CA1039142A - Controlled-sudsing detergent compositions - Google Patents
Controlled-sudsing detergent compositionsInfo
- Publication number
- CA1039142A CA1039142A CA221,553A CA221553A CA1039142A CA 1039142 A CA1039142 A CA 1039142A CA 221553 A CA221553 A CA 221553A CA 1039142 A CA1039142 A CA 1039142A
- Authority
- CA
- Canada
- Prior art keywords
- suds
- silicone
- weight
- silica
- wax
- 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
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Degasification And Air Bubble Elimination (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Granular built laundry detergent compositions are disclosed which contain a suds-suppressing mixture of a water-insoluble wax and a silicone in a water soluble or water dispersible carrier.
Granular built laundry detergent compositions are disclosed which contain a suds-suppressing mixture of a water-insoluble wax and a silicone in a water soluble or water dispersible carrier.
Description
The present invention relates to granular built laundry detergent compositions which have controlled sudsing properties.
Especially when washing is performed in front-loading automatic washing machines, excessive sudsing in the washing step is undesirable. Not only does it interfere with the action of the wash liquor upon the fabrics, but also the foam may reach unintended parts of the washing machine and, in particular, it may not be properly swept out of the machine before the rinse liquor is added. The last problem can considerably increase the amount of foaming in the rinse, and correspondingly increase the difficulty of suppressing this foaming.
Copending, commonly assigned Canadian patent applica-tion 217,689 filed January 10, 1975 discloses that certain waxes, when used in granular, built detergent compositions, are capable of suppressing the suds in the rinse; such waxes can also be ~' ~
~3~ Z
used either to cause little or no suds depression in the washing step, or, if desired, to cause a controllable degree of suds suppression in the washing step. In particular, the invention of the said application provides a granular, built detergent composition which comprises:
(a) from about 2% to about 40% by weight of an organic syn-thetic detergent selected from the group consisting of nonionic, zwitterionic, and anionic detergents and mixtures thereof;
0 (b) from about 0.02% to about 5% by weight of a substantially water-insoluble microcrystalline wax having a melting point in the range from 35C to 115C and saponification value less than 100 or mixtures thereof; and (c) from about 10% to about 90% by weight of a detergency building salt or mixtures thereof;
said wax being in intimate admixture with the said organic detergent.
It is also disclosed, in our copending Canadian Patent Application 117,771, filed July 31, 1973, that certain sili-cone suds-suppressing agents, suitably isolated from premature contact with the surface-active agents, are very effective for controlling sudsing during the wash.
It is now found that a combination of the above-men-tioned wax and silicone suds-suppressing agents has a synergistic effect, so that a lower level of the combination can be used to give effective suds control in the wash and in the rinse than would be required if either were used alone. The advantage can best be made clear by an illustration. A built, granular detergent composition containing a nonionic organic surface-active agent oversudsed severely in a drum automatic washingmachine. The sudsing in the wash could be adequately controlled 1~?39J.4Z
by addition of 2% by weight of a prilled silicone/silanated silica suds-depressing component (containing about 8% silicone/
silanated silica in a non-surface-active carrier); the rinse sudsing was not very well controlled. Higher l~evels of this type of suds-depressant were found to cause excessive,'defoamant action in the wash and had some undesirable side effects, for instance upon cleaning performance. Alternatively, adequate control in the wash and in the rinse could be obtained by use '' of 3% of microcrystalline wax. However, a combination of only 1/2% each of the wax and of the silicone/silanated silica prills was quite satisfactory for control of suds in both the wash and the rinse.
The present invention thus provides a granular, built detergent composition that comprises:
(a) from 2% to 40%, preferably 10% to 30%, by weight of an organic, synthetic nonionic, zwitterionic or anionic surfactant, or a mixture of any of these;
(b) from 10% to 90%, preferably 10~ to 70%, by weight of one or more inorganic or organic detergency-building salts;
(c) from 0.02% to 5% by weight of a substantially water-insoluble microcrystalline wax having a melting point of from 35C to 125C and a saponification value less than 100, or a mixture of such waxes; and (d) a stable suds-controlling component comprising a silicone suds-controlling agent releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier, said silicone suds-controlling agent being selected from the group consisting of (i) a silioxane having the general structure R
~SiOtX
R' 1~)3914Z
wherein x is from about 20 to about 2,000 and R and R' are each alkyl or aryl groups, (ii) an alkylated siloxane of (i) above combined with solid silica wherein the silica has a particle size of not more than 100 millimicrons and the surface area thereof exceeds 50 m /g, (iii) an alkylated siloxane of (i) above combined with hydro-phobic silica wherein the silica has a particle size of not more than 100 millimicrons and the surface area thereof exceeds 50 m2/g, (iv) a siloxane o~ (i) above sorbed onto and into a solid wherein the weight ratio of siloxane to solid is from 20:1 to about 1:20, (v) a mixture of (i) above, alkylated silicone resin and silica xerogels and xerogels having a particle size of not more than 100 millimicrons and a surface area exceeding 50 m /g, and (vi) mixtures thereof wherein the ratio of wax to said suds-controlling component is from 20:1 to 1:10 by weight;
said wax or waxes being in an intimate mixture with some or all of said organic surfactant or surfactants.
Polyethoxy nonionic surfactants and mixtures thereof with zwitterionic surfactants are preferred. Other suitable organic, synthetic surfactants as well as suitable detergency-building salts are disclosed in Canadian patent application 217,689 discussed above.
The waxes suitable for the present invention are any of those suitable for the invention of Canadian patent application 217,689, particularly those described therein as suitable where suds depression in the wash is required. Particularly preferred are microcrystalline petrolatum waxes known as "Be Square 175" *, * Trademark lQ3~4Z
sold by the Bareco division, Petrolite Corporation, Tulsa, Oklahoma; "Mobilwax 2305"**, sold by the Mobil Oil Company Limited, Wallasey Bridge Road, Birkenhead, Cheshire, England; and Shell "MicrowaX 185/190"***.
In preparing the compositions it is important that the wax be intimately associated with the surfactant. Methods of achieving this by mixing the wax with the liquid or pasty surfactant during the preparation of the product are described in Canadian patent application 217,689.
The suds-controlling component (d) of the present com-positions comprises a silicone suds-controlling agent which is incorporated in a water-soluble or water-dispersible, sub-stantially non-surface-active, detergent-impermeable carrier material. The carrier material contains within its interior substantially all of the silicone suds-controlling agent and effectively isolates it from, i.e. keeps it out of contact with, the detergent component of the compositions. The carrier material is selected such that, upon admixture to water, the carrier matrix dissolves or disperses to release the silicone material in-corporated therein to perform its suds-controlling function.
The silicone materials employed as the suds-controlling agents herein can be alkylated polysiloxane materials of several types, either singly or in combination with various solid materials such as silica aerogels and xerogels and hydrophobic silicas of various types. In industrial practice, the term "silicone" has become a generic term which emcompasses a variety of relatively high-molecular-weight polymers containing siloxane units and hydrocarbyl groups of various types. Generally, the silicone suds-controllers can be described as siloxanes having ** Trademark *** Trademark J~)39~4Z
the general structure:
R
~siotX
~' wherein x is from about 20 to about 2,000, and R and R' (which may be alike or different) are each an alkyl or aryl group, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes (R and R' are methyl) having a molecular weight within the range of from about 200 to about 200,000, and higher, are all useful as suds-controlling agents. Suitable silicone fluids of this type are commercially available from the Dow Corning Corporation under the trademark "silicone 200 Fluids".
