Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K13/00—Apparatus or processes specially adapted for manufacturing or adjusting assemblages of electric components
  • H05K13/04—Mounting of components, e.g. of leadless components
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21D39/00—Application of procedures in order to connect objects or parts, e.g. coating with sheet metal otherwise than by plating; Tube expanders
  • B21D39/06—Application of procedures in order to connect objects or parts, e.g. coating with sheet metal otherwise than by plating; Tube expanders of tubes in openings, e.g. rolling-in
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0013—Liquid compositions with insoluble particles in suspension
• • 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
  • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
  • D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
  • D06B23/04—Carriers or supports for textile materials to be treated
  • D06B23/042—Perforated supports
• • 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
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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

Definitions

• This invention relates to liquid detergent compositions adapted for cleaning hard surfaces. More particularly, this invention relates to a liquid detergent composition having a yield value of from about 5 to about 600 dynes per square centimeter.
• liquid detergent compositions adapted for cleaning hard surfaces.
• These liquid detergent compositions are provided in convenient form and are especially formulated for this particular cleaning application.
• these detergent compositions must be homogeneous and easily pourable.
• These compositions when intended for the retail consumer market, shouldmaintain their homogeneity during ordinary periods of storage and use, and should have acceptable freeze-thaw characteristics; It is highly desirable that liquid detergent compositions for cleaning hard surfaces should exhibit Bingham plastic characteristics; that is, they should exhibit a substantial yield value in order to keep particulate material from settling to the bottom of the container.
• liquid detergent compositions When these liquid detergent compositions are intended for industrial applications, extended product stability, as described above, is not as important as it is in the retail consumer market.
• the compositions can be reintegrated and the particulate material redistributed before use, for example, by mixing or shaking the compositions.
• even these products should be stable for at least a 24-hour period.
• non-Newtonian liquids the consistency is a function of the material, pressure, temperature, and also the shear stress applied to the system.
• a Bingham plastic system is capable of supporting indefinitely insoluble particulate material which has a density greater than that of the supporting medium, so long as the material has such a particle size and density that the shear stress which each particle places on the supporting medium does not exceed the yield value.
• insoluble particulate material insoluble particulate material is suspended only because the rate of flow is slow. ln Bingham plastics, insoluble particulate material is suspended because the stress imposed by the particles does not exceed the yield value of the liquid, and therefore, there is no flow at all. Of course, if the yield value of the supporting medium should sufficiently decrease for any reason, the particles would no longer be suspended. This could be caused, for ex ample, by a physical or chemical change in the supporting medium.
• the yield value can be lost temporarily; but in such a case, the original composition can be reconstituted by mixing. If a chemical reaction either consumes a vital component or produces a damaging one, the loss of yield value can be permanent.
• Liquid detergent compositions containing a combination of alkali metal soaps, ethanol amides and potassium pyrophosphates are known (see U.S. Pat. No. 3,234,138). Although liquid detergent compositions containing alkali metal soaps, amides and phosphates exhibit useful properties, these compositions also have some disadvantageous features. For example, when particulate materials are added to these compositions and the compositions are then subjected to ordinary storage conditions, they may separate into two layers. As these liquid detergent compositions separate, they lose their ability to support particulate material and, accordingly, the particulate material settles.
• amides in these compositions are hydrolyzed to soap if the compositions are subjected to high storage temperatures, e.g., F.
• high storage temperatures e.g., F.
• the liquid detergent com positions separate and lose their Bingham plastic characteristics.
• the particulate material in these compositions is deposited on the bottom of the respective containers.
• a variety of detergent compositions containing synthetic anionic detergents, soaps, or both, as well as detergency builders and abrasives, are known. See, for example, U.S. Pat. Nos. 3,149,078; 3,210,285; 3,281,367; Canadian Pats. Nos. 635,321 and 685,394. These compositions usually require the presence of amides, and frequently contain soaps.
