WO1992021741A1

WO1992021741A1 - Cleaning compositions containing ethoxylated cardanol

Info

Publication number: WO1992021741A1
Application number: PCT/US1992/004480
Authority: WO
Inventors: Gerald Leslie Hart; Anjum Fatima Ahmed
Original assignee: S. C. Johnson & Son, Inc.
Priority date: 1991-05-31
Filing date: 1992-05-28
Publication date: 1992-12-10
Also published as: AU2160092A; NL9100944A

Abstract

An aqueous cleaning composition comprising 15 % or less of mixtures of cardanol ethoxylation products having a cardanol ethoxylate with a relatively low average n value mixed with a cardanol ethoxylate having a higher average n value. The difference between the n values being at least 2.3.

Description

Cleaning Compositions Containing Ethoxylated Cardanol

Technical Field This invention relates to detergent compositions containing ethoxylated cardanol.

Background of Invention It is known that technical cashew nut shell liquid (CNSL) contains mainly two components, i.e. cardanol and cardol. Natural CNSL contains mainly anacardic acid which is converted to cardanol by decarboxylation:

In cardanol the aliphatic side chain is predominantly

^C15^H27 (^{χ =} 2) ; the average number of double bonds is 1.8. For the preparation of cardanol, reference can be made to

GB 2,152,925.

When the cardanol is ethoxylated with ethylene oxide, a compound having the formula Ci5H3 __2 CgH4θ(C2H4O) _nH is obtained for x = 2:

This cardanol ethoxylate (hereinafter also referred to as "CE" or "cardanol n.EO") is suitable as a surfactant.

Indian patent 111326 discloses in Example 4 the reaction of 30 moles of ethylene oxide with 1 mole of cardanol; the resulting product is reported to have surface active properties. Said Indian patent discloses more generally the products of alkylene oxides with the phenolic constituents obtainable from e.g. CNSL and phenolic constituents obtainable from e.g. CNSL and mentions that these products are useful as emulsifiers, detergents, dispersants, etc..

"Fette, Seifen, Anstrichmittel", 77:197-199, 1975, discloses the preparation of ethylene oxide adducts of cardanol; the products are reported to have surface-active properties which depend on the average number of ethoxy groups in the adducts.

U.S. patent 4,233,194 relates to an aqueous-dispersed film-forming vehicle for lacquers and lacquer binding agents, which films contain as a non-ionic surfactant an adduct of ethylene oxide and cardanol wherein the aliphatic chain is a mixture of

said adduct containing 5-40 ethylene oxide units. Furthermore alkylphenol ethoxylates such as nonylphenol ethoxylate

are known as surfactants. These alkylphenol ethoxylates, although excellent hydrotropes and mobile liquids at higher HLB-values than more non-phenolic alcohol ethoxylates, lead to a high aquatic toxicity in effluents and poor biodegradability, and therefore these materials are restricted in many countries. Generally non-phenolic alternatives to alkyl phenol ethoxylates are very poor viscosity builders. A high viscosity in detergent compositions is very desirable since this leads to longer contact times with the material or surface treated and therefore to a more effective cleaning action. A higher viscosity also prevents particulate additives from precipitating out. It will be clear that it would be advantageous if a separate viscosity builder will not have to be added. Cardanol ethoxylates, in particular those having 13 EO units, show all the above-mentioned positive features of alkylphenol ethoxylates, but none of the negatives; cardanol ethoxylates are fully biodegradable, liquid at high HLB-values, cheap and good viscosity builders. Summary Disclosure of Invention It has now been found that combinations of at least two cardanol ethoxylation products, as defined hereinafter, produce a surprisingly high viscosity; this viscosity is considerably higher than would be expected from the viscosities obtained with the separate ethoxylation products of cardanol.

