Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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1.
CASE 5154
"COMPOSITIONS FOR TEXTILE MATERIAL ~ASHING"
The present invention re~ates to conpositions for
~ash;ng texti~e materia~s in automatic cyc~es
characterized in that the bui~der additives contained
in said compositions are constituted by, or co~prise,
in mixture with conventiona~ bui~ders, one or more
po~yaminoacid~s) at a leve~ of Less than SX by ~eight.
~ y the term "textile materia~s", ~ithin the
context of the instant invention, ~oven materiaLs or
texti~e fibres either of natura~ origin or man-made,
are meant.
8y the terms "composition", "formu~ation" or
"formulate", those products are meant ~ithin the
context of the present invention, ~hich are designed
for use in texti~e materia~s washing.
It is ~ide~y kno~n that the detergency products
are among the causes of the presence of phosphorus in
waters: among a~ of them, the effect of sodium
tripolyphosphate ~STPP), used as a detergency builder,
~as evidenced.
Also kno~n are the efforts aiming at searching
for a~ternatives to po~yphosphates, but the solutions
tried from time to time not aLways supplied
satisfactory resu~ts because, ~hen STPP is either
re~oved or its content in formu~ates is reduced, the
negative effect on the ~ashing process is greater than
as expected from the simp~e decrease in se~uestering
capabi~ities of the detergent matrix.
This unsatisfactory situation results from the
impossibi~ity of ~ocat;ng a product ~hich disp~ays the
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sane character;stics as of SPTT, i.e., bes;des
contro~ing ~ater hardness, acting as a buffer, and
acting as a soi~ re~ease and soi~ suspending agent, as
~e~ as perforning soi~ anti-redeposition actions.
The most wide~y used compound in order to rep~ace
STPP in such formulates, is Zeolite A ~sodium alu~ino
si~icate).
At present, Zeolite A is used both in powder and
in ~iquid compositions
1û As regards the negative effects on the
environment, this product is acceptab~e: it does not
constitute a risk for ~ater bodies and, by being
inorganic and insolub~e, it does not increase the aoD
~oad to ~aste ~aters treating facilities.
From the vie~ point of detergency, Zeolite A
disp~ays good adsorption capabi~ities for dyes and
pigments re~eased by fabrics and its ion-exchange
capability increases ~ith increasing temperature.
Dra~backs are its s~ow exchange kinetics, in
2û particu~ar as regards magnesium, its absence of
buffering action, and its having to be dispersed.
Therefore, Zeo~ite A is a~ays used in
association ~ith other components (referred to as
"bui~der additives" or "co-bui~ders").
The presently used products for such a purpose,
in association ~ith Zeo~ite A, are sodium salts of
poLymeric po~ycarboxy acids.
Among those po~yneric po~ycarboxy acids ~hich
~ere eva~uated for that purpose, acryLic acid-ma~eic
anhydride copo-ymers are those ~hich proved to be the
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~ost efficient ones.
These products are good co~p-exing agents,
disp-ay good soi- dispersing and anti-redeposition
capabi~ities, i~prove the texture of ~aundry
detergents, preventing c-umps from getting formed.
O~ing to the fact that, as ~el~ kno~n, the
po-ymeric po~ycarboxy acids, by being provided with a
~ -C-C- backbone, are rather s~o~y biodegraded, intense
efforts ~ere carried out aiming at deve~oping
a~ternative compounds displaying simi-ar performance
characteristics, additiona~y ~ith improved
biodegradabi~ity.
The improvement in biodegradabi~ity was the
starting point for the definition of bui~ders ~hich
might prove to be a va~uab~e rep~acement for those
bui~ders ~hich are used at present. Thus, copo~ymers
of ma-eic anhydride and/or acry~ic acid ~ith natura-
substances, as starch or dextrins, copo~ymers of
ma~eic anhydride and substances capab~e of
contributing a~y- and viny~ moieties, ma~eic
anhydridelethy-ene oxide copo~ymers, g~yoxy-ic
acid/forma-dehyde copo-ymers, and so forth, ~ere
studied, unfortunate-y ~ith resu~ts ~hich are far from
the desired outGomes.
