Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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BACKGROUND OF T~IE INVENT~ ON
Field of the invel)tion
The present ;nventiorl concerns a washin~, blea~b;ng
and cleaning pr~duct that is particularly suit~bl~ for use
at lower temperatures. The invention is part;(~ rly CO~l-
cerned with such products that comprise as bleachin~ agel~t;
an alkalimetal monopersulphate and as activator therefor
an alkalimetal halogenide.
Description of the prior art
The published German patent application DAS 1,144,675
describes washing, bleaching and cleaning pro~ucts compris-
` ` ing an alkalimetal monopersulphate and an alkalimetal ihalo-
genide. According to this publication halogen ions improve
the bleachin~ action that is obtainable by means of the
.
, 15 alkalimetal monopersulphate. This improvement is achieved
~ . .
by the addition e.g. of sodium chloride as the halogen-ion
~i - releasing compound.
~` The improvement Or the bleaching erfect is however
`~, not very marked and the object of thè present invention
is therefore to improve significantly the bleaching effi-
ciency Or the alkalimetal persulphates, in particular at
: lower temperatures.
US Patent Specification 3,458,446 describes a
~i acouring product which comprises an alkalimetal monoper- ~ -
sUlphate and a water-soluble bromide as activator there-
. .
or. According-to this specirication the addition of the ~-
~ . .
bromide ensures a bleaching power on hard surraces that
i8 far superior to that ~btained by means of~chloride.
~- On studying the alkali monopersulphate/alkali bro-
mide system ~or bleachin~ ra~rics, which is an applica-
.
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tion that is not menticned in U,~, Patent Specification
3,548,44b, it has been found that incorporating a bromide
as activator for an alkalimetal monopersulphate does sig-
nificantly improve the bleaching power on fabrics but si-
multaneously causes completely unaccepta~le damage to the
~ibres.
The object Or the invention is therefore to provide
a solution Por the problem Or the disadvantage of the
damage to the ~ibres on using an alkalimetal monopersul-
phate as bleaching agent and a compound supplying bromide
ions a~ activator for the alkalimetal monopersulphate.
According to the published German patent ap~lica-
tion DAS 1,221,752 it is known to add to an alkalimetal
monopersulphate/alkalimetal chloride system a nitrogen-
containing compound acting as chloride-hypochlorite ac-
, . . .
ceptor. This system however contains an alkalimetal chlo-
ride in such an amount that particularly when in solution
~ at a pH Or 0-8 an undesirable amount of chlorine is re-
,' leased which is taken up by the nitrogen-containing com-
pound. The amount o~ alkalimetal chloride u~ed according
.~ to the published German patent application varies from
i 1 to 10 times the amount of alkali monopersulphate, where-
as the small amount Or alkali bromide according to the ~ -
inv~ntion is considerably smaller.
5`` 25 Summary o~ the ;nvention
It has now been found that the damage to fibres,
which is caused by the system alkalimetaI monopersul-
i phate/bromide-ions supplying compound~can be substantial-
3 ly decreased by adding a minor amount of a nitrogen-con- -
~ ~ t~ining compound acting as bromide acceptor.
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- The present inverltioll therefore relates to a washirlg,
bleaching and (leanin~, product with a redu(~ed f~bric-~3~ln~ge
efre~t, compri~ing an :llkalimetal monopersulphate, an alk~-
limetal halogenide arlv' a nitrogen-containing compound w~,ere-
in the alkalimetal hak,genide is alkali bromide.
De~cription Or the pre~erred embodiments
The alkalimetal monopersu1phate may be any persul-
phate, e.g. sodium or pota~sium monopersulphate. According
to the invention a triple salt o~ the rormula KHS05: ~HS04:
K2S04 in a molar ratio of about 2:1:1, e.g. such as that
` sold by Degussa under the registered trade-name Or Caroat
- or by Du Pont under the registered trade-name of Oxone, is
- preferred. The amount Or alkalimetal monopersulphate to -
`- be used varies over a wide range according to the use `
intended for the product according to the invention. This
amount varies ~rom i t~ QO~, prcferably from 5 to 60~ and
more particularly from 10 ~o 40% by weight.
The alkalimetal bromide may be any bromide, e.g.
` sodium or potassium bromide. Sodium bromide is preferred.
