
of enzymes with different effects, such as proteases, carbo-
hydrases, esterases, lipases, oxidoreductases, catalases, pero-
xidases, ureases, isomerases, lyases, transferases, desmolases,
or nucleases. Of particular interest are the enzymes, obtained
:.
from bacteria strains or from fungi, such as Bacillus subtilis
or Streptomyces griseus, particularly proteases and amylases,
which are relatively stable towards alkalis, percompounds, and
anionic tensides and are still effective at temperatures up to
70C.
~:
, ~:
: 28 ~ ~:
- ,
:' . :~ `
... ~.~ ':``
db/~
.
. ::
1039608
' Enzyme preparations are marketed by the manufacturers
..
mostly as aqueous solutions of the actlve substances or as powders,
granulates or as cold-sprayed products. They frequently contain
sodium sulfate, sodium chloride, alkali metal ortho-, pyro- and
polyphosphates, particularly tripolyphosphate, as fillers. Dust-
:..
free preparations are particularly valued. These are obtainedin a known manner by incorporating of oily or pasty nonionics or
by granulation with the aid of melts of water-of-crystallization-
containing salts in their own water-of-crystallization.
Enzymes may be incorporated which are specific for certain
types of soil, for example, proteases or amylases or lipases.
Preferably, combinations of enzymes with different effects are
used, particularly combinations of proteases and amylases.
The washing agents can contain optical brighteners such
as those for cotton, particularly derivatives of diaminostilbene-
disulfonic acid or its alkali metal salts. Suitable are, for
example, salts of'4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazin-
6-yl-amino)-stilbene-2,2'-disulfonic acid or similarly compounds
which have instead of the morpholino group, a diethanolamino group,
a methylamino group or a 2-methoxy-ethylamino group. ~righteners
for polyamide fibers which can be used are those of the type of
the 1,3-diaryl-2-pyrazolines, for example, the compound l-(p-
sulfamoylphenyl)-3-(p-chlorophenyl)-2-pyrazoline, as well as com-
pounds of similar composition which have instead of the sulfamoyl
group, for example, the methoxycarbonyl group, the 2-methoxy-
ethoxycarbonyl group, the acetylamino group or the vinylsulfonyl
group. Suitable polyamide brighteners are also the substituted
aminocumarins, for example, 4-methyl-7-dimethylamino-cumarin or
4-methyl-
.
~ 29 "
-~ :
.
db/Sj~
~ , .
, . ~ , . ~
1039608
7-dlethylaminocumarin. Furthermore, the compound~ 1-(2-
benzimidazolyl)-2-(1-hydroxyethyl-2-benzimidazolyl)-ethylene
and l-ethyl-3-pheny1-7-dlethylamino-carbo~tyril can al~o be
used as polyamide brightener~. Brighteners for polyester and
polyamide ~ibers which can be u~ed are the compounds 2,5-dl-
(2-benzoxazolyl)-thiophene,2-(2-benzoxazolyl)-naphtho-[2,3-b~-
thiophene and 1,2-di-(5-methyl-2-benzoxazolyl)-ethylene.
Furthermoro, brighteners Or the type of the substituted 4,4'-
distyryl-diphenyl~ can be utilize~, for examplo, the compound
4,4'-bl~-(4-chloro-3-sul~ostyryl)-diphengl. ~ix~ure~ of the
above-mentio~ed brlghtener~ can likewi3e be u~ed.
The rollowlng speclflc embodi~ent~ aro ill~stratlve
Or the inventlon without being li~ltatlv~ in any r~s~ect.
E X A M P L E S
The alumin~silicate u~ed in the example~ has the
folloNing composltion:
O.9 Na20 A1203 2.0 SiO2 4 ~2
a~d a calclum bind~ng power o~ 165 mæ CaO/g~ AS. The partlclo
8iz~ distrlbutiQ~ wa8 within the ~ollowlng range:
~ 40Ju ~ 0% by wolght Maxi~um rang~ o~ the particle
30~u ~ 100% by weight ~ize diatributi0~ curve at
< 10Jl = 90% ~y ~eight 1 to 5)u.
