WO1992021743A1

WO1992021743A1 - Rinsing composition

Info

Publication number: WO1992021743A1
Application number: PCT/EP1992/001217
Authority: WO
Inventors: Frank Wieczorek; Michael Leslie Durrant; Pia Depypere
Original assignee: Exxon Chemical Patents Inc.
Priority date: 1991-05-31
Filing date: 1992-05-29
Publication date: 1992-12-10

Abstract

Acetals having at least 27 carbon atoms, and derived from C7 to C15 alcohols and aldehydes, or olefin hydroformylation products treated to form products containing such acetals, are useful in automobile car wash fluids, especially the final rinsing solution.

Description

"Rinsing Composition"

This invention relates to a surface rinsing composition and to a composition for rendering a surface more hydrophobic or water repellant, to a method of treating a surface using such a composition, and to the use of such a composition in surface treatment.

It is customary to include in the final rinsing water of an automobile washing procedure a number of additives for various purposes. These include, for example, hydrophobic additives that cause beading of the rinse water on the surface, enabling it to be more readily removed by a high pressure air dryer, and additives that impart a gloss to the surface, for example, silicone oils or carnauba wax. Incorporating such additives into the final rinsing water is normally achieved by the use of an aqueous additive concentrate - which typically includes one or more surfactants, e ulsifiers, oils, coupling agents, as well as the additives of interest.

Many commercially available compositions employ hydrocarbon oils as hydrophobic components, but these suffer a number of disadvantages. Among these, there may be mentioned the requirement to remove the resulting hydrophobic film from windscreens, otherwise smearing occurs on subsequent use of windscreen wipers. More recently, however, there have been environmental objec-

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tions to the use of hydrocarbon oils, as they will be retained in the rinse water and cause difficulty in sewage works or if allowed to run off into watercourses, since they are not readily biodegradable.

It has been proposed in DE-PS 3427726 to increase the water-repellency of surfaces by incorporating in the final rinsing water a small proportion of a composition comprising a cationic surfactant, an emulsifier, an organic solvent, and an acetal of the formula

R¹¹OCH(OR¹²)R¹³ in which R¹¹, R¹², and R¹³, which may be the same or different, represent alkyl or alkenyl radicals with from 3 to 10 carbon atoms, provided that the total number of carbon atoms is from 18 to 24.

Such materials are environmentally more acceptable but are, however, expensive to produce.

There remains a need, accordingly, for compositions having acceptable anti-wetting properties, more especially compositions having reduced proportions of slowly biodegradable organic materials, and environmen¬ tally acceptable, that may be produced economically.

In a first aspect the present invention provides a composition capable of depositing a hydrophobic layer on a surface, the composition comprising a surfactant, an emulsifier, and an acetal of the formula

R¹OCR (OR²)R³ in which R¹, R², and R³,^" which may be the same or different, represent aliphatic, advantageously alkyl or alkenyl, radicals with from 7 to 15 carbon atoms, and R⁴ represents hydrogen or an aliphatic, advantageously an alkyl or alkenyl, radical with from 7 to 15 carbon atoms, provided that the total number of carbon atoms is at least 27.

The invention also provides the use of such an acetal in a hydrophobic composition and in an automobile washing composition and treatment.

In a second aspect of the invention, there is provided a composition capable of depositing a hydrophobic layer on a surface, comprising a surfactant, an emulsifier, and at least one organic material specified below. As specified organic material there may be used the distillation residue obtainable, and preferably obtained, by hydroformylating a C₆ to C₁₄, advantageously a C₈ to C₁₀, olefin feedstock, hydrogenating the resulting product, and removing the resulting alcohol by distillation. The distillation residue contains ether, ether-alcohol, ester, and acetal components. The specified organic material may also be the product obtainable, and advantageously obtained, by catalytically cracking the distillation residue defined above, and optionally hydrogenating the cracked com¬ ponents. The specified organic material may also be one or more of the products obtainable and advantageously obtained by further distillation of the optionally

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hydrogenated cracked product, or of the optionally hydrogenated distillation residue itself, and recovering the residue after removal of light alcohols, or the ether-comprising product obtainable by distillation of the light alcohol-depleted residue, or the ether-depleted residue of such distillation, or the ether-alcohol- comprising product obtainable by distillation of the ether-depleted residue, or the residue of such distillation.

The invention also provides the use of such a specified organic material in a hydrophobic composition, and in an automobile washing composition and treatment.

In a third aspect of the invention, there is provided a composition capable of depositing a hydrophobic layer on a surface, comprising a surfactant, an emulsifier, and an organic material comprising

(a) from 1 to 10% by weight of aliphatic aldehydes and/or alcohols having from 7 to 15 carbon atoms,

(b) from 70 to 99% by weight of functional aliphatic molecules having from 18 to 24 carbon atoms, and

(c) from 0 to 20% by weight of aliphatic acetals and/or esters having from 27 to 40 carbon atoms.

