US3520818A - Abrasive liquid detergent compositions - Google Patents
Abrasive liquid detergent compositions Download PDFInfo
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- US3520818A US3520818A US603098A US60309866A US3520818A US 3520818 A US3520818 A US 3520818A US 603098 A US603098 A US 603098A US 60309866 A US60309866 A US 60309866A US 3520818 A US3520818 A US 3520818A
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- 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
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- 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
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- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
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- 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
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- 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
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- 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
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- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
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- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
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- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
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- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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- 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
- C11D3/395—Bleaching agents
- C11D3/3955—Organic bleaching agents
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- 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
- C11D3/395—Bleaching agents
- C11D3/3958—Bleaching agents combined with phosphates
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/20—Water-insoluble oxides
-
- 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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/002—Non alkali-metal soaps
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- 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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/02—Compositions of detergents based essentially on soap on alkali or ammonium soaps
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- 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
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- 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
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- 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
- Liquid detergent compositions suitable for cleaning hard surfaces which are capable of supporting particulate material, e.g., abrasives; said detergent compositions contain water, soap, zwitterionic synthetic detergents and tetrapotassium pyrophosphate, and can, additionally, contain borate ions and inter polymers of methyl vinyl ether and maleic anhydride esterified with a zwitterionic synthetic detergent.
- 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 to about 200 dynes per square centimeter.
- liquid detergent compositions adapted for cleaning hard surfaces.
- These liquid detergent compositions are provided in convenient form and are specially formulated for this particular cleaning application.
- these detergent compositions must be homogeneous and easily pourable.
- These compositions when intended for the retail consumer market, should maintain their homogeneity during ordinary periods of storage and use, e.g., up to four months, 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 hold particulate material in suspension in the detergent composition and prevent that particulate material from settling to the bottom of the container.
- liquid detergent compositions When these liquid detergent compositions are intended for industrial applications, excellent product stability, as described above, is not as important as it is in the retail consumer market. In industrial applications, phases can be recombined and particulate material redistributed before use. However, even these products should be stable for at least a 24 hour period.
- Liquid detergent compositions containing a combination of alkali metal soaps, ethanol amides and potassium pyrophosp'hates are known (see US. Pat. 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 precipitates.
- amides in these compositions are hydrolyzed to soap if the compositions are subjected to high storage temperatures, e.g., 110 F.
- high storage temperatures e.g. 110 F.
- the liquid detergent compositions separate and lose their Bingham Plastic characteristics. Again, the particulate material in these compositions is deposited on the bottom of the respective containers.
- 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. Yet another object of this invention is to provide liquid detergent compositions which have acceptable freeze-thaw characteristics. Another object of this invention is to provide liquid detergent compositions which exhibit Bingham Plastic characteristics and which do not contain amides. It is another object of this invention to provide a detergent composition in convenient, pourable form.
- soap having an iodine value of from about 0 to about 4 5; the cation of said soap being selected from the group consisting of monoethanolammonium, diethanolammoniaum and triethanolammonium cations; said soap having an acyl chain containing from about 14 to about 22 carbon atoms;
- R is an alkyl chain containing from about 10 to about 18 carbon atoms and -R" is a radical selected from the group consisting of ethylene and hydroxyethylene; the ratio of soap to the zwitterionic synthetic detergent ranges from about O.8:1.0 to about 1.2:1.0 and the combined weight of the soap and the zwitterionic synthetic detergent ranges from about 8% to about 20% by weight of the finished composition;
- liquid detergent composition of this invention will be characterized, in its entirety, at this juncture in order to facilitate a better understanding of the individual components and their functions in these liquid detergent compositions.
- liquid detergent compositions of this invention will suspend insoluble, particulate materials which meet the particle size and specific gravity specifications set forth above.
- Compositions such as these are generally described as being Bingham Plastic or Real Plastic. These Bingham Plastic compositions possess a yield value and, therefore, provide resistance to flow forces or stresses. It is this reitarlce to flow that maintain the particulate material in suspension.
- the yield value is the minimum force required to initiate fiow. It is measured as the intercept on the shearing stress axis of a rate of shear versus shearing stress diagram. Because it is usually not known whether a system behaves in a truly plastic manner at low shear rates, the measurement of exact yield values is quite difficult. A close approximation can be obtained by using a Brookfield viscometer. The yield value is estimated, in dynes per square centimeter, by the following relationships:
- This relationship represents an extrapolation of the shear curve to 0 r.p.m. since an absolute shear stress cannot be measured at 0 rpm.
