Note: Descriptions are shown in the official language in which they were submitted.
~A~EGRO~ND AND SU~MARY O~ ~HE INVEN~ION
============_====_=_====_===_========
~ he present invention refers to dried, ~inPlly
divicLed detergent compositions, and more particularly to
those powaery detergent compo3ition for use either by
hand washing or in automatic washing machines, to
launder or wa~h any type of fabric.
It i8 known that in order to be efficient to a
satiefactory degree, a detergent composition mu3t be
formed by at lea~t 5
(a) one or more surface active agents;
(b) one or more hardness ions removal agents, in
oder to reduce the hardnees of the washing
~ater;
(¢) agents performing an alkalizing function;
(d) optic~l brighteners or chem~cal bleaching
agents, in order to increase the whiteness of
the fibers treated ~ith them.
~ he composition i8 genera~ly completed by additive3
to be present in sm~ll amounts, exerting ~ariou3 supporting
a¢tion~, a8 ~ell as by inert fillers.
~he hardness ion~ seques.tering agents are commonly
te~med "buildersn, and are ~urther responsible of variou3
desirable actions, exerted concurrentlg with their
sequestering action, su¢h as for example, the peptizing
action, the aispersing action, the anti-redeposition
. . ~F
~i3~
acti~)n,
r~he cla~ of substances which nowadays still perform
this number o~ functions in the most satiefactory manner
are the polypho~phates. ~o the polypho~phate3, however,
it has been attributed a crucial action in promoting
under particular conditions ~n uncontrolled propagatio~
of seaweedes within any surface ~aters (eutrophication
factor), which leads to an adverse effect resulting from
the alteration of the environmental conditions with
consequent lo~ering of the oxygen content of the waters,
due to ~ermentatio~ processes connected with the final
stage o~ the seæweeds vit~l ¢ycle. ~he lowering of the
oæygen content in the waters also adversely affects the
vitPl cycle of the aquatic fauna.
In detergents, the substitution of polyphosphates is
not an ~asy matter, since at present no other substaxce~
are avP~lable which are ~ureIy harmless from the
vie~point of the environmental pollution and which
pos~es~ the number of requirements ~hich are typic~l of
a good builder.
D~E~__IPIIQN=O~ ~HE INVEN~ION
Quite surprisingly, it has bee~ found that it is
pos9ible to substantiPlly reduce or even eliminate the
polypho~phate content in the detergent composition3,
without affeoting their ~ashing efficiency, by parti~lly
~38~9~
or totally substituting the polyphosphate~ in the detergent
composition by a synergic combination of a ~oap and a
soluble salt of the citric acid,
hccording to a main aspect, the detergent compositions
according to the present invention are characterized by
a content of from 10% to 50% of a water soluble, pre~erably
an alkzline-metal salt of the citric acid, a~d from 5~
to 60% of a water soluble, preferably an aIk~line-metal
g~lt of natur~l or synthe~ic fatty acids, with a chain
7ength of from 6 to 24 atoms o~ carbon.
~ h; g kind o~ alkaline-metals fatty acias s~lts are
commonly aesigned as "soaps", and 80 they will be ter~ed
heins~ter.
It is essential that the two aforementioned
compounds be simultaneously present in a detergent
compo~ition, slnce ~either of them has the power of
individually performing the action of builder, ~
required ~f a substantial reduction or a complete
substitution of the polyphosphates is desired in the
detergent compositio~
~ he sy~ergic action o~ the citrate and of the soap
according to the invention i8 best shown when the
~sshing i~ done at high temperature~, where the
diminished complexing po~er of the citrate is
compensated by the de-hardening action of the soap
-- 3 --
1~3~Z94
-.,
c2using the precipitation of the hardness ions present
in the water, in the form of water-insoluble soaps.
~he lprecipitate thu~ ~ormed within the wa~hing solutio~
kas no eignificant tendency to ~tick to the w~shing
machine or to the ~abrics.