Additionally, other silicone materials wherein the side chain groups R and R' are alkyl, aryl or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds-controlling pro-perties. These materials are readily prepared by the hydrolysis of the appropriate alkyl, aryl or mixed alkylaryl silicone dichlorides with water in the manner well known in the art. As specific examples of such silicone suds-controlling agents use-ful herein there can be mentioned, for example, diethyl poly-siloxanes; dipropyl polysiloxanes; dibutyl polysiloxanes; methyl-ethyl polysiloxanes; phenylmethyl polysiloxanes; and the like.
The dimethyl polysiloxanes are particularly useful herein owing to their low cost and ready availability.
A second type of silicone suds-controlling agent useful in the compositions herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica.
Such mixtures of silicone and silica can be prepared by affixing the silicone to the surface of silica (SiO2), for example by means of the catalytic reaction disclosed in U.S. Patent 3,235,509. Suds-controlling agents comprising mixtures of ~Q3~ Z
silicone and silica prepared in; this manner preferably comprise silicone and silica in a silicone:silica weight ratio of from 19:1 to 1:2, preferably 10:1 to 1:1. The silica can be chemically and/or physically bound to the silicone in an amount which is preferably about 10% to 15~ by weight, based on the silicone. The particle size of the silica employed in such silica/silicone suds controlling agents should preferably be not more than 100 millimicrons, preferably from 10 millimicrons to 20 millimicrons, and the specific surface area of the silica should exceed about 50 m2/g.
Alternatively, suds-controlling agents comprising silicone and silica can be prepared by admixing a silicone fluid of the type hereinabove disclosed with a hydrophobic silica having a particle size and surface area in the range disclosed above.
Any of several known methods may be used for making a hydro-phobic silica which can be employed herein in combination with a silicone as the suds-controlling agent. For example, a fumed silica can be reacted with a trialkyl chlorosilane (i.e.
"silanated") to affix hydrophobic trialkylsilane groups on the surface of the silica. In a preferred and well known process, fumed silica is contacted with trimethylchlorosilane and a preferred hydrophobic silanated silica useful in the present compositions is secured.
In an alternative procedure, a hydrophobic silica use-ful in the present compositions and processes is obtained by contacting silica with any of the following compounds: metal, ammonium and substituted ammonium salts of long-chain fatty acids, such as sodium stearate, aluminium stearate, and the like; silylhalides, such as ethyltrichlorosilane, butyl-trichlorosilane, tricyclohexylchlorosilane, and the like;and long-chain alkyl amines or ammonium salts, such as cetyl ~C~3~4Z
trimethyl amine, cetyl trimethyl ammonium chloride, and the like.
A preferred suds-controlling agent herein comprises a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from about lO
millimicrons to 20 millimicrons and a specific surface area above about 50 m /g intimately admixed with a dimethyl silicone fluid having a molecular weight in the range of from about 500 to about 200,000, at a weight ratio of silicone to silanated silica of from about l9:1 to about 1:2. Such suds-controlling agents preferably comprise silicone and the silanated silica in a weight ratio of silicone:silanated silica of from lO:1 to l:l. The mixed hydrophobic silanated tespecially trimethyl-silanated) silica-silicone suds-controlling agents provide suds control over a broad range of temperatures, presumably due to the controlled release of the silicone from the surface of the silanated silica.
Another type of suds control agent herein comprises a silicone material of the type hereinabove disclosed sorbed onto and into a solid. Such suds controlling agents comprise the silicone and solid in a silicone: solid ratio of from 20:1 to about 1:20, preferably about 5:1 to anout 1:1. Examples of suitable solid sorbents for the silicones herein include sodium carbonate, sodium tripolyphosphate, any of the sodium silicates, c~ay, starch, kieselguhr, Fuller's earth, and the like. The alkalinity of the solid sorbents is of no consequence to the compositions herein, inasmuch as it has been discovered that the silicones are stable when admixed therewith. As disclosed hereinabove, the sorbent-plus-silicone suds controlling agent must be coated or otherwise incorporated into a carrier material of the type hereinafter disclosed to effectively isolate the silicone from the detergent component of the present compositions.
1039~2 Yet another type of silicone suds-controlling agent hereincomprises a silicone fluid, a silicone resin and silica.
The silicone fluids useful in such suds-controlling mixtures are any of the types hereinabove disclosed, but are preferably dimethyl silicones. The silicone "resins" used in such compo-sitions can be any alkylated silicone resins, but are usually those prepared from methylsilanes. Silicone resins are commonly described as "three-dimentional" polymers arising from the hydrolysis of alkyl trichlorosilanes, whereas the silicone fluids are "two-dimensional" polymers prepared from the hydrolysis of dichlorosilanes. The silica components of such compositions are the micro-porous materials such as the fumed silica aerogels and xerogels having the particle sizes and surface areas herein-above disclosed.
The mixed silicone fluid/silicone resin/silica materials useful in the present compositions can be prepared in the manner disclosed in U.S. Patent 3,455,839. These mixed materials are commercially available from the Dow Corning Corporation. According to U.S. Patent 3,455,839, such materials can be described as mixtures consisting essentially of:
(a) fromlabout 10 parts to about 100 parts by weight of a polydimethylsiloxane fluid having a viscosity in the range of from 20 cs. to 1500 cs. at 25C;
(b) 5 to 50 parts by weight of a siloxane resin composed of (CH3)3SiOl/2 units and SiO2 units in which the ratio of the (CH3)3SiOl/~ units to the SiO2 units is within the range of from 0.6:1 to 1.2:1; and (c) 1 to 10 parts by weight of a silica aerogel.
Such mixtures can also be sorbed onto and into a water-soluble solid as disclosed above.
Again, such mixed silicone resin/silica suds-controlling agents must be combined with a detergent-impermeable carrier material to be useful in the compositions herein.
The silicone suds-controlling agents of the afore-mentioned type must be incorporated within (i.e. coated, en-capsulated, covered by, internalized, or otherwise substantially contained within) a water-soluble or water-dispersible carrier material which must be impermeable to detergents and which, itself, must be substantially non-surface active. By sub-stantially non-surface active is meant that the carrier material, itself, does not interact with the silicone material in such fashion that it is emulsified or otherwise excessively dis-persed throughout an aqueous medium, rather than at the air/water interface.
Of course, when preparing a dry powder or granulated detergent composition it is preferable that the silicone suds controlling component thereof also be substantially dry and non-tacky at ambient temperatures. Accordingly, it is pre-ferred herein to use as the carrier material or vehicle plastic, organic compounds which can be conveniently melted, admixed with the silicone suds-controlling agent, and thereafter cooled to form solid powders, granules or prills. There are a wide variety of such carrier materials useful herein. Since the silicone suds-controlling- agent is to be releasably incorporated in the carrier, such that the silicone is released into the aqueous bath upon admixture of the composition therewith, it is preferred that the carrier material be water-soluble. However, water-dis-persible materials are also useful, inasmuch as they will also release the silicone upon addition to an aqueous bath.
