AU628539B2

AU628539B2 - Liquid detergent compositions

Info

Publication number: AU628539B2
Application number: AU54536/90A
Authority: AU
Inventors: Claude Eckhardt; Kurt Weber
Original assignee: Ciba Geigy AG
Current assignee: BASF Schweiz AG
Priority date: 1989-04-28
Filing date: 1990-04-27
Publication date: 1992-09-17
Anticipated expiration: 2010-04-27
Also published as: JPH02302498A; DE59010228D1; AU5453690A; EP0394998A3; EP0394998A2; JP2685329B2; NZ233443A; CA2015565A1; ES2085296T3; EP0394998B1

Description

z r 8uuJL. JL 4UV 01 4478 270490 5845/2 y S F Ref: 125808 FORM COMMONWEALTH OF S'L8 3 9 PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class a.

at 6 ai a a t It

II~

III C Complete Specification Lodged: Accepted: Published: Priority: Related Art: Name and Address of Applicant: Address for Service: a a tat tap.

It ca a Ciba-Geigy AG Klybeckstrasse 141 4002 Basle

SWITZERLAND

Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia a *ta.

«ft at 61 a II 14 4 I C C 6. CC C Complete Specification for the invention entitled: Liquid Detergent Compositions The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 1 CIBA-GEIGY AG Werner Waldegg i Single Signature, by special power To: The Commissioner of Patents 2.88 521 WW 1-17573/= Liquid detergent compositions Abstract of the Disclosure The present patent application describes novel liquid detergent compositions containing specifically disulfonated dibenzofuranylbiphenyls of the formula *0t 0 B B

Z

in which X is a sulfonic acid radical, hydrogen or Ci-C4 alkyl and Y and 0006 Z independently of the other are a sulfonic acid radical, hydrogen, C 1

-C

4 alkyl, CI-C4 alkoxy, halogeno, CN, phenoxy or benzyloxy, with the proviso that either X or Y or Z is a sulfonic acid radical and the remaining substituents are not a sulfonic acid radical, and the preparation and use thereof; these detergent compositions prevent spotting on textile fabric when it comes into direct contact with the liquid detergent composition.

o a..

e a o; s i' ii 1-17573/= Liquid detergent compositions .The present invention relates to novel liquid detergent compositions containing specifically disulfonated dibenzofuranylbiphenyls as fluorescent whitening agents, to the preparation thereof and to the use thereof.

,o The use.of fluorescent whitening agents in liquid detergent compositions is known. During the treatment, they exhaust on to the material to be D 8 washed and, through their special light absorption/emission property, Se they result in the elimination of the yellowish shades or an improvement in the degree of whiteness.

•4 Soo 0 However, this effect is also responsible for the appearance of bleach spots when textile fabric comes into direct contact with the liquid detergent composition, e.g. during a pretreatment. To solve this problem, European patent application A-167 205 proposes the use of monosulfonated stilbenetriazolyl, stilbenet-riazine or distyrylbiphenyl whitening agents in anionic liquid detergent compositions.

Surprisingly,. thef ormation f bleach spots-Can also be-prente-- ;:b fluorescent whitening agents of the formula Y- _I t+-Y (I) the liqu' etergent composition having an excellent white effect and rtorg proprtias-- G

_AZ/

A r 1 j According to a first embodiment of the present invention there is provided a storage-stable liquid detergent composition, which, based on the weight of the detergent composition, comprises a) 0.01 to 2% of a fluorescent whitening agent of the formula

MO

3 0 3

M

s r o r r

I

o r r rl~ r a o e r o o cc o r o r orr~r r in which R, is hydrogen, Ci-C 4 alkyl, chloro, Ci-C 4 alkoxy, phenoxy or benzyloxy, R2 is hydrogen or C-C 4 alkyl and M is hydrogen and/or one equivalent of a nonchromophoric cation and 10 b) 1 to 60% of anionic, non-ionic, zwitterionic or cationic surfactants.

Suitable Ci-C 4 alkyl radicals (or Ci-C 4 alkoxy radicals) are unbranched or branched alkyl (or alkoxy) radicals. These alkyl (or alkoxy) radicals can in turn be substituted by e.g. aryl (phenyl, naphthyl), Ci-C 4 alky, C 1

-C

4 alkoxy, OH or CN groups.

M as a non-chromophoric cation is preferably an alkali metal such as lithium, 15 sodium or potassium, or substituted or unsubstituted ammonium such as ammonium, mono-, di- or tri-ethanolammonium, mono-, di- or tri- propanolammonium or tri- or tetiamethylammonium.