This invention provides aqueous cleaning compositions comprising a) at least one cardanol ethoxylation product having an average number of ethylene oxide units n of about 8 or less, in combination with at least one cardanol ethoxylation product having an average n value of about 8 or more, the difference between the n values of the two groups of cardanol ethoxylation product being at least 2.3, in a weight ratio of at most about 1:2 and at a combined concentration up to about 15 % by weight; or b) at least one cardanol ethoxylation product having an average n value of about 8 or less, in combination with at least one cardanol ethoxylation product having an average n value of about 19 or more, in a weight ratio of more than about 1:2 to about 2:1 and at a combined concentration up to about 7 % by weight; or c) at least one cardanol ethoxylation product having an average n value of about 8-13 in combination with at least one cardanol ethoxylation product having an average n value of about 13 or more, the difference between the n values of the two groups of cardanol ethoxylation product being at least 2.3, in a weight ratio of at most 4 : 1 and at a combined concentration up to about 15 % by weight.

Combinations within the above ranges are stable, i.e. they remain homogeneous and no phase separation occurs.

The present combinations of cardanol ethoxylation products show the above discussed advantages over single cardanol ethoxylation products, i.e. they cause an unexpected synergistic increase in the viscosity in aqueous compositions into which they are incorporated, compared to the separate cardanol ethoxylation products, as will be demonstrated in the Examples of the present application. Best Mode for Carrying Out The Invention

The above viscosity increase or viscosity building enables one to adjust the viscosity at a desired level using a relatively small amount of ethoxylation product. It is believed that with the present combination a physical interaction takes place, the components exerting a dissolving action on each other.. However, the invention is not limited by theoretical considerations.

The present combination of cardanol ethoxylation products is incorporated into cleaning compositions, in particular home care and personal care and institutional cleaning compositions. By "home care cleaning compositions" are meant cleaning compositions for fabrics (clothes, furniture) and hard surfaces, especially "pre- spotters" which are used on fabrics prior to a washing treatment; these home care products also include compositions containing a disinfectant such as WC cleaner. "Personal care cleaning compositions" are e.g. shampoos, skin lotions, etc.. "Institutional cleaning compositions" are in fact large scale home care products which may differ from home care products in their formulations, e.g. they may be more concentrated.

The preferred cardanol ethoxylate composition consists of cardanol 13 EO and cardanol 8 EO in a weight ratio of 4:1, which combination is the most effective in terms of viscosity building.

Toilet cleaning compositions containing cardanol ethoxylate wherein the average n value is 13 and cardanol ethoxylate wherein the average n value is 40, in a ratio of 1:4, are preferred, because this combination has a strong solubilizing action on the perfume in the composition.

The above defined combinations of cardanol ethoxylates can be stored as such (i.e. without water) or as a concentrated aqueous solution, e.g. a solution having a concentration of up to 20 % by weight.

The present combinations are defined above by means of the n values in the above formula for CE. They can also be defined in terms of their HLB values. HLB means hydrophilic-lipophilic balance and could be calculated as follows:

HLB = crra mol weight of hvdrophilic groups x 20 gram mol weight of total molecule

Molecular weight of cardanol is 302; molecular weight of ethylene oxide is 44; and molecular weight of OH group is

17; therefore, if n in the above formula is 13, the HLB value = 3¹⁷02⁺+f¹(³13^xX⁴⁴44>) x^x 2² ₀ ^{ϋ ~}- ₁ ¹3-⁵- 5⁵.

The following table shows the HLB values corresponding to a number of n values mentioned in this application

N HLB

3 6.8

8 11.3

13 13.5 19 15

40 17.2

Industrial Applicability The compositions of this invention relate to low cost biodegradable cleaning compositions for a wide variety of uses include products for use in the home. Example I

A cardanol ethoxylate containing 8 moles of ethylene oxide (Cardanol 8 EO) was prepared as follows:

A 5 litre autoclave, fitted with a water-cooled stirrer, condenser, thermometer, and gas dispersion thimble was connected through two 1 litre safety bottles to a graduated cylinder containing white oil and a manifold connected to low-pressure nitrogen and a tank of ethylene oxide. 906 g (3 g moles) of cardanol was charged to the autoclave followed by 2 g of powdered sodium hydroxide. - i - The autoclave thermometer, gas disperser and contents were weighed. A slow stream of nitrogen was started through the alcohol and the temperature raised to 150-160°C by means of a heating mantle. Ethylene oxide gas was admitted to the manifold and allowed to escape momentarily to the atmosphere through a three-way stopcock. This stopcock was then turned to vent the nitrogen to the atmosphere and the ethylene oxide was simultaneously introduced into the flask. The white oil in the graduated flask allowed a small hydrostatic head to build up (about 2.5 cm Hg) , and the ethylene oxide rate was increased to the point where an occasional bubble of ethylene oxide escaped.

The absorption of ethylene oxide into the cardanol was immediate and the temperature was allowed the rise to

180-220°C. It was held there during the course of reaction until the required weight of ethylene oxide had been absorbed. In the present case (cardanol 8 EO) this weight was 1,056 g. In shutting down, the apparatus was completely purged using nitrogen and then re-weighed. The free alkali was then neutralized with acetic acid to a phenolphthalein end-point (external indicator) .

The value for n(= 8) was confirmed by measuring the average mole weight by "Supercritical Fluid

Chro atography" (D.W. Later et al., Anal. Laboratory, Aug. 1986, page 108; and P.R. Geissler, JAOCS. , 66 (1989) 685).

In the same way as described above, using the same amount of cardanol as starting material, the following cardanol ethoxylates were prepared:

Cardanol 3 EO: weight absorbed ethylene oxide 396 g Cardanol 13 EO: weight absorbed ethylene oxide 1,716 g Cardanol 40 EO: weight absorbed ethylene oxide 5,280 g Example II 10% cardanol 3 EO in water showed a viscosity of 10 mPas, and 10% cardanol 13 EO in water showed a viscosity of 100 mPas. However, 1.0% cardanol 3 EO/cardanol 13 EO in a weight ratio of 1:4 in water exhibited a viscosity of 1130 mPas, while an aqueous mixture of 15% cardanol 8 EO/cardanol 13 EO in a weight ratio of 1:4 showed a viscosity of 50,000 mPas and a aqueous mixture of 7% cardanol 8 EO/cardanol 13 EO in a weight ratio of 1:4 showed a viscosity of 10,000 mPas. With 3% cardanol 8 EO and cardanol 13 EO in water the results were as follows

CE viscosity

3% cardanol 8 EO 10 mPas

3% cardanol 13 EO 10 mPas 3% cardanol 8 EO/ cardanol 13 EO in a weight ratio of 1:4 2800 mPas

The aqueous binary solutions for viscosity measurement were prepared as follows: Mixtures of the two surfactants were made up by weighing out the requisite quantities of surfactants into

50% of the total deionized water, and then making up to

100%. The mixture was stirred for 3-5 minutes and allowed to stand overnight before viscosity measurements were taken at 22°C.

In this example and in the following examples the viscosity measurements were taken of samples which were stable. The Brookfield LVT, spindle No. 3, at 30 rpm was used to check the viscosities of samples with low viscosity and a Viscolog MLV-8, pin-spindle PC, at 1.5 rpm employing a helical drive unit was used to check the higher viscosities, i.e. above 15,000 mPas. Example III

The viscosities of aqueous CE combinations of the present application and of aqueous nonylphenol ethoxylate mixtures and of C13-C-L5 isoalcohol ethoxylate mixtures having equivalent HLB values were compared. HLB Combination Cardanol ethoxylate 6.8/13.5

Nonylphenol ethoxylate 0.8/13.5 ^c13~^c15 isoalcohol ethoxylate 6.8/13.5 5 Weight ratio 1:4