A wide variety of carrier materials having the re-quisite solubility/dispersibility characteristics and theessential features of being non-surface active and detergent-iQ39~l42 impermeable are known. For example, the high-molecular-weight "Carbowax"*-es which have substantially no surface-active characteristics are useful herein. Examples of this type of material include the polyethyleneglycols having a molecular weight of from about 1,500 to about 10,000, especially about 4,000. Surprisingly, highly ethoxylated fatty alcohols such as tallow alcohol condensed with about 25 molar proportions of ethylene oxide are useful herein. Other alcohol condensates containing extremely high ethoxylate proportions (ca. 25 and above) are also useful herein. Such high ethoxylates apparently lack sufficient surface-active characteristics to interact or otherwise interfere with the desired suds-control properties of the silicone agents herein. A particularly preferred ethoxyl-ated carrier material herein is tallowalcohol condensed with about 25 molar proportions of ethylene oxide, and abbreviated TAE25.
A variety of other materials useful as the carrier agents herein may also be mentioned: gelatin; agar; gum arabic;
and various algae-derived gels.
The silicone suds controlling component of the present invention can be conveniently prepared by admixing or spraying the silicone suds-controlling agent with a carrier material to form a granular product. Conveniently, a melt of carrier material and silicone suds-controlling agent is prepared and sprayed in a cooling tower to form droplets comprising the carrier material with the silicone suds-controlling agent releasably incorporated therein. When this procedure is used, the silicone suds-controlling agent is contained within the carrier material so effectively that when this material is * "Carbowax" is a trademark of Union Carbide Corporation for a series of polyethylene glycols. They have characteristics as described in The Merck Index, 9th Ed. (1976) pp. 983-384.
iO391~2 eventually admixed with or incorporated into a detergent composition, the silicone does not substantially come into contact with the detergent surfactant ingredient.
In order to provide a granular, non-tacky suds controll-ing component useful in dry granular detergent compositions, the composite of the silicone suds controlling agent and carrier material should be substantially solidified. This can be achieved by use of long drying towers or rapid refrigeration processes which quickly cool the droplets such that the carrier melt is hardened. However, such procedures are not preferred in an industrial process because of extra plant requirements.
It has been discovered that a rapid and effective way for solidifying a carrier melt containing the silicone suds-con-trolling agent is by spray-drying the carrier melt into and onto a fluidized bed of a solid, preferably water-soluble material to form coated granules. The resulting coated granules of suds-controlling component are crisp and free-flowing, and are especially adapted for use in detergent compositions.
Any type of powdered material is useful to form a fluidized bed suitable for cooling and coating the spray-dried melts therein. Of course, it is particularly suitable to choose dry powders which are useful per se in detergent compositions for their builder, soil-suspending, softening, and the like properties. Specific examples of suitable powdered coating materials useful in the flùidized bed processes herein include, for example, sodium tripolyphosphate tSTPP)~ sodium carbonate, sodium carboxymethyl-cellulose, granulated starch, clay, sodium citrate, sodium acetate, sodium sulfate, and the like. The particle size of such coating materials is in no way limited but must be such that a fluidized bed can be conveniently secured.
In general, particle size range will be from about 0.1 micron to ~3~3~l4Z
about 100 microns.
It is recognized that the amount of carrier used to isolate the silicone suds-controlling agent herein from the detergent component of the compositions herein is not critical.
It is only necessary that enough carrier be used to provide sufficient volume that substantially all the silicone can be incorporated therein. Likewise, it is preferred to have sufficient carrier material to provide for sufficient strength of the resultant granule to resist prematuxe breakage.
Likewise, the amount of solid powder material which optionally coats the carrier-plus-silicone granule is not critical. For most purposes, sufficient powder is employed to substantially coat the mixture of carrier having the silicone incorporated therein with one or two layers of the powder. In addition to cooling and solidifying the carrier, the particulate coating material provides additional protection from the detergent component of the compositions, but it is not essential for this purpose.
It is usually preferred, however, that the suds-con-trolling component (d) should contain about 1 to 50% especiallyabout 2 to 20% and in particular about 4 to 10~ of the silicone suds controlling agent by weight.
The size of the particles of the suds-controlling component td) in the present compositions is not critical to their use and performance characteristics. In general, spray-drying processes result in particles in a size of from about 1 micron to about 1000 microns in diameter.
The amount of microcrystalline wax and of silicone suds-suppressing component required in a particular detergent composition depends upon many factors, such as the degree of suds suppression required, the nature of the detergent composition, ~ 3~ Z
the kind of washing machine, and so on. Generally, as indicated above, less of each is required than would be needed if it were used alone. Thus usually the amount of silicone suds-suppressing agent (.e.g silicones and silanated silica) is from 0.004 to 1%
by weight of the composition, preferably from 0.01 to 0.2%
and especially from 0.04 to 0.1%. Preferably, the level of wax component is from 0.25 to 3%, especially from 0.3 to about
Especially when washing is performed in front-loading automatic washing machines, excessive sudsing in the washing step is undesirable. Not only does it interfere with the action of the wash liquor upon the fabrics, but also the foam may reach unintended parts of the washing machine and, in particular, it may not be properly swept out of the machine before the rinse liquor is added. The last problem can considerably increase the amount of foaming in the rinse, and correspondingly increase the difficulty of suppressing this foaming.
Copending, commonly assigned Canadian patent applica-tion 217,689 filed January 10, 1975 discloses that certain waxes, when used in granular, built detergent compositions, are capable of suppressing the suds in the rinse; such waxes can also be ~' ~
~3~ Z
used either to cause little or no suds depression in the washing step, or, if desired, to cause a controllable degree of suds suppression in the washing step. In particular, the invention of the said application provides a granular, built detergent composition which comprises:
(a) from about 2% to about 40% by weight of an organic syn-thetic detergent selected from the group consisting of nonionic, zwitterionic, and anionic detergents and mixtures thereof;
0 (b) from about 0.02% to about 5% by weight of a substantially water-insoluble microcrystalline wax having a melting point in the range from 35C to 115C and saponification value less than 100 or mixtures thereof; and (c) from about 10% to about 90% by weight of a detergency building salt or mixtures thereof;
said wax being in intimate admixture with the said organic detergent.
It is also disclosed, in our copending Canadian Patent Application 117,771, filed July 31, 1973, that certain sili-cone suds-suppressing agents, suitably isolated from premature contact with the surface-active agents, are very effective for controlling sudsing during the wash.
It is now found that a combination of the above-men-tioned wax and silicone suds-suppressing agents has a synergistic effect, so that a lower level of the combination can be used to give effective suds control in the wash and in the rinse than would be required if either were used alone. The advantage can best be made clear by an illustration. A built, granular detergent composition containing a nonionic organic surface-active agent oversudsed severely in a drum automatic washingmachine. The sudsing in the wash could be adequately controlled 1~?39J.4Z
by addition of 2% by weight of a prilled silicone/silanated silica suds-depressing component (containing about 8% silicone/
silanated silica in a non-surface-active carrier); the rinse sudsing was not very well controlled. Higher l~evels of this type of suds-depressant were found to cause excessive,'defoamant action in the wash and had some undesirable side effects, for instance upon cleaning performance. Alternatively, adequate control in the wash and in the rinse could be obtained by use '' of 3% of microcrystalline wax. However, a combination of only 1/2% each of the wax and of the silicone/silanated silica prills was quite satisfactory for control of suds in both the wash and the rinse.