• Soaps and amides are undesirable in many situations, however. Soaps react with calcium, magnesium, and other ions present in hard water, forming undesirable scum. Soaps containing about eight or fewer carbon atoms in their molecular structure act as solubilizing agents, and cause multiple phase systems to lose their Bingham plastic characteristics. Soaps in which the alkyl group is derived from coconut are relatively expensive, as compared to alkylbenzenesulfonate synthetic anionic detergents.
• Amides are subject to hydrolysis, especially when compositions are stored at high temperatures, e.g., 1 10 F.
• amides yield ammonium soaps, which are subject to the disadvantages outlined above. For these and other reasons, the use of soaps and amides is to be avoided in practicing the present invention.
• liquid detergent compositions which exhibit Bingham plastic characteristics and which are stable for protracted periods of time. It is a further object of this invention to provide liquid detergent compositions which remain stable when subjected to both depressed and elevated storage temperatures. A still further object of this invention is to provide Bingham plastic, liquid detergent compositions in which particulate material will not settle to the bottom of the containers when the compositions are stored for protracted periods of time. Another object of this invention is to provide liquid detergent compositions which exhibit Bingham plastic characteristics and which do not contain soaps or amides. It is another object of this invention to provide a detergent composition in convenient pourable form.
• R l/M CGHIIM $03 63 wherein R is an alkyl chain containing from about: nine to about l5 carbon atoms, and M is a cation selected from the group consisting of potassium, sodium, ammonium, monoethanolammonium, diethanolammonium, and triethanolammonium cations;
• a zwitterionic quaternary ammonio synthetic detergent having the general formula:
• R is an alkyl chain containing from about 10 to about 18 carbon atoms, and R" is selected from the group consisting of a hydrogen atom and a hydroxyl group; the ratio of alkylbenzenesulfonate detergent to the zwitterionic synthetic detergent ranges from about 0.4:l to about 4: l; and the combined weight of the alkylbenzenesulfonate and zwitterionic synthetic detergents ranges from about 5 percent to about 20 percent by weight of the finished composition;
• liquid detergent composition of this invention will be characterized, in its entirety, in order to facilitate a better understanding of the individual components and their functions in these liquid detergent compositions.
• the supporting medium of the liquid detergent composition of this invention (that is, the total composition less the insoluble particulate material) is a suspension which comprises two phases.
• One phase is isotropic and continuous, and consists mainly of inorganic materials such as water, base, and electrolyte.
• the other phase is present as discrete particles, and consists mainly of organic materials such as detergent. These discrete particles are mesomorphic and have a highly oriented physical structure. it is apparently this high degree of orientation which imparts the yield value to the system.
• the presence of two liquid phases is possible only in the absence of hydrotropes and other solubilizing agents.
• electrolyte is required in the system to salt out" the organic materials from the continuous phase; i.e., to lower the solubility of the discrete (mainly organic) phase in the continuous (mainly inorganic) phase.
• the yield value of the liquid detergent compositions of this invention ranges from about 5 to about 600 dynes per square centimeter. If the yield value is too low, the insoluble, particulate material will not be suspended, because the weight of the individual particles, distributed over the area which supports the particles, will exceed the yield value. However, if the yield value is too great, the composition will become thick and unmanageable because as the yield value increases, so will the apparent viscosity.
• a preferred range of yield values to support the insoluble particulate material used in the liquid detergent compositions of this invention is from about 100 to about 400 dynes per square centimeter.
• the essential individual components of the liquid detergent composition of this invention are alkylbenzenesulfonate detergent, zwitterionic synthetic detergent, insoluble particulate materials, electrolyte, and water.
• Optional components include detergency builders, strong base to adjust pH level, and minor ingredients which have aesthetic value or which improve the effectiveness of the composition. Strong base is not optional, however, if the pH of the detergent composition without it is below about 7.5. The pH of a composition of course varies with the identity and relative amounts of the components used in it; usually no base is necessary.