- liquid detergent composition of this invention is a suspension of a mesomorphic neat phase (discrete phase) suspended in an isotropic medium which is probably lye (continuous phase).
- the physical structure of the system is highly oriented. Hence, it is this high degree of orientation that imparts the yield value to the system.
- the essential individual components of this invention are soap, zwitterionic synthetic detergents, tetrapotassium pyrophosphate and water.
- the soap, the zwitterionic synthetic detergent and the tetrapotassium pyrophosphate are Yield Value the primary cleaning or detergent components of this composition.
- borate ions and interpolymers of methyl vinyl ether and maleic anhydride esterified with a zwittterionic synthetic detergent, as hereinafter defined can be added to the liquid detergent composition of this invention. All of these compositions are capable of suspending particulate materials of the hereinafter specified specific gravity and particle size and, accordingly, these particulate materials can be included as components of these liquid detergent compositions.
- the soap utilized in the liquid detergent composition of this invention has an iodine value of from about 0 to about 45, a cation selected from the group consisting of monoethanolammonium, diethanolammonium and triethanolammonium, and an acyl chain length of from about 14 to about 22 carbon atoms and, preferably, from about 16 to about 22 carbon atoms.
- the iodine value, or degree of saturation, of the soap is very important in this invention. If the iodine value of the soap is over 45, detergent systems with unacceptably low yield values and poor phase stability are Obtained. When the iodine value is between and 45, the product is acceptable for industrial uses, that is, the product is stable for at least 24 hours. When the product is to be sold in the retail consumer market, it is preferred that the 4 iodine value of the soap utilized in these compositions be from about 0 to about 35 to obtain maximum product stability and acceptable yield values.
- the cations of the soap component of this invention are selected from the group consisting of monoethanolammonium, diethanolammonium or triethanolammonium. If ammonium soap or alkali-metal soap is utilized in this invention, the compositions may separate into two layers and, generally, the compositions have unacceptably low yield values. Table I, set forth hereinafter in Example V, illustrates the importance of the cation of the soap component. The monoethanolammonium and diethanolammonium soap compositions are more stable over protracted periods of time than the triethanolammonium soap compositions and are, therefore, highly preferred.
- the acyl chain length of the soap utilized herein is from about 14 to about 22 carbon atoms.
- a particularly preferred chain length distribution is obtained by utilizing tallow soap.
- saponifiable, natural and synthetic materials having acyl chain lengths of from about 14 to about 22 carbon atoms and mixtures of these materials can be used in making the soap for use in this invention.
- From about 4% to about 10% of the above-described soap by weight of the finished detergent composition is utilized in the detergent compositions of this invention.
- the above-described soap is utilized in these compositions in amounts of from about 4.5% to about 8% by weight of the finished composition.
- the zwitterionic quaternary ammonio synthetic detergent of this invention has the following structural formula:
- R is an alkyl radical containing from about 10 to about 18 carbon atoms and R is a radical selected from the group consisting of ethylene and hydroxyethylene. It is preferred that R be hydroxyethylene.
- the zwitterionic synthetic detergent described above is utilized in this invention in amounts of from about 4% to about 10% by weight of the finished detergent composition. It is preferred that the zwitterionic synthetic detergent be utilized in amounts of from about 4.5 to about 8% by weight of the finished composition.
- the weight ratio of soap to zwitterionic synthetic detergent in the range between from about 0.8:1.0 to about 1.2:1.0.
- the detergent compositions of this invention may have unacceptably low yield values if too much soap is utilized or they may separate into two layers at room temperature if too much zwitterionic synthetic detergent is utilized.
- the combined weight of the soap and zwitterionic synthetic detergent should range from about 8% to about 20% by weight of the finished detergent composition. It is preferred that the soap to zwitterionic synthetic detergent ratio be about 1:1 and the combined weight of the soap and zwitterionic synthetic detergent be from about 9% to about 16% by weight of the finished detergent composition.
- Tetrapotassium pyrophosphate is added to the detergent compositions of this invention as a cleaning aid and as a pH buffer. Tetrapotassium pyrophosphate is utilized herein, in preference to other detergency builders, because of its good cleaning characteristics and excellent solubility characteristics.
- the liquid detergent compositions built with tetrapotassium pyrophosphate also exhibit excellent stability characteristics over a wide range of temperatures.
