CA1307438C - Synergistic surfactant compositions - Google Patents
Synergistic surfactant compositionsInfo
- Publication number
- CA1307438C CA1307438C CA000587483A CA587483A CA1307438C CA 1307438 C CA1307438 C CA 1307438C CA 000587483 A CA000587483 A CA 000587483A CA 587483 A CA587483 A CA 587483A CA 1307438 C CA1307438 C CA 1307438C
- Authority
- CA
- Canada
- Prior art keywords
- surfactant
- surface tension
- methyl
- zwitterionic
- synergistic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/92—Sulfobetaines ; Sulfitobetaines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/03—Organic sulfoxy compound containing
Abstract
SYNERGISTIC SURFACTANT COMPOSITIONS
ABSTRACT
A synergistic surfactant composition comprising an alkylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe2O]x[SiMer1O]ySiMe3 and wherein R1 =
CH2CH2CH2N+(R2)2(CH2)zSO?; R = methyl or ethyl; x = 0-3;
y = 1-2 and z = 3-4. The particular zwitterionic surfactants are represented by the following formulas:
(Me3SiO2Si(Me)(CH2)3N+Me2(CH2)3SO? and
ABSTRACT
A synergistic surfactant composition comprising an alkylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe2O]x[SiMer1O]ySiMe3 and wherein R1 =
CH2CH2CH2N+(R2)2(CH2)zSO?; R = methyl or ethyl; x = 0-3;
y = 1-2 and z = 3-4. The particular zwitterionic surfactants are represented by the following formulas:
(Me3SiO2Si(Me)(CH2)3N+Me2(CH2)3SO? and
Description
7 4 ~ 8 This invention relates to a synergistic surfactant composition formed by combining an alkylbenzene~ulfonate anionic surfactant with at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiOtSiMe20~x~SiMeRlO]ysiMe3 and wherein Me =
methyl; Rl = CH2CH2CH2N(R2)2(CH2)~S03; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z - 3-4.
More particularly, the ~witterionic surfactants are represented by the following formulas:
(Me3SiO)2Si(Me)(CH2)3NMe2(CH2)3 3 Me Me3SiO(SiO)2SiMe3 (C}~2)3NMe2(CH2)3S03 A surfactant i3 a compound thst reduces surface tension when dissolv~d in a liquid decreasing the attractive force exerted by molecules below the surface of the liquid upon those molecules at the surface of the liquid enabling the liquid to flow more readily. Liquids with low surface tensions flow more readily than water9 while mercury with the highest surface tension of any liquid does not flow but disintegrates into droplets.
Surfactants exhibit combination~ o$ cleaning, detergency, foaming, wetting, emulsifying, solubilizinK and dispersing properties. They are classiiied depending upon the charge of the surface active moiety, usually the larger part of the molecule. In anionic surfactants, the moiety carries a negative charge as in 80ap. In cationic surfactants, the charge i8 yositive. In non-ionic 1 30743~
surfactants, there is no charge on the molecule and in zwitterionic surfactants, solubilization is provided by the presence of positive and negative charges in the molecule.
Zwitterionic surfactantQ of the type disclosed herein are generally considered specialty surfactants. They do not irritate skin a~d eyes and exhibit good surfactant properties over a wide pH range. This category of surfactant i~
compatible with anionic, cationic and nonionic surfactants.
The use of these zwitterionic surfactants ranges from detergents, emulsifiers, wetting and hair conditioning agents, foaming agents, fabric softeners, to anti-static agents. In cosmetic formulations, certain specialized zwitterionicsurfactants reduce eye irritation caused by sulfate and sulfonate surfactants present in such products.
In U.S. Patent No. 3,562,786 issued February 9, 1971, to Bailey et al., there is disclosed the broad concept of blending organic surfactants with silicone-glycol type su-factants in order to achieve a synergy. The surfactants in ~ailey et al., however, are generally considered to be of the standart non-ionic silicone type, rather than æwitterionic 8S in the present invention. Thus, in contrast to Bailey et al., the present invention blends organic surfactants with a new class of silicone sulfobetaine zwitterionic surfactants in order to achieve a synergistic effect. The sulfobetaine surfactants of the present invention, because they are a new class of silicone surfactant, possess advantages not inherent in Bailey et al. For example, one would not e~pect a zwitterionic or amphoteric surfactant to perform in the same fashion as a non-ionic surfactant as in Bailey et al. becau~e of the differences in the charged natures of the two categories of surfactants. Further, the zwitterionic surfactants of the present invention are ~olids and have a low water solubility in comparison to the Bailey et al.
~' 1 7,!~7438 liquid surfactants which are very water soluble. In addition, the 7witterionic surfactants of the present invention possess much lower critical micelle concentrations than the non-ionic sur~actants in Bailey et al.
Such disadvantages of the prior art are overcome with the present invention wherein not only is a new class o~
silicone surfactant disclosed but a surfactant that possesses synergistic properties when combined with organic surfactants.
This invention relates to a synergistic surfactant composition comprisinK an alkylbenzenesulfonate anionic surfactant and at least one zwitterionic organofunctional siloxane surfactant, This invention also relates to a synergistic surfactant compositions comprising a linear alkylate sulfonate anionic surfactant and at least one silicone sulfobetaine zwitterionic surfactant.