• the alkylbenzenesulfonate detergent, zwitterionic synthetic detergent, and, if employed, the detergency builders are the primary cleaning or detergent components of this composition.
• abrasives and detergency builders are added to the liquid detergent composition of this invention. All of these compositions are capable of suspending insoluble particulate materials of the hereinafter specified density and particle size and, accordingly, these particulate materials can be included as components of these liquid detergent compositions.
• alkylbenzenesulfonate detergent used in the liquid detergent compositions has the general formula:
• R is an alkyl chain containing from about nine to about 15 carbon atoms
• M is a cation selected from the group consisting of potassium, sodium, ammonium, monoethanolammonium, diethanolammonium, and triethanolammonium cations; it is preferred that R average from 12 carbon atoms and be a normal (straight chain) alkyl group.
• the finished detergent composition contains from about 2 percent to about 6 percent alkylbenzenesulfonate. More important than the amount of alkylbenzenesulfonate or zwitterionic detergent present individually, however, is the total amount of these two detergents, and the relative amounts in which they are present, as described below.
• the zwitterionic quaternary ammonio synthetic detergent of this invention has the following structural formula:
• R is an alkyl radical containing from about to about 18 carbon atoms, and R" is selected from the group consisting of a hydrogen atom and a hydroxyl group. It is preferred that R be dodecyl or the alkyls derived from coconut fatty alcohol, and that R" be a hydroxyl group.
• the zwitterionic synthetic detergent described above is utilized in this invention in amounts of from about 2 percent to about 14 percent by weight of the finished detergent composition. It is preferred that the zwitterionic synthetic detergent be utilized in amounts of from about 2 percent to about 7 percent by weight of the finished composition.
• the total amount of alkylbenzenesulfonate and zwitterionic detergents, and the relative amounts in which they are present, are more important than the absolute amount of either. While the absolute amount of each detergent is of little independent significance, the total amount of both detergents determines yield value and ability to dissolve grease and dirt, and if excessive, makes the detergent composition too thick and unmanageable.
• the relative amounts of alkybenzenesulfonate and zwitterionic detergents sharply affect the ability of the system to support abrasive.
• alkylbenzenesulfonate nor zwitterionic synthetic detergent alone, will provide a stable support for insoluble particulate material; however, when they are used together as herein described, they cooperate synergistically in a surprising and unexpected way to provide a stable medium with a yield value that will support insoluble particulate material.
• the combined weight of alkylbenzenesulfonate and zwitterionic detergents in the detergent compositions of this invention is from about 5 percent to about percent of the total weight of the finished composition.
• a preferred embodiment contains from about 5 percent to about 12 percent of these detergents.
• About 6 percent to about 7 percent was found to be a level which produces a sufficiently high yield value, but not an unduly thick composition.
• insoluble particulate material (about 40 percent to about 50 percent, see below), it can be further said that between about 10 percent and about l8 percent of the supporting medium (that is, the entire composition less suspended insoluble particulate material) should be deter gent, and about 10 percent to about 16 percent is preferable. About 12 percent to about 14 percent gives the best results.
• the combined deter gent and abrasive make the compositions too thick to be manageable; at the lower detergent concentrations there is not enough detergent to provide sufficient yield value to support the abrasive.
• the upper limit on combined detergent and abrasive is a functional one, and is best expressed in terms of apparent viscosity.
• the detergent compositions of this invention have an apparent viscosity below about 12,000 centipoises; it is preferred that the apparent viscosity be below about 10,000.
• apparent viscosity means the value obtained with a Brookfield viscometer, Model LVF, using spindle number 3 at 12 r.p.m. At lower (below 40 percent) abrasive concentrations, the concentration of total detergent in the supporting medium becomes less important, and up to about 20 percent of the total composition can be detergent.