By the term "functional aliphatic molecules" is meant molecules other than hydrocarbons, and includes

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ethers, alcohols, aldehydes, esters, acetals and ether- alcohols.

The invention also provides the use of such an organic material in a hydrophobic composition, and in an automobile washing composition and treatment.

Advantageously, in the composition comprising surfactant, emulsifier and the specified material, the percentages by weight are:

Most Advantageous Preferred Preferred

Surfactant 0.5 to 10 0.5 to 5 1.5 to 3

Emulsifier 5 to 30 10 to 15 13 to 15

Specified Material 10 to 30 10 to 25 15 to 22

Other remainder remainder remainder

The composition may also comprise a component that adds gloss or lustre to the surface, e.g., a silicone oil or a phthalate ester, e.g., di-iso- heptyl, di-i_so- octyl, di-2-ethylhexyl, or di-iso-nonyl, phthalate, an organic solvent functioning as a coupling agent, e.g., a glycol, for example ethylene or propylene glycol, a glycol ether, for example ethylene glycol monobutyl ether or propylene glycol monobutyl ether, or an alcohol, e.g., a C2 to C₆ alcohol, or an acetate of a C₃ to C₆ alcohol and water.

In order to facilitate mixing of the specified material, surfactant and emulsifier with the rinsing water, the composition is advantageously employed as an — D —

aqueous solution, and accordingly then comprises the specified material, surfactant, emulsifier, coupling solvent, and water. In such a composition, the solvent advantageously represents from 1 to 5, preferably from 2.5 to 4, percent by weight and the water advantageously represents from 55 to 65, preferably from 58 to 63, percent by weight.

The composition may be incorporated in the final rinse water at a concentration of, for example, 1 to 4 g per kg, i.e., from 0.1 to 0.4%, but advantageously at a concentration of from 0.15 to 0.25%, and preferably about 0.20% by weight.

The surfactant is advantageously a non-ionic surfactant, for example, polyalkylene ether derivatives of alcohols and alkyl phenols, advantageously having from 3 to 30 alkylene, preferably ethylene, oxy groups and from 8 to 20 carbon atoms in the hydrocarbon chain. Preferably, there are used polyethylene oxy derivatives with from 5 to 20, more preferably from 5 to 15, repeat units with a linear or branched primary alcohol from 8 to 18, more preferably from 10 to 16, carbon atoms in the chain or with an alkyl phenol with a linear or branched alkyl group with from 6 to 14 carbon atoms. Most preferably there is used an ethoxylated fatty alcohol having from 5 to 20, advantageously 7 to 10, ethoxy groups and 11 carbon atoms in the chain which may be linear or branched. - 7 -

The surfactant may, less preferably, be a cationic surfactant, for example an imidazoline derivative, for example a fatty imidazoline salt of a strong monoprotic acid, for example one as described in U.S. Patent No. 3585051, or a quaternary ammonium salt having at least one long chain alkyl or alkenyl substituent, e.g. , one having from 8 to 20 carbon atoms, the remaining substituents being alkyl groups with up to 4 carbon atoms, especially methyl, the anion being, for example chloride, bromide, iodide, phosphate, sulfamate, or acetate.

As emulsifier there may be mentioned fatty amine alkoxylates, aromatic alkoxylates or an ether amine alkoxylate. Advantageously, however, the emulsifier is a quaternary ammonium salt, e.g., a long chain alkyl tri ethyl or dialkyl dimethyl ammonium chloride, and preferably the guaternized reaction product of an oxyalkylated polyamine with a fatty acid, for example the product of reaction of a soya or coco fatty acid, or a blend of the two, with diethylene triamine, ethoxylation, and subsequent quaternization with methyl chloride.

In the first aspect of the invention, in which an acetal is employed as such, advantageously, in the acetal, R¹ and R² represent alkyl or alkenyl radicals with from 8 to 13, preferably from 9 to 12, carbon atoms. Advantageously, also, R³ represents an alkyl or alkenyl radical with from 8 to 10, preferably from 7 to 9, carbon

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atoms. Advantageously, R⁴ represents hydrogen. The total number of carbon atoms is advantageously from 27 to

40, preferably from 27 to 33.

The alkyl or alkenyl groups may be straight or, preferably, branched chain; if they are branched they advantageously contain methyl and ethyl branches.

Mixtures of acetals may be used.

The acetals may be made by methods that are per se known, conveniently by reaction of an aldehyde (less preferably a ketone) with one or more alcohols in the presence of an acid catalyst with heating to distil off the water produced.

