Note: Descriptions are shown in the official language in which they were submitted.
N B/2-21861 /A
CA 02348555 2001-04-24
Washing and cleanings method
The present invention relates to novel catalysts that significantly improve
the bleaching
action of hydrogen peroxide without at the same time causing any appreciable
damage to
fibres and dyeing:;, to washing and cleaning agent formulations that comprise
such
catalysts and to a method of cleaning and/or bleaching substrates, which
method involves
such washing and cleaning agent formulations.
Peroxide-containing bleaching agents have been used in washing and cleaning
processes
for a long time. Their action is excellent at a liquor temperature of
90°C or higher. As the
temperature falls, however, their performance deteriorates noticeably. It is
known that
various transition metal ions, added in the form of suitable salts or
coordination compounds
containing such cations, catalyse the decomposition of H202. In that manner it
is possible to
increase the bleaching action of Hz02 or H202-releasing precursors and of
other peroxo
compounds, which is unsatisfactory at relatively low temperatures. Only those
combinations
of transition metal ions and ligands having peroxide activation which results
in an increased
tendency to oxidation with respect to substrates, and not merely in catalase-
like
disproportionation, are of importance for practical applications, since the
latter activation,
which is undesirable in the present case, can further impair the bleaching
effects of H202
and its derivatives that are insufficient at low temperatures.
In respect of bleaching-active HZOZ activation, at present mono- and poly-
nuclear variants of
manganese comb>lexes with varic>us ligands, especially with 1,4,7-trimethyl-
1,4,7-triaza-
cyclononane and optionally oxygen-containing bridging ligands, are regarded as
being
especially effective. Such catalysts are sufficiently stable under practical
conditions and
comprise in Mn~"+' an ecologically harmless metal cation. Unfortunately,
however, their use
is associated with considerable damage to dyes and fibres. The catalysts
according to the
invention, on the other hand, enable the bleaching activity of H202 to be
increased
significantly without causing any appreciable damage to the goods being
washed.
The present invention accordingly relates to a washing and cleaning method
wherein from 1
to 500 pmol of one or more compounds of formula
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R5 R, R2
,N N
Ra ~ Rs ~ 1 )
R6 X R~
wherein
R, is hydrogen, linear or branched C,-Caalkyl, or O-R9, wherein R9 is
hydrogen, linear or
branched C,-CBalkyl,
R2, R3, Ra, Rs, Rs and R, are each independently of the others hydrogen,
linear or branched
C,-Caalkyl, or linear or branched C,-Caalkyi-R,o, wherein R,o is a radical O-
R9 or COORS,
and
X is a group N-Re, N-O-R9, N-O or N=O, wherein
R8 is hydrogen, acyl, linear or branched C,-Caalkyl, or linear or branched C,-
Cealkyl-R,o,
are added per litre of liquor to a liquor that comprises a peroxide-containing
washing and
cleaning agent.
R, to R8 are each independently of the others preferably hydrogen or alkyl.
The alkyl groups are preferably C,-Caalkyl, such as methyl, ethyl, n-propyl,
isopropyl, n-
butyl, sec-butyl or tert-butyl.
When R8 is an ac:yl group, there come into consideration, for example, C,-
C,oalkylcarbonyl
radicals or phenylcarbonyl radicals, it being possible for the last-mentioned
radicals to be
substituted by electron-displacing substituents, e.g. cyano, halogen, nitro,
C,-Caalkyl or
C,-Caalkoxy. Preference is given to acetyl, propionyl, butyryl or benzoyl.
The compounds of formula (1 ) can be added in the form of the free base or in
the form of
salts of organic and/or inorganic acids, e.g. in protonated form in the form
of the chloride,
bromide, iodide, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate,
nitrate,
perchlorate, tetrafluoroborate, hexafluorophosphate, carboxylate, such as e.g.
formate,
acetate, propionate, lactate, citrate, tartrate, triflate, benzoate or
tosylate. Special
preference is given to chloride, bromide, sulfate, acetate, nitrate, carbonate
and citrate.