- tetrapotassium pyrophosphate From about 10% to about 17% of tetrapotassium pyrophosphate by weight of the finished detergent composion is utilized in this invention. To maximize stability and optimize the cleaning characteristics of the liquid detergent compositions, from about 12% to about 15.5% tetrapotassium pyrophosphate should be utilized herein.
- liquid detergent compositions comprising soap, zwitterionic synthetic detergents and tetrapotassium pyrophosphate, described above, clean well and have yield values which are adequate to suspend particulate material.
- freeze-thaw properties and stability properties of these compositions can be improved and the yield value raised by the addition of other components as will be described hereinafter.
- Borate ions can be added to these detergent compositions, in this preferred embodiment, to improve low temperature stability properties and to raise the yield value.
- the borate ions can be introduced into the detergent composition in several forms, e.g., anhydrous sodium borate, sodium borate pentahydrate, and sodium borate decahydrate.
- Sodium borate decahydrate is preferred for use herein as it is readily available to the detergent industry.
- liquid detergent compositions hereinbefore described which do not contain borate ions.
- the yield values of these liquid detergent compositions may also be lowered at low temperatures with the concomitant precipitation of a minor portion of the particulate material.
- the addition of the hereinafter specified amounts of borate ions prevents the formation of these large emulsion particles at low temperatures and maintains the yield values of these compositions at an acceptable figure.
- borate ions by weight of the finished detergent composition, can be utilized in this invention. It is preferred that from about 1.75% to about 2.25% borate ions be utilized. This preferred range corresponds to about 4.3% to about 5.5% sodium borate decahydrate by weight of the finished composition.
- the interpolymer utilized herein has the following unit structural formula:
- the interpolymer is comprised of vinyl ether and maleic anhydride in a molar ratio of about 1:1.
- the interpolymers suitable for use in this invention have a specific viscosity of from about 0.1 to about 3.5 and, preferably, have a specific viscosity of from about 0.1 to about 0.5.
- the specific viscosity is determined from a solution of 1 gram of the interpolymer in ml. of methyl ethyl ketone at 25 C. As is well known in the art, molecular weight is directly related to the specific viscosity.
- the interpolymer is esterified with a zwitterionic synthetic detergent having the following formula:
- R contains from about 10 to about 18 carbon atoms. From about 0.1 to about 1.0 parts by weight of additional zwitterionic, as hereinbefore defined, should be utilized per part of interpolymer in this esterification process.
- the esterification reaction is carried out at elevated temperatures, e.g., from about F. to about 200 F. In most cases, some electrolyte, such as sodium chloride, is present when the interpolymer is being esterified. The electrolyte, however, is not necessary in this prOcess.
- the interpolymer esterification mechanism is believed to follow the route outlined below:
- this esterified polypolymer is utilized in this invention. It is preferred that from about 0.1% to about 0.25% of this esterified interpolymer be used in the composition of this invention.
- the insoluble, particulate material 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 specific gravity of from about 0.5 to about 3.0. It is preferred that the diameter of the particles range from about 2 microns to about 60 microns and that the specific gravity range from about 1.0 to about 2.8.
- the abrasives which can be utilized in this invention include, but are not limited to, pumice, pumicit-e, talc, silica sand, china clay, bentonite, diatomaceous earth, whiting, feldspar and aluminum oxide. Quartz is the preferred abrasive for use herein.
- Bactericides which can be utilized herein include trifluoromethyl dichlorocarbanilide and diphenyl bismuth acetate.
- composition of this invention is comprised of insoluble particulate material. It is preferred, however, that from about 7% to about 15% by weight of the finished composition be insoluble, particulate material.
- From about 25% to about 85% of this composition is comprised of water. It is preferred that water comprise from about 55% to about 70% by weight of the finished composition to optimize yield values and cleaning characteristics of the finished product. It is also preferred that soft water be utilized in this invention.
- the pH of the composition is adjusted to from about 7.5 to 13, preferably from about 9 to 12, by adding a strong base.
- strong bases for use herein are sodium hydroxide and potassium hydroxide. Potassium hydroxide is highly preferred.
- the liquid detergent compositions of this invention have higher yield values and greater stability.
- compositions of this invention may 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, fiuorescers, dyes, bluing agents, perfumes, bactericides and corrosion inhibitors.
- Hydrotropes such as sodium or potassium xylene sulfonate, toluene sulfonate, and benzene sulfonate, should not be present in the compositions of this invention. Even very small amounts of these hydrotropes solubilize the discrete phase into the continuous phase.