In the second aspect of the invention, the specified organic material may be obtained as described in EP-A-

185477, the disclosure of which is incorporated herein by reference.

In the third aspect of the invention, advantageously the components (a) , (b) and (c) are present in weight percentages in the ranges 1 to 10: 70 to 93: 5 to 20.

Advantageously, component (a) contains alcohols or aldehydes with from 9 to 12 carbon atoms.

Advantageously, in component (b) the functional aliphatic molecules comprise, by weight: ethers - from 25 to 90% ether alcohols, and/or alcohols, and/or aldehydes - from 10 to 40% esters - from 5 to 15% others - from 5 to 15%

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The organic material may conveniently be prepared by the procedure described in the above-mentioned EP-A- 185477, the middle fraction, containing the ether/ether alcohol portion, of the final stage being recovered.

In the second and third aspects of the invention, the organic material advantageously contains an acetal as specified in the first aspect of the invention, although in presently less preferred embodiments the acetal may contain fewer carbon atoms, for example 25 or 26 carbon atoms.

The compositions according to the invention may be used as a carrier for hot or cold waxes, for example carnauba wax emulsion or silicone oil. They have the major advantage that they may be based on an aqueous medium, thus avoiding the need to use a flammable organic liquid, for example isopropanol, as primary solvent. The compositions are suitable for use not only in soft, or softened, water but in hard water of all types thus avoiding the necessity of preparing different formulations for different geographical areas.

The compositions of the invention have low mammalian and fish toxicity and good biodegradability.

The following examples, in which all parts and percentages are by weight unless otherwise indicated, illustrate the invention:

Example 1 In the following Samples A to F, the component

SUBSTITUTESHEET denoted "Additive A" is in each case the organic material obtained according to the procedure described above in accordance with the second aspect of the invention, specifically, the residue remaining after distillation to remove light alcohols from hydrogenated cracked product. The emulsifier is in each case the product of reaction between a mixture of soya and coco fatty acids with diethylene tria ine, followed by ethoxylation and then quaternization using methyl chloride. The nonionic surfactant and bridging solvent were varied, as shown below. In Samples B and E, the undecanol is a mixture of branched isomers. Sample A %

Additive A 20.0

Emulsifier 13.5

Ethoxylated (20 moles) nonyl phenol 2.5 Propylene glycol monobutyl ether 3.0

Water 61.0

Sample B

Additive A 20.0

Emulsifier 13.5

Ethoxylated (10 moles) undecanol 2.5

Ethylene glycol monobutyl ether 3.0

Water 61.0 Sample C %

Additive A 20.0

Emulsifier 14.0

Ethoxylated (20 moles) nonyl phenol 2.0

Ethylene glycol monobutyl ether 2.5

Water 61.5

Sample D

Additive A 20.0

Emulsifier 14.0

Ethoxylated (10 moles) octyl phenol 2.0

Ethylene glycol monobutyl ether 3.5

Water 60.5

Sample E

Additive A 20.0

Emulsifier 13.5

Ethoxylated (10 mole) undecanol 2.5

Propylene glycol monobutyl ether 3.5

Water 60.5

Sample F

Additive A 20.0

Emulsifier 13.5

Lutensol A030 2.5

Propylene glycol monobutyl ether 3.0

Water 61.0 Lutensol A030 is an ethoxylated (30 moles) fatty alcohol. The compositions were made up by mixing the organic components while stirring to obtain a clear solution and - 12 -

then slowly adding water, which is advantageously soft or softened. Initially, the solution becomes brighter as a water-in-oil emulsion is established, then the emulsion becomes more viscous and opaque as the phase inversion point is reached. Then, as more water is added, the viscosity falls, and the emulsion, now oil-in-water, clarifies. Any haziness disappears on standing as the microemulsioή becomes established.

The compositions were tested at a concentration of 2 g per litre of water.

All of the samples compared favourably with a commercial rinse aid in the "bonnet" test, in which test samples are poured from a beaker onto a clean automobile bonnet, the comparison sample being poured over one side of the bonnet, the sample under test being poured over the other, and the time for each to run off measured. Beading qualities were also satisfactory. All samples were stable to freeze-thaw and heating tests.

While the estimates of beading qualities are somewhat subjective - bigger beads of water being preferred because they run off more rapidly - they are believed to correlate well with the ability of a rinsing composition to lay down a hydrophobic layer on a surface.