This invention further relates to a synergistic surfactant composition comprising an alkylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiOtSiMe20] [SiMeR10] SiMe3 and wherein Me =
methyl; Rl = CH2CH2CH2~ R2)2(CH2)zSO3; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4.
This invention still further relates to a synergistic surfactant composition comprising sodium dodecylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe20]x[SiMeRlO]ySiMe3 and wherein Me = methyl;
R = CH2CH2CH2NlR )2(CH2)zS03; R = methyl or ethyl; x = 0-3;
y - 1-2 and z = 3-4.
~ ..
The zwitterionic surfactant is a compound having the formula (Me3SiO)2Si(Me)(CH2)3 2( 2 3 3 Me Me3SiO~ $io )2siMe3 (CH2)3~e;~(CH2)3S03 It is therefore an object of the present invention to provide a synergistic surfactant composition comprising an alkylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula M;3SiO[SiMe20]x[SiMeRlO]ySiMe3 and wherein Me - methyl;
R = CH2CH2CH2N(R )2(CH2)zSO3; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4 and wherein the amphoteric surfactants are represented by the following formulas:
(1) ( 3 )2Si(Me)(cH2)3NMe2(cH2)3s03~ and Me (2) Me3SiO(Ii)2SliMe3 (CH2)3NMe2(CH2)3S03 It is another ob~ect of the present invention to provide a method of reducing the surface tension of an aqueous solution by adding to the aqueous solution an effective amount of a synergistic surfactant composition comprising sodium dodecylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula M;3SiO[SiMe20]x[SiMeRlO]ySiMe3 and wherein Me = methyl;
R = CH2CH2CH2N~R )2(CH2)zS03; R = methyl or ethyl; x = 0-3;
y = 1-2 and z = 3-4; whereby the surface tension of the aqueous solution is lower than if either of the anionic 1-~
1 3f~7~38 surfactant and the zwitterionic surfactant were present in the aqueous solution individually.
These and other features, objects and advantages of the present invention will become apparent from the following detailed description wherein reference is made to the several fi~ures in the accompanying drawings.
Figure 1 is a graphical representation illustrating the effects on equilibrium surface tension of combining one of the zwitterionic surfactants of the present invention with an anionic surfactant.
Figure 2 is another graphical representation illustrating the effects on equilibrium surface tension of combining another of the zwitteriomc surfactants of the present invention with an anionic surfactant.
Figure 3 is a graphical representation illustrating the effects on dynamic surface tension of combining the zwitterionic surfactant of Figure 1 with an anionic surfactant at a slow bubble evolution, and Figure 4 is a graphical representation illustrating the effects on dynamic surface tension of combining the zwitteriomc surfactant of Figure 1 with an anionic surfactant at a fast bubble evolution.
In the present invention, silicone sulfobetaine surfactants have been found to behave synergistically in terms of surface tension reduction when used in combination with an alkylbenzenesulfonate such as sodium dodecylbenzene-sulfonate. It has been determined experimentally, that the surface tension of an aqueous solution containing a silicone sulfobetaine surfactant together with the alkylbenzene-~ulfonate is lower than if the aqueous solution contained only one of the ingredients individually. Data were obtained relating to both the equilibrium surface tension as well as the dynamic surface tension. A DuNouy ring tensiometer was ..
~,, 1 7`r)7~3~
used to generate equilibrium surface tension data, whereas the dynamic surface tension data were obtained by a procedure which is a refinement of the standard maximum bubble pressure method with the aid of a"SensaDyne"5000 surface tensiometer manufactured by CHEM-DYNE Research Corporation, Madison, Wisconsin.
The experimental data has been set forth graphically in the form of Figures 1-4 as seen in the accompanying drawings in order to better facilitate an understanding of the present invention. It should be ~oted that Fieures 1, 3 and 4, pertain to the zwitterionic surfactant represented by Formula 1, whereas Figure 2 pertains to the zwitterionic surfactant represented by Formula 2. Further, Fi~ures 1 and 2 portray equilibrium surface tension data, whereas Fi~ures 3 and 4 portray dynamic surface tension data.
Specifically, Figure 1 shows the effects of blending the surfactant represented by Formula 1 with linear sodium dodecylbenzenesulfonate. This figure depicts the relationship between equilibrium surface tension and a series of blends of the Formula 1 surfactant with the sulfonate surfactant. The blends range from pure sodium dodecyl-benzenesulfonate anionic surfactant to pure zwitterionic surfactant represented by Formula 1. As noted above, the equilibrium surface tension data were generated by employing a DuNouy ring tensiometer in accordance with the method described in ASTM D1331-54-T.