- the detergent composition thus, becomes a one-phase solution and loses its Bingham Plastic characteristics with concomitant precipitation of insoluble, particulate material, e.g., abrasive.
- the composition in this condition, is aesthetically undesirable and not saleable on the retail consumer market or the industrial market.
- EXAMPLE I An interpolymer of methyl vinyl ether and maleic anhydride, in a molar ratio of about 1:1 having a specific viscosity, as hereinbefore defined, of about 0.4, was esterified with a zwitterionic synthetic detergent having the following formula wherein R contained a mixture of alkyl radicals con taining from to 18 carbon atoms. Ten parts of the interpolymer were mixed with 3 parts of a zwitterionic synthetic detergent solution and 87 parts of soft water. The 30% zwitterionic solution contained 6% electrolyte, i.e., sodium chloride, 30% zwitterionic synthetic detergent as hereinbefore described and 64% soft water. Therefore, the interpolymer was esterified with 0.27 part of the zwitterionic per part of the interpolymer. The above described mixture was maintained at a temperature of 160 F. while being agitated for 40 minutes at which time esterification was completed.
- a separate mixer 300 parts of commercial borax (sodium borate decahydrate) were added to 1888 parts of soft water. This mixture was maintained at a temperature of about 140 F. while being agitated. Sixty parts of the esterified interpolymer were then added to the mixture followed by 99.6 parts of diethanolamine. 260 parts of tallow fatty acid having an iodine value of 30 were also added to the mixture. Agitation was continued until neutralization of the tallow fatty acid was completed, i.e., the tallow soap had been formed. 1385 parts of a tetrapotassium pyrophosphate solution were then slowly poured into the mixture to form a creamy emulsion. The tetrapotassium pyrophosphate solution comprised water and 65% tetrapotassium pyrophosphate.
- the final detergent composition was opaque and easily pourable and consisted essentially of, by weight of the finished composition
- the remainder of the composition i.e., about 1.5%, was comprised of sodium chloride.
- the sodium chloride is, however, not necessary to the proper functioning of this invention.
- Bottles were filled with the abrasive, liquid detergent composition and stored under varying conditions for nine months.
- the bottles were separately stored under conditions of 40 F., 60 F., F., F. and F. At the end of this storage period, there were no signs of layering and no precipitation of the particulate material.
- abrasive, liquid detergent compositions were especially suited for cleaning hard surfaces. They can be used as full-strength compositions for heavy-duty cleaning or they can be diluted with water for the lighter cleaning jobs.
- EXAMPLE H An abrasive, liquid detergent composition is prepared from the following components according to the procedure of Example I.
- Soft water 1838 Tetrapotassium pyrophosphate solution see Example I) 1300 Diethanol amine 99.6 Tallow fatty acid (neutralized to diethanolammonium soap) 260 30% zwitterionic synthetic detergent solution (see Example I) 1241 Quartz (see Example I) 600 1 Potassium hydroxide solution to pH of 10.5 137
- the finished detergent composition is stable and has a yield value of about 75. The composition does not separate on standing for a period of about one month.
- the following fatty acids are substituted for the tallow fatty acid of Example I: stearic acid, myristic acid, palmitic acid, rapeseed acid, and a mixture of 20% myristic fatty acid and 80% tallow fatty acid.
- Stoichiometric equivalents of monoethanolamine or triethanolarnine are substituted for the diethanolamine of Example I.
- the zwitterionic quaternary ammonio synthetic detergent of Example I is replaced by a similar zwitterionic synthetic detergent wherein R" is ethylene instead of hydroxyethylene.
- insoluble, particulate materials are substituted for the quartz in Example I: pumice, pumicite, talc, china clay, aluminum oxide, feldspar, whiting, bentonite, silica sand, diphenyl bismuth acetate, trifluoromethyl dichlorocarbanilide. All of these particulate materials have particle sizes ranging from 1 micron to 200 microns and specific gravities ranging from 0.5 to 3.0. The particulate material does not precipitate.