• lt is important in the practice of this invention to maintain the weight ratio of alkylbenzenesulfonate to zwitterionic synthetic detergent in the range between from about 0.4:1 to
• the detergent compositions of this invention may have unacceptably low yield values, or they may separate into two layers at room temperature, or both. It is preferred that the alkylbenzenesulfonate to zwitterionic synthetic detergent ratio be in the range of about 0.421 to about 20:1. The exact value of this ratio depends on other materials present in the system. For example, a ratio of about 0.86:! was found particularly effective for a system containing alkylbenzenesulfonate and zwitterionic detergents, sodium sulfate and sodium chloride.
• the insoluble, particulate material which is utilized in this invention can comprise abrasives, bactericides, or other insoluble, particulate material having a particle size diameter ranging from about 1 to about 200 microns and a density of from about 0.5 to about 5.0. It is preferred that the diameter of the particles range from about 2 microns to about 60 microns and that the density range from about 1.0 to about 2.8.
• the abrasives which can be utilized in this invention include, but are not limited to, quartz, pumice, pumicite, talc, silica sand, calcium carbonate, china clay, zirconium silicate, bentonite, diatomaceous earth, whiting, feldspar, and aluminum oxide.
• Silica is the preferred abrasive for use herein.
• lf aluminum oxide is used, the pH of the composition should not be above about 1 l, or the aluminum oxide will dissolve.
• a high density abrasive such as aluminum oxide, pumice containing aluminum oxide, or zirconium silicate
• the yield value required can be calculated from the density and particle size of the suspended particles, and from the density of the supporting medium. The yield value required is equal to the pressure per unit area which the weight of the particle exerts on the supporting medium, taking into account the buoyant force of the supporting medium.
• this yield value is given by the formula where f is the yield value in dynes per square centimeter, D is the particle diameter in centimeters; g is the gravitational constant, 980.665 centimeters per second per second; d is the density of the particle to be supported; and d is the density of the supporting medium (both densities in grams per cubic centimeter).
• This theoretical yield value should be multiplied by a safety factor of about 1.5 or 2.0, to take into account such factors as nonspherical particles, inaccuracy in estimating yield value, and occasional agglomeration of two or more particles, in order to calculate the yield value (as observed) which is necessary to support the particular material which is to be suspended.
• Polyvalent Electrolyte From about 1 percent to about 10 percent of the finished composition is required to be polyvalent electrolyte. For example, from about 1 percent to about 10 percent sodium sulfate can be employed, but from about 2 percent to about 3 percent is preferred, as this allows higher amounts of detergencybuilders to be used.
• One or more detergency builders can be included in this electrolyte to serve as a cleaning aid and as a pH buffer. The amount of detergency builder to be included depends on the particular builder used, but in any case should be between 0 percent and about l0 percent by weight of the finished composition. It is preferred that the total amount of builders be from about 1 percent to about 7 percent. Many builders, if present in too great a quantity, will cause the system to lose its yield value and suspending capability.
• Tetraborate can be added to these detergent compositions to improve cleaning (as a detergency builder), to improve low temperature stability properties, and to raise the yield value.
• the tetraborate can be introduced into the detergent composition in several forms, e.g., anhydrous sodium tetraborate, sodium tetraborate pentahydrate, and sodium tetraborate decahydrate.
• Sodium tetraborate decahydrate is preferred for use herein as it is readily available to the detergent industry.
• the anhydrous or hydrated tetraborate compounds are utilized, they ionize and tetraborate ions are then present in these liquid detergent compositions. It has been found that from percent to about 0.8 percent tetraborate, by weight of the finished detergent composition, can be utilized in this invention. This range corresponds to 0 percent to about 2 percent sodium tetraborate decahydrate by weight of the finished composition.
• detergency builders which can be employed without destroying the particle suspending ability of the composition include trisodium ethanehydroxydiphosphonate, CH COH(PO ch2HNa in an amount ranging from 0 percent to about percent; sodium tripolyphosphate, Na P 0 in an amount ranging from 0 percent to about 3 percent, and
• trisodium orthophosphate Na P0, in an amount ranging from 0 percent to about 7 percent. Mixtures of these builders can also be employed.