The surface tension data for the various blends were obtained by utili~ing solutions containing 0.1% of the blend of the anionic and zwitterionic surfactants. Hence, a 0.0% silicone sample was in actuality a 0.1% solution of the anionic surfactant. A 507O silicone sample contained 0.05% of the zwitterionic surfactant and 0.05% of the anionic surfactant. The 100% silicone sample was equivalent to 0.1%
*Trade mark 1 3rl747)~, ~-itterionicsurfactant. Figure 1, therefore, shows the relationship that exists between the surface tension versus the percentage of silicone in the blend. The figure in addition illustrates what the surface tension would be in the event that only the individual surfactants were present at the effective concentrations of the blend.
An examination of Figure 1 reveals that a synergistic effect is achieved by blending the linear sodium dodecylbenzenesulfonate anionic surfactant with the silicone sulfobetaine zwitterionic surfactant represented by Formula 1.
It should be noted that throughout the range, the surface tension of the blend is lower than the surface tension exhibited by either of the two components individually. For example, the surface tension of a 0.1% solution of a 10/90 blend of the two surfactants can be seen to be 28.34 dynes/cm. The effective concentration of silicone sulfobetaine zwitterionic surfactant in such blend (0.01%) yields a surface tension value of 38.73 dynes/cm. Similarly, the effective concentration of the anionic surfactant (0.09%) provides a surface tension value of 43 dynes/cm. A synergy of 10.39 dyne/cm was therefore achieved by employing a blending of each of the two materials rather than using them individually. The synergistic effect, it should be noted, begins to diminish in the e~ent that the blend of the anionic surfactant and the Zwitterionic surfactant contains less than about 5% and more than about 15% silicone sulfobetaine zwitterionic surfactant.
Figure 2 is similar to Figure 1 except that the zwitterionic surfactant represented by Formula 2 was employed, otherwise the procedurss noted above with respect to Figure l are the same in Figure 2. In Figure 2, the synergistic effect is not as pronounced as is illustrated in Figure 1, yet the synergistic effect in Figure 2 is still apparent.
.~
1 30743P`
Thus, a 0.1% solution of a 5/95 blend of the anionic surfactant with the zwftteriomc surfactant represented by Formula 2 yielded a surface tension of 37.64 dynes/cm. By way of comparison, the effective concentration employing the zwitterionic surfactant alone yielded a surface tension of about 52 dynes/cm, whereas the effective concentration utilizing only the anionic surfactant provided a surface tension of 41.5 dynes/cm. Thus, there can be seen a synergistic effect in the amount of 3.86 dynes/cm.
With reference to Figures 3 and 4, there is illustrated therein the response of the surfactants of the present invention to dynamic surface tension measurements.
Dynamic surface tension is a second measure of surface activity and measures the surface energy of the test fluid and the speed of surfactant migration. As noted above, dynamic surface tension is measured utilizing the maximum bubble pressure method with a"SensaDyne"5000 surface tensiometer. This instrument measures surface tension by determining the force required to blow bubbles from an orifice and into the test solution. Thus, a low surface energy fluid requires less energy to force a bubble out of the orifice than does a fluid of hi8h surface energy. The speed of surfactant migration, however, is determined by changing the speed of the evolution of the bubbles. With a slow bubble rate, the surfactants have more time to reach the bubble-liquid interface and to orient in order to reduce the surface energy at the interface. With a fast bubble rate, the surfactants have less time to reach the newly formed bubble before the bubble is forced from the orifice. Hence, the surface energy for the fast rate is higher than the surface energy for the slow rate. In the instrument itself, a process gas such as dry nitrogen or clean dry air, is bubbled through two tubes of different diameter that are *Trade mar~
1 3~74 3~)!
immersed in the fluid being tested. At each orifice, a bubble is formed in a controlled manner until the bubble reaches a maximum value where it breaks off rising to the surface of the test fluid. Since the two orifices differ in diameter, the two bubbles differ in maximum size and in the maximum pressure required to expand each bubble. This differential pressure is sensed by a transducer and the resulting output signal is used to measure dynamic surface tension directly.
The foregoing technique was used in order to determine the dynamic surface tension of blends of the Zwitterionic surfactant represented by Formula l and the anionic surfactant sodium dodecylbenzenesulfonate and the results are graphically represented in Figures 3 and 4.
Blends were prepared of the anionic and the Zwitterionic surfactants ranging from 100% of sodium dodecylbenzene-sulfonate to 100% of the silicone sulfobetaine surfactant represented by Formula 1. The various blends were tested at concentrations of 0.1%. Evaluations of the blends was made on the"SensaDyne"5000 tensiometer, with such evaluations being conducted at a low bubble speed and at a high bubble speed. Data from the tests was then plotted graphically and represented as Figures 3 and 4 in order to show the synergistic effects of employing both materials in comparison to using either individually.
Specifically, in Figure 3 there will be seen the relationship between surface tension and percentage of silicone in the blend and at a slow bubble evolution rate.
The concentration of the blends evaluated was 0.1% and the surface tension of the various blends was compared to the surface tension of the individual components at the effective concentration of the blend. Figure 3 clearly reveals that the combination of the two surfactants is far superior to ' .
i 1 -~j Q~ 4 3~
either of the surfactants when employed individually. Thus, the surface tension of the blend is lower than the surface tension of the individual components at any blend ratio.