The present invention thus provides a granular, built detergent composition that comprises:
(a) from 2% to 40%, preferably 10% to 30%, by weight of an organic, synthetic nonionic, zwitterionic or anionic surfactant, or a mixture of any of these;
(b) from 10% to 90%, preferably 10~ to 70%, by weight of one or more inorganic or organic detergency-building salts;
(c) from 0.02% to 5% by weight of a substantially water-insoluble microcrystalline wax having a melting point of from 35C to 125C and a saponification value less than 100, or a mixture of such waxes; and (d) a stable suds-controlling component comprising a silicone suds-controlling agent releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier, said silicone suds-controlling agent being selected from the group consisting of (i) a silioxane having the general structure R
~SiOtX
R' 1~)3914Z
wherein x is from about 20 to about 2,000 and R and R' are each alkyl or aryl groups, (ii) an alkylated siloxane of (i) above combined with solid silica wherein the silica has a particle size of not more than 100 millimicrons and the surface area thereof exceeds 50 m /g, (iii) an alkylated siloxane of (i) above combined with hydro-phobic silica wherein the silica has a particle size of not more than 100 millimicrons and the surface area thereof exceeds 50 m2/g, (iv) a siloxane o~ (i) above sorbed onto and into a solid wherein the weight ratio of siloxane to solid is from 20:1 to about 1:20, (v) a mixture of (i) above, alkylated silicone resin and silica xerogels and xerogels having a particle size of not more than 100 millimicrons and a surface area exceeding 50 m /g, and (vi) mixtures thereof wherein the ratio of wax to said suds-controlling component is from 20:1 to 1:10 by weight;
said wax or waxes being in an intimate mixture with some or all of said organic surfactant or surfactants.
Polyethoxy nonionic surfactants and mixtures thereof with zwitterionic surfactants are preferred. Other suitable organic, synthetic surfactants as well as suitable detergency-building salts are disclosed in Canadian patent application 217,689 discussed above.
The waxes suitable for the present invention are any of those suitable for the invention of Canadian patent application 217,689, particularly those described therein as suitable where suds depression in the wash is required. Particularly preferred are microcrystalline petrolatum waxes known as "Be Square 175" *, * Trademark lQ3~4Z
sold by the Bareco division, Petrolite Corporation, Tulsa, Oklahoma; "Mobilwax 2305"**, sold by the Mobil Oil Company Limited, Wallasey Bridge Road, Birkenhead, Cheshire, England; and Shell "MicrowaX 185/190"***.
In preparing the compositions it is important that the wax be intimately associated with the surfactant. Methods of achieving this by mixing the wax with the liquid or pasty surfactant during the preparation of the product are described in Canadian patent application 217,689.
The suds-controlling component (d) of the present com-positions comprises a silicone suds-controlling agent which is incorporated in a water-soluble or water-dispersible, sub-stantially non-surface-active, detergent-impermeable carrier material. The carrier material contains within its interior substantially all of the silicone suds-controlling agent and effectively isolates it from, i.e. keeps it out of contact with, the detergent component of the compositions. The carrier material is selected such that, upon admixture to water, the carrier matrix dissolves or disperses to release the silicone material in-corporated therein to perform its suds-controlling function.
The silicone materials employed as the suds-controlling agents herein can be alkylated polysiloxane materials of several types, either singly or in combination with various solid materials such as silica aerogels and xerogels and hydrophobic silicas of various types. In industrial practice, the term "silicone" has become a generic term which emcompasses a variety of relatively high-molecular-weight polymers containing siloxane units and hydrocarbyl groups of various types. Generally, the silicone suds-controllers can be described as siloxanes having ** Trademark *** Trademark J~)39~4Z
the general structure:
R
~siotX
~' wherein x is from about 20 to about 2,000, and R and R' (which may be alike or different) are each an alkyl or aryl group, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes (R and R' are methyl) having a molecular weight within the range of from about 200 to about 200,000, and higher, are all useful as suds-controlling agents. Suitable silicone fluids of this type are commercially available from the Dow Corning Corporation under the trademark "silicone 200 Fluids".
Additionally, other silicone materials wherein the side chain groups R and R' are alkyl, aryl or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds-controlling pro-perties. These materials are readily prepared by the hydrolysis of the appropriate alkyl, aryl or mixed alkylaryl silicone dichlorides with water in the manner well known in the art. As specific examples of such silicone suds-controlling agents use-ful herein there can be mentioned, for example, diethyl poly-siloxanes; dipropyl polysiloxanes; dibutyl polysiloxanes; methyl-ethyl polysiloxanes; phenylmethyl polysiloxanes; and the like.
The dimethyl polysiloxanes are particularly useful herein owing to their low cost and ready availability.
A second type of silicone suds-controlling agent useful in the compositions herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica.
Such mixtures of silicone and silica can be prepared by affixing the silicone to the surface of silica (SiO2), for example by means of the catalytic reaction disclosed in U.S. Patent 3,235,509. Suds-controlling agents comprising mixtures of ~Q3~ Z
silicone and silica prepared in; this manner preferably comprise silicone and silica in a silicone:silica weight ratio of from 19:1 to 1:2, preferably 10:1 to 1:1. The silica can be chemically and/or physically bound to the silicone in an amount which is preferably about 10% to 15~ by weight, based on the silicone. The particle size of the silica employed in such silica/silicone suds controlling agents should preferably be not more than 100 millimicrons, preferably from 10 millimicrons to 20 millimicrons, and the specific surface area of the silica should exceed about 50 m2/g.
Alternatively, suds-controlling agents comprising silicone and silica can be prepared by admixing a silicone fluid of the type hereinabove disclosed with a hydrophobic silica having a particle size and surface area in the range disclosed above.
Any of several known methods may be used for making a hydro-phobic silica which can be employed herein in combination with a silicone as the suds-controlling agent. For example, a fumed silica can be reacted with a trialkyl chlorosilane (i.e.
"silanated") to affix hydrophobic trialkylsilane groups on the surface of the silica. In a preferred and well known process, fumed silica is contacted with trimethylchlorosilane and a preferred hydrophobic silanated silica useful in the present compositions is secured.
In an alternative procedure, a hydrophobic silica use-ful in the present compositions and processes is obtained by contacting silica with any of the following compounds: metal, ammonium and substituted ammonium salts of long-chain fatty acids, such as sodium stearate, aluminium stearate, and the like; silylhalides, such as ethyltrichlorosilane, butyl-trichlorosilane, tricyclohexylchlorosilane, and the like;and long-chain alkyl amines or ammonium salts, such as cetyl ~C~3~4Z
trimethyl amine, cetyl trimethyl ammonium chloride, and the like.
A preferred suds-controlling agent herein comprises a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from about lO
millimicrons to 20 millimicrons and a specific surface area above about 50 m /g intimately admixed with a dimethyl silicone fluid having a molecular weight in the range of from about 500 to about 200,000, at a weight ratio of silicone to silanated silica of from about l9:1 to about 1:2. Such suds-controlling agents preferably comprise silicone and the silanated silica in a weight ratio of silicone:silanated silica of from lO:1 to l:l. The mixed hydrophobic silanated tespecially trimethyl-silanated) silica-silicone suds-controlling agents provide suds control over a broad range of temperatures, presumably due to the controlled release of the silicone from the surface of the silanated silica.
Another type of suds control agent herein comprises a silicone material of the type hereinabove disclosed sorbed onto and into a solid. Such suds controlling agents comprise the silicone and solid in a silicone: solid ratio of from 20:1 to about 1:20, preferably about 5:1 to anout 1:1. Examples of suitable solid sorbents for the silicones herein include sodium carbonate, sodium tripolyphosphate, any of the sodium silicates, c~ay, starch, kieselguhr, Fuller's earth, and the like. The alkalinity of the solid sorbents is of no consequence to the compositions herein, inasmuch as it has been discovered that the silicones are stable when admixed therewith. As disclosed hereinabove, the sorbent-plus-silicone suds controlling agent must be coated or otherwise incorporated into a carrier material of the type hereinafter disclosed to effectively isolate the silicone from the detergent component of the present compositions.