• Water From about 25 percent to about 85 percent of this composition is water. It is preferred that from about 30 percent to about percent by weight of the finished composition be water to optimize yield values and cleaning characteristics of the finished product. It is also preferred that soft water be utilized in this invention. 5
• Strong Base The pH of the composition is from about 7.5 to about 13, preferably from about 8 to about 1 1. If necessary, the pH is adjusted to this level by adding a strong base.
• the most desirable strong bases for use herein are sodium hydroxide and 50 potassium hydroxide. In the preferred pH range (about 8 to about 1 l the liquid detergent compositions of this invention have higher yield values and greater stability, as well as better cleaning capability. Frequently no pH adjustment is required,
• the builder salts included raise the pH ofthe composition to within the desired range.
• Minor Ingredients Minor amounts of materials which make the composition of this invention more attractive or more effective can be added if they do not significantly alter the excellent physical properties of this composition.
• the following materials are mentioned merely by way of example: soluble sodium carboxymethyl cellulose, tarnish inhibitors, such as benzotriazole or ethylenethiourea, brighteners, bleaches, fluorescers, dyes,
• the detergent composition thus, becomes a one-phase solution and loses its Bingham plastic characteristics with concomitant settling of insoluble, particulate material, e.g., abrasive.
• the composition in this condition, is aesthetically undesirable and not salable on the retail consumer market or the industrial market.
• soaps, amides, and other materials which are presently or potentially solubilizing agents, or which combine with water hardness ions.
• the abrasive except in Runs 17 and 18, was silica (quartz, specific gravity about 2.65) of the following particle size distribution:
• microns 0.4% 36 microns 4.1% 6- 10 microns 11.5% 10-15 microns 16.0% 15-20 mlcrons 16.0% 20-30 microns 24.0% 30-40 microns 17.0% 40-60 microns 1 1.0%
• Run 17 contained feldspar, specific gravity about 2.65, of the following particle size distribution:
• Runs 1 and 2 show the effect of too small a relative amount 55 of alkylbenzenesulfonate detergent; Run 7 shows the effect of percent abrasive, was too thick to yield value (dynes per square sity (centipoises) were meaparation resulted in about the 70 ple bottle containing the bulk of too great a relative amount of alkylbenzenesulfonate detergent.
• Runs 8 and 13 illustrate the use of too little or too much total detergent, respectively: Run 8 does not contain enou total detergent to support the abrasive, even thou of alkylbenzenesulfonate to zwitterionic deter timum; Run 13, containing 20 percent deter porting medium and 50 form a workable composition, and was discarded. All runs except 13 were divided into three p0 tively for one week at 50 F and and the pH centimeter) and apparent visco sured. Since the maximum se bottom 40 percent of the sam the abrasive, this was defined as 100 percent separation.
• viscosity and yield value data were measured at room temperature (about 74 F.), even though the samples may have been stored at higher or lower temperatures.
• the apparent viscosities were read with a Brookfield viscometer, Model LVF, using spindle number 3 at 12 r.p.m.
• viscosity measurements for yield values were made with a Brookfield viscometer, Model RVT, using spindle number C2 at one-half and l r.p.m.
• the above runs can be considered to be five series, each of which illustrates a different point.
• a horizontal line separates each series.
• the first series contains Runs 1-7, showing the effect of varying the ratio of sodium dodecylbenzenesulfonate to zwitterionic detergent.
• the second series contains Runs 8, 9, l0, 4, ll, 12, and 13, showing the effect of varying the total amount of detergent.
• Run 4 is repeated in several locations for ease of comparison.
• the other variables were held as near constant as practicable, in order to clearly show the effect of varying the ratio or total detergent, respectively.
• Runs 1, 2 and 7 (outside the ratio of detergents to be used in compositions of this invention) were poor in suspending abrasive, as was Run 8 (below the range of total detergent amount); Run 12 (at high end of total detergent amount) was very thick, and not easily manageable.