The alkalimetal bromide is used according to the invention
~ .;
in an amount from 0.1 to 5% by weight, the weight ratio of
alkalimetal monopersulphate to alkalimetal bromide being
preferably higher than 1~
The nitrogen-containirlg compound used according to the
3~ invention ~hould on the one hand decrease damage to ~he ri-
bres without on the other hand undesirably arfectincr the
bleaching power. In this connection it has been foun~ that ~
~ variousnitrogen-containing compoundscited in the pub~ished ~ -.
:~ German patent applicationDAS 1,221,752do notmeet these re-
- 30 ~rements.~b~ ~tance,melamirlenegatively aff~ctsboth blèach-
ingpower~nd dama~eto thef~bres,andthe ~iulnsalt Or sul- -~
-~ . : . ,
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phamic acid has appeared to be entirely unsuitable for
decreasing the damag~ to the l`ibres.
Exampl~s o~ suita~le co~pounds ~or us~ in the inven-
tion are sulphamides, amides such as acetamide and urea.
It has been found that particularly nitrogen-cont~ining
compounds containin~ a -C0~ radical meet ttle ~esited
criteria. The latter compounds and particularly urea
`~ are preferred. In general the nitrogen-containin~ Com-
pounds are used in an amount from 0.1 to 20g and prefer-
ably from 1 to 10% by weight.
The combination according to the invention may be
used as such, but it may als~ be present in a conven-
tional ~s~ng and cleaning product. Such washing and
cleaning products comprise, besides the combination
according to the invention, a detergent-active material
` and as the case may be builder salts and other additives.
In general the cleanin~ product may compJise from
` 2 to 20% by weight of an anionic detergent in the form ~ -
of the sodium, potassium,ammonium or triethanolamine- .
.f -
~ 20 3alts. Examples thereo~ are alkyl benzene sulphonates ~ `
`~`a ~ the alklyl radical of which has 12 to 18 carbon atoms,
alkyl sulphates the alkyl radical o~ which has 10 to 24
` carbon atoms, olefin sulphonates obtained by sulphona-
~`~ tion of ~traight-chain alpha olefins havin~ 10 to 20
carbon atoms followed by neutralization and hydrolysis `
.~ Or the sulphonation products, acyl~sethionates the acyl .
radical of which has 12 to 18 carbon atoms and acy1- .-
., . - . . : -- :
~- taurates the acyl radical Or which has 12 to 18 carbon
.~ ~ atomæ. Moreover, the products~aocording to the invention --
may comprise 1 to 1~% ~y weight o~ a nonionic detergent. ~- `
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Examples thereof are the condensation product3 of alkyl-
ene oxide, ror e~ample ethylene oxide or propylene oxid~
with alcohols Or which th~ alkyl radical ha~ 12 to 24
carbon atoms, with alkyl phenols Or which the alkyl
5 ` radical has 8 to 18 carbon atoms, with fatty acid amides
comprising a fatty acid radical with 10 to 24 carbon aton,s,
with polyalkylene glycols and with mixed alkyleneoxide
condensation products.
~ ,.. ..
The products according to the invention may also
comprise an alkalimetal soap in an amount of 1 to 10
by weight. Examples thereof are alkalimetal ~uch as sodi-
um or potassium)soaps of ratty acids with 12 to 22 carbon
atoms such as fatty acids derived from palm oil, coconut
oil, tallow and hardened fish oil.
For medium Poaming the amount of the various deter-
gents is 8 to 15~ by weight of the anionic detergent, 1
to 6% by weight of the nonionic detergent, 1 to 5% by
~ .
weight of the alkalimetal soap, whereas ~or low foaming
the amounts are from 2 to 9% by weight of the anionic
detergent, 2 to 10% by weight of the nonionic detergent
;~ and 5 to 10% by weight o~ the alkalimetal soap.
. . .
The balance o~ the product according to the inven- ~ --
tion can be rormed by the usual constituents of washing ~
. ~ . . ~ . .
and cleaning products. For instance, these products may -
$ - . 25 comprise up to 50% by weight Or a condensed phosphate
8uch as pentasodium triphosphate. Part of the condensed
phosphate may be replaced by an~organic builder such
as trisodium nitrilotriacetate.