- a stable, liquid detergent composition which is substantiall free of amides and hydrotropes and which has a yield value of from about 10 to about 200 dynes per square centimeter consisting essentially of, by weight of the finished composition,
- tallow fatty acid soap having a iodine value of from about 0 to about 45; the cation of said soap being selected from the group consisting of monoethanolammonium, diethanolammonium and triethanolammonium cations;
- a zwitterionic quaternary ammonio synthetic detergent having the general formula wherein R is an alkyl chain containing from about 10 to about 18 carbon atoms and R is a radical selected from the group consisting of ethylene and hydroxyethylene; the ratio of soap to the zwitterionic synthetic detergent ranges from about 08:10 to about 1211.0 and the combined weight of the soap and the zwitterionic synthetic detergent ranges from about 8% to about 20% by weight of the finished composition;
- R is an alkyl radical containing from about 10 to about 18 carbon atoms
- composition of claim 1 wherein the soap has an iodine value of from 0 to about 35 and the cation of the soap is selected from the group consisting of monoethanolammonium and diethanolammonium cations.
- composition of claim 3 wherein the soap comprises from about 4% to about 10% "by weight of the finished detergent composition and the zwitterionic synthetic detergent comprises from about 4% to about 10% by weight of the finished detergent composition.
- composition of claim 1 wherein the soap comprises from about 4.5% to about 8% by weight of the finished detergent composition and the zwitterionic synthetic detergent comprises from about 4.5% to about 8% by weight of the finished detergent composition.
- composition of claim 1 wherein the zwitterionic quaternary ammonio synthetic detergent has the general formula:
- R is an alkyl radical containing from about to about 18 carbon atoms.
- composition of claim 1 wherein the soap to zwitterionic synthetic detergent ratio is about 1:1 and the combined weight of the soap and zwitterionic synthetic detergent is from about 9% to about 16% by weight of the finished detergent composition.
- composition of claim 1 wherein tetrapotassium pyrophosphate comprises from about 12% to about 15.5% by weight of the finished detergent composition.
- borate ions comprise from about 1.75% to about 2.25% by weight of the detergent composition.
- a stable, liquid detergent composition which is substantially free of amides and hydrotropes and which has a yield value of from about 10 to about 200 dynes per square centimeter consisting essentially of, by weight of the finished composition,
- fatty acid soap having an iodine value of from about to about 45; the cation of said soap being selected from the group consisting of monoethanolammonium, diethanolarnmonium and triethanolammonium cations; said soap having an acyl chain containing from about 14 to about 22 carbon atoms;
- a zwitterionic quaternary ammonio synthetic detergent having the general formula wherein R is an alkyl chain containing from about 10 to about 18 carbon atoms and R" is a radical selected from the group consisting of ethylene and hydroxyethylene; the ratio of soap to the zwitterionic synthetic detergent ranges from about 0.8210 to about 1.2: 1.0 and the combined weight of the soap and the zwitterionic synthetic detergent ranges from about 8% to about 20% by weight of the finished composition;
- R is an alkyl radical containing from about to about 18 carbon atoms; ('6) from 0% to about 40% of an insoluble, particulate material selected from the group consisting of water 5 insoluble abrasives and bactericides having particle diameters ranging from 1 micron to about 200 microns and a specific gravity of from about 0.5 to about 3.0; (7) from about 25% to about 85% water; and (8) sufficient strong base to adjust the pH of the com- 10 position to from about 7.5 to about 13.0.
- composition of claim 1 containing from about 7% to about by weight of a water insoluble abrasive having particle diameters ranging from about 1 15 micron to about 200 microns and a specific gravity of from about 0.5 to about 3.0.
- the detergent composition of claim 10 wherein the abrasive is selected from the group consisting of quartz, pumice, pumicite, talc, silica sand, china clay, bentonite, diatomaceous earth, whiting, feldspar and aluminum oxide.
