CA2348555A1

CA2348555A1 - Washing and cleaning method

Info

Publication number: CA2348555A1
Application number: CA002348555A
Authority: CA
Inventors: Gunther Schlingloff; Frank Bachmann; Josef Dannacher; Menno Hazenkamp; Kaspar Hegetschweiler; Jorg Pauly
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 1998-10-30
Filing date: 1999-10-19
Publication date: 2000-05-11
Also published as: AU1040500A; BR9914842A; WO2000026332A1; JP2002528636A; EP1124928A1; CN1325434A; MXPA01004023A; ID28223A; KR20010082267A

Abstract

The invention relates to a bleaching method which is carried out during washing and cleaning processes. The inventive method is characterized in tha t 1-500 .mu.mole per liter/bath of one or more compounds of the 3,5- diaminopiperidine type, or the salts or metal complexes of compounds of said type are added to the corresponding bath which comprises a peroxide-containi ng washing and cleaning agent.

Description

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 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 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) 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 ~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.

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.

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.

_7_ 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-_8_ 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 _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).

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 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 .............................. .....
.. ;?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.

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 ......:..... ......................_..~

~
~
=

...............................................................................
. . ...........................
1 ...1...... . ....................J
.......................... 0 ............................
......

Vat Brown 1 10 5 20 55 ................................................,..............................
......i............................a......................,.....i..............
..............a............................

Reactive I~ed 5 0 5 ...............................................................................
..................................~............................;...............
..........................................

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.

Claims

claims

1. A washing and cleaning method wherein from 1 to 500 µmol of one or more compounds of formula wherein R1 is hydrogen, linear or branched C1-C8alkyl, or O-R9, wherein R9 is hydrogen, linear or branched C1-C8alkyl, R2, R3, R4, R5, R6 and R7 are each independently of the others hydrogen, linear or branched C1-C8alkyl, or linear or branched C1-C8alkyl-R10, wherein R10 is a radical O-R9 or COOR9, and X is a group N-R8, N-O-R9, N-O or N=O, wherein R8 is hydrogen, acyl, linear or branched C1-C8alkyl, or linear or branched C1-C8alkyl-R10, are added per litre of liquor to a liquor that comprises a peroxide-containing washing and cleaning agent.

2. A method according to claim 1, wherein the compound of formula (1) is used in the form of the free base or in the form of a salt of an organic and/or inorganic acid.

3. A method according to claim 1 or claim 2, wherein from 5 to 350 µmol of one or more compounds of formula (1) are added per litre of washing liquor.

4. A method according to any one of claims 1 to 3, wherein from 10 to 250 µmol of one or more compounds of formula (1) are added per litre of washing liquor.

5. A method according to any one of claims 1 to 3, wherein one or more compounds of formula (1) is/are used in the form of the free base or in the form of the chloride, bromide, sulfate, acetate, nitrate, carbonate or hydrogen carbonate.

6. A method according to any one of claims 1 to 5, wherein there is used a compound of formula (1) wherein R1 to R8 are each independently of the others hydrogen or alkyl.

7. A method according to claim 5, wherein there is used a compound of formula (1) wherein each of the alkyl groups has from 1 to 4 carbon atoms.

8. A method according to any one of claims 1 to 7, wherein there is/are used one or more compounds of formula wherein R2', R4' and R8' are each independently of the others C1-C4alkyl, in each case preferably methyl.

9. A compound of formula wherein R1 is hydrogen, linear or branched C1-C8alkyl, or O-R9, wherein R9 is hydrogen, linear or branched C1-C8alkyl, R2, R3, R4, R5, R6 and R7 are each independently of the others hydrogen, linear or branched C1-C8alkyl, or linear or branched C1-C8alkyl-R10, wherein R10 is a radical O-R9 or COOR9, and X is a group N-R8, N-O-R9, N-O or N=O, wherein R8 is hydrogen, acyl, linear or branched C1-C8alkyl, or linear or branched C1-C8alkyl-R10, wherein at least one of the substituents R1 to R7 has a meaning other than hydrogen or wherein X is N-O-R9, N-O or N=O.

10. A process for the preparation of compounds of formula (1) according to claim 1, wherein a compound of formula wherein R1 to R7 are as defined for formula (1) and X is N, is hydrogenated with hydrogen in the presence of a suitable catalyst at from 1 to 150 bar.

11. A process according to claim 10, wherein Ru, Pd, Ni or Ir, but especially Rh or Pt, is used as catalyst and hydrogenation is carried out at a hydrogen pressure of from 1 to 150 bar.

12. A process according to claim 11, wherein hydrogenation is carried out at a hydrogen pressure of from 1 to 40 bar, preferably from 1 to 10 bar.

13. A method according to any one of claims 1 to 8, wherein metal complexes comprising one or more compounds of formula (1) are added.

14. A method according to any one of claims 1 to 13, wherein transition metal salts or complexes of salon compounds are additionally used.

15. A washing and cleaning agent containing I) from 5 to 90 % A) of an anionic surfactant and/or B) of a non-ionic surfactant, II) from 5 to 70 % C) of a builder substance, III) from 0.1 to 30 % D) of a peroxide, wherein the percentages are in each case per cent by weight, based on the total weight of the washing and cleaning agent, and IV) one or more compounds of formula (1) or salts thereof in an amount that yields in the washing or cleaning process a solution that is from 1 to 500 µmolar, preferably from 5 to 350 µmolar, especially from 10 to 250 µmolar, based on the content of free base.

16. A washing and cleaning agent according to claim 15 that contains from 5 to 70 % of component I), from 5 to 50 % of component II) and from 1 to 12 % of component III).

17. A washing and cleaning agent according to claims 15 and 16 that additionally contains from 0.05 to 5 % by weight, especially from 0.2 to 1.7 % by weight, of polyvinylpyrrolidone that is optionally anionically or cationically modified.

18. A washing and cleaning agent according to any one of claims 15 to 17 that additionally comprises manganese, iron, cobalt or copper salts or complexes, preferably the salen complexes described in European Patent Application Nos. 98 810 870.0 and 98 810 289.3.

19. A washing and cleaning agent according to any one of claims 15 to 18 that additionally contains from 0.05 to 5 % by weight, especially from 0.2 to 2.5 % by weight, of TAED and/or SNOBS.