Of special intere~;t for use in the method according to the invention are the
compounds of
formulae
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H2N NHS,
NJ (1a)
H
and
H H
I I
/N N.R2
R4' NJ (ib)
I
H
and
H H
I I
~~N N.R2.
N (1 c)
R4 J
I
R8'
wherein R2', R4' and R8' are each independently of the others C,-C4alkyl, in
each case
preferably methyl.
Those compounds of formulae (1 a), (1 b) and (1 c), the use of which is
preferred, can also be
added in the form of the free base or in the form of salts of the acids listed
under
formula (1 ).
The compound of formula (1 ) in which R, to R, are hydrogen and X is N-H, the
3,5-
diaminopiperidine (1 a), and its hydrobromide and hydrochloride are known.
They can be
prepared from the appropriately substituted pyridine or salt thereof by
catalytic
hydrogenation under a high hydrogen pressure (250-300 atm) (G. De Weck,
Dissertation,
Eidgenossisch-TE:chnische Hochschule Zurich, 1972).
The compounds ~of formula
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~s R~ R2
R..N N~R
4 ~ 3
Rs X w R7
wherein
R, is hydrogen, linear or branched C,-CBalkyl, or O-Rs, wherein R9 is
hydrogen, linear or
branched C,-Caalkyl,
R2, R3, R4, R5, R6 .and R, are each independently of the others hydrogen,
linear or branched
C,-Csalkyl, or linear or branched C,-CBalkyl-R,o, wherein R,o is a radical O-
R9 or COORS,
and
X is a group N-R8, N-O-R9, N-O or N=O, wherein
Ra is hydrogen, ac:yl, linear or branched C,-Csalkyl, or linear or branched C,-
Caalkyl-R,o,
wherein at least one of the substituents R, to R, has a meaning other than
hydrogen or
wherein X is N-O-Rs, N-O or N~O,
are new.
The invention relates also to those new compounds.
They are prepared, for example, by hydrogenating a compound of formula
RS Ri R2
Ra N / N. Rs (3),
R X" R
s
wherein R, to R, are as defined for formula (1 ) and X is N, with hydrogen in
the presence of
a suitable catalyst at from 1 to 1 ~~0 bar.
As catalysts there come into cansideration the metals customary for similar
hydrogenations,
for example Ru, F'd, Ni or Ir, but especially Pt and Rh, which can be applied
to carriers, e.g.
activated carbon, in order to increase their activity. The hydrogenation is
preferably carried
out under elevated hydrogen pressure, especially at a pressure of about from 1
to 40 bar,
more especially from 1 to 10 bar.
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The compounds of formula (1 ) can be used individually or in mixtures
comprising two or
more compounds of formula (1 ). It is also possible to use the compounds of
formula (1 ) in
the form of metal complexes comprising those compounds, there coming into
consideration
as metals especially manganese, iron, cobalt or copper.
It is also possible to use the compounds of formula (1 ) together with
transition metal salts or
complexes, for e~;ample with compounds or salts of manganese, iron, cobalt or
of copper.
For example, the salen complexes described in European Patent Application Nos.
98 810 870.0 and 98 810 289.3 are suitable.
The present invention relates also to a washing and cleaning agent containing
I) from 5 to 90 %, preferably from 5 to 70 %, A) of an anionic surfactant
and/or B) of a non-
ionic surfactant,
II) from 5 to 70 %, preferably from 5 to 50 %, especially from 5 to 40 %, C)
of a builder
substance,
III) from 0.1 to 30 %, preferably from 1 to 12 %, D) of a peroxide, and
IV) one or more of the compounds of formula (1 ) defined above or salts
thereof in an
amount that yield, in the washing or cleaning process a solution that is from
1 to
500 Nmolar, preferably from 5 to 350 Nmolar, especially from 10 to 250 Nmolar,
based on
the content of free base.
