Method of boosting foam in low sudsing detergents

Abstract: A method of boosting foam in a low sudsing detergent system containing high levels of cationic or nonionic fabric softening surfactants in a textile wash liquor wherein there is added to the wash liquor in addition to the detergent a foam boosting effective amount of a short chain non-toxic organosulfobetaine zwitterionic siloxane based silicone surfactant compound and causing the detergent and the silicone compound to be homogeneously intermixed in the wash liquor along with the textiles.

Description: GB-A 2 161 172 discloses a shampoo composition which comprises a shampoo detergent base, a quaternised polymer and a cationic or amphoteric organofunctional silicone. This amphoteric silicone is used together with a quaternised polymer as conditioning agent, that is to impart good shine and body to the hair and to facilitate combing. If desired, a foam booster may be added to this composition. Moreover, DE-A 34 17 912 describes betaine group containing siloxanes which are used in cosmetic compositions. The siloxanes are used to condition the hair. EP-A 0 276 114 discloses zwitterionic polysiloxane compositions which may contain a betaine group. These silicone betaines are used to stabilize oil-in-water and water-in-oil emulsions. The invention relates to a method of boosting foam in a low sudsing detergent system which contains high levels of cationic or nonionic fabric softening surfactants in a textile wash liquor comprising adding to the wash liquor in addition to the detergent a foam boosting effective amount of an organobetaine zwitterionic siloxane based compound having the general formula selected from the group consisting of Me₃SiO(SiMeR¹O) y SiMe₃ and Me₃SiO(SiMe₂O) x (SiMeR¹O) y SiMe₃ wherein: Me= methyl; R¹= -CH₂CH₂CH₂N ⁺(R²)₂(CH₂) z SO⁻₃, or -CH₂CH₂CH₂N ⁺(R²)₂(CH₂) z COO⁻; R²= an alkyl group having from one to six carbon atoms or (CH₂) m OH; m= 1-6; x= 1-10; y= 1-3; and z= 1-4 and causing the detergent and the silicone compound to be homogenously intermixed in the wash liquor along with the textiles. The silicone compound is preferably present in the wash liquor in an amount of from one-tenth of one percent to one percent by weight based on the weight of wash liquor. It is the object of the present invention to provide a non-toxic foam boosting substitute for the otherwise conventional organic amine oxide profoamers which under thermal decomposition form toxic nitrosamines, the new foam boosting agent being in the form of short chain non-toxic betaine zwitterionic organofunctional siloxane based surfactant compounds. These and other objects, features and advantages of the present invention will become apparent from a consideration of the following detailed description of the invention. A surfactant is a compound that reduces surface tension when dissolved in a liquid. Surfactants exhibit combinations of cleaning, detergency, foaming, wetting, emulsifying, solubilizing and dispersing properties. They are classified depending upon the charge of the surface active moiety. In anionic surfactants, the moiety carries a negative charge as in soap. In cationic surfactants, the charge is positive. In non-ionic surfactants, there is no charge on the molecule, and in amphoteric surfactants, solubilization is provided by the presence of positive and negative charges linked together in the molecule. A zwitterion is a special category and is a molecule that exists as a dipolar ion rather than in the un-ionized form. The molecule is neutral overall but has a large charge separation like an amino acid. Zwitterions are also known as hybrid ions and internal or intramolecular salts. In the case of amino acids, they are electrolytes having separated weakly acidic and weakly