Concentrated aqueous betaine-type surfactant compositions...

Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...

Reexamination Certificate

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C510S119000, C510S237000, C510S347000, C510S433000, C510S469000

Reexamination Certificate

active

06207629

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to concentrated aqueous betaine-type surfactant compositions which include, as fluidizing additives, dimers of fatty acids and/or phosphoric esters esters of fatty alcohols or polyethoxylated fatty alcohols which provide the said compositions with reduced viscosity and a low gel point.
STATE OF THE ART
Among the amphoteric type of surfactants the betaine compounds corresponding to general formula (I),
in which R is a long C
7
-C
24
alkyl or alkenyl chain; R
1
and R
2
are, independently, short-chained C
1
-C
4
alkyl; and n is a value from 1 to 5, stand out owing to their interest and their broad industrial and commercial use. Of the betaines included in general formula (I), those which have major industrial significance are the ones in which R
1
and R
2
are methyl and n is equal to 3.
The betaine compounds mentioned possess, in addition to outstanding detergent power, excellent dermal compatibility characteristics which means that they are currently widely used in the manufacture of a large number of products for cleaning and personal hygiene that require contact with the human skin, such as for example shampoos, liquids and gels for the bath and shower or for washing the hands, washing-up liquids, etc.
It has been well known for some time that the betaines of general formula (I) may be prepared industrially by means of processes based on the sequence of chemical reactions represented in Diagram:
in which R′ denotes a hydrogen atom or an alkyl group and the remaining variable substituents R, R
1
, R
2
and n have the values already set out for the general formula (I), such that the starting product (IV) may be a fatty acid or a fatty acid ester, including fatty acid esters with polyhydroxy compounds such as for example the mono, di or triglycerides.
Thus, in a first amidation step the starting diamine (V) is reacted with the fatty acid or any of its esters (IV) to obtain as an intermediate the amidoamine (II) which, in a second quaternisation step, is reacted with monochloroacetic acid or a salt thereof (III) to obtain the betaine compound (I).
The manufacturer of consumer goods such as shampoos, bath and shower liquids or gels, washing-up liquids etc. prefers to use as a raw material liquid aqueous betaine-type surfactant compositions which can readily be mixed with the other components to obtain his finished products. In addition, it is preferable that the said aqueous betaine-type surfactant compositions have a high concentration, greater than 40% and preferably of the order of 50% or more, expressed as percentages by weight of dry residue, since this reduces transport and storage costs and enables any desired degree of dilution to be obtained in the finished consumer product.
For the surfactant manufacture, however, the manufacture of such concentrated betaine-type surfactant compositions creates serious problems in maintaining the flowable liquid state thereof with a suitable viscosity, owing to the tendency of betaines to increase the viscosity of aqueous compositions and to gel them at conventional transport and storage temperatures.
Numerous proposals are known for trying to solve this problem, for example those described in the following patents or patent applications: U.S. Pat. No. 4861517, EP-B-0353580, EP-B-0560114, corresponding to U.S. Pat. No. 5354906, EP-A-0647613, corresponding to U.S. Pat. No. 5464565, WO-A-9512571, WO-A-9514658, EP-A-0656346, WO-A-9524377, EP-A-0677509 and DE-C-19505196, corresponding to WO-A-9625389.
Most of the said documents relate to the incorporation, before or after the above-mentioned second reaction step (quaternisation), of different additives (non-ionic surfactants, free fatty acids, trimethylglycine and other betaines, quaternary ammonium compounds, alkaline earth metal hydroxides etc.) which help to fluidize the concentrated compositions.
In relation to the present invention it is worth while citing the European Patent EP-B-0560114 (Goldschmidt), which describes betaine-type surfactant compositions with a dry residue or solid content of at least 40 wt % which are characterised by containing as fluidizing agent 1% to 3% of C
8
-C
18
saturated or C
8
-C
24
unsaturated free fatty acids. In addition, German Patent DE-C-19505196 (Henkel), which describes the same type of compositions in which the fluidizing additives, are very varied types of nitrogen-containing compounds, including the mono or diamides of fatty acid dimers, may also be mentioned.
The large quantity of patents and patent applications on the problem of the fluidity of concentrated betaine compositions, most of them very recent, indicates that the technical problem posed allows a large number of novel and inventive solutions, since each of the techniques described has its disadvantages and limitations. Thus, the solution described in the above-mentioned Goldschmidt patent poses the problem that the fluidizing effect of the free fatty acids is rather limited, which creates manufacturing and stability problems and makes it impossible to achieve compositions with good fluidity when a concentration in the region of 50% dry residue or solid content is desired.
OBJECT OF THE INVENTION
The main object of the present invention is to obtain a concentrated aqueous betaine-type surfactant composition or compositions corresponding to the above-mentioned general formula (I), with a dry residue content or solid content of at least 40 wt %, preferably more than 48 wt %, which maintain excellent properties at these concentrations with respect to low viscosity and low gel point.
An additional object of the present invention is a process for the preparation of the said betaine-type surfactant compositions.
DESCRIPTION OF THE INVENTION
In accordance with the present invention, the aqueous betaine-type surfactant compositions of general formula (I),
in which R is a long C
7
-C
24
alkyl or alkenyl chain; R
1
and R
2
are, independently, short-chained C
1
-C
4
alkyl; and n is value from 1 to 5, contain a dry residue of at least 40 wt %, preferably more than 48 wt %, and are characterised in that they contain, by way of fluidizing additives, proportions of from 0.5 to 3.5 wt %, based on the total weight of the composition, of:
i) dimers of fatty aids, and/or
ii) phosphoric esters of fatty alcohols or polyethoxylated fatty alcohols of the general formula
(R—(OCH
2
CH
2
)
n
—O)
x
—P(O)—(OH)
y
in which R is a C
8
-C
24
, linear or branched alkyl or alkenyl chain; n is a number from 0 to 10; x and y, independently, may assume the values of 1 or 2, such that the sum of x and y must always be equal to 3,
in addition to other optional components as conventionally used by the expert in formulations of this type.
Betaines
Among the betaines of general formula (I), betaines corresponding to the general formula (Ip)
in which R has the meaning explained above, are particularly indicated, those in which R is a saturated C
7
-C
22
alkyl chain, such as for example those arising from the use of fatty acids or their glycerides, of hydrogenated coconut or of hydrogenated tallow, being particularly preferred.
R has 7 to 24 carbon atoms, and may have 8 to 24 carbon atoms.
The betaines in question are prepared by means of the process already discussed.
Fluidizing additives
i) Fatty acid dimers
These are dicarboxylic acids produced from the condensation of two molecules of an unsaturated fatty acid, preferably oleic acid, such that the number of carbon atoms for each molecule of dimeric acid is 36, since the starting oleic acid has 18 carbon atoms. Fatty acid dimers are generally accompanied by other acids with a different degree of polymerisation, for example C
54
trimers, or products originating from the process for their preparation and from the type of oil used as the starting product, for example C
27
dicarboxylic acids, as well as the starting fatty acids themselves. For the object of the present invention it is preferable for the fatty acid dimers to contain more than 60% of C
36
dimers, less than 1 wt % of non-dimerised fatty ac

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