The washing and cleaning agent may be in solid or liquid form, for example in
the form of a
liquid, non-aqueous agent, containing not more than 5 % by weight, preferably
from 0 to 1%
by weight, water, and can have as basis a suspension of a builder substance in
a non-ionic
surfactant, e.g. as described in C~E3-A-2 158 454.
The washing and cleaning agent is, however, preferably in the form of a powder
or
granulate. This can be prepared, for example, by firstly preparing a starting
powder by
spray-drying an aqueous suspension containing all the above-listed components
with the
exception of components D) and E), and then adding the dry components D) and
E) and
mixing everything together. It is also possible to add component E) to an
aqueous
suspension containing components A), B) and C), thereafter carry out spray-
drying, and
then mix component D) with the dry mass.
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It is also possible to start from an aqueous suspension that contains
components A) and C),
but contains none, or only some, of component B). The suspension is spray-
dried, then
component E) is mixed with component B) and added thereto, and component D) is
subsequently mixed in dry.
The anionic surfactant A) may be, for example, a sulfate, sulfonate or
carboxylate
surfactant or a mixture thereof. Preferred sulfates are those having from 12
to 22 carbon
atoms in the alkyl moiety, optionally in combination with alkylethoxysulfates,
the alkyl moiety
of which contains from 10 to 20 carbon atoms.
Preferred sulfonates are, for example, alkylbenzenesulfonates having from 9 to
15 carbon
atoms in the alkyl moiety. The cation in the anionic surfactants is preferably
an alkali metal
cation, especially sodium.
Preferred carboxylates are alkali metal sarcosinates of the formula R-CO-N(R')-
CH2COOM',
wherein R is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or
alkenyl moiety,
R' is C,-C4alkyl and M' is an alkali metal.
The non-ionic surfactant B) can be, for example, a condensation product of
from 3 to 8 mol
of ethylene oxide with 1 mol of primary alcohol containing from 9 to 15 carbon
atoms.
As builder substance (C) there come into consideration, for example, alkali
metal
phosphates, especially tripolyphosphates, carbonates or hydrogen carbonates,
especially
their sodium salts, silicates, aluminium silicates, polycarboxylates,
polycarboxylic acids,
organic phosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures of
those
compounds.
Especially suitable silicates are sodium salts of crystalline layer silicates
of the formula
NaHSi,02,+npH20 or Na2Si,02,i,.pH20, wherein t is a number from 1.9 to 4 and p
is a
number from 0 to 20.
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Of the aluminium silicates, preference is given to those commercially
available under the
names zeolite A, !B, X and HS and to mixtures comprising two or more such
components.
Among the polycarboxylates, preference is given to the
polyhydroxycarboxylates, especially
citrates, and acrylates and copolymers thereof with malefic acid anhydride.
Preferred
polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic
acid, and
ethylenediamine disuccinate, both in the racemic form and in the (S, S) form.
Especially suitable phosphonates or aminoalkylenepoly(alkylenephosphonates)
are alkali
metal salts of 1-h~ydroxyethane-1,1-diphosphonic acid,
nitrilotris(methylenephosphonic acid),
ethylenediaminetetramethylenephosphonic acid and
diethylenetriaminepentamethylene-
phosphonic acid.
As peroxide component D) there come into consideration, for example, the
commercially
available organic and inorganic, peroxides known in the literature that bleach
textile
materials at customary washing temperatures, for example at from 10 to
95°C.
The organic pero:Kides are, for example, mono- or poly-peroxides, especially
organic per-
acids or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic
acid,
diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic
acid,
diperoxyphthalic ;acid or salts thereof.
It is preferred, however, to use inorganic peroxides, such as, for example,
persulfates,
perborates, percarbonates and/or persilicates. It is, of course, also possible
to use mixtures
of inorganic and/or organic peroxides. The peroxides may be present in a
variety of
crystalline forms .and having different water contents, and they can also be
used together
with other inorganic or organic cornpounds in order to improve their storage
stability.