Figure 4 covers the same concept as Figure 3 except that in Figure 4 the surface tension was measured at a fast bubble rate of evolution. The effect of the fast bubble rate in Figure 4 in comparison to the slow bubble rate in Figure 3 is that the surface tension values in Figure 4 are higher than the surface tension values computed for Figure 3. However, even at the fast bubble rate in Figure 4, the synergistic effect is still apparent at blend ratios greater than 10/90.
Therefore, the foregoing data as represented by Figures 1-4 clearly shows that blends of silicone sulfobetaines with linear dodecylbenzenesulfonates exhibit properties superior than if either material was used individually. The synergistic effect is also apparent for both the equilibrium surface tension as well as the dynamic surface tension measured.
The compounds of the present invention, more particularly the zwitterionic organofunctional siloxanes represented by Formulas 1 and 2, for example, are prepared by the quaternization of precursor aminofunctional siloxanes with either cyclic propane sultone or cyclic butane sultone.
Specifically, these silicone sulfobetaines are prepared by a two-step process as set forth below:
Me Me Me3SitSiO)X($iO)YSiMe3 ~ H2C=CH2CH2NR2 _ _2_ _ 6_ _ >
Me H
Me Me Me3SiO($iO)x($io)ysiMe3 Me ~CH2)nNR2 '~
1 3~743P~
Me Me l l MeOH or Me3SiO(SiO)x(SiO~ySiMe3 + (I ~ 2 Toluene Me (CH2~3NR2 Me Me Me3si(Si~x(SiO)ySiMe3 Me (CH2)3NR2(CH2)ns03 where Me = methyl; x = 0-3; y = 1, 2; R = methyl or ethyl and n = 3, 4.
These types of compounds are colorless solids and are non-toxic and useful as organic surfactant enhancers.
They have been found to be particularly useful in order to enhance detergent surfactants, in liquid detergents, cleaners, automatic dishwashing detergents and in powdered detergents for washing machines. Details of the synthesis of these materials are set forth in c~pending Canadian Patent Application Serial No. 555,230 of William N. Fenton et al., filed December 23, 1987, and assigned to the same assignee as the present case.
It will be apparent from the foregoing that many other variations and modifications may be made in the structures, compounds, compositions and methods described herein without departing substantially from the es~ential concepts of the present invention. Accordingly, it should be clearly understood that the forms of the invention described herein and depicted in the accompanying drawings are exemplary only and are not intended as limitations on the scope of the present invention.
methyl; Rl = CH2CH2CH2N(R2)2(CH2)~S03; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z - 3-4.
More particularly, the ~witterionic surfactants are represented by the following formulas:
(Me3SiO)2Si(Me)(CH2)3NMe2(CH2)3 3 Me Me3SiO(SiO)2SiMe3 (C}~2)3NMe2(CH2)3S03 A surfactant i3 a compound thst reduces surface tension when dissolv~d in a liquid decreasing the attractive force exerted by molecules below the surface of the liquid upon those molecules at the surface of the liquid enabling the liquid to flow more readily. Liquids with low surface tensions flow more readily than water9 while mercury with the highest surface tension of any liquid does not flow but disintegrates into droplets.
Surfactants exhibit combination~ o$ cleaning, detergency, foaming, wetting, emulsifying, solubilizinK and dispersing properties. They are classiiied depending upon the charge of the surface active moiety, usually the larger part of the molecule. In anionic surfactants, the moiety carries a negative charge as in 80ap. In cationic surfactants, the charge i8 yositive. In non-ionic 1 30743~
surfactants, there is no charge on the molecule and in zwitterionic surfactants, solubilization is provided by the presence of positive and negative charges in the molecule.
Zwitterionic surfactantQ of the type disclosed herein are generally considered specialty surfactants. They do not irritate skin a~d eyes and exhibit good surfactant properties over a wide pH range. This category of surfactant i~
compatible with anionic, cationic and nonionic surfactants.
The use of these zwitterionic surfactants ranges from detergents, emulsifiers, wetting and hair conditioning agents, foaming agents, fabric softeners, to anti-static agents. In cosmetic formulations, certain specialized zwitterionicsurfactants reduce eye irritation caused by sulfate and sulfonate surfactants present in such products.
In U.S. Patent No. 3,562,786 issued February 9, 1971, to Bailey et al., there is disclosed the broad concept of blending organic surfactants with silicone-glycol type su-factants in order to achieve a synergy. The surfactants in ~ailey et al., however, are generally considered to be of the standart non-ionic silicone type, rather than æwitterionic 8S in the present invention. Thus, in contrast to Bailey et al., the present invention blends organic surfactants with a new class of silicone sulfobetaine zwitterionic surfactants in order to achieve a synergistic effect. The sulfobetaine surfactants of the present invention, because they are a new class of silicone surfactant, possess advantages not inherent in Bailey et al. For example, one would not e~pect a zwitterionic or amphoteric surfactant to perform in the same fashion as a non-ionic surfactant as in Bailey et al. becau~e of the differences in the charged natures of the two categories of surfactants. Further, the zwitterionic surfactants of the present invention are ~olids and have a low water solubility in comparison to the Bailey et al.
~' 1 7,!~7438 liquid surfactants which are very water soluble. In addition, the 7witterionic surfactants of the present invention possess much lower critical micelle concentrations than the non-ionic sur~actants in Bailey et al.
Such disadvantages of the prior art are overcome with the present invention wherein not only is a new class o~
silicone surfactant disclosed but a surfactant that possesses synergistic properties when combined with organic surfactants.
This invention relates to a synergistic surfactant composition comprisinK an alkylbenzenesulfonate anionic surfactant and at least one zwitterionic organofunctional siloxane surfactant, This invention also relates to a synergistic surfactant compositions comprising a linear alkylate sulfonate anionic surfactant and at least one silicone sulfobetaine zwitterionic surfactant.
This invention further relates to a synergistic surfactant composition comprising an alkylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiOtSiMe20] [SiMeR10] SiMe3 and wherein Me =
methyl; Rl = CH2CH2CH2~ R2)2(CH2)zSO3; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4.
This invention still further relates to a synergistic surfactant composition comprising sodium dodecylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe20]x[SiMeRlO]ySiMe3 and wherein Me = methyl;
R = CH2CH2CH2NlR )2(CH2)zS03; R = methyl or ethyl; x = 0-3;
y - 1-2 and z = 3-4.
~ ..
The zwitterionic surfactant is a compound having the formula (Me3SiO)2Si(Me)(CH2)3 2( 2 3 3 Me Me3SiO~ $io )2siMe3 (CH2)3~e;~(CH2)3S03 It is therefore an object of the present invention to provide a synergistic surfactant composition comprising an alkylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula M;3SiO[SiMe20]x[SiMeRlO]ySiMe3 and wherein Me - methyl;
R = CH2CH2CH2N(R )2(CH2)zSO3; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4 and wherein the amphoteric surfactants are represented by the following formulas:
(1) ( 3 )2Si(Me)(cH2)3NMe2(cH2)3s03~ and Me (2) Me3SiO(Ii)2SliMe3 (CH2)3NMe2(CH2)3S03 It is another ob~ect of the present invention to provide a method of reducing the surface tension of an aqueous solution by adding to the aqueous solution an effective amount of a synergistic surfactant composition comprising sodium dodecylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula M;3SiO[SiMe20]x[SiMeRlO]ySiMe3 and wherein Me = methyl;
R = CH2CH2CH2N~R )2(CH2)zS03; R = methyl or ethyl; x = 0-3;
y = 1-2 and z = 3-4; whereby the surface tension of the aqueous solution is lower than if either of the anionic 1-~
1 3f~7~38 surfactant and the zwitterionic surfactant were present in the aqueous solution individually.
These and other features, objects and advantages of the present invention will become apparent from the following detailed description wherein reference is made to the several fi~ures in the accompanying drawings.
Figure 1 is a graphical representation illustrating the effects on equilibrium surface tension of combining one of the zwitterionic surfactants of the present invention with an anionic surfactant.
Figure 2 is another graphical representation illustrating the effects on equilibrium surface tension of combining another of the zwitteriomc surfactants of the present invention with an anionic surfactant.
Figure 3 is a graphical representation illustrating the effects on dynamic surface tension of combining the zwitterionic surfactant of Figure 1 with an anionic surfactant at a slow bubble evolution, and Figure 4 is a graphical representation illustrating the effects on dynamic surface tension of combining the zwitteriomc surfactant of Figure 1 with an anionic surfactant at a fast bubble evolution.
In the present invention, silicone sulfobetaine surfactants have been found to behave synergistically in terms of surface tension reduction when used in combination with an alkylbenzenesulfonate such as sodium dodecylbenzene-sulfonate. It has been determined experimentally, that the surface tension of an aqueous solution containing a silicone sulfobetaine surfactant together with the alkylbenzene-~ulfonate is lower than if the aqueous solution contained only one of the ingredients individually. Data were obtained relating to both the equilibrium surface tension as well as the dynamic surface tension. A DuNouy ring tensiometer was ..
~,, 1 7`r)7~3~
used to generate equilibrium surface tension data, whereas the dynamic surface tension data were obtained by a procedure which is a refinement of the standard maximum bubble pressure method with the aid of a"SensaDyne"5000 surface tensiometer manufactured by CHEM-DYNE Research Corporation, Madison, Wisconsin.
The experimental data has been set forth graphically in the form of Figures 1-4 as seen in the accompanying drawings in order to better facilitate an understanding of the present invention. It should be ~oted that Fieures 1, 3 and 4, pertain to the zwitterionic surfactant represented by Formula 1, whereas Figure 2 pertains to the zwitterionic surfactant represented by Formula 2. Further, Fi~ures 1 and 2 portray equilibrium surface tension data, whereas Fi~ures 3 and 4 portray dynamic surface tension data.
Specifically, Figure 1 shows the effects of blending the surfactant represented by Formula 1 with linear sodium dodecylbenzenesulfonate. This figure depicts the relationship between equilibrium surface tension and a series of blends of the Formula 1 surfactant with the sulfonate surfactant. The blends range from pure sodium dodecyl-benzenesulfonate anionic surfactant to pure zwitterionic surfactant represented by Formula 1. As noted above, the equilibrium surface tension data were generated by employing a DuNouy ring tensiometer in accordance with the method described in ASTM D1331-54-T.
