GB1563808A - Cleaning composition - Google Patents

Description

(54) CLE. ANING COMPOSITION (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London SWIP 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 a cleaning composition and to a method of cleaning surfaces contaminated with polyester resins.

The composition comprises (a) an alkoxylated C, to Ce alcohol which has a molecular weight of at most 500 which is dispersible in both oil and water, (b) a surfactant with good wetting properties which has a molecular weight in the range 200 to 800 and, (c) at least one alkyd resin one component of which is a water-soluble polyalkylene glycol.

The alkoxylated lower alcohol is suitably derived from a C, to C6 alkanol, e. g. methanol by reaction with an alkylene oxide, preferably propylene oxide. Ethylene oxide and/or butylene oxide may also be used but in order to obtain the desired despersibility in both oil and water it is necessary to use combinations of ethylene oxide with propylene oxide and/or butytene oxide or butylene oxide with ethylene oxide and/or propylene oxide. The molecular weight of the alkoxylated lower alcohol is preferably at most 300, e. g. methanol combined with an average of 3. 5 units of propylene oxide per molecule.

The low molecular weight surfactant with good wetting properties preferably has a molecular weight in the range 250 to 600.

Commerciallv available surfactants may be used for this purpose and the surfactant may be anionic cationic or nonionic in nature.

Thus the surfactant may be an olefine or alkane sulphonate or an alkyl benzene sulphonate. Preferably however the surfactant is non-ionic, particularlv an alkoxylate of a long chain (i. e. a C8 to Cis preferably Cl2 to C, 6) alkanol : an alkvlphenol, containing for example 6 to 16 and preferably 8 to 12 carbon atoms in the alkyl group : a glycol e. g. a Cz to C6 glycol or a carboxvlic acid e. g. a Ce to C20 aliphatic acid. The alkoxylate is preferably an ethoxyiate afthough a mixed ethylene oxide and propylene oxide chain may form part of the surfactant. particularly when the latter is derived from a glycol. Preferably the alkoxylate chain contains 2 to 10 alkylene oxide units more preferably 3 to 6 units.

Particularly useful surfactants include an ethoxylated p-nonyl or p-octyl-phenol containing an average of four mo ! es ethylene oxide per mole of phenol ; a similar ethoxylate of a mixture of C, and C, s alcohols which has been obtained by the hydroformylation of a mixture of C12 and C, 4 alpha olefines ; and ofeic or tall oil acids ethoxylated with an average of 5 ethylene oxide units.

The alkyd resin constituent of the composition comprises one component which is a water-soluble polyalkylene glycol. By"water-soluble"we mean that at the temperature at which the composition is used the polyalkylene glycol which is a component of the alkyd woutd 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 alkvd resins useful in the present invention preferably comprise the water-soluble polyalkvlene glycol as at least a part of the polyhydric alcohol component. Additional polyhydric alcohols which mai be used include diols for example containing up to 20 carbon atoms, such as mono, di- and tri-ethylene glycol, mono-, di and tri-propylene glycol, monodi-and tri-butytene glycol, and neopentvl glycol : water-insotubte polyglycols such as poly-propylene glycol and polybutylene glycol; triols suitably containing up to 20 carbon atoms such as elycerol, trimethylol propane and trimethylol ethane : polyols also for example containing up to 20 carbon atoms such as pentaerythritol, dipentaerythritol and sorbitol: and ethoxylated amines also for example 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, iso or 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 tri-or tetra-basic, for example an aromatic acid containing up to tos preferably up to 10 carbon atoms, e. g. trimellitic acid or pyromellitic acid respectively."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 preferably 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, soya oil, whale oil, dehydrated castor oil, tung oil, fish oil, safflower oil, oitacica oil, cottonseed oil or coconut oil. Individual acids which are acceptable include isooctanoic acid, 2-ethylhexanoic 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 monohydric alcohol chain terminators which are also known for this purpose, e. g. C, to C20 alkanols.

"Polyalkylene glycol"is the general name for polymers of an alkylene glycol which have the general formula I I H (OC-C) OH I I where the structure I I . o. c. c.

! ! is derived from an olefine oxide and forms a polyoxyalkylene chain. For example polyethylene glycol H (QCH2CH2) nOH is derived from ethylene oxide

The water-soluble polyalkylene glycol is preferably polyethylene glycol but low molecular weight polypropylene glycol of polyalkylene glycols containing a major proportion of ethyleneoxy groups together with minor proportions of randomly distributed propyleneoxy and/or butyleneoxy groups may also be used. In addition to the water-soluble polyalkylene glycol residue the alkyd resin may contain residues of one or more water-insoluble 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 watersoluble polyalkyleneoxy blocks together with water insoluble polyalkyleneoxy blocks, for example polyethyleneoxy/ polypropyleneoxy block copolymers (poly (ethylene/propylene) glycol).