basic groups. For example, while shown as H₂N-R-COOH, in aqueous solution, ⁺H₃N-R-COO⁻ is the actual species where an internal proton transfer from the acidic carboxyl to the basic amino site is complete. The uncharged species has separate cationic and anionic sites but the positive and the negative ions are not free to migrate. Thus, it is a complex ion that is both positively and negatively charged. Alkyl betaines are also representative of zwitterions and are a special class of zwitterion where there is no hydrogen atom bonded to the cationic site. Some silicones are also zwitterions and it is this special category of silicone zwitterion to which the present invention relates. The zwitterionic organofunctional siloxanes used in the present invention are prepared by the quaternization of precursor aminofunctional siloxanes with either cyclic propane sultone or cyclic butane sultone. Specifically, representative ones of the and silicone sulfobetaines used in the present invention as shown hereinafter in formulas (1) and (3) are prepared by a two-step process as set forth below: where Me= methyl x = 0-3 y = 1, 2 R = methyl or ethyl, and n = 3, 4. Representative of the silicone betaines used in the present invention as shown hereinafter in formula (2) are prepared by the same two-step process outlined above, except that the second step is modified as set forth below: where Me= methyl x = 0-3 y = 1, 2 z = 1-4 R = methyl or ethyl, and M = Cl⁻, Br⁻ or I⁻. These compounds are colorless solids. They have a low water solubility and low critical micelle concentrations. The compounds are compatible with a wide range of surfactants and possess good thermal and oxidative stability, along with their high surface activity. Details of the synthesis of these materials are set forth in EP-A-0276114. This application shows the preparation of the surfactant. The compounds used in the present invention are represented by the following formula: Me₃SiO[SiMe₂O] x [SiMeR¹O] y SiMe₃ wherein: Me= methyl R¹= -CH₂CH₂CH₂N ⁺(R²)₂(CH₂) z SO₃⁻, or -CH₂CH₂CH₂N ⁺(R²)₂(CH₂) z COO⁻ R²= an alkyl group having from one to six carbon atoms or (CH2) m OH m= 1-6 x= 0-10 y= 1-3, and z= 1-4. Exemplary of compounds according to the present invention and covered by the foregoing generic structure are, for example R-N ⁺Me₂(CH₂)₃SO₃⁻ (1) R-N ⁺Me₂(CH₂)COO⁻ (2) R-N ⁺Me[(CH₂)₂OH](CH₂)₃SO₃⁻ (3) where in each case R is (Me₃SiO)₂Si(Me)-(CH₂)₃-. Compounds (1)-(3) are short chain silicone surfactants, more particularly, silicone betaine or sulfobetaine zwitterionic organofunctional siloxane based surfactants. Each contain zwitterionic hydrophilic portions. For purposes of the present invention, the term short chain is a short siloxane chain where the degree of polymerization of the siloxane is less than about twenty and preferably less than about ten. Specific examples of compounds within the scope of the invention include, but are not limited to, compounds of the Formula (1) and (2) types and of the following formulae: A) R(CH₃)₂SiOSi(CH₃)₂R, B) (CH₃)₃SiOSi(CH₃)₂R, C) (CH₃)₃SiO-SiCH₃ROSi(CH₃)₃, D) (CH₃)₃SiO-[SiCH₃RO]₂-Si(CH₃)₃, E) (CH₃)₃Si-OSi(CH₃)₂O-SiCH₃RO-Si(CH₃)₃, F) (CH₃)₃Si-OSi(CH₃)₂O]-[SiCH₃RO]₂Si(CH₃)₃, G) (CH₃)₃Si-O[Si(CH₃)₂O]₂-SiCH₃ROSi(CH₃)₃ and H) (CH₃)₃Si-O[Si(CH₃)₂O]₃-SiCH₃ROSi(CH₃)₃. where R represents a monovalent zwitterionic radical chosen from radicals which include, but are not limited to -(CH₂)₃N⁺(R″)₂(CH₂)₃SO₃⁻ and -(CH₂)₃N⁺(R″)₂(CH₂)₄SO₃⁻. These compounds are synthesized by the aforementioned two step process comprising: 1.) a hydrosilation reaction which involves reacting a Si-H functional precursor with N-allyl-N,N-dimethylamine, or other functionally similar chemicals, in the presence of platinum metal catalyst to form a tertiary amine functional siloxane