~-~ Moreover, besides 0.5 to 3% sodium carboxymethyl
cellulose or another suitable anti-redeposition agent,
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the products according to the invention may comprise 2
to 10% sodium silicate.
Furthermore, the products :~ccording to the invention
comprise inorganic alkalimetal salts such as sodium-sul-
`j!' phate, -carbonate, -borate or -orthophosphate, sodium
hydroxide and also other (prererably ch1Orine-stabl~)
additives such as anti-tarnishing agents, perrumes ~pre-
ferably chlorine-stable), germicidesj colouring a~ents,
foam-modifying agents, fluorescers tpreferably chlorine-
stable), solvents etc.
The products according to the invention are parti-
cularly suita~le for bleaching at lower temperatures, to
wit 30 to 60C. It has been found that even at high pH
` values, viz higher than 8, a distinctly improved bleach-
ing power and a distinctly decreased fibre damage are
achieved; the use of sodium hydroxide to adjust the pH
in that range yields better results than those obtained
e.g. by means of trisodium orthophosphate or sodium car-
bonate. In general the best results are obtained at a -
` 20 pH rrom 8 to 11. The invention will be further illu-
strated by the following Examples.
EXAMPLE I
Standard cotton Krefeld test cloths were washed in
a Tergotometer with various compositions and the chemi-
- cal damage to the fibres was determined. The bleaching
power on cotton fabrics, stained by tea, was determined. ~
The operating conditions in the Tergotometer were ~ ;
)~ as ~ollow~:
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Time/t~mperature : ~ miNI~eS ~o 60~C, 40ninutes at ~0C
Water hardness : 12 Certnan hardness
Cloth/1iquor ratio~ 0()
Number Or washes : 10 (l~or ribre dama~e tes~s)
1 (for bleaching power)
The bath contained per litre the additivesmentiorl~d in
the Table given below.
The chemical dama~e to the Pibres was det~rmined
by measuring the decr~se of the average polymerization
degree (DP) determined by viscosimetry.
The damaging factor = DF =
` ~ 2000 2000
log ~
\ DP arter damage initial DP
.. . . . .
_ ._
~5 log 2
`~- was measured ~ r~in~ to DIN 44983.
~ The b~eàching or brighteningerficiency A R was - -~
.. : , . ~ . ,
; - measured by means Or the Zeiss Elrepho re~lectometer.
` In the following Table, OM standsfor a spray-dried -
~: A20 heavy-duty detergent sold under the trado-n~mc of OMO and
~; TM standsfor a wash liquor containing per litre 0.5 g of
; a secondary C11-C15 alcohol condensed with 9 moles of ~ ~ -
`~ ethylene oxide and 3.0 g sodium tripolyphosphate. Alkali
. .~, . . .
~as added to the liquor in an amount required ror adjust--
ing the pH. The product sold under the trade-name Caroat - ;
by the rirm o~ Degussa i the triple salt XHS05: KHS0
l K2S04 (2~
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TABI,E
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Washin~ Alk~li Caroat Na[3r ~litr(>gen- P~l ~ri~ht- D~
product (g) (l~ containir,~ ening
~ (g~ __ ~ cvmpound A R
8.o OM Na3PO4 2.0 1.0 ___ 10.1 l15.0 totally
d~struc-
8.o OM Na3PO4 2.0 1.02.0 urea 9.8 27.4 0.4
8.o OM Na3PO4 1.0 1.02.() urea 9.9 21.2 Q.5
8.o OM Na3PO4 1.0 o~52.0 urea 9.9 2l1.0 0.3
8.o OM N~3PO4 1.0 o.51.0 urea 9.9 24.3 0.4
6.5 OM Na2C3 1.5 o.r~5 1.5 urea9.1 20.2 0.2
4.7 OM Na2C3 1.1 o.55 1~1 urea9.1 18.3 0.24
7.0 bM Na2C3 1.0 o.5 1.0 urea9.2 19.0 0.24
5.25OM Na2C3 0.75 o.37 0.75 urea9.2 17.1 0.33
6.o OM Na2C3 2.0 0.7 0.3 urea8.9 22.1 0.14
` 6.0 OM Na2C3 2.0 0.5 0.5 urea8.9 23 0.2
5.2 OM Na2C3 2.4 0.6 0.6 urea8.8 24 0.2
7~450M NaOH 1.5 0.1 0.5 urea10.0 39.2 0.65
7.350M NaOH 1.5 0.2 0.5 urea10.0 38.2 o.6
` 1.450M NaOH 1.5 0.1 0.5 urea9!6 37.2 0.6
1.750M NaOH 1.0 o.5 0.5 urea9.8 24.2 0.4
6.5 OM NaOH 2.0 o.5 0.5 urea9.8 37.3 o.6
` 25 6.5 OM NaOH 1.5 0.1 0.5-urea 9.2 32.4 0.6
rP Na3PO4 2.0 1.02.0 urea 10.1 30 0.7
J` rP Na3PO4 2.0 1.0 2.0 ace- 10.1 30 0.5
tamude
rP ~3PC4 2.0 1.0 2 0 el~ 10.2 27 Z ^
.~ ~
The~e results clearly show that the combination according
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to the invention cau~es less damage to the ~i~res ar~d
exerts a satisra-tory bleaching erfe~t and also clearly
show the ravoul~a~e in~uence Or sodium hydroxi~e on the
bleaching power.