The surface tension data for the various blends were obtained by utili~ing solutions containing 0.1% of the blend of the anionic and zwitterionic surfactants. Hence, a 0.0% silicone sample was in actuality a 0.1% solution of the anionic surfactant. A 507O silicone sample contained 0.05% of the zwitterionic surfactant and 0.05% of the anionic surfactant. The 100% silicone sample was equivalent to 0.1%
*Trade mark 1 3rl747)~, ~-itterionicsurfactant. Figure 1, therefore, shows the relationship that exists between the surface tension versus the percentage of silicone in the blend. The figure in addition illustrates what the surface tension would be in the event that only the individual surfactants were present at the effective concentrations of the blend.
An examination of Figure 1 reveals that a synergistic effect is achieved by blending the linear sodium dodecylbenzenesulfonate anionic surfactant with the silicone sulfobetaine zwitterionic surfactant represented by Formula 1.
It should be noted that throughout the range, the surface tension of the blend is lower than the surface tension exhibited by either of the two components individually. For example, the surface tension of a 0.1% solution of a 10/90 blend of the two surfactants can be seen to be 28.34 dynes/cm. The effective concentration of silicone sulfobetaine zwitterionic surfactant in such blend (0.01%) yields a surface tension value of 38.73 dynes/cm. Similarly, the effective concentration of the anionic surfactant (0.09%) provides a surface tension value of 43 dynes/cm. A synergy of 10.39 dyne/cm was therefore achieved by employing a blending of each of the two materials rather than using them individually. The synergistic effect, it should be noted, begins to diminish in the e~ent that the blend of the anionic surfactant and the Zwitterionic surfactant contains less than about 5% and more than about 15% silicone sulfobetaine zwitterionic surfactant.
Figure 2 is similar to Figure 1 except that the zwitterionic surfactant represented by Formula 2 was employed, otherwise the procedurss noted above with respect to Figure l are the same in Figure 2. In Figure 2, the synergistic effect is not as pronounced as is illustrated in Figure 1, yet the synergistic effect in Figure 2 is still apparent.
.~
1 30743P`
Thus, a 0.1% solution of a 5/95 blend of the anionic surfactant with the zwftteriomc surfactant represented by Formula 2 yielded a surface tension of 37.64 dynes/cm. By way of comparison, the effective concentration employing the zwitterionic surfactant alone yielded a surface tension of about 52 dynes/cm, whereas the effective concentration utilizing only the anionic surfactant provided a surface tension of 41.5 dynes/cm. Thus, there can be seen a synergistic effect in the amount of 3.86 dynes/cm.
With reference to Figures 3 and 4, there is illustrated therein the response of the surfactants of the present invention to dynamic surface tension measurements.
Dynamic surface tension is a second measure of surface activity and measures the surface energy of the test fluid and the speed of surfactant migration. As noted above, dynamic surface tension is measured utilizing the maximum bubble pressure method with a"SensaDyne"5000 surface tensiometer. This instrument measures surface tension by determining the force required to blow bubbles from an orifice and into the test solution. Thus, a low surface energy fluid requires less energy to force a bubble out of the orifice than does a fluid of hi8h surface energy. The speed of surfactant migration, however, is determined by changing the speed of the evolution of the bubbles. With a slow bubble rate, the surfactants have more time to reach the bubble-liquid interface and to orient in order to reduce the surface energy at the interface. With a fast bubble rate, the surfactants have less time to reach the newly formed bubble before the bubble is forced from the orifice. Hence, the surface energy for the fast rate is higher than the surface energy for the slow rate. In the instrument itself, a process gas such as dry nitrogen or clean dry air, is bubbled through two tubes of different diameter that are *Trade mar~
1 3~74 3~)!
immersed in the fluid being tested. At each orifice, a bubble is formed in a controlled manner until the bubble reaches a maximum value where it breaks off rising to the surface of the test fluid. Since the two orifices differ in diameter, the two bubbles differ in maximum size and in the maximum pressure required to expand each bubble. This differential pressure is sensed by a transducer and the resulting output signal is used to measure dynamic surface tension directly.
The foregoing technique was used in order to determine the dynamic surface tension of blends of the Zwitterionic surfactant represented by Formula l and the anionic surfactant sodium dodecylbenzenesulfonate and the results are graphically represented in Figures 3 and 4.
Blends were prepared of the anionic and the Zwitterionic surfactants ranging from 100% of sodium dodecylbenzene-sulfonate to 100% of the silicone sulfobetaine surfactant represented by Formula 1. The various blends were tested at concentrations of 0.1%. Evaluations of the blends was made on the"SensaDyne"5000 tensiometer, with such evaluations being conducted at a low bubble speed and at a high bubble speed. Data from the tests was then plotted graphically and represented as Figures 3 and 4 in order to show the synergistic effects of employing both materials in comparison to using either individually.
Specifically, in Figure 3 there will be seen the relationship between surface tension and percentage of silicone in the blend and at a slow bubble evolution rate.