The ~ was a commercial product of the
approxim~te com~o~ition:
~aB2 ~22 3 H~O, bulk d~nsity 830 gm/l.
: "TA + 5 ~0", "TA + 14 EO", "OC~ + 10 EO" are the
additlon products of 5, 14 and 10 mols of ethylene oxlde ~EO)
to 1 mol of tallow ~atty alcohol (TA) (lodine number = 0.5)
and oleyl/cotyl al~ohol (lodine nu~ber - 50).
...
. .
,'
- 30 -
. . . ~ . : .
` 1039608
Th~ ~'sllica~ o~ the premixe~ was a highly disper~ed
slllcon dlQxlde wlth a partlcle size r~Dge of 1 to 12 ~, a
llter weight of 90 to 100 gm/l, and a BET-sur~acs area of 300
m2/gm.
The follewlng Table I conta~ns the formulas of
some premixos ~hich had been produce~ ln a closod mixor by
spraylng the liquid Non-ioDlcs on the moving powd~r mlxture.
.. 'i .
. . .
- .
. .
,~
-'
.
. .
.
- 31 -
: ;
~03960~9
' _ o oo ~. .:
.,.................. ~ ' ~ ' ~,, ' ,,
., ~ o~ o ~ o U~ o ,. ~
~ ~ i ~:
. ~ 0 o o o ~ ~.
3
,,` Y~ ~
: ~ ~ ~ ~ t
H P- ~ ~ ~1 ~: ~
or~ ~o I I ~
~1 ~ ~ ,, o ~
~.
~ ~ ~
~ ~'
~' ~ ~ ~ U~ C~ O ':
"/ ~ o O
~. ~ ~ l ~ ' . `.
r~1 O O ,.~
; ~ I U~ I I I ,~ I : '
L~ ~ ~ a d~l
.. ~ O ~'aD
,`
~"'.
_ 32 - ~
`. . ..
1039608
e following examples give formulas oi ~ashing
agent compo~ltion~ which contain the pre~ixes according to
- Examples V l to V lO.
Ths salt constituent~ contained in the de*ertents
of the examples, such as sur~actant~ ln ~alt forL, other
: organic salts, as well as inorg~nic ~alts, Nere present as
sodium salt, unless explicit~ ~tated otherwise.
"ABS" - the salt o~ alkglbenzenesulfonic acld ~lth
~0 to 15, pre~erably ll to 13, carbon atoma ~n the alkyl chain
obtained by co~d~nsation of ~traight-chain ole~ wlth benzene
and ~ulfonation Or the alkylbenzene thu~ o~tained.
nOlefinsulfonat~" - a sulfonate obtained from a-ole~in
~l~tures having 12 to 18 carbon ato~s by sulronatlng wlth S03
and hydrolyzing the ~ul~onatlon product wlth sodlu~ hydroxide
801utio~, conslstlng essentlally o~ alken~ sulfonat~ and
hydroxyalkan sulfonate, but also containing sm~ll amounts o~
alkanedisulronate 8 .
: "~s-ester ~ulfonate" - a ~ulfonate obtained by ~ul-
.- fonat~6 hydrogenated palm ker~el fatty aci~ methyl ester
-
.` 20 with S03.
: nAl~anesulfonate" - a 8ul~0nate obtainsd by 8ulfo~1-
datio~ Or para~fin~ haviag 12 to 18 carbon atoms.
nSoap" - the gatty acld co~pone~t of a hardened
~ixture o~ equal part8 ~y ~eight of tallo~ and ra~ oil ~atty
acid~ (Cl~-C~2, iodine ~umber ~ l).
'~ A" - the salt Or ethylenedia~lnotetraacetic
~cid.
CMCn - the ~alt ~r carboxymethyl cellulose.
. , .
- - 33 -
1039~08
The follo~ing cQ~talns ~ormulations of some ~a~hing
agent compositions according to the ln~entlon. These compo~
~lons were obtained ~rom the premixe~ according to Examples
. Vl to V 10 by mlxing with a powder produced by hot ato~ization
of an aqueou~ solutlon containing the listed lngred~ent~.
