GB1575007A

GB1575007A - Cleaning composition

Info

Publication number: GB1575007A
Application number: GB1662876A
Authority: GB
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1976-04-23
Filing date: 1976-04-23
Publication date: 1980-09-17
Also published as: BE853683A

Description

(54) CLEANING COMPOSITION (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London SW1P 3JF a British Company do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to surfactant compositions suitable for heavy duty cleaning applications, e.g. tank cleaning, engine cleaning and metal degreasing.

In our British patent No. 1,459,104, we have described and claimed a method of dispersing oil in water and compositions suitable for use in the method. The method involves contacting the oil and water with an alkyd resin in which one component of the resin comprises the residue of a polyalkylene glycol, said polyalkylene glycol being soluble in water. One use of this method which was described in British patent No. 1,459,104 was in the cleaning of oil contaminated storage tanks.

We have now devised a particularly active composition which finds application in heavy duty cleaning applications particularly for cleaning surfaces contaminated with oil or other organic hydrophobic material and which utilises the method described in British patent No.

1,459,104.

According to the invention a composition which is suitable for formulating a heavy duty cleaner comprises, (a) an alkyd resin in which one component of the resin is the residue of a polyalkylene glycol, the said residue constituting at least 5 % by weight of the resin, said polyalkylene glycol bein soluble in water, (b í an oxyethylene/ oxypropylene copolymer which preferably contains 15 to 70 oxypropylene units and 12 to 200 oxyethylene units and, (c) a non-ionic surfactant other than the oxyethylene/oxypropylene copolymer of (b).

This composition contains the active ingredients for an effective heavy duty cleaner but it is highly viscous and difficult to handle. It is advantageous therefore to add a solvent. The solvent may be a hydrocarbon solvent as hereinafter described but preferably the composition is blended with a solvent which is both oil and water miscible to form a concentrate which is mobile and which can be readily packed and transported. This concentrate can then be subsequently diluted with the same or another solvent or diluent before use, e.g. with water.

A preferred oil and water miscible solvent is a glycol ether, e.g. the methyl ether of a polypropylene glycol containing 2 to 12 propylene oxide units.

The polyalkylene glycol component of the alkyd resin is soluble in water, and by "soluble in water" we mean that at the temperature at which the composition is used as a cleaner the polyalkylene glycol would be below its cloud point.

Alkyd resins generally are the condensation products of a polybasic acid, a polyhydric alcohol and usually a monobasic acid. The alkyd resins useful in the present invention preferably comprise the water-soluble polyalkylene glycol as at least a part of the polyhydric alcohol component. Additional polyhydric alcohols which may be used include diols suitably containing up to 20 carbon atoms, such as mono-, di and tri-ethylene glycol, mono-, di and tri-propylene glycol, mono- di- and tri-butylene glycol, and neopentyl glycol; water-insoluble polyglycols such as poly-propylene glycol and polybutylene glycol; triols suitably containing up to 20 carbon atoms such as glycerol, trimethylol propane and trimethylol ethane; polyols also suitable containing up to 20 carbon atoms such as pentaery-thritol, dipentaerythritol and sorbitol; and ethoxylated amines also suitably containing up to 20 carbon atoms such as di and tri-ethanolamine.

The polybasic acid component of the alkyd resin may be saturated, or unsaturated either by olefinic or aromatic unsaturation. Commonly used acids are aliphatic or aromatic dibasic acids containing up to 20 carbon atoms, preferably up to 10 carbon atoms such as ortho-, isoor terephthalic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, azelaic acid, succinic acid, adipic acid, glutaric acid or suberic acid. The polybasic acid may also be tribasic or tetrabasic, suitably an aromatic acid containing up to 20, preferably up to 10 carbon atoms, e.g. trimellitic acid or pyromellitic acid. "Dimer" acids, i.e. mixed dibasic and tribasic carboxylic acids obtained by the polymerisation of unsaturated monobasic acids may also be used.