HLB Combination Cardanol ethoxylate 11.3/13.5

Nonylphenol ethoxylate 11.3/13.5

10 C₁₃-C₁₅ isoalcohol ethoxylate 11.3/13.5

HLB Combination Cardanol ethoxylate 11.3/13.5

Nonylphenol ethoxylate 11.3/13.5

15 C₁₃-C₁₅ isoalcohol ethoxylate 11.3/13.5

Weight ratio 1:2

Nonylphenol ethoxylate n HLB name commercial product

30 17.3 Berol 274 (Berol Nobel)

10 13.3 Berol 09 (Berol Nobel)

5 6.5 11.0 Ethylan 77 (Harcros)

2 6.8 Berol 259 (Berol Nobel) ^c13~^c15 alcohol ethoxylate n HLB name commercial product

30 17 Lutensol A030 (BASF)

10 10 13.5 Lutensol A010 (BASF)

5/7 11 Lutensol A05/7 (BASF)

2/3 6.8 Synperomc A2/3 (ICI)

-ιo-

When comparing cardanol ethoxylates with the nonylphenol ethoxylates and the C13-C15 isoalcohol ethoxylates, the HLB values should be the same in order for the test results to be comparable. From the above it is clear that the cardanol ethoxylates give superior results. Example IV

The following liquid laundry pre-spotter composition was prepared:

Sodium hydroxide Citric Acid (anhydrous) Preservative (Kathon 886F) Water (deionized) Perfume

Antifoam (Sag 10)

Dye (Acilan Turquoise Blue AE,

Bayer) , 1% solution Cardanol 8EO Cardanol 13 EO

pH 7.0 This formulation was prepared as follows: The above quantity of water was added to the main mix vessel. Thereafter the citric acid was added and the mixture thoroughly blended until a solution was obtained. Then the above quantity of sodium hydroxide was added and mixed thoroughly. It was checked if the pH was in the range 6.9-7.1 and if necessary NaOH was added to adjust the pH. The solution was heated to 60-65°C. In a separate vessel the cardanol 8 EO and the cardanol 13 EO were added and heated to 50-60°C until a clear mixture was obtained and mixed thoroughly. This CE blend was added to the main mix vessel at 60°C and mixed thoroughly to disperse. The mixture was then cooled whilst continuously stirring. At the same time, dye solution and antifoair. were added to minimize air entrapment. Thereafter the mixture was cooled to 30°C. The Kathon 886 was added whereafter thorough mixing was carried out. Then the perfume was added and thorough mixing was continued for at -ir least 10 minutes. Finally the composition was filtered through a 10 micron bag filter.

The viscosity of the composition was found to be 800 mPas. In comparison the same compositions, containing however 8% of only cardanol 8 EO and no cardanol 13 EO and 8% of only cardanol 13EO and no cardanol 8E0, respectively, showed viscosities of only 100 mPas and 150 mPas, respectively. Example V The following WC cleaning composition was prepared:

Parts by weight 37% Formaldehyde 0.20

Deionized water 90.15

Citric acid, monohydrate 2.20 Sodium lauryl ether (2 EO) -

Sulphate (SLES) 1.00

Perfume 0.45

Dye solution¹^ 1.00

Cardanol 13 EO 4.80 Cardanol 8 EO 1.20 pH = 2.0 ^χ) F + D + C Yellow No. 5, Anstead cl Acid Blue 147598, Williams This formulation was prepared by charging deionized water to the main vessel and stirring, and then blending in the following ingredients in the order listed: SLES, cardanol 8 EO, cardanol 13 EO, formalin, citric acid, dye solution and perfume. Stirring was continued for at least 30 minutes after the final addition. The viscosity of the composition was found to be 1500 mPas. The same compositions, containing however 6.00% of only cardanol 8 EO and no cardanol 13 EO and 6.00% of only cardanol 13 EO and no cardanol 8 EO, respectively, showed viscosities of only 60 mPas and 100 mPas, respectively. Example VI

The following automotive shampoo was prepared: Parts by Weight

Water (deionized) 84.024

Sodium Lauryl ether (2 EO) Sulphate (SLES) 5.000 Pearlising agent (ethylene glycol sodium lauryl ether sulphate 1.250