At present, most ~aundry detergents contain from
2 to 4% of po-y~ers, usua--y acry~ic-ma~eic
copo-ymers, a-so combined uith other bui~ders.
It is kno~n as we~ ritish patent No.
1,404,814) that functiona~ized po~yaminoacids can be
used as surfactants, by being obtained by reacting
4. 2116320
po~yimidic derivatives ~ith ~ong-chain al;phatic
amines; from the control of the type of chain of the
~atter, or fro~ the poly~erization degree of the
po~yimide, the possibilities of se~ecting the end
characteristics of the interesting po~ya~inoacid
arise.
Ho~ever, the products disclosed in said 8ritish
patent do not seem to possess, at the h;ghest level,
that desired bat-ance ~f-properties ~hich cou~ a~-~o~
them to be more genera~ly used in other app~ications
than as suggested, i.e., just to briefly ~ist them,
such characteristics as biodegradability, ~ack of
toxicity, Lack of irritant effects, high ~ater
soLubi~ity, ~hich -- besides detergent properties --
deter m ine the app~icability and use versatility inconsequent formu~ations.
From European Patent Application Public. No. 454 126
it is kno~n as ~e~ that po~yaminoacids, or their
derivatives, can be used as builders or co-builders in
detergent fornu~ations, because they disp~ay extreme~y
good ca~cium comp~exing capabi~ities and inhibit the
formation of CaC03 crysta~ germs, provided that they
are used at concentrations of not Less than 5Z.
The products set forth in the above said
app~ication disp~ay good effectiveness as comp~exing
agents, high heat and pH stabi~ity, are not toxic, not
irritating and are tota~y biodegradab~e, ~hich ~ou~d
enab~e them to be used without causing environmenta~
prob~ems to arise.
Ho~ever, the use of such concentrations as
5. 211~32~
disc~osed in the above said paten~ appl;cat;on might
lead to prob~ems of excessive organ;c ~oadings ;n the
~aste ~aters.
The present App~;cant has found no~, ~hat is the
object of the present ;nvention, that the above said
dra~back can be complete~y eliminated ;f detergent
formu~ations are used ~hich comprise, as buiLders or
co-bu;lders, po~yaminoac;ds at concentrations
comprised ~ithin the range of from 0.5 to SX by
~eight; part;cu~ar advantages ~ere atta;ned ~hen
po~yaspartates ~ere used.
Th;s resu~t is alL the more so surprising,
because it ;s kno~n that a~though they display good
trans;t;on meta~ complexing capabi~ities, such am;no
acids as L-aspartic acid and L-glutamic acid are
unab~e to form stab~e comp~exes ~ith alkaline or
a~ka~;-earth metals CAnge~. Chem. Ind. Engl;sh Ed., 29
~1990) 1090-1103~.
Therefore, in its ~idest form, the present
Zû invention re~ates to su;tabLe compositions for textile
mater;a~ ~ash;ng, character;zed ;n that they conta;n
surfactants and other sa~ts.
As an;on;c surfactants, ~e may remind here, for
exemp~;fy;ng purposes, sod;um, potass;um or ammon;um
salts of ~;near-cha;n C10-C20 fatty acids, aLky~
su-fates, a~ky~benzene su~fonates, alkane su~fonates,
hydroxya~kane su~fonates, a~kene sulfonates and a~ky~
ethoxy sulfates; ~e furthermore ~;sh to cite various
su-fonates, such as alkyL su~fosuccinates and a~ka~i-
meta~ and/or ammonium N-acy~-N-methy~ taurinates, and
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so forth, or ~ixtures thereof.
As non;onic surfactants ~e ~ou~d mention, for
exemp~ifying purposes, the products of condensation of
ethy-ene oxide ~ith substances containing active
hydrogen atons, such as C10-C~ fatty acids; as ~e~ as
amides, fatty alcohols and amines, sucrose esters and
alkyl phenols ~ith C6-C12 alkyl chains; as nonionic
surfactants, aLso amino oxides may be cited.
As ampholytic surfactants, may we cite in genera~
those compounds ~hich derive from aliphatic amines,
characterized by the presence of at least one C8-Cl8
chain and at least one chain containing a hydrophy~ic
anionic moiety, e.g., a carboxy or sulfonic acid
group.