Both the premlxes and the finl~hed washlng agent composition~
~ ~howed good powder properties. They were easily pourable,
: despite their content o~ oily or pasty Non-lonlc~.
' E ~ W 1
Low-phosphate ~ull ran~e washing a~ent compo~ition
The pr~parA~lon ~as obtained by mixlng 59 part~ by
-~ weight Qf pro~ix V 3 with 41 part~ by welght of.a powder
obtained by hot atomixation (Tower Powd~r No. 1) of th~
following compo~ition:
~ By Welght
: ~BS 19.6
Soap 9.5
:: EDTA o.9
odiu~ tripolyphosphate 28.0
Watergla~s (1:3.3) 14.0
. Sodi~m sulfate 1.4
: Magnesium slllcate 5.S
- CMC 4.2 :
;:~ Balance (water, perfu~e, optical
brighteners) 16.8
The fin~l full range ~a~hing age~t compo~ition
cp~ained the following~
~ ~ ,
,
10396Q8 %13y Wei~ht
ABS ~ 8.03
TA + 5 E0 3-7
TA + 14 E0 7.08
Soap 3.89
Sodium trlpolyphosphate 11.49
EDTA 0 37
Aluminosilicate 20.36
P~rborato 28 . 50
ME~gne~ium æillcate 2.29
Water~lass 5.74
Sodium ~ul~ate o.57
CMC 1. 72
Balance (water, perrume, optical
brlghteners ) 6 . 89
ELU~E W 2
osphato-rree full ra~e ~a~hing aç~ent compo~itioQ
.~ The prsp~ration wa# obtalne~ by ~ g 57 part~ of
th~ prer~ V 4 with 43 part8 by ~eight oi a powder obtaln~d by
20 hot ato~ization o~ the ~ollow~g ~ompc~ition (~ower P~wder ~o.2):
% By Wei~ht
Fs-ester 8ul~0nate 7.0
~ ~DTA o . 6
Sodium cltrate 20.0
Alulaino~illcate 25.3
Waterglaes (1:3.3) 10.2
Sodium sul~ate 13.8
Magn s~um ~ilic~te 4.8
CMC 3 . 9
~alanc~ (~rater, perruEIle~ optical
br~ ~htener) 14 .4
- 35 ~
. ~ .
~039608
The preparation contalns 28.5% by ~elght ef ~odium
perborate. Ihe water-insoluble calcium-blnding aluminosllicate
Wa8 incorporRted ln the preparation both through the premix
and through the Tower Powder in a total amount of 29.2% by
~alght.
EXAMP~ W 3
Low-pho~phat~ pre~a~hing a~ent compo~itlon
The prepar~tlon was obtained by ml~in~ 50 parts by
~eight Or pr mix ~ 1 and 50 parts by ~eight o~ Tower Powder
No. 1 indicated ln Example ~
~XAMPIE W 4
Phos~hate-iree main ~ashln~iagent compo~ition
.
. The prepnratlon wae obta~aed by mixi~g 60 part~ by ~:
~E weieht Or premix V 2 wlth 40 par~ by ~oight o~ Tower Powder
` No. 2 indicated ~ Example W 2.
,, EXA ~ W 5
The preparation W~B ob~ained by ~ixlng 40 p~rt~ by
weight of premix V 8 ~ith 60 parts by weight Or a Tower powder
~-. obtalned by hot atomizati~a of the following compo~ition: :
Tower Po~der No. 3 ~ By Weight
Alkane~7~onate 8.Q
: Soap 5 0
TA + 14 ~0 5.0
EDTA 5
.~ Sodium tripolyphosphata 30.0
Waterglas~ 3.3) a.o
Sodlum carbonate 8.0
CMC 3.o
: Sodiu~ sulrate 20.0 `
Balanee (water, perfume, optical
bri~htener) 12.5
~: '
.: .
- 36 -
. . . ~ . , . ~
1039608
EXAMPIE W 6
_ osphate-~ree prewashlng agent compositlon
m e preparatlon wa8 obtained by mixing 50 parts by
~elght o~ pre~lx V 1 and 50 par~s..by weight Or a Tower pow~er
obtalned by hot atomization of the roll~wing compo~ltlon:
Tower Powder No. 4 % ~ Wei~ht
. .