The optional monobasic acid component of the alkyd resin, which functions as a monofunctional chain terminator, may be derived from a free acid or from an ester of the acid particularly a glyceride. The acid may be an aromatic acid, particularly an alkyl substituted benzoic acid but is suitably an aliphatic saturated or ethylenically unsaturated acid containing up to 30 carbon atoms, preferably 6 to 22 carbon atoms. Mixtures of acids or their esters may also be used to derive the monobasic acid component, particularly naturally occurring mixtures such as tall oil acids, or acids derived from linseed oil, soyabean oil, whale oil, dehydrated castor oil, tung oil, fish oil, safflower oil, oiticica oil, cottonseed oil or coconut oil.

Individual acids which are acceptable include iso-octanoic acid, 2-ethyl-hexanoic acid, isodecanoic acid, lauric acid and pelargonic acid. Other mono-basic acid chain terminators known to those expert in the field may also be used as may chain terminators in general, e.g.

monohydric alcohol chain terminators, particularly C1 to C20 alkanols and monobasic amine chain terminators particularly Cm to C20 primary amines.

"Polyalkylene glycol" is the general name for polymers of an alkylene glycol I I II which have the general formula H(O.C - G)n where the structure .O.C-C. is I I II derived from an olefine oxide and forms a polyoxyalkylene chain. For example polyethylene glycol H(OCH2CH2)nOH is derived from ethylene oxide

The water-soluble polyalkylene glycol is preferably polyethylene glycol but low molecular weight polypropylene glycol or polyalkylene glycols containing a major proportion of ethylenoxy groups together with minor proportions of randomly or block distributed propylenoxy and/or butylenoxy groups may also be used. In addition to the water-soluble polyalkylene glycol residue the alkyd resin may contain residues of one or more waterinsoluble polyalkylene glycols such as those of higher molecular weight polypropylene or polybutylene glycols.Furthermore the alkyd resin may contain residues of one or more polyalkylene glycols containing water-soluble polyalkylenoxy blocks together with water insoluble polyalkylenoxy blocks, for example polyethylenoxy (watersoluble)/polypropylenoxy (water insoluble) block copolymers (poly(ethylene/propylene)glycol). Alternatively the blocks of propylene oxide and ethylene oxide/units may be present in an alkoxylated amine e.g. a C1 to C20 diamine such as ethylene diamine.

The alkyd resin preferably contains at least 10% by weight of the residue of the water soluble polyalkylene glycol. More preferably the alkyd resin contains 40 to 90% more preferably 50 to 80% by weight of the residue of the polyalkylene glycol. It is desirable that the alkyd resin be such that it has a viscosity of at least one poise as a 95% solid solution in xylene.

The water-soluble polyalkylene glycol which forms a part of the alkyd resin suitably has a molecular weight in the range 100 to 10,000 preferably 400 to 10,000 more preferably 600 to 5,000. One of the terminal hydroxyl groups of the polyalkylene glycol incorporated in the resin may, if desired, be etherified, e.g. with a lower (C1 to C6) alcohol such as methanol or ethanol or esterified with a lower (Cl to C6) alkanoic acid.

Although the polymeric nature of the alkyd and its carbon and hydrogen content help to confer an oleophilic character it is preferred that the oleophilic character be enhanced by a suitable choice of the components of the alkyd other than the water-soluble polyalkylene glycol. Thus it is preferred that components be chosen which would be soluble in the oil under the conditions of cleaning. By "soluble in the oil" we mean that the component in question is soluble and non-self-associated in the particular contaminating oil under the conditions of the treatment. The solution characteristics of a given oil will vary but suitable components may readily be selected by means of simple tests. An oil soluble component of the alkyd resin may be chosen from the alkyd constituents described earlier in this specification. In particular the oil soluble component may be a long-chain saturated or unsaturated aliphatic monobasic acid or long chain-alkylsubstituted aromatic monobasic acid or a "dimer" acid. Similarly the oil soluble component may be a water-insoluble polyalkylene glycol e.g. polybutylene glycol or a polyalkylene glycol containing a significant proportion of blocks of butylene-oxy units.

Alkyd resins which are useful in the present invention may be prepared by reacting a carboxyl or ester group containing alkyd resin with the hydroxyl-terminated polyalkylene glycol by a standard esterification or a trans-esterification technique. Alternatively the alkyd resin may be prepared from ingredients, one or more of which comprise the polyalkylene glycol unit. For example, a polyol such as glycerol may be reacted with an olefine oxide such as ethylene oxide so that the glycerol -OH groups react to produce what is in effect a glycerol/poly-ethylene glycol ether. This product is then reacted with the polybasic acid and optional monobasic acid under esterification conditions to form the alkyd.Similarly, a polybasic acid may be reacted with an olefine oxide to form the ester of the polyalkylene glycol and provided that it has been ensured that the polybasic acid retains one or more free -COOH groups it may be used in the alkyd forming reaction. In a third method of preparation the alkyd resin may be prepared from its basic ingredients in which the polyalkylene glycol forms one of such ingredients.

The oxyethylene/oxypropylene copolymer preferably comprises a block of 20 to 40 propylene oxide units particularly about 30 units and an average of 20 to 30 ethylene oxide units per molecule, particularly about 26 ethylene oxide units per molecule.

The nonionic surfactant preferably comprises one or more of an ethoxylate of C6 to C20 alcohol containing 3 to 15 ethylene oxide units per molecule, an ethoxylate of an alkyl phenol and/or an ethoxylate of a carboxylic acid.

The alcohol ethoxylate is suitably derived from an alcohol containing 8 to 20 preferably 10 to 15 carbon atoms and is more preferably a primary alcohol with a minimum of branching in the carbon chain. Particularly suitable is isodecanol or a mixture of C13 and C15 primary alcohols comprising 40 to 60% straight chain and 60 to 40%chains with methyl branch in the 2-position. The alcohol ethoxylate preferably comprises an average of 2 to 10 more preferably 4 to 8 ethylene oxide units per molecule and when the mixture of C13 and C15 alcohols referred to above is used the average number of ethylene oxide units per molecule is advantageously 6.

The alkyl phenol ethoxylate preferably comprises a C6 to C16 alkyl group e.g. an octyl or nonyl group located in the para-position to the ethoxylated phenolic hydroxyl group. The ethoxylate suitably comprises 2 to 20 ethylene oxide units, preferably 3 to 10 ethylene oxide units.

The ethoxylate of the carboxylic acid is preferably derived from an aliphatic carboxylic acid containing 8 to 20 carbon atoms in the molecule e.g. lauric acid, stearic acid or a naturally occurring acid such as coconut oil or tall oil acids. The ethoxylate preferably contains an average of 2 to 10 ethylene oxide units per acid molecule, more preferably 3 to 7 ethylene oxide units.

The composition according to the invention may also contain other ingredients conventionally used in cleaning formulations. For example, the composition may contain an ingredient to reduce the foaming of the composition in use. Flurocarbon surfactants are suitable for this application, e.g. those sold under the trademark MONFLOR by Imperial Chemical Industries Limited, which are only required in a low concentration, e.g. 1 to 100 ppm.

The diluent with which the composition or concentrate may be diluted is usually chosen so as to be a solvent for the hydrophobic material which the composition according to the invention is intended to clean from a surface such as the inside of a tank. The compositions according to the invention are mostly commonly used to clean surfaces contaminated with residues from crude petroleum or from petroleum fractions and we have found, for this purpose, that a hydrocarbon diluent, preferably an aromatic hydrocarbon diluent is most suitable, particularly a diluent comprising mixed aromatic hydrocarbons containing 6 to 20 carbon atoms. Suitable diluents include kerosine, xylenes and white spirit although in many instances water itself may be used.

Compositions according to the invention are preferably concentrates which comprise 1 to 20 parts by weight alkyd resin, 0.1 to 10 parts by weight oxyethylene/oxypropylene copolymer, 1 to 20 parts by weight non-ionic surfactant and optionally 5 to 100 parts by weight of oil- or oil and water-miscible solvent. For use as a cleaner 1 part of the concentrate may be diluted with a further 5 to 10,000 parts by weight of diluent.

The concentrate or concentrate plus diluent according to the invention are suitably applied in water to the surface to be cleaned. The concentrate or concentrate plus diluent may conveniently be used in a concentration in the range 0.05 to 20%by weight of its total weight with the water, preferably in a concentration of 0.1 to 10% by weight. The most effective method of application is to spray the aqueous mixture onto the surface to be cleaned the spray forming part of a circulatory system through which the aqueous mixture is recirculated.

Compositions according to the present invention besides being effective in removmg a hydrophobe from the surface to be cleaned also possess the added advantage of not giving rise to a stable emulsion so that the hydrophobe which is washed from the surface readily forms a separate phase from the water and may thus easily be removed.

Some purposes for which compositions according to the invention may be used include the following:- Tank cleaning, drum cleaning, metal degreasing, enging cleaning, chassis cleaning, concrete degreasing (e.g. workshop and garage floors) as a cleaner for surfaces contaminated with unpolymerised unsaturated polyester resins, alkyd resins, natural fat and edible oil deposits and in the general purpose cleaning of, for example ceramics, PVC, and melamine/formaldehyde plastics.

The invention will now be further described with reference to the following Example in which the test apparatus used was as follows: The apparatus consisted of a four litre beaker mounted on a hot plate and provided with a thermometer for measuring the temperature of the solution under test. A mild steel plate was clamped within the beaker but above the liquid level and a glass tube drawn out to a jet positioned at 5 cms. from the plate. The glass tube was connected via rubber tubing to a circulatory pump which took suction also via a rubber tube from the solution in the beaker. In operation, the plate was coated with a hydrophobe (heavy fuel oil tank residue) and the solution under test (500 mls) placed in the beaker.The solution was then heated to 50"C and the pump started (rate 100 litres/hour) when the solution was circulated through the jet onto the coated plate. The circulation was continued for five minutes and observations of the cleanliness of the plate were recorded at regular time intervals.

Example The composition according to the invention consisted of: 3.0 parts by weight alkyd resin comprising 1.75 mole polyethylene glycol (m. wt 600) 0.6 mole pentaerythritol, 0.97 mole trimellitic anhydride and 3.0 moles tall oil fatty acids, 10.0 parts by weight ethoxylated isodecanol containing an average of 6 ethylene oxide units per molecule, 5.0 parts by weight ethoxylated tall oil containing an average of 5 ethylene oxide units per molecule, 1.0 parts by weight of a propylene glycol/propylene oxide reaction product of molecular weight 1500 to 1800 reacted with ethylene oxide until the ethylene oxide units comprise 10 weight % of the final molecule.

This composition was converted to a concentrate by adding 10 parts by weight of the methyl ether of a polypropylene glycol containing an average of 3.7 propylene oxide units per molecule.

The concentrate was diluted with a solution of synthetic sea water (3.5 weight % sodium chloride in water) to form a 0.1 weight % solution which was then evaluated in the plate cleaning test described above. At the end of the five minute test period the plate was 90% clean.

The concentrate was also evaluated by diluting with kerosine (1 part concentrate to 5 parts kerosine) and using the resulting mixture as a metal cleaner. 50 litres of the mixture were placed in a bucket and a heavily soiled machine part immersed therein. The part was then lightly brushed and finally water washed under a tap when the oil and grease were removed to reveal the bright metal surface.

The concentrate was also used as a garage floor cleaner by diluting 1 part of the concentrate with 3 parts of 'CAROMAX' 20 (a mixture of aromatic hydrocarbons include methyl and ethyl substituted benzenes, naphthalenes, idenes and methylindenes; 'CAROMAX' is a trade mark) and brushing the resulting mixture into a stained and weathered garage floor.

After leaving for a minute the floor was washed down with water, a substantial amount of the oil stain being removed.

WHAT WE CLAIM IS: 1. A composition which is suitable for formulating a heavy duty cleaner and which com rises (a an alkyd resin in which one component of the resin is the residue of a polyalkylene glycol the said residue constituting at least 5 % by weight of the resin, said polyalkylene glycol being soluble in water, b an oxyethylene/oxypropylene copolymer and, c) a non-ionic surfactant other than the oxyethylene/oxypropylene copolymer of (b).

2. A composition as claimed in Claim 1 in which the alkyd resin is the condensation product of a polybasic acid a polyhydric alcohol and a monobasic acid in which the polyal kylene glycol comprises at least a part of the polyhydric alcohol component.

3. A composition as claimed in Claim 2 in which the polyhydric alcohol also comprises a diol containing up to 20 carbon atoms, a triol containing'up to 20 carbon atoms, a polyol containing up to 20 carbon atoms, an ethoxylated amine containing up to 20 carbon atoms or a water-insoluble polyglycol.

4. A composition as claimed in Claim 3 in which the polyhydric alcohol also comprise'

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. separate phase from the water and may thus easily be removed. Some purposes for which compositions according to the invention may be used include the following:- Tank cleaning, drum cleaning, metal degreasing, enging cleaning, chassis cleaning, concrete degreasing (e.g. workshop and garage floors) as a cleaner for surfaces contaminated with unpolymerised unsaturated polyester resins, alkyd resins, natural fat and edible oil deposits and in the general purpose cleaning of, for example ceramics, PVC, and melamine/formaldehyde plastics. The invention will now be further described with reference to the following Example in which the test apparatus used was as follows: The apparatus consisted of a four litre beaker mounted on a hot plate and provided with a thermometer for measuring the temperature of the solution under test. A mild steel plate was clamped within the beaker but above the liquid level and a glass tube drawn out to a jet positioned at 5 cms. from the plate. The glass tube was connected via rubber tubing to a circulatory pump which took suction also via a rubber tube from the solution in the beaker. In operation, the plate was coated with a hydrophobe (heavy fuel oil tank residue) and the solution under test (500 mls) placed in the beaker.The solution was then heated to 50"C and the pump started (rate 100 litres/hour) when the solution was circulated through the jet onto the coated plate. The circulation was continued for five minutes and observations of the cleanliness of the plate were recorded at regular time intervals. Example The composition according to the invention consisted of: 3.0 parts by weight alkyd resin comprising 1.75 mole polyethylene glycol (m. wt 600) 0.6 mole pentaerythritol, 0.97 mole trimellitic anhydride and 3.0 moles tall oil fatty acids, 10.0 parts by weight ethoxylated isodecanol containing an average of 6 ethylene oxide units per molecule, 5.0 parts by weight ethoxylated tall oil containing an average of 5 ethylene oxide units per molecule, 1.0 parts by weight of a propylene glycol/propylene oxide reaction product of molecular weight 1500 to 1800 reacted with ethylene oxide until the ethylene oxide units comprise 10 weight % of the final molecule. This composition was converted to a concentrate by adding 10 parts by weight of the methyl ether of a polypropylene glycol containing an average of 3.7 propylene oxide units per molecule. The concentrate was diluted with a solution of synthetic sea water (3.5 weight % sodium chloride in water) to form a 0.1 weight % solution which was then evaluated in the plate cleaning test described above. At the end of the five minute test period the plate was 90% clean. The concentrate was also evaluated by diluting with kerosine (1 part concentrate to 5 parts kerosine) and using the resulting mixture as a metal cleaner. 50 litres of the mixture were placed in a bucket and a heavily soiled machine part immersed therein. The part was then lightly brushed and finally water washed under a tap when the oil and grease were removed to reveal the bright metal surface. The concentrate was also used as a garage floor cleaner by diluting 1 part of the concentrate with 3 parts of 'CAROMAX' 20 (a mixture of aromatic hydrocarbons include methyl and ethyl substituted benzenes, naphthalenes, idenes and methylindenes; 'CAROMAX' is a trade mark) and brushing the resulting mixture into a stained and weathered garage floor. After leaving for a minute the floor was washed down with water, a substantial amount of the oil stain being removed. WHAT WE CLAIM IS:

1. A composition which is suitable for formulating a heavy duty cleaner and which com rises (a an alkyd resin in which one component of the resin is the residue of a polyalkylene glycol the said residue constituting at least 5 % by weight of the resin, said polyalkylene glycol being soluble in water, b an oxyethylene/oxypropylene copolymer and, c) a non-ionic surfactant other than the oxyethylene/oxypropylene copolymer of (b).

mono- di- or tri-ethylene glycol, mono- di- or tri-propylene glycol, mono-, di- or tri-butylene glycol, neopentyl glyeol, glycerol, trimethylol propane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol, polypropylene glycol, polybutylene glycol, di- or tri ethanolamine.

5. A composition as claimed in any one of claims 2 to;4 in which the polybasic acid comprises an aliphatic or aromatic dibasic acid containing up to 20 carbon atoms.

6. A composition as claimed in Claim 5 in which the dibasic acid comprises ortho-, iso- or terephthalic acid.

7. A composition as claimed in Claim 5 in which the dibasic acid comprises maleic'acid, fumaric acid, itaconic acid, mesaconic acid or citraconic acid.

8. A composition as claimed in Claim 5 in which the di-basic acid comprises succinic acid or adipic acid.

9. A 'composition as claimed in any one of claims 2 to 4 in which the polybasic acid comprises a tri- or tetra-basic aromatic acid containing up to 20 carbon atoms.

10. A composition as claimed in Claim 9 in which the polybasic acid is trimellitic acid or pyromellitic acid.

11. A composition as claimed in any one of claims 2 to 4 in which the polybasic acid comprises "dimer" acids.

12 A composition as claimed in any one of Claims 2 to 11 in which the monobasic acid component of the alkyd resin is derived from an ester.

13. A composition as claimed in Claim 12 in which the ester is a glyceride.

14. A composition as claimed in any one of Claims 2 to 12 in which the monobasic acid is 'an aliphatic'saturated or unsaturated acid containing up to 30 carbon atoms.

15. A composition as claimed in Claim 14 in which the monobasic acid contains 6 to 22 carbon atoms.

16. A composition as claimed in Claim 14 in which the monobasic acid comprises taIl oil acids, isooctanoic acid, 2-ethylhexanoic acid, isodecanoic acid, lauric acid, pelargonic acid or acids dèrived from linseed oil, soyabean oil, whale oil, dehydrated castor oil, tung oil, fish oil, safflower oil, oiticica oil, cottonseed oil or coconut oil.

17. A composition as claimed in Claim 1 in which the alkyd resin is chain terminated by a y honohydric alcohol or a monobasic amine.

18. A composition as claimed in any one of the preceding claims in which the water soluble polyalkylene glycol is polyethylene glycol.

19. A composition as claimed in any one of Claims 1 to 17 in which the water-soluble pdlyalkylene glycol is a low molecular weight polypropylene glycol or a polyalkylene glycol containing a major proportion of ethylenoxy groups together with a minor proportion of randomly or block distributed propylenoxy or butylenoxy groups.

20. A: composition as claimed in any one of Claims 1 to 17 in which the alkyd resin contains residues of one or more polyalkylene glycols containing water-soluble. polyal kylenoxy blocks together with water-insoluble polyalkenxoy blocks.

21. A composition as claimed in Claim 20 in which the water-soluble polyalkylenoxy block is a polyethylenoxy block and the water-insoluble block is a polypropyleneoxy block.

22. A composition as claimed in any preceding Claim in which the alkyd resin contains 40 to 90% by weight of the water soluble polyalkylene glycol.

23. A composition as claimed in any one of the preceding claims in which the water soluble polyalkylene glycol has a molecular weight in the range 100 to 10,000.

24. A composition as claimed in Claim 23 in which the molecular weight of the water soluble polyalkylene glycol lies in the range 600 to 5,000.