~ he detergent compositions according to the present
invention are furthermore characterized by a P content
ranging between 0~ and 2.~% by weight in the final
~etergenu compositio , ~hich i8 a significantly reduced
content if co~pared to the ordinary detergent~ used for
t~e w&shing of fabrics, in which the P content ge~erP~ly
has a much higher v~lue, in the range of 6 to 8% or
more. ~he detergent ¢ompositions acoording to the
pr2sent invention are therefore provided with a low
eutrophication po~er, since the percentage o~ P is at a
lo~ or at a zero vPlue. ~he citrate ~ich i8 present i
~hese compositions has a very low toxicity to~ard any
se~weeds, invertebrates, fishes and ma~mal~. ~oreover
it has a good biological degr2dabilty both in the w~ter
~a in the eart~ both in aerobic and anaerobic conaitions~
~he soPp too h~ a very low level of toxicity, ~n~ it c~n
be wholly degraded into C02 and water i~ a very quick
manner. ~herefore tke pollution power of the citrate and
the soap results to be a particularly low one, wkile the
dsgree of thsir ecologic consistency appears to be high.
-- 4 --
.
Z94
~ Tarious surface-active agent~, ~Ikalizing agent~,
supportin~ agents, atain removing agents, bleaching
age~i~, optical brightener~, anti-redeposition agents,
~d ~ulert filler~ may be added to the composition
according to the invention. ~he said agents are ~ell
known in the art, ~nd will be not described ~urther.
1~ the composition according to the in~ention PlSo
other sequesteri~g agents dif~erent from polyphosphates
Pnd citrate mlght be used, in order to achieve some
Pdditional performances of the detergents, i~ addition
to tho~e ~lready quite satis~actory, which can be
obtained wlth the detergents according to the inventio~.
Among the several sequestering agents ~hich cPn
be u ed in combination in the composition according to
the invention, the following organic acids, ~nd their
salts, c~n be me~tioneas poly-carboxyl acids (other
than citric acid); hydroxy-carboxyl acids; ~mino-
carboxyl acids; carboxyl-~lkil-ethers; carboxyl -
2nd phosphonic acids (with a m~ximum P ~alue of 2.5
in weight/c~lculated on the total weight of the
composition); polyPnionic polymers.
~ g æ~ ex~ple of inorganic type agents de~elopping
a comple~ing action, the compound~ corresponaing to the
general formula:
(~at2/~1)X Me23-(sio23Y
113~Z9~L
may be mentioned, ~here ~at i8 a cation of the valénce
n, exchangeable wQth calcium, x i8 a number from 0,7
to 1.5, Me i~ a member selected from the group
co~ ting of aluminum and boron, and y is a ~umber
from 0.8 to 6~
he compo~ition according to the in~ention c~n be
prepared by any process which i8 suitable for the
production of powdery detergents-
~ he~e compositions are preferably prepared by aproces3 by ~hich the alkali metal ~alt of the citric
acid, the soap ~nd the other components of the
composition, which are stable under heat condition~
the form of aqueous pulpy batche3 are transformed by hot
drying, preferably by hot atomization, into easy to
handle powders, particularly into beads. ~o the thu~
obtai~ed powdered composition it is pos~ible to add
some compone~ts, such as perborates, enzymes, perfumes
nd the like components that cannot be subjected to the
heat-drying proce~s.