- m 3 can of Patflnta Awning Offic r
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US603098A US3520818A (en) | 1966-12-20 | 1966-12-20 | Abrasive liquid detergent compositions |
DE1967P0043582 DE1617193B2 (de) | 1966-12-20 | 1967-12-12 | Fluessiges reinigungsmittel |
FR132784A FR1548948A (xx) | 1966-12-20 | 1967-12-15 | |
FI03367/67A FI48479B (xx) | 1966-12-20 | 1967-12-18 | |
NO171023A NO121800B (xx) | 1966-12-20 | 1967-12-18 | |
FI673367A FI48479C (fi) | 1966-12-20 | 1967-12-18 | Nestemäinen pesuaineseos. |
BE708198D BE708198A (xx) | 1966-12-20 | 1967-12-19 | |
DK634967AA DK128377B (da) | 1966-12-20 | 1967-12-19 | Stabilt flydende rensemiddelprodukt. |
GB57565/67A GB1167597A (en) | 1966-12-20 | 1967-12-19 | Liquid Detergent Composition |
SE17407/67A SE344471B (xx) | 1966-12-20 | 1967-12-19 | |
NL6717424A NL6717424A (xx) | 1966-12-20 | 1967-12-20 | |
CH199768A CH505198A (de) | 1966-12-20 | 1968-02-12 | Beständiges flüssiges Reinigungsmittel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US603098A US3520818A (en) | 1966-12-20 | 1966-12-20 | Abrasive liquid detergent compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US3520818A true US3520818A (en) | 1970-07-21 |
Family
ID=24414092
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US603098A Expired - Lifetime US3520818A (en) | 1966-12-20 | 1966-12-20 | Abrasive liquid detergent compositions |
Country Status (11)
Country | Link |
---|---|
US (1) | US3520818A (xx) |
BE (1) | BE708198A (xx) |
CH (1) | CH505198A (xx) |
DE (1) | DE1617193B2 (xx) |
DK (1) | DK128377B (xx) |
FI (2) | FI48479C (xx) |
FR (1) | FR1548948A (xx) |
GB (1) | GB1167597A (xx) |
NL (1) | NL6717424A (xx) |
NO (1) | NO121800B (xx) |
SE (1) | SE344471B (xx) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3956158A (en) * | 1974-01-07 | 1976-05-11 | Lever Brothers Company | Pourable liquid compositions |
US4122025A (en) * | 1976-04-29 | 1978-10-24 | Henkel Kommanditgesellschaft Auf Aktien | Liquid scouring cleaning compositions containing cristobalite |
US4245022A (en) * | 1975-10-13 | 1981-01-13 | Fuji Xerox Co., Ltd. | Dry electrophotographic developers |
US4786369A (en) * | 1986-05-05 | 1988-11-22 | Go-Jo Industries, Inc. | Integral dry abrasive soap powders |
JPH0234699A (ja) * | 1988-06-13 | 1990-02-05 | Unilever Nv | 液体洗剤組成物 |
JPH0234700A (ja) * | 1988-06-13 | 1990-02-05 | Unilever Nv | 液体洗剤組成物 |
US5147576A (en) * | 1988-06-13 | 1992-09-15 | Lever Brothers Company, Division Of Conopco, Inc. | Liquid detergent composition in the form of lamellar droplets containing a deflocculating polymer |
US5866040A (en) * | 1990-06-15 | 1999-02-02 | Shiseido Company, Ltd. | Complex and emulsified composition |
FR2851573A1 (fr) * | 2003-02-20 | 2004-08-27 | Rhodia Chimie Sa | Composition nettoyante ou rincante pour surfaces dures |
FR2851572A1 (fr) * | 2003-02-20 | 2004-08-27 | Rhodia Chimie Sa | Composition nettoyante ou rincante pour surfaces dures |
US20050197271A1 (en) * | 2004-02-24 | 2005-09-08 | Kao Corporation | Process for producing an emulsion |
WO2012078154A1 (en) * | 2010-12-09 | 2012-06-14 | Colgate-Palmolive Company | Cleansing composition |
EP2865740A1 (de) * | 2013-10-24 | 2015-04-29 | Werner & Mertz GmbH | Flüssiges Scheuermittel |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8328991D0 (en) * | 1983-10-31 | 1983-11-30 | Unilever Plc | Liquid scouring compositions |
FR2738255B1 (fr) * | 1995-09-05 | 1997-10-17 | Talc De Luzenac | Composition de nettoyage a base de savon presentant de faibles proprietes dessechantes, et procede de preparation |
US7715821B2 (en) | 2005-02-18 | 2010-05-11 | Alcatel-Lucent Usa Inc. | Method of updating a unique call back number for a wireless emergency call |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3149078A (en) * | 1960-06-27 | 1964-09-15 | Colgate Palmolive Co | Liquid abrasive cleanser |