KXW/1 25808 .doc However, especially preferred compounds are those of the formula I 11 II I (IV) S0/3 S0/ '03M 3 M S0 3 M \or N O in which the radicals R 3 independently of the others are hydrogen, methyl or ethyl and M is preferably sodium or potassium.

9 o 9 The fluorescent whitening agents can be prepared by 0* a) reacting one mol of a compound of formula R4 Re II 11 (x) which can be polysubstituted by radicals R hydrogen, CI-C4 alkyl, C1-C alkoxy, halogeno, phenoxy and benzyloxy, R 4 being hydrogen or C1-C alkyl, with at least stoichiometric amounts of an S0 3 /base complex, in an S inert organic solvent, at temperatures in the range from 200C to the boiling point of the solvent used, or b) reacting one mol of a compound of formula with at least stoichiometric amounts of chlorosulfonic acid, in an-inert organic solvent, at 9 00 temperatures in the range from 00 to 40 0 C, or c) heating a compound of formula with concentrated sulfuric acid or with sulfuric acid/glacial acetic acid or oleum/glacial acetic acid at temperatures in the range from 40 to 140°C, or d) etherifying one mol'of a 4,4'-bis(halogenomethyl)biphenyl with at least 2 mol' of salicylaldehyde or its anils of formula (XI) or (XII):

SI

t -j 1 1 l 4- /CHO \/CH=N-R

SO

3 M-i+ I (XI) bzw. SO 3 M-4- II (XII) OH OH which can be polysubstituted by radicals R hydrogen, CI-C4 alkyl, C1-C 4 alkoxy, halogeno, phenoxy and benzyloxy and in which M hydrogen and/or one equivalent of a non-chromophoric cation and Rs phenyl or chlorophenyl, and cyclizing the resulting bisbenzyl ethers of formula (XIII) or (XIV): CHO OHC\/

SO

3 CH- .I -SO 3 M (XIII) Co-* -CH 2 o e or r CH=N-Rs Rs-N=HC S3M- II S 0 M (XIV) CH2 -CH 2 with bases.

I

The starting compounds of formulae (XI) and (XII) are known and can S be prepared by known methods. Advantageously, however, process d) is carried out as a one-pot process without isolation of the intermediates (XIII) and (XIV).

Specifically, the compounds of formulae (III) and (IV) are prepared by S process a).

The term S0 3 /base complexes will be understood as meaning addition compounds of S03 on to organic bases, e.g. dioxane, and preferably nitrogenous bases such as triethylamine, N-ethyldiisopropylamine, dimethylformamide (DMF) and, in particular, pyridine, the stability of these addition compounds being decisive for the degree of sulfonation. Thus, for example, compounds of formulae (III) and are prepared by using 2 to 6 or especially 3 to 5 mol of SO3/pyridine complex (based on the SO3 content) per mol of the compound of formula SO3/base complexes are 'i known and can be prepared by known methods Gilbert, E.P. Jones, Ind. Enging. Chem. 49, n 0 9, part II, p. 1553 et seq. (1957); Beilstein III/IV, 2232).

Examples of inert organic solvents are saturated aliphatic hydrocarbons such as gasoline, petroleum ether and ligroin, halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane, dichlorodifluoromethane and dichlorotetrafluoroethane, chlorobenzenes such as mono-, di- and tri-chlorobenzene, nitrobenzenes such as nitrobenzene and nitrotoluene, and dicyclic hydrocarbons such as cyclohexane, a methylcyclohexane and decalin.

a The compounds of formulae (II) and in particular, are prepared by e process c).

a at The etherification in process d) is carried out at temperatures in the range from 60° to 140°C and especially 100° to 120 0 C, in known manner, by means of one equivalent of a base such as a tertiary amine or a base mentioned for the following cyclization, or by using the compounds of formula XI or XII already in the form of the phenate of this base. The reaction is carried out in a polar aprotic solvent or solvent mixture, for example dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, tetramethylurea or, preferably, dimethyl sulfoxide.

The cyclization in process d) is also carried out in a polar aprotic solvent, preferably in the same one as that used for the etherification, at temperatures slightly higher than those used for the etherification, and in the presence of a base, e.g. quaternary ammonium bases, alkaline earth metal hydroxides, alkali metal amides, alkali metal hydrides, alkali metal carbonates or, preferably, alkali metal alcoholates such as potassium t-butylate and sodium methylate, and especially alkali metal hydroxides such is sodium, potassium and lithium hydroxide. The basic condensation agents are used in at least stoichiometric. amounts, preferably in excess. The reaction is preferably carried out in the absence of atmospheric oxygen and under an inert ,,gas atmosphere.

-6- The term liquid detergent compositions will be understood as meaning known and commercially available detergent compositions such as those described in European patent application A-167 205, US patent 4 507 219 or British patent 8712430.

The content of fluorescent whitening agent in the liquid detergent compositions is 0.01-2%, preferably 0.01-1% and most preferably 0.03-0.3%.

In particular', in addition to the fluorescent whitening agents, the liquid detergent compositions contain 1 to 60% of anionic, non-ionic, a zwitterionic and, if desired, cationic surfactants and 25 to 65%, prefer- Sably 40 to 55%, of water. Specifically in addition to the fluorescent whitening agent, the detergent composition contains 3 to 50%, preferably S 15 to 25%, of anionic surfactants, 2 to 30%, preferably 4 tc 15%, of non-ionic surfactants, 3 to 30%, preferably 5 to 20%, of ethoxylated or S* *oe non-ethoxylated ClO-C14 fatty acids such as capric acid, lauric acid, thereof, 1 to 25%, preferably 1 to 10%,.of builders and, if desired, 1 to preferably 1 to of zwitterionic surfactants, 0.5 to prefern ably 0.7 to of quaternary ammonium, amine or amine oxide surfactants and 1 to 10% of conventional additives such as enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and S colourants, complexing or sequestering agents and solvents.

Useful surfactants are described e.g. in US patents 4 285 841, 3 929 678 and 4 284 532 and British patent 2 041 986. The surfactants indicated in European patent application A-167 205 as being preferred are used in particular. It is most preferable, however, to use ethoxylated or nonethoxylated CI-Cia alkylsulfates, e.g. in the form of the triethanolamine salts, C 1-C15 alkylbenzenesulfonates or mixtures thereof as anionic surfactants and condensation products of one mol of Cio-C15 fatty alcohol with 3 to 8 mol of ethylene oxide as non-ionic surfactants.- Suitable builders are the preferably polycarboxylated compounds mentioned in US patents 4 '21 165 and 4 284 532, for example citric acid.

7 Specifically sulfonated dibenzofuranylbiphenyls containing liquid detergent compositions can also contain bleaching agents, as described e.g. in British patent 8712430. Perborate is preferably used as the bleaching agent.

The following Examples will serve to illustrate the invention; parts and percentages are by weight; the spotting test is carried out in the following manner: a) Whitening agent/detergent composition formulation: o 0.1% (100% of active substa ce) of fluorescent whitening agent or b mixture of whitening agents is dissolved in a liquid detergent composition. 0.6 g of this detergent composition containing whitening agent is diluted with 400 ml of water (100-120 of hardness) at a temperature of 3 0 °C (wash liquor B).

e t b) A 20 g piece of bleached cotton fabric is fastened to a tenter frame.

c) Using a pipette, 0.6 ml of the solution of detergent composition is uniformly applied to a premarked round area (5 cm diameter) of this cotton fabric and, after an exposure time of 30 seconds, the fabric is placed in the prepared wash liquor and washed for minutes at 30 0 C. It is then rinsed with cold water and dried at 70 0

C.

S d) The difference in the degree of whiteness measured according to the I* method of Ganz between the treated area and the surrounding area is a a measure of the so-called spotting behaviour (formation of bleach spots) and is determined for a single-ply textile with a Zeiss RFC3 photometer.

Example 1: A liquid detergent composition comprising parts of C 11

-C

13 alkylbenzenesulfonate 14 parts of C14-Cis polyethoxylated fatty alcohol (7 ethylene oxide) parts of soap 9 parts of ethanol

I

1

;I

r,;l 8 parts of triethanolamine 4 parts of sodium citrate 43 parts of water and 0.1 part of the fluorescent whitening agent of the formula S0 3 Na S0 3 Na\ 0 0= 0 (100) is prepared.

The spotting test shows only very insignificant spotting, the degree of whiteness being very high.

a eo 0 0 000 S* 0 00 00o 000 0 The detergent formulation is stable on storage.

Example 2: A liquid detergent composition is prepared as in Example 1, except that it contains the compound of the formula

/CH

3

CH

3 NaSO 3 0 0 S0 3 Na (200) 0 0 000 0 0 *0 instead of compound (100).

As regards its properties, the liquid detergent composition is identical with that of Example 1.