1039~2 Yet another type of silicone suds-controlling agent hereincomprises a silicone fluid, a silicone resin and silica.
The silicone fluids useful in such suds-controlling mixtures are any of the types hereinabove disclosed, but are preferably dimethyl silicones. The silicone "resins" used in such compo-sitions can be any alkylated silicone resins, but are usually those prepared from methylsilanes. Silicone resins are commonly described as "three-dimentional" polymers arising from the hydrolysis of alkyl trichlorosilanes, whereas the silicone fluids are "two-dimensional" polymers prepared from the hydrolysis of dichlorosilanes. The silica components of such compositions are the micro-porous materials such as the fumed silica aerogels and xerogels having the particle sizes and surface areas herein-above disclosed.
The mixed silicone fluid/silicone resin/silica materials useful in the present compositions can be prepared in the manner disclosed in U.S. Patent 3,455,839. These mixed materials are commercially available from the Dow Corning Corporation. According to U.S. Patent 3,455,839, such materials can be described as mixtures consisting essentially of:
(a) fromlabout 10 parts to about 100 parts by weight of a polydimethylsiloxane fluid having a viscosity in the range of from 20 cs. to 1500 cs. at 25C;
(b) 5 to 50 parts by weight of a siloxane resin composed of (CH3)3SiOl/2 units and SiO2 units in which the ratio of the (CH3)3SiOl/~ units to the SiO2 units is within the range of from 0.6:1 to 1.2:1; and (c) 1 to 10 parts by weight of a silica aerogel.
Such mixtures can also be sorbed onto and into a water-soluble solid as disclosed above.
Again, such mixed silicone resin/silica suds-controlling agents must be combined with a detergent-impermeable carrier material to be useful in the compositions herein.
The silicone suds-controlling agents of the afore-mentioned type must be incorporated within (i.e. coated, en-capsulated, covered by, internalized, or otherwise substantially contained within) a water-soluble or water-dispersible carrier material which must be impermeable to detergents and which, itself, must be substantially non-surface active. By sub-stantially non-surface active is meant that the carrier material, itself, does not interact with the silicone material in such fashion that it is emulsified or otherwise excessively dis-persed throughout an aqueous medium, rather than at the air/water interface.
Of course, when preparing a dry powder or granulated detergent composition it is preferable that the silicone suds controlling component thereof also be substantially dry and non-tacky at ambient temperatures. Accordingly, it is pre-ferred herein to use as the carrier material or vehicle plastic, organic compounds which can be conveniently melted, admixed with the silicone suds-controlling agent, and thereafter cooled to form solid powders, granules or prills. There are a wide variety of such carrier materials useful herein. Since the silicone suds-controlling- agent is to be releasably incorporated in the carrier, such that the silicone is released into the aqueous bath upon admixture of the composition therewith, it is preferred that the carrier material be water-soluble. However, water-dis-persible materials are also useful, inasmuch as they will also release the silicone upon addition to an aqueous bath.
A wide variety of carrier materials having the re-quisite solubility/dispersibility characteristics and theessential features of being non-surface active and detergent-iQ39~l42 impermeable are known. For example, the high-molecular-weight "Carbowax"*-es which have substantially no surface-active characteristics are useful herein. Examples of this type of material include the polyethyleneglycols having a molecular weight of from about 1,500 to about 10,000, especially about 4,000. Surprisingly, highly ethoxylated fatty alcohols such as tallow alcohol condensed with about 25 molar proportions of ethylene oxide are useful herein. Other alcohol condensates containing extremely high ethoxylate proportions (ca. 25 and above) are also useful herein. Such high ethoxylates apparently lack sufficient surface-active characteristics to interact or otherwise interfere with the desired suds-control properties of the silicone agents herein. A particularly preferred ethoxyl-ated carrier material herein is tallowalcohol condensed with about 25 molar proportions of ethylene oxide, and abbreviated TAE25.
A variety of other materials useful as the carrier agents herein may also be mentioned: gelatin; agar; gum arabic;
and various algae-derived gels.
The silicone suds controlling component of the present invention can be conveniently prepared by admixing or spraying the silicone suds-controlling agent with a carrier material to form a granular product. Conveniently, a melt of carrier material and silicone suds-controlling agent is prepared and sprayed in a cooling tower to form droplets comprising the carrier material with the silicone suds-controlling agent releasably incorporated therein. When this procedure is used, the silicone suds-controlling agent is contained within the carrier material so effectively that when this material is * "Carbowax" is a trademark of Union Carbide Corporation for a series of polyethylene glycols. They have characteristics as described in The Merck Index, 9th Ed. (1976) pp. 983-384.
iO391~2 eventually admixed with or incorporated into a detergent composition, the silicone does not substantially come into contact with the detergent surfactant ingredient.
In order to provide a granular, non-tacky suds controll-ing component useful in dry granular detergent compositions, the composite of the silicone suds controlling agent and carrier material should be substantially solidified. This can be achieved by use of long drying towers or rapid refrigeration processes which quickly cool the droplets such that the carrier melt is hardened. However, such procedures are not preferred in an industrial process because of extra plant requirements.
It has been discovered that a rapid and effective way for solidifying a carrier melt containing the silicone suds-con-trolling agent is by spray-drying the carrier melt into and onto a fluidized bed of a solid, preferably water-soluble material to form coated granules. The resulting coated granules of suds-controlling component are crisp and free-flowing, and are especially adapted for use in detergent compositions.
Any type of powdered material is useful to form a fluidized bed suitable for cooling and coating the spray-dried melts therein. Of course, it is particularly suitable to choose dry powders which are useful per se in detergent compositions for their builder, soil-suspending, softening, and the like properties. Specific examples of suitable powdered coating materials useful in the flùidized bed processes herein include, for example, sodium tripolyphosphate tSTPP)~ sodium carbonate, sodium carboxymethyl-cellulose, granulated starch, clay, sodium citrate, sodium acetate, sodium sulfate, and the like. The particle size of such coating materials is in no way limited but must be such that a fluidized bed can be conveniently secured.
In general, particle size range will be from about 0.1 micron to ~3~3~l4Z
about 100 microns.
It is recognized that the amount of carrier used to isolate the silicone suds-controlling agent herein from the detergent component of the compositions herein is not critical.
It is only necessary that enough carrier be used to provide sufficient volume that substantially all the silicone can be incorporated therein. Likewise, it is preferred to have sufficient carrier material to provide for sufficient strength of the resultant granule to resist prematuxe breakage.
Likewise, the amount of solid powder material which optionally coats the carrier-plus-silicone granule is not critical. For most purposes, sufficient powder is employed to substantially coat the mixture of carrier having the silicone incorporated therein with one or two layers of the powder. In addition to cooling and solidifying the carrier, the particulate coating material provides additional protection from the detergent component of the compositions, but it is not essential for this purpose.
It is usually preferred, however, that the suds-con-trolling component (d) should contain about 1 to 50% especiallyabout 2 to 20% and in particular about 4 to 10~ of the silicone suds controlling agent by weight.
The size of the particles of the suds-controlling component td) in the present compositions is not critical to their use and performance characteristics. In general, spray-drying processes result in particles in a size of from about 1 micron to about 1000 microns in diameter.