compound; and, 2.) a sulfopropylation or sulfobutylation reaction which involves reacting the product of step 1 with either cyclic 1,3-propanesultone or cyclic 1,4-butanesultone or other similar chemicals. The Si-H functional precursors can be prepared by a number of different methods known in the art. For instance, the precursor can be prepared by equilibrating a commercially available long chain Si-H functional polysiloxane, cyclic polydimethylsiloxanes and hexamethyldisiloxane in the presence of an acid catalyst. The particular precursor prepared will be a function of the proportion of starting materials. Particularly pure precursors can be prepared by the same method with careful distillation of the reaction product. Many of the polysiloxane precursors used to make compounds within the scope of the invention are commercially available. The amine functional compound reacted with the Si-H functional precursor must have a tertiary amine functional radical in an allylic position. The tertiary amine functional compounds which are useful in the preparation of the present invention include N-allyl-N,N-dimethylamine and N-allyl-N,N-diethylamine. These tertiary amines are commercially available. Typically, the first step in the synthesis, the hydrosilation reaction, is run solventlessly at between 90 and 110°C with between 1 and 100 ppm platinum metal catalyst. The reaction is usually complete between 90 minutes and 2 hours, and the reaction product can be purified by distillation. The resulting tertiary amine functional polysiloxane can be produced with greater than 80 weight percent purity. The second step of the reaction is run at between about 50°C and 150°C in a mutual solvent of the cyclic alkylsultone and the tertiary amine functional polysiloxane for about 2 hours. The resulting reaction mixture can be purified by first removing the reaction solvent and then filter rinsing with toluene, alcohols or ethers. For comparative purposes, two other short chain silicone surfactant compounds are referred to hereinafter and are represented by the following formulas: R-N ⁺Me₂(CH₂)₂OHI⁻ (4) R-(CH₂CH₂O)₇H (5) In compounds (4) and (5) R is also (Me₃SiO)₂Si(Me)-(CH₂)₃-. Compound (4) is a cationic surfactant and a cationic silicone quaternary salt having a hydrophilic portion. Compound (5) is a neutral nonionic silicone glycol and a neutrally charged polyethoxylated organosilicon surfactant having a hydrophilic portion. In tests conducted below, compounds (4) and (5) served the function of control materials. In order to demonstrate the efficacy of the compounds of the present invention as foam boosters, four commercial low sudsing detergents were selected including ALL®, BOLD 3®, YES® and SOLO®. ALL® is a trademark and a granular detergent manufactured by Lever Brothers Company, New York, New York. YES® is a trademark and a liquid detergent manufactured by Morton Norwich Products, Greenville, South Carolina. BOLD 3® is a trademark and a granular detergent, SOLO® is a trademark and a liquid detergent, each manufactured by The Procter & Gamble Company, Cincinnati, Ohio. Each detergent was first evaluated for its foaming capability by a shaking foam test. In the initial evaluation, no silicone zwitterionic surfactant was included. A 237 ml (eight ounce) bottle was used for the test and the detergent was added at a one percent by weight level in one hundred milliliters of water. The bottle was capped and agitated for one minute. Foam heights were measured with a ruler immediately after agitation. Both YES® and SOLO® exhibited foams measuring 50.8 mm (two inches). The foam height of BOLD 3® was 12.7 mm (one-half inch) and the foam height of ALL® about 25.4 mm (one inch). Since the detergents ALL® and BOLD 3® produced the least amount of foam