Those agents ~hich complex alkali-earth cations
according to the present invention, are common~y
defined as "builders" and, as a~ready said, perform
severa~ positive actions for the purposes of good
textile ~ashing results. One of most important among
these actions, consists in sequestering meta~ ions, in
particular aLka~i-earth meta~ ions, ~hich constitute
the ~ater hardness (Ca~, Mg~). For use as "builders",
the prior art suggests severa~ inorganic compounds
such as, e.g., ~ater-so~ub~e a~kaLine sa~ts, such as
carbonates, silicates, etc., or ~ater inso~ub~e
compounds, such as alumino si~icates, e.g., natural or
; synthetic zeo~ites; furthermore, ~ater so~ub~e organic
compounds such as a~ka~i-meta~ or ammonium salts of
po~ycarboxy acids ~citric acid, carboxy-methyloxy
succinic acid, oxydisuccinic acid, and so on), are
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7.
suggested.
Among most suitab~e optical brighteners for
simu~taneous texti~e ~ashing and br;ghtening, the
opticaL brighteners from DAA ~aminostilbene-disulfonic
S derivatives~, DP tpyrazolinic~ and AC (a~ino-
coumarinic~ series may be nentioned here.
~ henever so required, said formulations may
contain, as bleaching agents, oxidixing or reducing
compounds, such as, e.g., hydrogen peroxide, alkali-
metal perborate, preferably sodium perborate, sodiumpercarbonate, hypochLorites, ch~orites, phosphites,
hydrosulfites.
In the event of use of persalts or hydrogen
peroxide in formulations for ~o~-temperature textile
~ashing, the use is suggested of bleach activators,
such as, e.g., tetraacetylenediamine, TAGU,
pentaacetyl glucose, nonanoyl phenol sulfonate tsodium
salt), and so forth.
As an alternative, for lo~-temperature wash
requirements, the use is possible of organic
peroxides, such as peracetic acid, dodecanediperdioic
acid, phthalimino caproic acid, and so forth.
Uesides the already mentioned ingredients, the
formu~ates according to the present invention may
obviously contain other common ingredients, such as,
e.g., perfumes, antifoaming agents, stabilizers,
- anticaking agents, buffering agents, through-the-~ash
co-our protecting agents, and, final~y, extenders,
such as, e.g., sodium sulfate.
Furthermore, the formulates according to the
, _ ,,,,, , . , , . , .. , . ., . . . . ... , . .. .. . . ... . . , .. , .. .. . ... _
8. 2116320
present invent;on also contain at least one poly-amino
acid, ~hich can a~so be in partial~y solidified form~
at a concentration comprised ~ithin the range of from
0.5 to 5X by ~eight and, possibly, a conventiona~ co-
bui~der se~ected fro~ the copolymers of ma~e;canhydride and/or acry-ic acid w;th such natura~
substances as starch or dextrins or gLucose,
copolymers of maleic anhydride and compounds bearing
a~lyl or v;ny~ moieties, ma~eic anhydride/ eehyt-ene
oxide copolymers, glyoxylic acid/formaLdehyde
copolymer, and stil~ other polyelectrolytes.
The molecu~ar ~eight of useable polyaminoacids
can be comprised within the range of from 1,000 to
300,000, preferably of from 10,000 to 100,000, ~ith a
sa~ification degree preferably comprised ~ithin the
range of from 70 to 85%.
In the formulations according to the present
invention, al~ those aminoacids can be used ~hich are
disclosed in above cited European Patent Application Public.
No. 454 126, including polyaspartic actd and its
salts. ;~ ~-
An exemplifying, ho~ever non-limitative,
composition for the detergent formulations according
to the present invention, can be as follo~s:
25 * Surfactants 5-40% by ~eight
* 4A Zeo~ite 5-50X by veight
* Po~ymer 0.5-5X by ~eight
* Sodium perborate tetrahydrate 0-30X by ~eight
* Tetraacetyl ethylene diamine 0-5X by ~eight
30 * Sodium disilicate 0-10X by ~eight
* Sodium carbonate 5-25X by ~eight
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9.