Steinamid DO 280 1.500

Preservative (Kathon 886F) 0.010 Sodium chloride 0.200

Dye (F, D + C Yellow No. 5) (Anstead) C.OOl

Dye (Cibacron Blue 2GE) (Ciba Geigy) 0.015

Cardanol 8 EO 1.600

Cardanol 13 EO 6.400

pH 9.0

Steinamid DO280 is oleic acid polydiethanolamide (Rewo)

Steinamid DO280 and the cardanol ethoxylates were charged into the main mix vessel and blended to a smooth homogeneous liquid at a temperature of 50°C. 60% of the total water was added to the mix vessel little by little while stirring and maintaining the temperature at 50°C. As the water was added slowly the surfactant blend gelled, and the mixture was maintained as homogeneous as possible. Towards the end of the addition the mixture became much more fluid. The SLES was added with stirring, followed by the two dyes and Kathon 886F. After the mixture was stirred until it was homogeneous, the heat was turned off. The pea lising agent was added and the mixture again stirred until homogeneous. In a separate vessel the sodium chloride was dispersed in the remaining water. This dispersion was added while stirring to the main mix vessel. After stirring until homogeneous, the product was allowed to cool to about 25°C.

The viscosity of the composition was found to be 1500 mPas. The same composition, containing however, 8.000 % by weight of only cardanol 13 EO and no cardanol 8 EO, showed a viscosity of only 50 mPas. Furthermore the same composition containing 8.000 % by weight of cardanol 8 EO and no cardanol 13 EO, was unstable.

Claims

What I Claim is :

1. Aqueous cleaning compositions, characterized by including a mixture of cardanol ethoxylates selected from a) at least one cardanol ethoxylation product having an average number of ethylene oxide units n of about 8 or less, in combination with at least one cardanol ethoxylation product having an average n value of about 8 or more, the difference between the n values of the two cardanol ethoxylation products being at least

2.3, in a weight ratio of at most about 1:2 and at a combined concentration up to about 15 % by weight of the cleaning composition; or b) at least one cardanol ethoxylation product having an average n value of about 8 or less, in combination with at least one cardanol ethoxylation product having an average n value of about 19 or more, in a weight ratio of more than about 1:2 to about 2:1 and at a combined concentration up to about 7 % by weight of the cleaning composition; or c) At least one cardanol ethoxylation product having an average n value of about 8-13 in combination with at least one cardanol ethoxylation product having an average n value of about 13 or more, the difference between the n values of the two groups of cardanol ethoxylation product being at least 2.3, in a weight ratio of at most about 4 : 1 and at a combined concentration up to about 15 % by weight of the cleaning composition.

2. Compositions according to claim 1, containing cardanol ethoxylate wherein the average n value is 13 and cardanol ethoxylate wherein the average n value is 8 in a ratio of 4:1.

3. Toilet cleaning compositions according to claim 1 or 2 , containing cardanol ethoxylate wherein the average n value is 13 and cardanol ethoxylate wherein the average n value is 40, in a ratio of 1:4. -i -

4. Compositions to be used in the preparation of cleaning compositions according to claims 1-3, consisting of a) at least one cardanol ethoxylation product having an average number of ethylene oxide units n of about 8 or less, in combination with at least one cardanol ethoxylation product having an average n value of about 8 or more, the difference between the n values of the two groups of ethoxylation products being at least

2.3, in a weight ratio of at most about 1:2; or b) At least one cardanol ethoxylation product having an average n value of about 8 or less, in combination with at least one cardanol ethoxylation product having an average n value of about 19 or more, in a weight ratio of more than about 1:2 to about 2:1; or c) at least one cardanol ethoxylation product having an average n value of about 8-13 in combination with at least one cardanol ethoxylation product having an average n value of about 13 or more, the difference between the n values of the two groups of cardanol ethoxylation products being at least 2.3, in a weight ration of at most about 4:1; and d) water in an amount of 1 to 20% by weight.