of the four detergents tested, ALL® and BOLD 3® were selected for further evaluation to show the foam boosting capacity of the silicone zwitterionic surfactant compounds of the present invention. ALL® and BOLD 3® are also known to contain cationic fabric softeners blended into the formulation which have traditionally interfered with high foam action causing a detergent to be classified as low sudsing. The silicone surfactants were added to the ALL® detergent at room temperature and to the BOLD 3® detergent at 50°C. Each detergent was evaluated for its foaming capability again by a shaking foam test. However, in the second evaluation, silicone zwitterionic surfactants as well as silicone control surfactants were included. The standard Ross-Miles foam test was not conducted since the shaking foam test employed better assimilated the action and the agitation present in an actual washing machine. A 237 ml (eight ounce) capped bottle was used for the test and the detergent was added at levels of one tenth of one percent by weight and at a level of one percent by weight, in one hundred milliliters of water. In each case, the bottle was capped and agitated for one minute. Foam heights were measured visually with a ruler immediately after agitation. The results of these tests are tabulated in Tables I and II. FOAMING OF 1.0 WT% BOLD 3® SOLUTIONS AT 50°C. WITH 1.0 WT% SILICONE SURFACTANT ADDED Silicone Surfactant Foam Height at Wt% Silicone mm (Inches) 0 0.1(5sec) 0.1(5min) 1.0(5sec) 1.0(5min) 1 12.7(0.5) 114.3(4.5) 38.1(1.5) 152.4(6) 127(5) 5 12.7(0.5) 25.4(1) 25.4(1) 25.4(1) 25.4(1) 4 12.7(0.5) 0(0) 0(0) 25.4(1) 25.4(1) 2 12.7(0.5) 101.6(4) 12.7(0.5) 254(10) 127(5) FOAMIMG HEIGHTS OF 1.0 WT% SOLUTIONS OF ALL® DETERGENT WITH SILICONE SURFACTANT ADDED Silicone Surfactant Wt% Silicone 0 0.1 1.0 2 12.7(0.5) 50.8(2) 50.8(2) 1 12.7(0.5) 76.2(3) 76.2(3) 3 12.7(0.5) 12.7(0.5) 50.8(2) 4 12.7(0.5) 12.7(0.5) 12.7(0.5) 5 12.7(0.5) 25.4(1) 38.1(1.5) In Table I, it will be seen that zwitterionic silicone surfactant compounds (1) and (2) were selected, along with silicone control compounds (4) and (5). The detergent used was BOLD 3® and foam heights were determined at intervals of time in order to show foam stability as well as foam boosting capacity. It should be apparent that the zwitterionic silicone surfactant compounds (1) and (2) performed admirably at concentrations of both one and one tenth of one percent levels and significantly boosted the foam height of the detergent solution. In Table II, the detergent was ALL® and the three zwitterionic silicone surfactant compounds (1)-(3) were used along with the silicone control compounds (4) and (5). The zwitterionic silicone compounds (1) and (2) performed admirably at both concentration levels employed and compound (3) performed well at the one percent level. Of particular noteworthiness, is the fact that compounds (1) and (2) were as effective at the lower level of one tenth of one percent as they were at the one percent level. In any event, the compounds of the present invention provided a significant boost in the foam heights of the detergent solutions. A series of tests were also conducted in order to demonstrate the effectiveness of the silicone zwitterionic surfactant compounds of the present invention in reducing the surface tension of detergent solutions. 