* CMC 0-2X by ~eight
* Enzy~es 0-1X
* Perfume, ant;foa~ers, etc. 0-2X
* Sodium su~fate + H20 ~.s. to 100%
The fol~owing examp~e is supp~ied in order to
further i~Lustrate the invention. The effectiveness of
the present products is aLso evidenced.
ExamDle
~ash tests ~ere carried out by using formu~ations
which contained either sodium salts of po~yaminoacids
as co-bui~ders, or, as reference, 85%-sa~ified 1:2
maleic-acrylic copo~ymers ~ith an average molecu~ar
~eight of 75,000, as ~ell as mixtures thereof.
The test conditions ~ere as fo~lo~s:
15 * Tested fabrics EMPA 103 (combined
strips)
~hite ~fK cloth
* ~ash temperature 90C
* ~ater hardness 40fH
20 * Washing liquor pH 10.5
* Detergent concentration 10 g/l
The composition ~va~ues as X by ~eight) of the
detergent used ~as the fol~o~ing:
* C11-C13 alky~benzene suLfonate 7.0
ZS * C12-C22 soap 2.0
* Lialet-145-7 E0 ~oxo C14ls
a~coho~ ~ 7.0 mo~ of E0) 5.0
* Po~ymer 0 - 4
* 4A Zeo~ite 27.0
30 * Sodiun perborate tetrahydrate 20.0
* Tetraacety~ ethy~enediamine 4.0
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10.
* Sodium disilicate 3.0
* Sodium carbonate 10.0
* Enzy~e 0.4
* Sodiu~ suLfate + H20 q.s. to 100
No carboxr~ethyLceLLuLose tCMC) ~as added in
order to better evidence the perfor~ance of the
poCymers; furthermore, optical brighteners ~ere aLso
excluded.
The tests ~ere carried out ~ithout po~y~sr; in
the presence of acry~ic/maLeic copoLymer; in the
presence of t~o different sampLes of po~yaspartic
acid; and in the presence of a bLend of acryLic/maLeic
copo~ymers and poLyaspartic acid.
The resu~ts are summarized in foLLo~ing TabLes 1
and 2.
TabLe 1 ~Detergent capabilities)
1 2 3 4 5
_____________---------------- .~ . ~:
Oily soil 23.7 25.1 26.6 26.126.3
Prote~nic soll 55.2 57.2 57.7 55;5~ 56.8
Oxidizable soil 48.2 53.5 52.1 52.452.8
Average value 42.4 45.3 45.5 44.745.3 ~
Remarks ~ i
1 = No po~ymers
2 = Sodium saLt ~85X) of acryLic-maleic copoLymer
~moLecu~ar ~eight C~] = 75,000) ~4X)
3 = Sodium saLt t80X) of poLyaspartic acid tm~ =
; 12,000) t4X)
4 = Sodium saLt ~80X) of poLyaspartic acid tm~ =
70,000) ~4X)
L ?~
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11 .
5 = Sodium sa~t of acrr~ic-maleic copolymer ~Z%)
sod;um sa~t of po~yaspart;c acid (m~ = 70,000)
(2X).
Fron the data reported in Tab~e 1, one may infer
that polyaspartate supplies detergency performances
~hich are at ~east comparab~e to those offered by the
commercia~ copo~ymers.
In Tab~e 2, the data are reported ~h;ch relate to
the va~ues of residual incrustations on o~ after
different numbers of ~ash cycLes, ~hich ~ere obtained
~ith the above cited formu~ates.
Table 2 (Ash content)
1 2 3 4 5
______________ :
155 cycles 0.5 0.5 0.5 0.4 0.5
10 cycles 1.1 0.6 1.0 0.7 0.7
15 cycles 1.4 0.7 1.1 0.8 0.8
The data reported in Tab~e 2 confirm that
po~yaspartic ac;d disp~ays pr;mary and secondary
Z0 detergency performance3 ~h;ch are perfect~y acceptable
and any~ay are equ;va~ent to those as offered by the
commerc;a~ly availab~e copo~ymers.
' 25