~ he detergent compositions of the present in~ention
do ~ot present the problems ~hich sre peculiar of the
compositions with a lo~, or no conte~t of polyphosphates~
~ ne of these problems is con~tituted by the tendency
to ~orm incrustations o~ the metallic parts of the
~ashing machine, and particularly on the tank or o~ the
-- 6
1;138294
drum of the wa~hing machine~, or on the movable parts
of the pump a~d o~ the discharge valve, on the pre~sure
~witch~ and especiPlly on the heati~g elements of the
said machines. Particularly in the case of incrustation~
on the heating elements several adverse effects might
occur. At ~irst, the thus formed incrustation tends to
reduce the heat e~change between the heating elements
a~d the ~ash~ng ~ater bath. ~his entrains the risk of
an undue increa~e in the temperature of the heating
element~, 80 that the heating elemerLts will probably
ha~e a shorter average life. ~oreover, the washing
cycle nill last for a longer time, if the switching
from the one to the next ~tep of the cy¢le is controlled
by a thermostat. As a re~ult, not only a waste of time
will be produced, but also a ~aste of energy. In the
case ~n w~ich the switching ~rom the one to the next
step of the cycle is controlled by a timer, the result
will be that a temperature lower than that requested
w~ll be attæined in the concerned washing step. ~hi~
w;ll produce, according to statistical data, a lo~ering
of the washing ef~iciency.
~ 11 the abo~e factors have an adverse influence on
the average liie of the washing machine.
~ nother problem connected with detergents having a
low, or even no content of polyphosphates, is that o~
the loading of the fabrics~ due to the deposition of
1~38Z94
sQlts on the washed fabrics. ~he fabrics might therefore
becom greyish and rougher to the feel, and these factor~
are both of a fundamental importance as to the stand~rd
of the ~a~hing.
~ he average life of the fabrics i8 al~o adversely
a~fectea.
- ~inslly, tho problem which probably is the mo~t
importa~t in detergent compositions with a lo~, or
eve~ no conte~t of polyphosphates is the prob~em o~ the
washing performance of the detergent.
~ he user~ are presently accustomed to employ high
sta~dara detergents ~hich permit to obtain guite
satisfactory results. ~his is also due to the
sign~ficant contribution of polyphosphates ~hich occur
in the presently used detergents.
~ he detergent~ of the present invention permit to
keep at a good standard the effects of the ~ashing of
fabrics, and to ~ep u~damaged, in the mec~n;cal
wa~hing~ the compnnents of a wa~hing machine. By the
u~e of the detergents according to the invention, the
incrustations on the machins drum, on the tank surfaces
~n~ on the heating element~ are eliminated or reduced
to a minimum, Pn~ also incrustations on ths washed fabric~
~re very reduced~ wi~h a good efficiency o~ deter~ency.
ere~ore the compo~itions a¢cording bo the i~ventio~
-- 8 --
, :
1~38294
per~it to keep the a~erage like of both the fabrics and
the washing machines almost stationary.
~ he ~ollowing ~pecific embodimente are illu~trative
of the invention, ~ithout being limitative in any
re~pect. In the following ~ample~, ~ome deterge~t
compositior3 made according to the invention have been
compared with ~ome commercial detergents having a high
P content, i~ order to compare their efficiency.
. . ~ . ;.. -..: .
. .. ;~.,Y;~ :
i~38Z94
a~
o
8 ~, ~ g ~
o
, . ~ .
m U
o
0 ~ N ~ V
g
O O
o m
V ~ , o
m U
o~.
mff~
. ~ a
V
V
QS:~ . m
C~ o - ~ ..
h o .,~~,
~4 F4 ' o~
P,
4'
O O O O O 0~ 0 0 ~ 3
O ~
O tt~ U~ N ~D ~ O O r I
~ ~ 8 . a3
.- ~ ~
m
,~
0 o ~
0 ~ o - ~ _
0~ O P~
P~ ~ ~I ~ O ~? Sl , ~ ~ ,,
M S~ OD h t~
O ~ r1 ~ 0 C.. l O S:
o a~ ~ ~~ 0d O
r~ r~ ~ ~o ~ o 11
h F~ 0. r~ ~ O ~ m ~ ~ 0
o, ~~ ,~ ~ ~ o a~
~rlh r O ~
0 Z O ~ V
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H ~`-- ~ ~ ~ m 0 ,~
o o~ o o3 0 o o h 0 ~ ,s: Id o
Q ~ m ,~ ~ ~ ~ ~ ~ ~ ~
w a~ o ,~ ~1 ~ 0 o ,~ ~ U
~1 0O OD O ~ ~ ~ h tD h s ~D
m O ~d ~ m ~ ~ o q) o o
O ~ O ,~ h -
h ,1 ~ m
O~ ~ ~0 ~O ~ ~0 ~0 ~ 0 ~ ~0 O''-- _ -
-- 10 --
.