The peroxides are added to the ~Nashing and cleaning agent preferably by
mixing the
components, for example using a screw feeder and/or a fluidized bed mixer.
The washing and cleaning agents may comprise, in addition to the combination
according to
the invention, onE~ or more fluorescent whitening agents, for example from the
class bis-
triazinylamino-stilbene-disulfonic acid, bis-triazolyl-stilbene-disulfonic
acid, bis-styryl-
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biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, a bis-
benzimidazolyl
derivative, a cournarin derivative or a pyrazoline derivative.
The washing and cleaning agents may also comprise dispersing agents for dirt,
e.g. sodium
carboxymethylcellulose, pH regulators, e.g. alkali metal or alkaline earth
metal silicates,
foam regulators, e.g. soap, salts to regulate the spray-drying and the
granulation properties,
e.g. sodium sulfate, fragrances, and optionally antistatics and softeners,
enzymes such as
amylase, bleaching agents, bleach activators such as TAED
(tetraacetylethylenediamine) or
SNOBS (sodium nonanoyloxybenzenesulfonate), pigments and/or shading agents.
Such
constituents must, of course, be stable towards the bleaching agent used.
Further preferred additives to the washing and cleaning agents according to
the invention
are polymers that, during washing, prevent textiles from becoming soiled by
dyes present in
the liquor that have been released by the textiles under the washing
conditions. Such
polymers are preferably polyvinylpyrrolidones, which may have been modified by
the
incorporation of anionic or cationic substituents, especially those having a
molecular weight
in the range of from 5000 to 60 000, especially from 10 000 to 50 000. Such
polymers are
preferably used in an amount of from 0.05 to 5 % by weight, especially from
0.2. to 1.7 % by
weight, based on the total weight of the washing agent.
The following Examples serve to illustrate the invention but do not limit the
invention
thereto. Parts and percentages relate to weight, unless indicated otherwise.
Example 1
5.91 g (0.022 mol) of 3,5-diaminopyridine dihydrobromide, 3 ml of concentrated
hydrobromic acid and 0.25 g of rhodium (5%) on carbon are added to 55 ml of
water and
hydrogenated in an autoclave at 5 bar of hydrogen pressure for 24 hours. When
the
reaction is complete, the catalyst is filtered off and the filtrate is added
to a strongly basic
anion-exchanger' (Dowex 2x8, 20 - 50 mesh). Elution with water is carried out
until the
eluate no longer reacts as a base. The eluate collected is concentrated and
adjusted to
pH 3 with dilute hydrochloric acid. The crude product obtained by
concentration using a
rotary evaporator (40°C, 10 mbar) is dissolved in water and then
precipitated by the addition
CA 02348555 2001-04-24
_g_
of ethanol. Dryings in vacuo yields 2.6 g (52 %) of cis-3,5-diaminopiperidine
trihydrochloride
in the form of colourless crystals. Calculated for CSH,6N3C13: C 26.74; H
7.18; N 18.71;
found: C 26.60; HI 7.26; N 18.58.
Alternatively, after concentration using a rotary evaporator (50°C, 10
mbar) the crude
product can be dissolved in methanol/water 9:1 and precipitated by the
addition of
concentrated hydrobromic acid at 4°C. Drying in vacuo yields cis-3,5-
diaminopiperidine
trihydrobromide in the form of colourless crystals in yields of 51-55 % based
on crude 3,5-
diaminopyridine clihydrobromide. Calculated for CSH,sNaBr3: C 16.78; H 4.51; N
11.74;
found: C 16.56; ~I 4.35; N 11.66. '3C-NMR (90 MHz, D20): 8 = 44.2; 43.7; 31Ø
Example 2
The bleaching tests are carried out as follows: 7.5 g of white cotton fabric
and 2.5 g of
cotton fabric stained with tea, red wine or blackberry are treated in 80 ml of
a washing
liquor. That liquor contains the standard washing agent ECE phosphate-free
(456 IEC)
EMPA, Switzerland, in a concentration of 7.5 g/litre and the concentrations of
oxidising
agent, catalyst and optionally activator indicated in the corresponding
Tables. The washing
process takes place in a steel container in a LINITEST apparatus for 30
minutes at 40°C.