00 0 0 00 Example 3: A liquid detergent composition is prepared as in Example 1, except that it contains the compound of the formula

C

2 H5 HSC2 Na/ 00Na NaS03 0 ON (300) instead of compound (100).

1: ?1 7 i i I r 1 1 1 i 9 i 9 Example 4: A liquid detergent composition is prepared as in Example 1, except that it contains the compound of the formula CH\ /CH 3

CH

3 ./3./CH3 I I I (400) NaS03 0 0 3 Na instead of compound (100).

The detergent formulation is very stable on storage. The spotting test shows only very insignificant spotting.

Example 5: A liquid detergent composition is prepared as in Example 1, except that it contains the compound of the formula Cl /CH 3

CH

3 Cl II II II II I (500) NaS03" 0 \SO 3 Na 1tt instead of compound (100).

The detergent formulation is very stable on storage. The spotting test *ota shows only insignificant spotting, the white effects being high.

Example 6: A liquid detergent composition comprising *ar 6.5 parts of triethanolamine parts of NaOH parts of ethanol 1.5 parts of propane-1,2-diol S11.5 parts of Clz-Cls polyethoxylated fatty alcohol (7 ethylene oxide) 2.5 parts of coconut fatty alkylsulfate 10.5 parts of linear dodecylbenzenesulfonic acid parts of oleic acid 10.5 parts of saturated C 1 2--C1 acid 43.0 parts of deionized water and 0.1 part of the fluorescent whitening agent of the formula 10

/CH

3

CH

3 I I I i I (200) O/ *O -SO NaSOa 3 0 .SO 3 Na is prepared.

The detergent composition is opaque, homogeneous and very stable on storage. The spotting test shows only very insignificant spotting, the degree of whiteness being very high.

Example 7: A liquid detergent composition is prepared as in Example 6, except that it contains the compound of the formula

CH

3

CH

3 CH CH 3 SI I I l 1 (400) t NaSO3 0 '0 SO 3 Na instead of compound (200).

As regards its properties, the liquid detergent composition is identical with that of Example 6.

00 *u i" S

Claims

1. A storage-stable liquid detergent composition, which, based on the weight of the detergent composition, comprises a) 0.01 to 2% of a fluorescent whitening agent of the formula 0.40* 00*4*0 in which R, is hydrogen, Ci-C 4 alkyl, chloro, C 1 -C 4 alkoxy, phenoxy or benzyloxy, R 2 is hydrogen or Ci-C 4 alkyl and M is hydrogen and/or one equivalent of a non- chromophoric cation and b) 1 to 60% of anionic, non-ionic, zwitterionic or cationic surfactants.

2. A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formula Q KXW/1 25808.doc 5845/3 WMMWMA I:. I

12- R 3 R 3 R3R I~~J II II I i so\0/ 0 SO 3 M ___SO 3 H S0 3 0 0 in which the radicals R 3 independently of the others are hydrogen, methyl or ethyl and M is preferably sodium or potassium. B go J S ~'GO 0O C2 1? o o @0 4 to,. 9@ B A A liquid detergent composition according to claim I fluorescent whitening agent of the formula ___S0 3 Na S0 3 0 0 which contains a (100). /t A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formula a P 9000 /H 3 CH 3 NaS0 0 I S 0:3N I (200). B. 4 h~. B, B *4 g~ S W. A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formuIR 215 H 5 C 2 NaSO 3 0 0 SO 3 Na liquid detergent composition according to claim 1 fluorescent whitening agent of the formula (300). which contains a 13 CH 3 /CH 3 CH 3 /./CH 3 NaS03 0 0 S0 3 Na 8 A liquid detergent composition according to claim 1 fluorescent whitening agent of the formula Cl /CHi CH 3 \./Cl N SII II II II I (400). which contains a (500). Pt OP 00 C O g o ot 0 0 a 0 a 00.. P p e 000 O 40 00 0 £i0 a 00 0 0 6*8 84 P O a £4 ,4 Use of the liquid detergent compositions according to any one of claims I-7 for washing and pretreating textile fabrics. 9 Preparation of the liquid detergent compositions according to any one of claims by mixing and homogenizing fluorescent whitening agent, surfactants, auxiliaries and builders, if desired a bleaching system, and water. ioA FI. A liquid detergent composition containing a fluorescent whitening agent substantially as hereinbefore described with reference to any one of the Examples. DATED this FOURTH day of APRIL 1990 Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON 2#,