- ~138Z94
The te~ts were made in a drum-type washing machine at
the following conditions~.
- Detergent concen~ration s 7.5 ~l in water
- ~araness of t~e water t 25F (french degrees)
- ~oad of laundry with natural dirt 2 4.5 Eg.
- Washing temperature : from ambient temperature up to
90~
- ~umber o~ washings : 14
~ he results of these tests ~ere the followings
Detergenc~: on fabric~ with ~atural dirt it appeared to be
~ignific~ntly at the same level for the composition I,
forming the ob~ect o~ the present invention~ as well as
for the compositions ~ and B; ~ resulted to be
sig~ificantly lo~er.
Degree of whiteness: the compositions I and ~ appeared to
be the best, according to the classification as sho~
hereunder:
~omposition I 1st
- " A 1st
n B 2nd
H C 3rd
Deposits on fabrics: a~sessed upon completion o~ the 14
~ashings, and expressea as the total ashes perce~tage on
a fabrio, they re~ulte~ to be as follows:
Composition I0.32%
1~38Z94
Composition A 0.25
n B - 35%
n C 1:). 90%
Deposits on heating element~ essed upon comple~ion
of 14 wa3hing~ and expressed as increa~e~ in wei~ht, they
gave the fo~lowing Y~1uess
Composition I +0.6 g.
n A 1 t). 8 g.
n 33 - +1.3 g.
C .1 2. 5 g.
.. . . . .
`:
~ 12 .---
:, .
1~38Z94
tn
..
O ~ ~r
.,, o
~ ~rl N
.,~
tn ~r ,1 11
~ W ' ~n N
O
U d O
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a) s '''"'
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W t`
O
O ~a
O ~1 5
U~
o Q~
~_ O C~
0 ~1
O ~)
O ~ .oP
C~ ~ t~
In _i
r~
4~ S ~1
~ ~ U
O ~ CO
a) u ~rl N
U U 11
h ~ 0 U~
H ~J ~1
H ~r ~ U
W ~
~ ~ dP
~ ~ O
~ d~ dP d~ dPdP d~ dP
X o o 1' ~~D ~In o o u~ 11
W ~ ~'7 N O
4-1 ,_
O
'I ~ a.
O ~ ~ ~P
s a~
o
u~ ~U ~ r~
O--I X O
O ~ O ~
U ~ u~ ~~1 h ~1
_ ~1 3~ Q~N O ~: ~ U
o a~ o ~ R~rl
o ~ ou~ ~ ~ ~ a
NO ~)
U ~rl N ~ Q~Z :~ 3 R ~ 11
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~:1 h ~R ~Q Oal a~ O ~1au E U
1~ ~ u o u ~ O
H ~ ~ ~ ~~ ~ d U~'
o ~a u~d aJ U
O (1~ O~1 ~IIJ O ~1 0 ~ ~
o o ;J~ o ~ 0 o
~,q h ~ ~E3 0 ~IE~ X S O E
o ~ ~ ~ ~u ~ o
O ~rl O ~O O ~10 ~a) ~ o o ~ ~1
O U~ U ~ U~ O
-- 13 --
~.
~ h~ efficiency asses~ment~ haYe been m&de i~ the ~ame
conditions as for e~ample I.
~ he following results were obtained:
Detergenc~: no significant differences bet~een the four
examined detergents were noted.