Example 2 The procedure of Example 1 was repeated, replacing "Additive A" by "Additive B", which differs from Additive A in being the residue remaining after distillation to - -

remove light alcohols from cracked product that has not been hydrogenated. The composition was as follows:

% Additive B 20.0

Emulsifier 13.0

Ethoxylated (10 moles) octylphenol 3.0 Ethylene glycol monobutyl ether 2.5 Water, softened 61.5

The product was tested at a concentration of 1 g per litre of water and compared favourably with a commercial rinse aid in the "bonnet" test.

Similar results are obtained when Additive C, the low-boiling product obtained by distillation of the light alcohol-depleted residue, is used in the above compositions. This contains about 85% ethers, about 10% ether-alcohols, and about 5% esters.

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Claims

- - Claims :

1. A composition comprising a surfactant, an emulsifier and an acetal of the formula

R¹OCR⁴(OR²)R³ in which R¹, R² and R², which may be the same or different, each represent an alkyl or alkenyl radical with from 7 to 15 carbon atoms, and R⁴ represents a hydrogen atom or an alkyl or alkenyl radical, preferably a hydrogen atom, the total number of carbon atoms in the molecule being at least 27.

2. A composition as claimed in claim 1, wherein the acetal contains from 27 to 40, preferably from 27 to 33, carbon atoms.

3. A composition as claimed in any one of claim 1 or claim 2, wherein R¹ and R² have from 8 to 13, preferably from 9 to 12, carbon atoms.

4. A composition as claimed in any one of claims l to 3, wherein R³ has from 7 to 12, preferably 8 to 10, carbon atoms.

5. A composition comprising a surfactant, an emulsifier, and an organic material selected from

(a) the distillation residue obtainable by hydroformylating a C₆ to C₁₄ olefin feedstock, hydrogenating the resulting product, and distilling off the resulting alcohol;

SUBSTITUTESHEET (b) the product obtainable by catalytic cracking of (a) ;

(c) the product obtainable by hydrogenation of (a) or (b) ;

(d) the product obtainable by removal of light alcohols from (b) or (c) by distillation;

(e) the low boiling fraction obtainable by distillation of (d) ;

(f) the high boiling fraction obtainable by distillation of (d) ;

(g) the low boiling fraction obtainable by distillation of (f) ; or

(h) the high boiling fraction obtainable by distillation of (f) .

6. A composition comprising a surfactant, an emulsifier and an organic material comprising

(c) from 0 to 20% by weight of aliphatic acetals and/or esters having from 27 to 33 carbon atoms.

7. A composition as claimed in claim 6, wherein the functional aliphatic molecules comprise, by weight:

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ethers - from 25 to 90% ether-alcohols, and/or alcohols, and/or aldehydes - from 10 to 40% and esters - from 5 to 15%.

8. A composition as claimed in any one of claims 1 to 7, which comprises the surfactant, the emulsifier, and the acetal or the organic material specified in any one of claims 5 to 7 in percentages within the range:

0.5 to 5: 10 to 15: 10 to 25, especially within the range

1.5 to 3: 13 to 15: 15 to 22.

9. A composition as claimed in any one of claims 1 to 8, which also comprises a wax, especially carnauba wax or a silicone wax.

10. A composition as claimed in any one of claims l to 9, which also comprises an organic solvent, advantageously a glycol ether.

11. A composition as claimed in any one of claims 1 to 10, in the form of an aqueous solution.

12. A composition as claimed in claim 11, wherein the surfactant, the emulsifier and the acetal or the organic material specified in any one of claims 5 to 7, are together present in a total concentration of from 20 to 45% by weight.

13. A composition as claimed in any one of

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claims 1 to 12, wherein the surfactant is a non-ionic surfactant.

14. A composition as claimed in claim 13, wherein the surfactant is a polyoxyalkylene derivative of an alcohol or an alkylphenol, especially a derivative of a C₈ to C₂o alcohol with from 3 to 30 alkyleneoxy groups.

15. A composition as claimed in claim 14, wherein the surfactant is a derivative of a C^ alcohol with from 5 to 20, advantageously from 7 to 10, ethoxy groups.

16. A composition as claimed in any one of claims 1 to 15, wherein the emulsifier is the quaternized reaction product of an oxyalkylated polyamine with a fatty acid.

17. A composition as claimed in claim 16, wherein the emulsifier is the product of reaction of diethylene triamine with soya or coco fatty acid or a mixture of the two acids, ethoxylation, and quaternization with methyl chloride.

18. An automobile rinsing solution containing a composition as claimed in any one of claims 1 to 17.

19. A solution as claimed in claim 18, wherein the components specified in any one of claims 1, 6 and 7 are present at a total concentration of from 0.1 to 0.4% by volume.

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20. The use of a composition as claimed in any one of claims 1 to 19 in an anti-wetting surface treating composition or in an automobile rinsing composition, treatment, or method.

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