EXAMPLE II
Thewashing product according to the invention was
~Atested in an AEG REgina de~ Lux~ "Bio" washing machine to
determine the bleaching and washing power. The washing
: was carried out in a cycle comprising two baths at 60C,
10the hardness Or the water being 1? German hardness.
The washing agent consisted Or 20 parts of Caroat(R), -,
2 partsor NaBr, S parts Or urea, 10 parts of sodium meta-
silicate and 63 parts Or the ~ollowing composition: ~ :
5% Or a condensation product Or 1 mol o~ a straight `~
.f 15chain alcohol witl- 16 to 18 carbon atoms and 12
. . ..
mol ethylene oxide ~ -
-10% sodium dodecyl benzene sulphonate ~:
4% tallow sodium soap
1% sodium carboxymethyl cellulose -
50% sodium tripolyphosphate ~ ~ -
~` 8.5% sodium tetrapyrophosphate
- 1.6% sodium orthophosphate
6S sodium metasilicate (Na20:SiO2~ 1:3.5)
~i 1S sodium hydroxide
::: .
~ 25 - 1% magnèsium silicate ~
-~ 0.2S sodium ethylene diamine tetraacetate
0.2S optical bleaching agent
- 11.6~ water and ~alts
.. . . . .
~ The do~e rOr the pre-wash was 200 g and ror the
~ de~tes +~ ~ c
- 1 0 ~
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main wash 150 g. The ,-11 in the pre-wash was.9,6.
The washing erficiency on experimentally soile(l
standard fabrics AS 8 all(3 the brightening power orl te~-
stained fabrics was d~t~rlnined.
The result~ were as f`ol~ows:
Washing efficiency on fabri~ ~S 8 :20 points~ er .
. one
Brightening power on tea-stained fabric:24 points wash
Damaging factor after 10 washes :0.25
'`
_XAMPLE III
The bleaching power Or the following compositions :
on cotton fabrics stained with tea was determined in a
Tergotometer. The operating conditions in the Tergoto-
meter were as follows:
.Time/temperature : 8 minutes to 60C, 20 minutes at 60C
:~ 15 Water hardness : 12 German hardness
-. Cloth/liquor ratio : l : lO0
Number Or washes : l
. The batch contained per litre 0.5 g of a condensa-
. ~ , . .` tion product of l mol of a Cl1-Cl5 secondary alcohol with
9 moles ethylene oxide and 3 grams sodium tripolyphos- .`
.j : - .:, .
. phate.
`~.` The compositions and the brightening obtained there-
~` with are represented in the following Table.
.,~ . Caroat NaBr NaCl Urea pH Bright~ing
. .
~225 (g~l)(~/1) (~/lj (g/l) .
. 1.0 -0.2 _ _ 9.5 42.2
. 1.0 _ -? .::: _ 9.5 16.9 :~ ~:
- . 1.0 0.2 _ ~.010.l 28.1 :: -
': ~ 1.0 ..... ~ 0.2 _1.0 10.1 16.~1 ~:
- .
.. . .
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These results cl~arly StlOW that, the products accor~lin~
to the invention are superior to systems cGntainin~
chloride as activator..
.
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