US3324038A (en) * | 1964-04-17 | 1967-06-06 | Procter & Gamble | Detergent composition |
US3328309A (en) * | 1963-10-21 | 1967-06-27 | Gen Aniline & Film Corp | Stabilized liquid heavy duty detergent composition |
US3346504A (en) * | 1962-08-10 | 1967-10-10 | Procter & Gamble | Detergent compositions |
US3346873A (en) * | 1962-08-10 | 1967-10-10 | Procter & Gamble | Liquid detergent composition containing solubilizing electrolytes |
US3351557A (en) * | 1964-10-06 | 1967-11-07 | Procter & Gamble | Detergent compositions |
-
1966
- 1966-12-20 US US603098A patent/US3520818A/en not_active Expired - Lifetime
-
1967
- 1967-12-12 DE DE1967P0043582 patent/DE1617193B2/de active Granted
- 1967-12-15 FR FR132784A patent/FR1548948A/fr not_active Expired
- 1967-12-18 FI FI673367A patent/FI48479C/fi active
- 1967-12-18 NO NO171023A patent/NO121800B/no unknown
- 1967-12-18 FI FI03367/67A patent/FI48479B/fi active
- 1967-12-19 DK DK634967AA patent/DK128377B/da unknown
- 1967-12-19 GB GB57565/67A patent/GB1167597A/en not_active Expired
- 1967-12-19 BE BE708198D patent/BE708198A/xx unknown
- 1967-12-19 SE SE17407/67A patent/SE344471B/xx unknown
- 1967-12-20 NL NL6717424A patent/NL6717424A/xx unknown
-
1968
- 1968-02-12 CH CH199768A patent/CH505198A/de not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3149078A (en) * | 1960-06-27 | 1964-09-15 | Colgate Palmolive Co | Liquid abrasive cleanser |
US3346504A (en) * | 1962-08-10 | 1967-10-10 | Procter & Gamble | Detergent compositions |
US3346873A (en) * | 1962-08-10 | 1967-10-10 | Procter & Gamble | Liquid detergent composition containing solubilizing electrolytes |
US3328309A (en) * | 1963-10-21 | 1967-06-27 | Gen Aniline & Film Corp | Stabilized liquid heavy duty detergent composition |
US3324038A (en) * | 1964-04-17 | 1967-06-06 | Procter & Gamble | Detergent composition |
US3351557A (en) * | 1964-10-06 | 1967-11-07 | Procter & Gamble | Detergent compositions |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3956158A (en) * | 1974-01-07 | 1976-05-11 | Lever Brothers Company | Pourable liquid compositions |
US4245022A (en) * | 1975-10-13 | 1981-01-13 | Fuji Xerox Co., Ltd. | Dry electrophotographic developers |
US4122025A (en) * | 1976-04-29 | 1978-10-24 | Henkel Kommanditgesellschaft Auf Aktien | Liquid scouring cleaning compositions containing cristobalite |
US4786369A (en) * | 1986-05-05 | 1988-11-22 | Go-Jo Industries, Inc. | Integral dry abrasive soap powders |
JPH0234699A (ja) * | 1988-06-13 | 1990-02-05 | Unilever Nv | 液体洗剤組成物 |
JPH0234700A (ja) * | 1988-06-13 | 1990-02-05 | Unilever Nv | 液体洗剤組成物 |
AU627461B2 (en) * | 1988-06-13 | 1992-08-27 | Unilever Plc | Liquid detergent compositions |
US5147576A (en) * | 1988-06-13 | 1992-09-15 | Lever Brothers Company, Division Of Conopco, Inc. | Liquid detergent composition in the form of lamellar droplets containing a deflocculating polymer |
JP2693827B2 (ja) | 1988-06-13 | 1997-12-24 | ユニリーバー・ナームローゼ・ベンノートシヤープ | 液体洗剤組成物 |
US6323246B1 (en) | 1990-06-15 | 2001-11-27 | Shiseido Company, Ltd. | Complex and emulsified composition |
US5866040A (en) * | 1990-06-15 | 1999-02-02 | Shiseido Company, Ltd. | Complex and emulsified composition |
FR2851573A1 (fr) * | 2003-02-20 | 2004-08-27 | Rhodia Chimie Sa | Composition nettoyante ou rincante pour surfaces dures |
FR2851572A1 (fr) * | 2003-02-20 | 2004-08-27 | Rhodia Chimie Sa | Composition nettoyante ou rincante pour surfaces dures |
WO2004083354A1 (fr) * | 2003-02-20 | 2004-09-30 | Rhodia Chimie | Composition nettoyante ou rincante pour surfaces dures |
US7923428B2 (en) * | 2003-02-20 | 2011-04-12 | Rhodia Chimie | Composition for cleaning or rinsing hard surfaces |
US20060217286A1 (en) * | 2003-02-20 | 2006-09-28 | Geoffroy Cedric | