AU623869B2 - Stable detergents containing fluorescent whitening agents - Google Patents

Description

-LL31~ S F Ref: 77210 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATIh S

(ORIGINAL)

FOR OFFICE USE: Class Int Class Li .4 Complete Specification Lodged: Accented: Published: 4 4* Priority: Related Art: Name and Address Priority: Related Art: Name and Address of Applicant: Ciba-Geigy AG Klybeckstrasse 141 4002 Basle

SWITZERLAND

Address for Service: Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Stable Detergents Containing Fluorescent Whitening Agents The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 I 1-16779/+ Stable detergents containing fluorescent whitening agents Abstract Detergents which, in addition to inorganic and/or organic peracids, contain specific stilbene compounds as fluorescent whitening agents. These detergents are stable for several months and already show the customary cleaning properties at washing temperatures of 20-60°C.

00o 0940 a o 0 90 0 S0 t ao o o S 6 r L~ I 1 n S1-16779/+ Stable detergents containing fluorescent whitening agents The Application relates to storage-stable detergents which, in addition to at least one peracid or salts thereof, contain at least one specific fluorescent whitening agent of the stilbene type, and to their use for washing textiles.

Because of the increased content of synthetic fibres and fibre blends in S the textiles manufactured today and the desire no longer to have to wash I coloured laundry separately and for energy saving measures, in many countries laundry is no longer washed at 90oC-95 0 C or at the boil but at i lower temperatures. This means that it has been necessary for the perborates which have usually so far been contained in detergents and act as bleaching agents to be activated by auxiliaries, such as tetraacetylethylenediamine (TAED) in order to achieve acceptable bleaching effects even at washing temperatures of 60-80 0 C. At still lower washing temperatures, S" even the perborate/activator systems no longer give satisfactory results.

Detergents which contain stronger bleaching agents, for example peracids, have therefore been described for some time (German Offenlegungsschrift 2,756,583, EP-A-145,438, GB 2,141,754, GB 2,141,755, US 4,028,263 and GB 59,272). Although these novel bleaching agents on the one hand already Sexhibit outstanding bleaching effects at temperatures from 20 0 C, on the other hand they destroy the customary fluorescent whitening agents contained in detergents.

It has now been found that specific stilbene compounds surprisingly have an excellent stability in detergents which contain such strong bleaching agents. Under average storage conditions and even under intensified conditions (temperatures above 30 0 C and atmospheric humidity above these specific stilbene fluorescent whitening agents are completely stable, or are at most degraded to a degree which causes no trouble in practice, in the detergent for several months.

PNM -I 2 The application thus relates to storage-stable detergents containing 0.5 to 30% based on total weight of the detergent of an inorganic or organic peracid or salts thereof or mixtures of peracids or salts thereof, said peracid being capable of bleaching textiles at a temperature from 200 to 60 0 C, and 0.03% to 0.5% based on total weight of the detergent of a fluorescent whitening agent or a mixture of fluorescent whitening agents wherein the fluorescent whitening agents are stilbene fluorescent whitening agents of the formula (I) CH--CH- A I-R A (I) SJ--

(SO

3

M)

a n a.a 10 in which A is hydrogen, -SO 3 M, halogen, phenyl or phenylpyrazol-l-yl; B is benzofuran-2-yl if A is hydrogen, 2-(stilben-4-yl)-oxadiazol-5-yl if A .is halogen, phenylpyrazol-l-yl if A is phenylpyrazol-l-yl, benzoxazol-2-yl if A is -SO 3 M or phenyl, or naphthoxazol-2-yl if A is hydrogen; R 1 and R 2 independently of one another are hydrogen, 15 halogen, C 1

-C

4 alky1 or C1-C alkoxy; M is hydrogen or one equivalent of a non-chromophoric cation and n is zero to 2, but the °o compound of the formula contains at least one -SO M group, with the proviso that when B is benzofuran-2-yl or 2-(stilben-4-yl)perborate is not used as the peracid.

20 M in formula is, for example, an alkaline earth metal, such as magnesium or calcium, but preferably an alkali metal, such as lithium, sodium or potassium, or substituted or unsubstituted ammonium, such as ammonium, mono-, di- or triethanol-ammonium, mono-, di- or tripropanolammonium or tri- or tetramethyl-ammonium.

The application also relates to a method of cleaning textiles, which method comprises washing said textiles with a detergent according to the invention at temperatures of 20" to 60 0 C in an amount which effectively cleans said textiles.

The application further relates to the preparation of a detergent according to the invention by dry mixing with the aid of automatic screw metering systems and/or fluidized bed mixers.

SKEH/328f 2A In particular, the detergents contain as fluorescent whitening agents compounds of the formulae R\0'\ I -I \0 (I in which R is H or halogen and M is as defined above, 00 0 i oe 0 a 0o e4 4 1' o 0 0i KEH/328f -3- 3 S

(III)

R2 in which R 1 and R 2 are H or C 1

-C

4 alkyl, R3 is -SO 3 M or "*S0 3 aM and M is as defined above,

(IV)

#900 /S0M o Hal~ 0 -CHCH- Hal in which M is as defined above, and/or and can be prepared by known methods.

The peracids and salts thereof are inorganic or organic compounds which xysebacic acid and/or diperoxyphthalic acid, are of particular inter- Hal-. inin which M is as defined above.

esAll these fluorescent whitening agents of the formula I to V are known suand can be prepared by known methods.

The peracids and salts thereof are inorganic or organic compounds which are described in the literature or are commercially available and which already bleach textiles at temperatures from 20°C. The organic peracids, 'for example mono- or polyperacids having alkyl chains of at least 3, preferably 6 to 20, carbon atoms, but in particular diperoxydicarboxylic acids having 6 to 12 carbon atoms, such as diperoxyazelaic acid, diperoxysebacic acid and/or diperoxyphthalic acid, are of particular interest. However, it is also possible for highly active inorganic peracids, such as persulfate and/or percarbonate, to be used. The amount of organic peracids to be used is preferably 0.5% to 10%, in particular 1% to and the amount of inorganic peracids to be used is preferably 1% i'.

I 4 -4to 30%, in particular 10% to 20%, based on the total weight of detergent, and if appropriate in combination with small amounts of compounds which intensify the bleaching action of the peracids.

Mixtures of organic and/or inorganic peracids or peracid salts can of course also be used.

The peracids are added to the detergent by dry mixing, for example with the aid of automatic screw metering systems and/or fluidized bed mixers.

I The detergents are dry detergents of customary compositions. As a rule, in addition to the combination according to the invention of peracid and I fluorescent whitening agent, they contain, for example, anionic, nonionic, I amphoteric and/or cationic surfactants, builders, for example pentasodium tripolyphosphate or substitute products, such as phosphonates, polyi carboxylates, acrylic/maleic copolymers, zeolites, nitrilotriacetate and ethylenediaminetetraacetic acid, soil-suspending agents, for example sodium carboxymethylcellulose, salts for adjusting the pH, for example alkali metal or alkaline earth metal silicates, foam regulators, for example soaps, salts for adjusting the spray-drying and granulation pro- I perties, for example sodium sulfate, perfumes and if appropriate antistatic and softening agents, enzymes, photobleaching agents, pigments Sand/or toning agents. These constituents should of course be stable towards the bleaching system used.

As a result of the combination according to the invention, it is possible I to provide detergents which meet the customary standard, for example as Sregards to washing power, spot removal and refreshing the appearance of s the washed articles, even if washing is carried out at temperatures of 20oC-60 0 C. Coloured laundry and white laundry can thus advantageously be washed together regardless of the fibre.

The following examples illustrate the invention without limiting it thereto. Percentage data are percentages by weight.

1.

5 Detergent formulation The detergents of the following examples are prepared in two stages by customary processes: Granules A also called "base detergent A" below are first prepared by drying and granulating a slurry consisting of about 1 part of water and 1 part of detergent of the following composition: 84 g of linear dodecylbenzenesulfonate 31 g of tallow alcohol tetradecane-ethylene glycol ether (14 mol of ethylene oxide) o*o 37 g of Na soap (chiefly of behenic acid and C 14

-C

2 0 I 458 g of Na tripolyphosphate 79 g of Na silicate I e 20 g of Mg silicate S12 g of carboxymethylcellulose S2 g of ethylenediamine tetraacetate 222 g of Na sulfate I i It 1 g of fluorescent whitening agent (FWA) according to the formula i The peracid B (70 g of K monopersulfate 2 mg of anhydrous CuSO 4 is homogeneously admixed in the dry state to 500 g of these granules A, which have a residual moisture content of 5% after drying.

Storage test Samples of the detergent D (granules A peracid B) thus obtained are: i on the one hand, for control of the starting value, immediately analyzed for the content of FWA by extraction and measurement of the spectrophotometric absorbance (theoretical: 0.1% of FWA, based on the weight of the base detergent A), on the other hand kept in cardboard packets suitable for commercial washing powder, that is to say with a coating, under selected and controlled conditions of temperature and atmospheric humidity for certain periods of time. After storage, the FWA content of each detergent is immediately determined. The difference from the starting value is expressed as a percentage and is a measure of the stability of the FWA 6 towards the corresponding bleaching agent in the washing powder.

The abovementioned FWA determination is carried out as follows: The washing powder is homogenized thoroughly by grinding and 1 g thereof is admixed with 200 ml of solvent consisting of 9 parts of dimethyl sulfoxide and 1 part of water, and the mixture is stirred at room temperature for 30 minutes. It is then centrifuged for 30 minutes. A sample of the clear solution thus obtained is transferred with a pipette into a 1 cm quartz cell and its absorbance is measured in the UV range at the absorption maximum against a standard solution of the pa' -icular FWA. The a| a B, absorbance is proportional to the FWA concentration. The reproducibility S, of the results is about 1% if the test conditions are kept exactly the same.

N t t Example The percentage FWA loss is determined under the conditions described above. Storage is in a closed packet at 20 to 25 0 C. After 6 II months, the FWA loss is as follows: i'i il o i /SO 3 Na

-=N

*N 0 H3C \C 1-CHCH- S3K 0 H3C CH3 a SH 3N I I 0 S0 3

K.

Ii \0

CJ._

-CH=CH-

7 0 1\N1 S03N

Claims (9)

1. A storage-stable detergent containing 0.5 to 30% based on total weight of the detergent of an inorganic or organic peracid or salts thereof or mixtures of peracids or salts thereof, said peracid being capable of bleaching textiles at a temperature from 200 to 60°C, and 0.03% to based on total weight'of the detergent of a fluorescent whitening agent or a mixture of fluorescent whitening agents, wherein the fluorescent whitening agents are stilbene fluorescent whitening agents of the formula (I) -Ri C \--R2 (SO 3 (I) i r( O1NK in which A is hydrogen, -S03M, halogen, phenyl or phenylpyrazol-l-yl; B is benzofuran-2-yl if A is hydrogen, 2-(stilben-4-yl)-oxadiazol-5-yl if A is halogen, phenylpyrazol-l-yl if A is phenylpyrazol-l-yl, benzoxazol-2-yl if A is -SO3M or phenyl, or naphthoxazol-2-yl if A is hydrogen; R 1 and R 2 independently of one another are hydrogen, halogen, C1-C 4 alkyl or C -C 4 alkoxy; M is hydrogen or one equivalent of a non-chromophoric cation and n is zero to 2, but the compound of the formula contains at least one -SO3M group, with the proviso that when B is benzofuran-2-yl or

2-(stilben-4-yl)-oxadiazol-5-yl, perborate is not used as the peracid. 2. A detergent according to claim 1, which contains, as the peracid or peracid salt, a mono- or polyperacid having 6 to 20 carbon atoms, a persulfate and/or a percarbonate, if appropriate in combination with small amounts of compounds which intensify the bleaching action of the peracids.

3. A detergent according to claim 2, in which the mono- or polyperacid is a diperoxydicarboxylic acid having 6 to 12 carbon atoms.

4. A detergent according to any one of claims 1 to 3, which contains, as the fluorescent whitening agent, a compound of the formula (II) C=CH--* (II) in which R is H or halogen and M is as defined in claim 1. /328f 9 A detergent as claimed in any one of claims 1 to 3, which contains, as the fluorescent whitening agent, a compound of the formula (III) R2 in which R 1 and R 2 are H or C 1 -C 4 alkyl, R 3 is -SO 3 M or ,-SO 3 H 3 and M is as defined in claim 1.

6. A detergent as claimed in any one of claims 1 to 3, which contains, as the fluorescent whitening agent, a compound of the fo. ,ula (IV) 00 (IV) /SO3M SO i in which M is as defined in claim 1.

7. A detergent according to any one of claims 1 to 3, which contains, as the fluorescent whitening agent, a compound of the formula (V) e S= o o0o nai-. Ch=CH- na S03-/ SO 3 M (V) in which M is as defined in claim 1.

8. A method of cleaning textiles, which method comprises washing said textiles with a detergent according to any one of claims 1 to 7 at temperatures of 20-60 0 C in an amount which effectively cleans said textiles.

9. The preparation of a detergent according to any one of claims 1 to 7 by dry mixing with the aid of automatic screw metering systems and/or fluidized bed mixers. A storage-stable detergent containing 0.5 to 30% based on total weight of the detergent of an inorganic or organic peracid or salts thereof or mixtures of peracids or salts thereof, said peracid being capable of bleaching textiles at a temperature from 200 to 60"C and wherein perborate 4 KEH/328f K~I *1 ~-LIVICI-~ 10 is not used as the peracid, and 0.03% to 0.5% based on total weight of the detergent of a fluorescent whitening agent or a mixture of fluorescent whitening agents, which detergent is substantially as herein described with reference to the Detergent Formulation. 11, A method of cleaning textiles, which method comprises washing said textiles in a detergent according to claim 10 at temperatures of

20-600C in an amount which effectively cleans said textiles. DATED this TWENTY-SEVENTH day of FEBRUARY 1992 Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON ij iI, II j Bit B j Q coo e ea e t Sa 4 <t t a *o 4 e o a tr rs i a w a r f o 9, KEH/328f