Ole~insulfo~ate 6.0
TA + 5 EO 4.o
Waterglas~ 3.3) 10.0
:. 10 CMG 3.0
Sodium citrate 8.0
Sodlum sul~Ate 58.5
Balance (water, p~rfu~e, optlca~
brigh~ener) 1~.5
. ~XA~PIæ W 7
.. Low-phosphate bleaching washin~gent co~posi~ion
: ~or 60C ~ashi~
~ 4
m e praparatlon ~a8 obtained by mixing 40 part~ by
. .
watght of premix V 9 and 60 part~ by weight of a T~wer po~der
obtainea by hot atomizatlon of the followlng composltlon:
Tow~r Po~dor No. 5 ~ By Nei~ht
ABS 5-8
Toluene sul~onat~ 2.5
Soap ~.2
~DTA o.5
Sodium trlpolypho~ph~to 25.0
~atergla~3 (1:3.3) 8.3
- C~C 3.o
Alumino~llicate 16.7
Magne~lum Billeate 3.o
Balance (~odium ~ulfate~ optical
brl~hte~or) 31.0
- 37 -
: ~.
10396(~8
The preparation cont~lns 10.4% by ~elght Or ~odlum
perborate and 9.6% by weight of tetraacetyl glycoluril a~ a
perborat~ activator. The w~ter-in~olubl~ calclu~ bindlng
alu~inosillcate ~as incorporated ln the preparatlon through
both the pre~ix and the Tower poNder in a total a~ount of
22.6% by weieht.
: BxAMPLæ W 8
~- Lo~-phosphate bleaching ~a~hing agent compositlon
~or washin~ at 60C
- 10 The prep~ration W~5 obtained by mixing 50 parts by
welght of premlx V 10, 40 parts by welght o~ Tower Powd~r No. ~ -
1 a~d 10 part~ ~y w~ight of sodium perborate.
If it i~ deslred to reduce the ~oaming p~er of
the ~ashlng age~t co~po~itlon~, known fo~m inhibltors are
work0d in. miB iB partlcularly tr~o for preparatio~ wh1ch
contai~ no 80ap.
m~ non-tensiae foam iDhibitor~ included N-alkylated
a~inotriazines, QptiQnally conta~nlng chlorine, wh~ch are
: obtainod by ~he reaction of 1 ~ol o~ cy~nuric acld Ghloride :.
~ith 2 to 3 mols of a mono- a~d/or dialkylamine with 6 to 20,
preferably a to 18, carbon atoms in the alkyl radieal~. SiQi-
larly ef~ctlve are propoxyl~tad and/or but0xylated amin -
triazine~, such as products that are obtalned by tbe a~ditlon
. ~ Or ~rom 5 to 10 mol~ o~ propylene oxiae to 1 mol Or ~elamine -:
: and fur~her additlon Or from 10 to 50 mol~ o~ butylene oxlde
to tbi8 propyle~e-oxide d~rivative.
Lik~wise suitable as non-t~ide *oam inhibitbr~
are water-~n~oluble organic compound~, like paraffin~, or
halogenated p~rar~ins w~th melti~g point~ below 100C,
aliph~tic G18 to C40 keton~, a~ well ~8 aliphatic carboxylic
.; .
- 38 -
` ~039f~08
acid esters whlch contain in the acid or alcohol resldue,
optionally, also in both of theso resi~ues, at least 18 carbon
atoms (such as triglycerides or fatty acid/fatty alcohol
esters). These compound~ can ~e used to reduce ~oaming,
particularly in combination~ of tensides of the ~ulfate and/or
sulfonate type with soaps. Also alkali-~table silicones ~ay
be incorporated as non-ten~ide foam t~hibitors.
The precedl~g specific embodiments are illu~tratlYe
oi the practice of the in~entio~. It ls to be understooa,
10 however, that other expedients hno~n to tho~e skllled ln the
art or disclosed herein, may be employed without departing
from the spirit of the in~ention or the scope of the appended
claims.
.
- 39 -