The concentration of the blends evaluated was 0.1% and the surface tension of the various blends was compared to the surface tension of the individual components at the effective concentration of the blend. Figure 3 clearly reveals that the combination of the two surfactants is far superior to ' .
i 1 -~j Q~ 4 3~
either of the surfactants when employed individually. Thus, the surface tension of the blend is lower than the surface tension of the individual components at any blend ratio.
Figure 4 covers the same concept as Figure 3 except that in Figure 4 the surface tension was measured at a fast bubble rate of evolution. The effect of the fast bubble rate in Figure 4 in comparison to the slow bubble rate in Figure 3 is that the surface tension values in Figure 4 are higher than the surface tension values computed for Figure 3. However, even at the fast bubble rate in Figure 4, the synergistic effect is still apparent at blend ratios greater than 10/90.
Therefore, the foregoing data as represented by Figures 1-4 clearly shows that blends of silicone sulfobetaines with linear dodecylbenzenesulfonates exhibit properties superior than if either material was used individually. The synergistic effect is also apparent for both the equilibrium surface tension as well as the dynamic surface tension measured.
The compounds of the present invention, more particularly the zwitterionic organofunctional siloxanes represented by Formulas 1 and 2, for example, are prepared by the quaternization of precursor aminofunctional siloxanes with either cyclic propane sultone or cyclic butane sultone.
Specifically, these silicone sulfobetaines are prepared by a two-step process as set forth below:
Me Me Me3SitSiO)X($iO)YSiMe3 ~ H2C=CH2CH2NR2 _ _2_ _ 6_ _ >
Me H
Me Me Me3SiO($iO)x($io)ysiMe3 Me ~CH2)nNR2 '~
1 3~743P~
Me Me l l MeOH or Me3SiO(SiO)x(SiO~ySiMe3 + (I ~ 2 Toluene Me (CH2~3NR2 Me Me Me3si(Si~x(SiO)ySiMe3 Me (CH2)3NR2(CH2)ns03 where Me = methyl; x = 0-3; y = 1, 2; R = methyl or ethyl and n = 3, 4.
These types of compounds are colorless solids and are non-toxic and useful as organic surfactant enhancers.
They have been found to be particularly useful in order to enhance detergent surfactants, in liquid detergents, cleaners, automatic dishwashing detergents and in powdered detergents for washing machines. Details of the synthesis of these materials are set forth in c~pending Canadian Patent Application Serial No. 555,230 of William N. Fenton et al., filed December 23, 1987, and assigned to the same assignee as the present case.
It will be apparent from the foregoing that many other variations and modifications may be made in the structures, compounds, compositions and methods described herein without departing substantially from the es~ential concepts of the present invention. Accordingly, it should be clearly understood that the forms of the invention described herein and depicted in the accompanying drawings are exemplary only and are not intended as limitations on the scope of the present invention.
Claims (5)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A synergistic surfactant composition comprising sodium dodecylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe2O]x[SiMer1O]ySiMe3 and wherein Me = methyl;
R1 = CH2CH2CH2N+(R2)2(CH2)zSO?; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4. - 2. A synergistic surfactant composition comprising an alkylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe2O]x[SiMer1O]ySiMe3 and wherein Me = methyl;
R1 = CH2CH2CH2N+(R2)2(CH2)zSO?; R = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4. - 3. The method of reducing the surface tension of an aqueous solution comprising adding to the aqueous solution an effective amount of a synergistic surfactant composition comprising an organic anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe2O]x[SiMer1O]ySiMe3 and wherein Me = methyl;
R1 = CH2CH2CH2N+(R2)2(CH2)zSO?; R = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4; whereby the surface tension of the aqueous solution is lower than if either of the anionic surfactant and the zwitterionic surfactant were present in the aqueous solution individually. - 4. The method of reducing the surface tension of an aqueous solution comprising adding to the aqueous solution an effective amount of a synergistic surfactant composition comprising an alkylbenzenesulfonate anionic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe2O]x[SiMer1O]ySiMe3 and wherein Me = methyl;
R1 = CH2CH2CH2N+(R2)2(CH2)zSO?; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4; whereby the surface tension of the aqueous solution is lower than if either of the anionic surfactant and the zwitterionic surfactant were present in the aqueous solution individually. - 5. A synergistic surfactant composition comprising an organic surfactant and at least one organic zwitterionic functional silicone surfactant represented by the formula Me3SiO[SiMe2O]x[SiMer1O]ySiMe3 and wherein Me =