• Runs l4-l6 form a third series, illustrating the use of builders.
• the following builders can be used, alone or in combination, in the amounts indicated, with substantially equivalent or better results (and in particular, without destroying the yield value and ability to suspend particles), provided the level of sodium sulfate does not exceed about 3 percent; tetrapotassium pyrophosphate, from 0 percent to about 6 percent, from about 3 percent to about 4 percent being preferred, as it increases yield value; sodium tetraborate, from 0 percent to about 2 percent (as decahydrate); trisodium ethanehydroxydiphosphonate, from 0 percent to about 5 percent; sodium tripolyphosphate from 0 percent to about 3 percent; and trisodium phosphate, from 0 percent to about 7 percent.
• Runs 4, l7 and 18 constitute the fourth series which illustrates the use of various abrasives.
• the following can be substituted, with substantially equivalent results, for the silica, feldspar and calcium carbonate illustrated: quartz, pumice, pumicite, talc, china clay, zirconium silicate, bentonite, diatomaceous earth, whiting and aluminum oxide, of the same particle sizes.
• quartz, pumice, pumicite, talc, china clay, zirconium silicate, bentonite, diatomaceous earth, whiting and aluminum oxide of the same particle sizes.
• Runs 19, 4 and 20 constitute the fifth series illustrating variations in the abrasive level.
• the supporting medium in each of these three runs is identical, with only the amount of abrasive varied. It can be seen that at 33.33 percent and at 60.00 percent abrasive level, some separation occurs; and although it is not excessive, except under adverse storage conditions (see, e.g., results for run 19 at 50 F.), it is therefore preferred that the total abrasive be between about 40 percent and about 50 percent.
• a stable, liquid detergent composition which is free of soaps, amides and hydrotropes and which has a yield value of from about 5 to about 600 dynes per square centimeter and an apparent viscosity below about 12,000 centipoises consisting essentially of 1.
• an anionic alkylbenzenesulfonate synthetic detergent having the general formula: 9 a
• R is an alkyl chain containing from about nine to about 15 carbon atoms
• M is a cation selected from the group consisting of potassium, sodium, ammonium, monoethanolammonium, diethanolammonium, and triethanolammonium cations
• R is an alkyl chain containing from about 10 to about 18 carbon atoms; R is selected from the group consisting of hydrogen and hydroxyl; the ratio of alkylbenzenesulfonate detergent to the zwitterionic synthetic detergent ranges from about 0.4:] to about 4:] and the combined weight of the alkylbenzenesulfonate detergent and the zwitterionic synthetic detergent ranges from about percent to about 20 percent by weight of the finished composition; 3. from about 1 percent to about 60.
• insoluble, particulate material having particle diameters ranging from about 1 micron to about 200 microns, and a density of from about 0.5 to about 5.0 (g./cc.) wherein the particulate material is an abrasive selected from the group consisting of quartz, pumice, pumicite, talc, silica sand, calcium carbonate, china clay, zirconium silicate, bentonite, diatomaceous earth, whiting feldspar and aluminum oxide; 4.
• a polyvalent electrolyte effective to lower the solubility and thereby salt out said anionic alkylbenzenesulfonate synthetic detergent and said zwitterionic quaternary ammonio synthetic detergent from a continuous phase
• said electrolyte is selected from the group consisting of sodium sulfate, tetrapotassium pyrophosphate, trisodium ethane hydroxydiphosphonate, tripolyphosphate, trisodium orthophosphate, sodium tetraborates, and mixtures thereof;
• sufircient strong base to adjust the pH of the composition to from about 7.5 to about 13.0; said yield value being sufiicien't to support said insoluble, particulate material; said pH being adjusted to a pH of up to about 1 I when said insoluble, particulate material is aluminum oxide.