De~ree of whiteness:
Composition ~ 1~t
n II 2nd
D 2nd
n ~ 2nd
Deposits on fabr~cs:
Compo3ition II 0.11%
n D 0.28%
. 23~o
~. P' 0~16%
Deposits on heating elements:
Composition II 0.5 g
" D 1.5 g
. n ~ 1.2 g
n F 0-9 g
-- 14 --
o 1138294
o ~ ~ ~
., ,, o~s
0
o
, ~ o 4~
o ~ ~ P~
0 .~
0 ~ s
o ~
a
.c ,,
g ~
o ~ ~
s
~ ~ U~
H U ~ 0
1~1 P1 3 R~
dP
o ~S o
E~ o O ~ U') ~D ~1 1-- 0 r-i O ~ Q
N ~I O Q) O
-- ~ s a~ ~ ~, o R
O
~i ~ o _I x o
~ ~ ~ 0 0
o 0 3 Q~ 3 Ul h ~ I
0 ~1 al ~ h .C ~ 0 ~
o ~ ~ nS ~I r~l a~ o o 0 ,~ 115
~ ~ h ~
~ '3 t) ~ o a~ Z ,~ .~ Q e o ~ ~ ~
~ H , ~ $ 0 0 Q~ ~ 0 0 N Q) ~ 0
`~ H rl~ItU ~1 a~ ~ 0 0 t) 1~ ~ O Q)
H ~ `~ ~ IJ 0 0 ~I rl a~ 0 0 tJ) a) ~1
~ ~ o o ~ 0 a~ rC O
~ 0 R~h O 0 r~l ~r~ ~ ~ ~ O ~ h ~ ~
O (d~'~ ~ O ~ ~J 0 0 rl ~1 0 ~: ~' h
rl ~ O~1 0 ~ O h ~ :1 I Q) O
,~ ~ 0 ~ ~ ~ 0 ~ 0 a)
o ,i ~ x s ~ 'o' ~ ~ e h O ~
O ~ O ~ 0 0 ,4 ~ ~ ~ h P~
r l ~ S r~ Q h r~ r~ Ul
.' ~3 S ~ '~ r~ O ~
O ~r l O~1 0 0 rl 0 ~ J h O O J ~1
; ,~ 3 tn O E~ E; O --
-- 15 --
';
1~38zg4
lQ . 1%, C12 Q . 6%, C14 = 3 . 3%, C14* = 0 . 3%, C = 1 2%
16 , C16* = ~ . 8%, C17 ~ 1 . 6~ ~ C18 = 8 . 8%
C18* = 51.1~, C18** = 7.196, C20 ~ ' 20*
C22 = 0, 4
.' ' '
,
- 15a -
'~'
~,
ii38Z94
~ he detergents A and ~ are the same as for the Examples
I ana II.
A180 in this instance, the method~ and the oondi.tion3
o~ ~sessment are similar to ~hose described in Example I.
etergency: no sign1ficant difference~ in e~ficiency haYe
been noted.
De~ree of ~hiteness: Composition III 1st
A 1st
~ 1st
De~o~it~ on fabrics; Composition III 0,2~%
A 0.25~
F 0.16%
Deposits on the heating elsments:
Composition III 0.8 g
0.8 g
0-9 g
A130 a series of 5~ consecutive washings ~a8 carried
out nith the composition~ o~ Examples I, II, III, in
order to disco~er any damages po~sibly caused to the
automatisms of wa~hing machines. In any case it was not
~ound a situation worse than the situation that occurs
with the commonly sold detergent A, ~, F, already mentioned
in the disclosure of the examples.
~ he prsceding ~peci~ic embodiments are merely
illustrsti~e of the in~ention. It is to be under~tood
- 16 - -
1~3829~
however that other expedients known to those skille
the ~rt, or di~clo~ed herein, may be employed without
departirg from the spirit of the invention or the
~cope of the appended claim~.
- 17 -