methyl; R1 = CH2CH2CH2N+(R2)2(CH2)zSO?; R2 = methyl or ethyl;
x = 0-3; y = 1-2 and z = 3-4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US149,241 | 1988-01-25 | ||
| US07/149,241 US4784799A (en) | 1988-01-25 | 1988-01-25 | Synergistic surfactant compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1307438C true CA1307438C (en) | 1992-09-15 |
Family
ID=22529374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000587483A Expired - Lifetime CA1307438C (en) | 1988-01-25 | 1989-01-04 | Synergistic surfactant compositions |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4784799A (en) |
| EP (1) | EP0326316B1 (en) |
| JP (1) | JP2785872B2 (en) |
| KR (1) | KR950013915B1 (en) |
| AU (1) | AU611756B2 (en) |
| BR (1) | BR8900284A (en) |
| CA (1) | CA1307438C (en) |
| DE (1) | DE68921080T2 (en) |
| ES (1) | ES2010853A6 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4879051A (en) * | 1988-08-08 | 1989-11-07 | Dow Corning Corporation | Method of boosting foam in low sudsing detergents with zwitterionic polysiloxane |
| MY107434A (en) * | 1989-10-26 | 1995-12-30 | Momentive Performance Mat Jp | Cleaning compositions. |
| US5035827A (en) * | 1989-12-05 | 1991-07-30 | Dow Corning Corporation | Liquid detergent containing stabilized silicates |
| US5503681A (en) * | 1990-03-16 | 1996-04-02 | Kabushiki Kaisha Toshiba | Method of cleaning an object |
| US5026489A (en) * | 1990-04-04 | 1991-06-25 | Dow Corning Corporation | Softening compositions including alkanolamino functional siloxanes |
| US4986922A (en) * | 1990-04-04 | 1991-01-22 | Dow Corning Corporation | Softening compositions including quaternary ammonium functional siloxanes |
| US5593507A (en) * | 1990-08-22 | 1997-01-14 | Kabushiki Kaisha Toshiba | Cleaning method and cleaning apparatus |
| US5360571A (en) * | 1992-03-31 | 1994-11-01 | Osi Specialties, Inc. | Surfactant compositions |
| GB9220339D0 (en) * | 1992-09-25 | 1992-11-11 | Johnson & Son Inc S C | Improved fabric cleaning shampoo composition |
| US5514302A (en) * | 1992-09-25 | 1996-05-07 | S.C. Johnson & Son, Inc. | Fabric cleaning shampoo compositions |
| WO1996002600A1 (en) * | 1994-07-15 | 1996-02-01 | Armor All Products Corporation | Water based paint protectant |
| US6403548B1 (en) | 1998-10-27 | 2002-06-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Wrinkle reduction laundry product compositions |
| US6426328B2 (en) | 1998-10-27 | 2002-07-30 | Unilever Home & Personal Care, Usa Division Of Conopco Inc. | Wrinkle reduction laundry product compositions |
| US6376456B1 (en) | 1998-10-27 | 2002-04-23 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Wrinkle reduction laundry product compositions |
| US6579923B2 (en) * | 2001-02-05 | 2003-06-17 | 3M Innovative Properties Company | Use of a silicone surfactant in polishing compositions |
| JP5829972B2 (en) * | 2012-05-10 | 2015-12-09 | 信越化学工業株式会社 | Silicone-modified zwitterionic compound and process for producing the same |
| JP2015059092A (en) * | 2013-09-18 | 2015-03-30 | 信越化学工業株式会社 | Silicone-modified zwitterionic compound and method of producing the same |
| EP4036199A1 (en) * | 2021-02-01 | 2022-08-03 | Unilever IP Holdings B.V. | Detergent composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1034782A (en) * | 1962-01-24 | 1966-07-06 | Union Carbide Corp | Organosilicon compositions |
| GB2161172B (en) * | 1984-07-03 | 1988-06-02 | Beecham Group Plc | Conditioning shampoo compositions |
| US4918210A (en) * | 1987-01-20 | 1990-04-17 | Fenton William N | Zwitterionic polysiloxane compositions |
-
1988
- 1988-01-25 US US07/149,241 patent/US4784799A/en not_active Expired - Fee Related
-
1989
- 1989-01-04 CA CA000587483A patent/CA1307438C/en not_active Expired - Lifetime
- 1989-01-23 ES ES8900214A patent/ES2010853A6/en not_active Expired
- 1989-01-24 BR BR898900284A patent/BR8900284A/en not_active Application Discontinuation
- 1989-01-24 EP EP89300629A patent/EP0326316B1/en not_active Expired - Lifetime
- 1989-01-24 DE DE68921080T patent/DE68921080T2/en not_active Expired - Fee Related
- 1989-01-25 AU AU28761/89A patent/AU611756B2/en not_active Ceased
- 1989-01-25 KR KR89000746A patent/KR950013915B1/en not_active IP Right Cessation
- 1989-01-25 JP JP1014241A patent/JP2785872B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE68921080T2 (en) | 1995-09-28 |
| KR950013915B1 (en) | 1995-11-18 |
| JPH01304032A (en) | 1989-12-07 |
| BR8900284A (en) | 1989-09-19 |
| EP0326316B1 (en) | 1995-02-15 |
| KR890011989A (en) | 1989-08-23 |
| DE68921080D1 (en) | 1995-03-23 |
| EP0326316A2 (en) | 1989-08-02 |
| ES2010853A6 (en) | 1989-12-01 |
| AU2876189A (en) | 1989-07-27 |
| EP0326316A3 (en) | 1990-11-22 |
| US4784799A (en) | 1988-11-15 |
| JP2785872B2 (en) | 1998-08-13 |
| AU611756B2 (en) | 1991-06-20 |
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