25. A composition as claimed in any one of the preceding claims in which one of the terminal hydroxyl groups of the water soluble polyalkylene glycol is etherified or esterified.

26. A composition as claimed in Claim 25 in which the hydroxyl group is etherified with a lower (C1 to C6) alcohol or is esterified with a lower (C1 to C6) alkanoic acid.

27. A composition as claimed in any one of the preceding claims in which the oxyethylene/oxypropylene copolymer contains 15 to 70 oxypropylene units and 12 to 200 oxyethylene units.

28. A composition as claimed in Claim 27 in which the oxyethylene/oxypropylene copolymer comprises a block of 20 to 40 propylene oxide units and an average of 20 to 30 ethylene oxide units per molecule.

29. A composition as claimed in any one of the preceding claims in which the non-ionic surfactant other than the oxyethylene/oxypropylene copolymer is an ethoxylate of a C6 to C20 alcohol containing 3 to 15 ethylene oxide units per molecule, an ethoxylate of an alkyl phenol or an ethoxylate of a carboxylic acid.

30. A composition as claimed in Claim 29 in which the alcohol ethoxylate is derived from an alcohol containing 8 to 20 carbon atoms.

31. A composition as claimed in Claim 30 in which the alcohol is a Cl0 to C1s primary alcohol with a minimum of branching in the carbon chain.

32. A composition as claimed in Claim 31 in which the alcohol is isodecanol or a mixture of C13 and C15 primary alcohols comprising 40 to 60% straight chain and 60 to 40% chains with a methyl branch in the 2-position.

33. A composition as claimed in any one of claims 30 to 33 in which the alcohol ethoxylate comprises 4 to 8 ethylene oxide units per molecule.

34. A composition as claimed in Claim 29 in which the alkyl phenol comprises a C6 to C16 alkyl group in the para-position to the ethoxylated phenolic hydroxyl group.

35. A composition as claimed in Claim 34 in which the alkylphenol is para-octyl phenol or para-nonyl phenol.

36. A composition as claimed in Claim 34 or Claim 35 in which the alkyl phenol ethoxylate comprises 2 to 20 ethylene oxide units.

37. A composition as claimed in Claim 29 in which the carboxylic acid contains 8 to 20 carbon atoms in the molecule.

38. A composition as claimed in Claim 37 in which the acid is lauric acid, stearic acid, coconut oil acids or tall oil acids.

39. A composition as claimed in Claim 37 or Claim 38 in which the carboxylic acid ethoxylate comprises 2 to 10 ethylene oxide units per molecule of acid.

40. A composition as claimed in any one of the preceding claims which also comprises a solvent.

41. A composition as claimed in Claim 40 in which the solvent is a hydrocarbon or is an oil and water miscible solvent.

42. A composition as claimed in Claim 41 in which the solvent comprises a glycol ether.

43. A composition as claimed in Claim 42 in which the glycol ether comprises the methyl ether of a polypropylene glycol containing 2 to 12 propylene oxide units.

44. A composition as claimed in any one of the preceding claims which comprises 1 to 20 parts by weight alkyd resin, 0.1 to 10 parts by weight oxyethylene/oxypropylene copolymer, 1 to 20 parts by weight non-ionic surfactant and, optionally, 5 to 100 parts by weight solvent.

45. A method of using a composition as claimed in any one of the preceding claims in which the composition is first diluted with a diluent,

46. A method as claimed in Claim 45 in which the diluent is a hydrocarbon-or an oil and water miscible-solvent as claimed in Claim 43 or Claim 44 or is water.

47. A method as claimed in Claim 46 in which the diluent is kerosine, xylenes, white spirit or mixed aromatic hydrocarbons containing 6 to 20 carbon atoms.

48. A composition in which one part by weight of the composition of claim 44 is diluted with 5 to 10,000 parts by weight diluent.

49. A method as claimed in Claim 46 in which the composition or composition and diluent are used with water in a concentration in the range 0.05 to 20%by weight of the total weight of concentrate and water.

50. A composition substantially as described in the Example.

51. A method of cleaning substantially as described in the Example.