• composition of claim 1 wherein the alkylbenzenesulfonate detergent is sodium n-dodecylbenzenesulfonate, and in the formula given for the zwitterionic detergent, R is hydroxyl.
• composition of claim 4 wherein the alkylbenzenesulfonate detergent comprises from about 2 percent to about 6 percent by weight of the finished detergent composition, the zwitterionic synthetic detergent comprises from about 2 percent to about 7 percent by weight of the finished detergent composition, the ratio of alkylbenzenesulfonate detergent to zwitterionic detergent is from about 0.4:] to about 2.0: l and the total amount of alkylbenzenesulfonate and zwitterionic detergents is from about 5 percent to about l2 percent of the finished detergent composition.
• composition of claim 1 wherein the ratio of alkylbenzenesulfonate detergent to zwitterionic detergent is about 0.08611, and the total amount of alkylbenzenesulfonate and zwitterionic detergents is from about 6 percent to about 7 percent by weight of the finished detergent composition.
• composition of claim 1 wherein the insoluble, particulate material comprises from about 40 percent to about 50 percent by weight of the finished detergent composition and wherein the insoluble, particulate material has particle diameters ranging from about 2 microns to about 60 microns and has a specific gravity of from 1 to about 2.8.
• the electrolyte comprises a builder salt selected from the group consisting of from 0 percent to about 6 percent of potassium pyrophosphate; from 0 percent to about 2 percent of sodium tetraborate decahydrate; from 0 percent to about 5 percent of trisodium ethanehydroxydiphosphonate; from 0 percent to about 3 percent'of sodium tripolyphosphate; from 0 percent to about 7 percent of trisodium orthophosphate; and mixtures of the above.
• a builder salt selected from the group consisting of from 0 percent to about 6 percent of potassium pyrophosphate; from 0 percent to about 2 percent of sodium tetraborate decahydrate; from 0 percent to about 5 percent of trisodium ethanehydroxydiphosphonate; from 0 percent to about 3 percent'of sodium tripolyphosphate; from 0 percent to about 7 percent of trisodium orthophosphate; and mixtures of the above.
• composition of claim 7 wherein the electrolyte comprises from about 3 percent to about 4 percent potassium pyrophosphate.
• the detergent composition of claim 1 wherein the pH is adjusted to from about 8 to about ll by adding a strong base selected from the group consisting of sodium hydroxide and potassium hydroxide.
• the yield value is Column 6, line 42, the formula f [2Dg(dd) ]/3,/" should read f 2 D91 (d- 1 3 Column 6, line 56, after the word “percent” insert of the composition of this invention is insoluble particulate Column 7, line 33, the formula CH COH(PO ch2HNa should 3 3 read CH3COII(PO3) HNa Column 9, Run 15, on the second table under the "100F.” heading the figure "6,350” should read 950 Columns 11 and 12, Run 3, under the heading "Percent Separation: Sample Stored At 100F” the figure “221” 3 should read 212 Columns 11 and 12 Run 15, under the heading "Apparent Viscosity: Sample Stored At 50F” the figure "120;” should read 1200 Column 14, line 28, Claim 7, after "decahydrate;” delete from 0 percent to about 5 percent of trisodium ethanehydroxydiphosphonate;

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• 1967
  • 1967-06-26 US US649019A patent/US3623990A/en not_active Expired - Lifetime
• 1968
  • 1968-06-25 FR FR1585069D patent/FR1585069A/fr not_active Expired
  • 1968-06-26 GB GB30483/68A patent/GB1181607A/en not_active Expired
  • 1968-08-23 CH CH1270168A patent/CH522031A/de not_active IP Right Cessation
  • 1968-12-18 US US784886A patent/US3579456A/en not_active Expired - Lifetime
• 1969
  • 1969-08-04 BE BE737033D patent/BE737033A/xx unknown
  • 1969-08-18 NL NL6912568A patent/NL6912568A/xx unknown
  • 1969-11-20 NL NL6917462A patent/NL6917462A/xx unknown

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