The increase in the lightness of the stain GY (difference in lightness
according to CIE)
caused by the treatment is used to evaluate the bleaching results. Table 1
contains the DY
values for all 3 stains on cotton after treatment with systems a) to e).
Table 1:
Cotton Increase in lightness DY
in system*
stained with a) b) c) d) e)
tea 0 16 26 26 21
red wine 3 11 22 23 17
blackberries 8 20 31 22 24
*a) Washing liquor without bleaching system. b) Washing liquor containing
8.6 mmol/litre H202. c) Washing liquor containing 1.125 g/litre sodium
perborate
monohydrate and 0.3 g/litre TAED. d) Washing liquor containing 8.6 mmol/litre
H202 and
pmol/IitrE: catalyst A. e) Washing liquor containing 8.6 mmol/litre Hz02 and
100 umol/litre catalyst (1a).
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Catalyst A:
~~N/ ~O,\ \N~
-NI -.M\OyMn-~N- .(~'F6)2~ H20
Ls o ~NJ
Example 3
The use of the catalyst according to the invention does not cause any
additional fading of
the dyes of dyed cotton goods being washed. When used as described above,
after
treatment 5 times the same relative dye losses are obtained as with the bleach-
free system,
even in the case of dyes that are known to be very sensitive. The values in
Table 2 are
relative percentage dye losses, determined on the basis of Kubelka-Munk values
in the
respective absorption maximum.
Table 2:
Cotton dyeing Relative %) in system*
decrease
(
with dye a) b) c) d) e)
Vat Blue ~4 '10 10 5 20 5
...............................................................................
....,............................~............................;................
.............,............................
.. 10 20 15 45 10
Reactive Brown
17
Reactive Black 10 10 30 45 5
Vat Brown 1 5 0 0 0 5
Reactive Red 123 10 15 15 40 10
....... .....................
.................. ............................
..
......................................................~ 15 15
15
.............................. .....
.. ;?0 ..
Direct Blue 85 20
*a) to e) as in Table 1
Example 4
The use of the c<~talysts according to the invention is extremely fibre-
friendly. When used as
described above, after treatment 5 times on average the same relative
decreases in the
average degree of polymerisation are observed as with the bleach-free system,
even in the
case of cotton dyeings known to be very sensitive to fibre damage.
CA 02348555 2001-04-24
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Table 3:
Cotton dyeing Relative decrease
(%) in system*
with dye a) b) c) d) e)
Vat Blue 4 5 5 5 40 0
............ .....
...... .
............ .....
............
.............
..
....Reactive,f3rown.~l~~................'~......: ~
.........1~.......
5 o
~ ~.
0 ........
....
,
........................
......
.
...............................................................................
. 20 0
Reactive Black 0 ......:..... ......................_..~
0 0
~
~
=
...............................................................................
. . ...........................
1 ...1...... . ....................J
.......................... 0
............................
......
Vat Brown 1 10 5 20 55
................................................,..............................
......i............................a......................,.....i..............
..............a............................
40 15
Reactive I~ed 5 0 5
123
...............................................................................
..................................~............................;...............
..........................................
Direct Blue 85 10 5 0 5 10
*a) to e) as in Table 1
Example 5:
The use of the catalysts according to the invention results in markedly
increased bleaching
effects, especiall~~ at very low washing temperatures. Under the test
conditions described in
Example 2, but now at 20°C, the still minimal inherent bleaching action
of H202 is increased
by more than 10 units of lightness (see Table 4).
Table 4:
*
Cotton Increase in lightness DY in system
stained with a) b) c) d) e)
tea
'a) to e) as in Table 1.