The alkyd resin contains at least 5/n by weight of the resin of the polyalkylene glycol e. g. 5 n to 95 , and, more preferably, at least 10or". For preference the alkyd resin contains 25 to 85 a by weight of the polyalkylene glycol.

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

The inherent nature of the alkyd i. e. its polymeric character and its carbon and hydrogen content confer upon it oleophilic properties. It is desirable however that the ingredients which go to make up the alkyd should be chosen to enhance the oleophilicity of the alkyd (i. e. to confer on the alkyd compatibility with organic media e. g. hvdrocarbons or substituted hydrocarbons). For example, a monobasic acid component in the alkyd may be particularly useful for this purpose as such an acid may possess a long oteophilic carbon chain. Similarly a higher polyalkylene glycol containing blocks of water insoluble oleophilic alkylene oxide e. g. butylene oxide units may also be used to confer oleophilic properties on the aikyd.

The composition may contain 595n"bY weight of the alkoxylated lower alcohol, 4 to So., weight of the low molecular weight surfactant and I to 40 "by weight of the alkyd. Preferably the composition contains 60 to 90". 10 to 30 and 2 to 10 respectively of the three ingredients.

The compositions according to the invention are particularly useful for cleaning surfaces contaminated with polyester resins especialiv unsaturated polyester resins. For exampfe, in processes which involve the manufacture or use of unsaturated polyester resins working surfaces, tools brushes etc. become coated with unpolymerised resin. This may be removed by soaking the surface or implement with a composition according to the present invention and then washing awav the resin in emulsified form in water.

The invention will now be further described with reference to the following Example.

EXAMPLE A liquid composition was made up comprising: 80 wt Propoxylated methanol containing an average of 3.5 moles propylene oxide per mole of methanol.

15 wt sa Ethoxylated p-nonylphenol containing an average of 4 ethylene oxide units per molecule.

2.5 wt -Alkvd comprising 1. 2 mole polyethylene glycol (mwt 600), 0.6 mole glyc rol, 0.6 mole pentaerythritol, 1. 2 mole trimellitic anhydride, 3.0 moles tall oil fatty acids.

2. 5 wt Alkyd comprising 1. 75 mole polyethylene glycol (mwt 600), 0.6 mole pentaerythritol, 0.97 mole trimellitic anhydride and 3.0 moles tall oil fatty acids.

Claims (37)

100 grams of a commercial unsaturated polyester resin was placed in a stainless steel metal tray. 200 grams of the formulation were poured onto the resin and the two mixed together using a paint brush. The resulting emulsion was finally washed away in a stream of cold water leaving the tray clean and"non-sticky" WHAT WE CLAIM IS : 1. A composition which comprises: (a) an alkoxylated C, to C6 alcohol which has a molecular weight of at most 500 which is dispersible in both oil and water, (b) a surfactant with good wetting properties which has a molecular weight in the range 200 to 800 and, (c) at least one alkyd resin one component of which is a water-soluble polyalkylene glycol.

2. A composition according to Claim I in which the alkoxylated lower alcohol is derived from methanol.

3. A composition according to Claim I or Claim 2 in which the alkoxylated lower alcohol is alkoxylated with propylene oxide or with combinations of ethylene oxide and propylene oxide and/or butylene oxide or with butylene oxide and propylene oxide.

4. A composition according to Claim 4 in which the alkoxylated lower alcohol is methanol combined with an average of 3.5 units of propylene oxide per molecule.

5. A composition according to any one of the preceding claims in which the low molecular weight surfactant is nonionic.

6. A composition according to Claim 5 in which the surfactant is an alkoxylate of a long chain alcohol, of an alkylphenol, of a glycol or of a carboxylic acid.

7. A composition according to Claim 6 in which the long chain alcohol contains 8 to 18 carbon atoms.

8. A composition according to Claim 6 in which the alkylphenol contains 6 to 16 carbon atoms in the alkyl group.

9. A composition according to Claim 6 in which the glycol contains 2 to 6 carbon atoms.

10. A composition according to Claim 6 in which the carboxylic acid contains 8 to 30 carbon atoms.

I I. A composition according to any one of claims 6 to 10 in which the alkoxylate is an ethoxylate or comprises a mixed ethylene oxide/propyfene oxide chain.

12. A composition according to any one of claims 6 to I I in which the alkoxylate chain contains 2 to 10 alkylene oxide units.

13. A composition according in which the low molecular weight surfactant is an ethoxylated p-nonyl-or p octyl-phenol containing an average of 4 moles ethylene oxide per mole of phenol, or an ethoxylate of a mixture of C, j and C, ; alcools which has been obtained by the hydroformylation of a mixture of C, 2 and (, alpha-o'lefines and which also contains an average of 4 moles ethylene oxide per mole of alcohol or it is oleic or tall oil acids ethoxvlated with an average of 5 moles ethylene oxide per mole of acid.

14. A composition according to any one of the preceding claims in which the alkyd resin is the condensation product of a polybasic acid, a polyhydric alcohol and a monobasic acid in which the polyalkylene glycol comprises at least part of the polyhydric alcohol component.

15. A composition according to Claim 14 in which the polyhydric alcohol also comprises mono-, di-or tri-ethylene glycol, mono-di or tri-propylene glycol, mono-di- or tri-butylene glycol, neopentyl glycol, gfycer l, trimethylol propane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol, polypropylene glycol, polybutylene glycol, di- ethanolamine or triethanolamine.

16. A composition according to Claim 14 or Claim 15 in which the polybasic acid comprises an aliphatic or aromatic dibasic acid containing up to 20 carbon atoms.

17. A composition according to Claim 16 in which the dibasic acid comprises ortho-, iso-or terephthalic acid, ma) eic acid, fumaric acid, itaconic acid, metaconic acid, citraconic acid, azelaic acid, succinic acid, ad ; pic acid, glutaric acid or suberic acid.

18. A composition according to Claim 14 or Claim 15 in which the polybasic acid comprises a tri-or tetra-basic aromatic acid containing up to 20 carbon atoms.

19. A composition according to Claim 18 in which the polybasic acid is trimellitic acid or pyromellitic acid.

20. A composition according to Claim 14 or Claim 15 in which the polybasic acid comprises"dimer"acids as hereinbefore defined.

21. A composition according to any one of claims 14 to 20 in which the monobasic acid component of the alkyd resin is derived from an ester.

22. A composition according to Claim 21 in which the ester is a glyceride.

23. A composition according to any one of claims 14 to 22 in which the monobasic acid is an aliphatic saturated or unsaturated acid containing up to 30 carbon atoms.

24. A composition according to Claim 23 in which the monobasic acid contains 6 to 22 carbon atoms.

25. A composition according to Claim 24 in which the monobasic acid comprises tall oil acids, iso-octanoic acid, 2-ethylhexanoic acid, isodecanoic acid, lauric acid, pelargonic acid or acids derived from linseed oil, soyabean oil, soya oil, whale oil, dehydrated castor oil, tung oil, fish oil, safflower oil, oiticica oil, cottonseed oil or coconut oil.

26. A composition according to any one of the preceding claims in which the polyalkylene glycol is polyethylene glycol.

27. A composition according to any one of claims 1 to 27 in which the polyalkylene glycol is a pol (ethylene/propylene) glycol.

28. A composition according to any one of the preceding claims in which the alkyd resin contains at least 0".. by weight of the polyalkvlene alycol.

? 9. A composition according to Claim 28 in which the alkyd resin contains 25 to 85 " by weight of the polyalkylene glycol.

30. A composition according to any one of the preceding claims in which the polyalkylene glycol has a molecular weight in the range 100 to 10, 000.

31. A composition according to Claim 20 in which the molecular weight of the polyalkylene glycol lies in the range 400 to 5,000.

32., l composition according to any one of the preceding claims in which one of the terminal hydroxyl groups of the water soluble polyalkylene glycol is etherified or esterified.

33. A composition according to Claim 32 in which the hydroxyl group is etherified with a lower (C, to C6) alcohol or is esterified with a lower (C, to C6) alkanoic acid.

34. A composition according to any one of the preceding claims which contains 5 to 95% by weight of the alkoxylated lower alcool, 4 to 50% by weight of the low molecular weight surfactant and 1 to 40 by weight of the alkyd.

35. A composition according to Claim 34 which contains 60 to 90 "by weight of the alkoxylated lower alcool, 10 to 30 "by weight of the low molecular weight surfactant and ? to 10 "by weight of the alkyd.

36. A composition substantially as described in the Example.

37. A method of cleaning a surface contaminated with a polyester resin by soaking the surface with a composition according to any one of the preceding claims and washing away the resin in emulsified form with water.