The amount of microcrystalline wax and of silicone suds-suppressing component required in a particular detergent composition depends upon many factors, such as the degree of suds suppression required, the nature of the detergent composition, ~ 3~ Z
the kind of washing machine, and so on. Generally, as indicated above, less of each is required than would be needed if it were used alone. Thus usually the amount of silicone suds-suppressing agent (.e.g silicones and silanated silica) is from 0.004 to 1%
by weight of the composition, preferably from 0.01 to 0.2%
and especially from 0.04 to 0.1%. Preferably, the level of wax component is from 0.25 to 3%, especially from 0.3 to about
2%. The ratio of wax to silicone suds-suppressing component (e.g. prills) is generally from 20:1 to 1:10, usually from 2:1 to 1:3, and especially about 1:1~
The compositions may, of course, contain other com-ponents usual in laundry detergent compositions; such adjuvants are mentioned in the complete specification of Canadian Patent Application 217,689, filed January 10, 1975.
The present invention is illustrated in and by the following Examples.
Example 1 Granular detergent compositions were prepared having the compositions given below. In these compositions "Dobanol 45-E-7" (trademark) is a mixture of primary alcohols having 14-15 carbon atoms condensed with 7 molar proportions of ethylene oxide; the silicone/silanated silica prills consisted essentially of 5% silicone, 5% silanated silica, about 50%
sodium tripolyphosphate and about 40% tallow alcohols condensed with 25 molar proportions of ethylene oxide; the wax is "Mobilwax 2305" (trademark), a microcrystalline petroleum wax of melting point 170F. The wax was predissolved in the "Dobanol 45-E-7" before mixing with the other components (except the silicone/silanated silica prills and perborate) for spray drying. The silicone/silanated silica prills and the perborate were dry mixed with the spray-dried granules constituting the remainder of the composition.
~ 3~l4Z
Composi*ion 1 2 3 4 5 6 7 8 9 10 "Dobanol 45-E-7" 12 1212 1212 12 12 1212 12 Sodium tripolyphos-phate 36 3636 3636 36 36 3636 36 Sodium silicate 7 7 7 7 7 7 7 7 7 7 Sodium sulphate 5.5 4.5 4.5 4.5 4 4 4 3.5 3.5 3.5 Sodium perborate 25 25 25 25 25 25 25 25 25 25 Water 12 12 12 12 12 12 12 12 12 12 Miscellaneous minor components 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Silicone/silanated silica prills - - 0.5 1.0 0 0.5 1.5 0 1.5 2.0 Wax - 1 0.5 - 1.5 1.0 0 2 0.5 0 These compositions were tested according to the method described in Example 2 of Canadian Patent Application 217,689.
Composition 1, with no suds-suppressant, oversudsed severely in the wash and was unsuitable for use in the washing machine. Results obtained for the other compositions are given below.
Suds height in the window of the "Hoover"* machine during the wash and coverage (%) of the window of the Indesit machine after pumping out the indicated liquors were as follows:
Suds % coverage Composition Height (ins.) Wash Rinse 1- 2 3 4 5 2 3.4 100 75 ~0 10 0 0
The compositions may, of course, contain other com-ponents usual in laundry detergent compositions; such adjuvants are mentioned in the complete specification of Canadian Patent Application 217,689, filed January 10, 1975.
The present invention is illustrated in and by the following Examples.
Example 1 Granular detergent compositions were prepared having the compositions given below. In these compositions "Dobanol 45-E-7" (trademark) is a mixture of primary alcohols having 14-15 carbon atoms condensed with 7 molar proportions of ethylene oxide; the silicone/silanated silica prills consisted essentially of 5% silicone, 5% silanated silica, about 50%
sodium tripolyphosphate and about 40% tallow alcohols condensed with 25 molar proportions of ethylene oxide; the wax is "Mobilwax 2305" (trademark), a microcrystalline petroleum wax of melting point 170F. The wax was predissolved in the "Dobanol 45-E-7" before mixing with the other components (except the silicone/silanated silica prills and perborate) for spray drying. The silicone/silanated silica prills and the perborate were dry mixed with the spray-dried granules constituting the remainder of the composition.
~ 3~l4Z
Composi*ion 1 2 3 4 5 6 7 8 9 10 "Dobanol 45-E-7" 12 1212 1212 12 12 1212 12 Sodium tripolyphos-phate 36 3636 3636 36 36 3636 36 Sodium silicate 7 7 7 7 7 7 7 7 7 7 Sodium sulphate 5.5 4.5 4.5 4.5 4 4 4 3.5 3.5 3.5 Sodium perborate 25 25 25 25 25 25 25 25 25 25 Water 12 12 12 12 12 12 12 12 12 12 Miscellaneous minor components 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Silicone/silanated silica prills - - 0.5 1.0 0 0.5 1.5 0 1.5 2.0 Wax - 1 0.5 - 1.5 1.0 0 2 0.5 0 These compositions were tested according to the method described in Example 2 of Canadian Patent Application 217,689.
Composition 1, with no suds-suppressant, oversudsed severely in the wash and was unsuitable for use in the washing machine. Results obtained for the other compositions are given below.
Suds height in the window of the "Hoover"* machine during the wash and coverage (%) of the window of the Indesit machine after pumping out the indicated liquors were as follows:
Suds % coverage Composition Height (ins.) Wash Rinse 1- 2 3 4 5 2 3.4 100 75 ~0 10 0 0
3 1.4 100 50 10 0 0 0
4 2.5 100 100 50 10 0 0 2.8 100 75 25 10 0 0 7 2.0 100 100 50 10 0 0 8 1.6 100 50 25 10 0 0 2.5 100 75 25 10 0 0 * Trademark 1~3~L4.Z
Suds coverage (~) of surface the container after the indicated liquids had been pumped into it were as follows:
Composition WashRinse 1 2 3 4 5 Example 2 The effect of the synergistic suds depressant com-binations of the invention upon the suds profile of the products listed below was evaluated using a Minidrum (miniature drum-type washing machine). The products were used at 0.5% by weight concentration in 18H (258 ppm as CaCO3) hard water to wash realistically soiled loads consisting of 2 cotton terry towels and one cotton tea towel. This gave a cloth to liquor ratio of about 1:10 by weight.
The wash water, with the load in it, was heated with intermittent agitation from about 25C to 90C during 45 minutes, and the suds height was measured in the window of the machine at intervals of 20C.
The products tested were as follows:
1~3~l4A~
Test Product 1 2 3 4 5 6 7 8 9 "Dobanol 45-E-7" 12 1212 12 12 12 12 12 12 Sodium linear dodecyl benzene sulphonate Sodium tripoly-phosphate 36 3636 36 36 36 36 36 36 Sodium silicate 7 7 7 7 7 7 7 7 7 Sodium perborate25 2525 25 25 25 25 25 25 Sodium sulphate 5 5 5 5 5 5 5 5 5 Water 10 1010 10 10 10 10 10 10 Minor components3 3 3 3 3 3 3 3 3 *Silicone depressant 1 - 0.5 - 0.5 - 0.5 - 0.5 "Mobilwax 2305" - 10.5 - - - - - -Shell "Microwax 185/190"- - - 10,5 Paraffin Wax (M.Pt.
120-125F) - - - - - 1 0.5 Beeswax - - - - - - - 1 0.5 * Prills containing 4% by weight of a 9:1 mixture of silicone-silanated silica.
Suds heights (ins.) at 30C 1 1 ~ 6 2 50C 3 - 1~~ ~ 0 1 ~ 62 42 70C 6 12 ~ 0 6 4 12 52 90C 1 7 0 4 0 12 3 12 2~
This table shows excellent performance of mixtures with microcrystalline waxes and limited effectiveness with paraffin wax and beeswax.
Example 3 Naturally soiled clothes were washed in the "boil-wash"
cycle of a Miele 421S washing machine, and the suds levels in the window of the machine were measured at stated temperatures during the heat up stage of the main wash. Washing conditions 1(~3~Z
were: cold water fill; 18H (258 ppm as CaCO3, Ca:Mg ratio 10:1 by weight); 70 g product in prewash, 140 g in main wash.
22 cms suds height corresponded to a full window. The com-positions compared and the suds heights are given in the following table.
Composition 1 2 3 4 5 "Dobanol 45-E-7" 8 8 8 8 8 C14.g alkyl dimethyl-ammoniopropane sulphonate 4 4 4 4 4 Sodium tripolyphosphate32 32 32 32 32 Sodium silicate 6 6 6 6 6 Sodium sulphate 9 6.5 4.0 8 6.7 Sodium perborate 23 23 23 23 23 Moisture and miscellaneous minors 17 17 17 17 17 Shell "Microwax 185/190"1 1 1 2 2 Silicone depressant (As employed in Example2) - 2.5 5.0 - 1.25 Suds heights, cms, at 1 2 3 4 5 40C 17 trace trace trace trace 60C 18 4 trace 4trace 80C 20 8 trace 13trace 95C oversudsed 9 trace 17 2 "
Suds coverage (~) of surface the container after the indicated liquids had been pumped into it were as follows:
Composition WashRinse 1 2 3 4 5 Example 2 The effect of the synergistic suds depressant com-binations of the invention upon the suds profile of the products listed below was evaluated using a Minidrum (miniature drum-type washing machine). The products were used at 0.5% by weight concentration in 18H (258 ppm as CaCO3) hard water to wash realistically soiled loads consisting of 2 cotton terry towels and one cotton tea towel. This gave a cloth to liquor ratio of about 1:10 by weight.
The wash water, with the load in it, was heated with intermittent agitation from about 25C to 90C during 45 minutes, and the suds height was measured in the window of the machine at intervals of 20C.
The products tested were as follows:
1~3~l4A~
Test Product 1 2 3 4 5 6 7 8 9 "Dobanol 45-E-7" 12 1212 12 12 12 12 12 12 Sodium linear dodecyl benzene sulphonate Sodium tripoly-phosphate 36 3636 36 36 36 36 36 36 Sodium silicate 7 7 7 7 7 7 7 7 7 Sodium perborate25 2525 25 25 25 25 25 25 Sodium sulphate 5 5 5 5 5 5 5 5 5 Water 10 1010 10 10 10 10 10 10 Minor components3 3 3 3 3 3 3 3 3 *Silicone depressant 1 - 0.5 - 0.5 - 0.5 - 0.5 "Mobilwax 2305" - 10.5 - - - - - -Shell "Microwax 185/190"- - - 10,5 Paraffin Wax (M.Pt.
120-125F) - - - - - 1 0.5 Beeswax - - - - - - - 1 0.5 * Prills containing 4% by weight of a 9:1 mixture of silicone-silanated silica.
Suds heights (ins.) at 30C 1 1 ~ 6 2 50C 3 - 1~~ ~ 0 1 ~ 62 42 70C 6 12 ~ 0 6 4 12 52 90C 1 7 0 4 0 12 3 12 2~
This table shows excellent performance of mixtures with microcrystalline waxes and limited effectiveness with paraffin wax and beeswax.
Example 3 Naturally soiled clothes were washed in the "boil-wash"
cycle of a Miele 421S washing machine, and the suds levels in the window of the machine were measured at stated temperatures during the heat up stage of the main wash. Washing conditions 1(~3~Z
were: cold water fill; 18H (258 ppm as CaCO3, Ca:Mg ratio 10:1 by weight); 70 g product in prewash, 140 g in main wash.
22 cms suds height corresponded to a full window. The com-positions compared and the suds heights are given in the following table.
Composition 1 2 3 4 5 "Dobanol 45-E-7" 8 8 8 8 8 C14.g alkyl dimethyl-ammoniopropane sulphonate 4 4 4 4 4 Sodium tripolyphosphate32 32 32 32 32 Sodium silicate 6 6 6 6 6 Sodium sulphate 9 6.5 4.0 8 6.7 Sodium perborate 23 23 23 23 23 Moisture and miscellaneous minors 17 17 17 17 17 Shell "Microwax 185/190"1 1 1 2 2 Silicone depressant (As employed in Example2) - 2.5 5.0 - 1.25 Suds heights, cms, at 1 2 3 4 5 40C 17 trace trace trace trace 60C 18 4 trace 4trace 80C 20 8 trace 13trace 95C oversudsed 9 trace 17 2 "
Claims (7)
1. A granular, built detergent composition that comprises:
(a) from 2% to 40% by weight of an organic, syn-thetic nonionic, zwitterionic or anionic surfactant, or a mixture of any of these;
(b) from 10% to 90% by weight of one or more in-organic or organic detergency-building salts;
(c) from 0.02% to 5% by weight of a substantially water-insoluble wax or mixture of waxes, said wax or mixture having a melting point of from 35°C to 125°C and a saponifica-tion value less than 100; and (d) a stable suds-controlling component comprising a silicone suds-controlling agent releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier, said silicone suds-controlling agent being selected from the group consist-ing of (i) a siloxane having the general structure wherein x is from about 20 to about 2,000 and R and R' are each alkyl or aryl groups, (ii) an alkylated siloxane of (i) above combined with solid silica wherein the silica has a particle size of not more than 100 millimicrons and the surface area thereof exceeds 50 m2/g, (iii) an alkylated siloxane of (i) above combined with hydrophobic silica wherein the silica has a particle size of not more than 100 millimicrons and the surface area thereof exceeds 50 m2/g, (iv) a siloxane of (i) above sorbed onto and into a solid wherein the weight ratio of siloxane to solid is from 20:1 to about 1:20, (v) a mixture of (i) above, alkylated silicone resin and silica xerogels and xerogels having a particle size of not more than 100 millimicrons and a surface area exceeding 50 m2/g, and (vi) mixtures thereof wherein the ratio of wax to said suds-controlling component is from 20:1 to 1:10 by weight;
said wax component being in an intimate mixture with some or all of said organic surfactant or surfactants.
(a) from 2% to 40% by weight of an organic, syn-thetic nonionic, zwitterionic or anionic surfactant, or a mixture of any of these;
(b) from 10% to 90% by weight of one or more in-organic or organic detergency-building salts;
(c) from 0.02% to 5% by weight of a substantially water-insoluble wax or mixture of waxes, said wax or mixture having a melting point of from 35°C to 125°C and a saponifica-tion value less than 100; and (d) a stable suds-controlling component comprising a silicone suds-controlling agent releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier, said silicone suds-controlling agent being selected from the group consist-ing of (i) a siloxane having the general structure wherein x is from about 20 to about 2,000 and R and R' are each alkyl or aryl groups, (ii) an alkylated siloxane of (i) above combined with solid silica wherein the silica has a particle size of not more than 100 millimicrons and the surface area thereof exceeds 50 m2/g, (iii) an alkylated siloxane of (i) above combined with hydrophobic silica wherein the silica has a particle size of not more than 100 millimicrons and the surface area thereof exceeds 50 m2/g, (iv) a siloxane of (i) above sorbed onto and into a solid wherein the weight ratio of siloxane to solid is from 20:1 to about 1:20, (v) a mixture of (i) above, alkylated silicone resin and silica xerogels and xerogels having a particle size of not more than 100 millimicrons and a surface area exceeding 50 m2/g, and (vi) mixtures thereof wherein the ratio of wax to said suds-controlling component is from 20:1 to 1:10 by weight;
said wax component being in an intimate mixture with some or all of said organic surfactant or surfactants.
2. A composition according to claim i, which contains from 10% to 70% by weight of component (b), and wherein said wax or mixture of waxes has a melting point in the range 35°C to 115°C.
3. A composition according to claim 1 or 2, which contains from 0.004% to 1% by weight of the silicone suds-controlling agent.
4. A composition according to claim 1 or 2, which contains from 0.04 to 0.1% by weight of the silicone suds-controlling agent.
5. A composition according to claim 1 or 2, wherein the suds-controlling component (d) contains from 1% to 50%
by weight of silicone suds-controlling agent.
by weight of silicone suds-controlling agent.
6. A composition according to claim 1 or 2, wherein the suds-controlling component (d) contains from 4% to 10%
by weight of silicone suds-controlling agent.
by weight of silicone suds-controlling agent.
7. A composition according to claim 1 or 2, which contains from 0.25 to 3% by weight of the microcrystalline wax.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1073474A GB1492939A (en) | 1974-03-11 | 1974-03-11 | Controlled-sudsing detergent compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1039142A true CA1039142A (en) | 1978-09-26 |
Family
ID=9973312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA221,553A Expired CA1039142A (en) | 1974-03-11 | 1975-03-07 | Controlled-sudsing detergent compositions |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS6020440B2 (en) |
| BE (1) | BE826505R (en) |
| CA (1) | CA1039142A (en) |
| DE (1) | DE2509508A1 (en) |
| FR (1) | FR2264086B2 (en) |
| GB (1) | GB1492939A (en) |
| IT (1) | IT1054609B (en) |
| NL (1) | NL7502809A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5989640A (en) * | 1996-10-21 | 1999-11-23 | No Touch North America | Propellant-free lustering and protecting agent for rubber, vinyl, and the like |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT388744B (en) * | 1975-10-14 | 1989-08-25 | Procter & Gamble | SOLID DETERGENT AND DETERGENT COMPOSITION |
| US4075118A (en) * | 1975-10-14 | 1978-02-21 | The Procter & Gamble Company | Liquid detergent compositions containing a self-emulsified silicone suds controlling agent |
| GB2040982B (en) | 1977-06-23 | 1982-08-25 | Procter & Gamble | Detergent composition with a suds-regulaing system |
| DE2857155C3 (en) * | 1977-06-23 | 1996-06-13 | Procter & Gamble | Detergent with foam control system |
| EP0008829A1 (en) * | 1978-09-09 | 1980-03-19 | THE PROCTER & GAMBLE COMPANY | Controlled sudsing detergent compositions |
| EP0008830A1 (en) | 1978-09-09 | 1980-03-19 | THE PROCTER & GAMBLE COMPANY | Suds-suppressing compositions and detergents containing them |
| FR2481942B1 (en) * | 1980-05-12 | 1988-04-22 | Unilever Nv | ANTI-MOSS GRANULES, THEIR MANUFACTURING PROCESS AND THEIR USE IN DETERGENT COMPOSITIONS |
| ZA833292B (en) * | 1982-05-11 | 1984-12-24 | Unilever Plc | Granules containing silicone-based anti-foam and a process for preparing them |
| US4451387A (en) * | 1982-08-19 | 1984-05-29 | Lever Brothers Company | Suds control agents and detergent compositions containing them |
| ZA838239B (en) * | 1982-11-10 | 1985-06-26 | Unilever Plc | Hydrocarbon anti-foam granules |
| DE3400008A1 (en) * | 1984-01-02 | 1985-07-11 | Henkel KGaA, 4000 Düsseldorf | FOAM REGULATORS SUITABLE FOR USE IN SURFACTANT AGENTS |
| US4652392A (en) * | 1985-07-30 | 1987-03-24 | The Procter & Gamble Company | Controlled sudsing detergent compositions |
| GB8521956D0 (en) * | 1985-09-04 | 1985-10-09 | Unilever Plc | Antifoam ingredient |
| JPH0672239B2 (en) * | 1986-08-21 | 1994-09-14 | タイホ−工業株式会社 | Polishing cleaning method |
| GB2200365A (en) * | 1987-01-26 | 1988-08-03 | Goodjet Ltd | Detergent composition |
| JPH0460749U (en) * | 1990-10-02 | 1992-05-25 | ||
| GB9101606D0 (en) * | 1991-01-24 | 1991-03-06 | Dow Corning Sa | Detergent foam control agents |
| DE69221391T2 (en) * | 1991-06-03 | 1998-03-19 | Procter & Gamble | Foam control agent in granular form |
| DE4304015A1 (en) * | 1993-02-11 | 1994-08-18 | Henkel Kgaa | Process for the production of granules |
| GB9622844D0 (en) * | 1996-11-01 | 1997-01-08 | Procter & Gamble | Cleansing compositions |
| ES2231122T3 (en) | 1999-08-13 | 2005-05-16 | Dow Corning S.A. | SILICONE-BASED FOAM CONTROL AGENT. |
| ATE401945T1 (en) | 1999-08-13 | 2008-08-15 | Dow Corning Sa | SILICONE FOAM REGULATOR |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1467615C3 (en) * | 1965-08-20 | 1975-02-13 | Henkel & Cie. Gmbh, 4000 Duesseldorf | Low-foaming detergent |
| IT862247A (en) * | 1968-03-29 | |||
| AU496849B2 (en) * | 1974-01-11 | 1978-11-02 | Procter & Gamble Company, The | LOW sudsing DETERGENT COMPOSITIONS |
-
1974
- 1974-03-11 GB GB1073474A patent/GB1492939A/en not_active Expired
-
1975
- 1975-03-05 DE DE19752509508 patent/DE2509508A1/en active Granted
- 1975-03-07 CA CA221,553A patent/CA1039142A/en not_active Expired
- 1975-03-10 NL NL7502809A patent/NL7502809A/en not_active Application Discontinuation
- 1975-03-10 FR FR7507442A patent/FR2264086B2/fr not_active Expired
- 1975-03-10 BE BE154196A patent/BE826505R/en not_active IP Right Cessation
- 1975-03-11 IT IT2111675A patent/IT1054609B/en active
- 1975-03-11 JP JP2942575A patent/JPS6020440B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5989640A (en) * | 1996-10-21 | 1999-11-23 | No Touch North America | Propellant-free lustering and protecting agent for rubber, vinyl, and the like |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2264086B2 (en) | 1978-06-23 |
| DE2509508C2 (en) | 1989-11-09 |
| NL7502809A (en) | 1975-09-15 |
| JPS50157403A (en) | 1975-12-19 |
| JPS6020440B2 (en) | 1985-05-22 |
| DE2509508A1 (en) | 1975-09-18 |
| BE826505R (en) | 1975-09-10 |
| IT1054609B (en) | 1981-11-30 |
| FR2264086A2 (en) | 1975-10-10 |
| GB1492939A (en) | 1977-11-23 |
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