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. Dynamic surface tension is a 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 high 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 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 various systems and the results are tabulated in Tables III to VII. DYNAMIC SURFACE TENSION MEASUREMENTS FOR 1% AQUEOUS COMMERCIAL DETERGENT SOLUTIONS (DYNE/CM) Detergent Bubble Rate (Hz.) 1 2 3 4 5 SOLO® 38.8 41.3 43.9 45.8 48.1 YES® 38.9 42.7 45.5 46.8 46.9 BOLD 3® 47.8 53.8 59.9 62.4 65.4 ALL® 39.7 43.7 46.5 48.5 50.4 DYNAMIC SURFACE TENSION MEASUREMENTS FOR 1% ALL® DETERGENT PLUS 1% SILICONE SURFACTANT SOLUTIONS (DYNE/CM) Silicone Surfactant Bubble Rate (Hz.) 1 2 3 4 5 2 27.9 29.3 30.9 32.2 34.0 1 27.1 28.3 29.5 30.5 32.1 3 25.3 27.3 29.3 31.3 33.8 DYNAMIC SURFACE TENSION MEASUREMENTS FOR 1% BOLD 3® DETERGENT PLUS 1% COMPOUND (2) AT VARIOUS TEMPERATURES (DYNE/CM) Average Temperature Bubble Rate (Hz.) 1 2 3 4 5 24 24.4 24.9 25.3 25.4 26.1 38 24.1 24.2 24.6 24.9 25.4 54 36.6 38.4 40.8 42.3 28.1 75 25.9 27.9 32.1 35.1 37.6 DYNAMIC SURFACE TENSION MEASUREMENTS FOR 1% BOLD 3® PLUS 1% COMPOUND (3) AT VARIOUS TEMPERATURES Average Temperature Bubble Rate (Hz.) 1 2 3 4 5 25 24.3 24.6 25.3 25.8 26.3 45 22.9 23.6 24.5 25.2 26.6 64 24.4 26.2 28.7 30.8 33.6 80 27.3 30.2 32.9 35.2 38.8 DYNAMIC SURFACE TENSION MEASUREMENTS FOR 1% BOLD 3® PLUS 1% COMPOUND (1) AT VARIOUS TEMPERATURES Average Temperature Bubble Rate (Hz.) 1 2 3 4 5 26 22.3 22.5 22.8 23.1 23.4 43 21.7 22.3 22.9 23.5 24.4 61 22.7 24.8 27.2 29.7 32.9 78 27.6 35.5 33.5 30.6 38.6 In Table III, the dynamic surface tension of the four detergents SOLO®, YES®, BOLD 3® and ALL® were determined at various bubble rates and as one percent aqueous solutions without the addition of a silicone surfactant. Tables IV-VII show the dramatic reduction in dynamic surface tension achieved upon inclusion of certain of the silicone surfactants of the present invention. In Table IV, for example, the dynamic surface tension of a one percent solution of the detergent ALL® was determined and including one percent of one of the silicone zwitterionic surfactant compounds (1)-(3), again at various bubble rates. In Tables V-VII, the detergent employed was BOLD 3® and separate ones of the silicone zwitterionic surfactant compounds (1)-(3) were used at levels of one percent and at various bubble rates. The data in tables V-VII was also determined at varying temperatures with each solution of the BOLD 3® detergent which included a particular one of the silicone zwitterionic surfactant compounds (1)-(3). The data in Tables III-VII indicates that at least for compounds (1)-(3), foam boosting silicone surfactant materials also substantially lower the dynamic surface tension of low sudsing detergent solutions and, therefore, provide the added benefit of improved detergency based on such surface tension reduction characteristics. 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 from the scope of the present invention as defined in the appended claims. Accordingly, it should be clearly understood that the forms of the invention described herein are exemplary only and are not intended as limitations on the scope of the present invention.

Claims: A method of boosting foam in a low sudsing detergent system which contains high levels of cationic or nonionic fabric softening surfactants in a textile wash liquor comprising adding to the wash liquor in addition to the detergent a foam boosting effective amount of an organobetaine zwitterionic siloxane based compound having the general formula selected from the group consisting of Me₃SiO(SiMeR¹O) y SiMe₃ and Me₃SiO(SiMe₂O) x (SiMeR¹O) y SiMe₃ wherein: Me= methyl; R¹= -CH₂CH₂CH₂N ⁺(R²)₂(CH₂) z SO₃⁻, or -CH₂CH₂CH₂N(R²)₂(CH₂) z COO⁻, R²= an alkyl group having from one to six carbon atoms or (CH₂) m OH; m= 1-6; x= 1-10; y= 1-3; and z= 1-4 and causing the detergent and the silicone compound to be homogenously intermixed in the wash liquor along with the textiles.

Inventors: LO SUNNY JOAN, SNOW STEVEN ASHLEY, LO, SUNNY JOAN, SNOW, STEVEN ASHLEY
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1989
Main classification: C11D1
IPC codes: C11D1, C11D3, D06L1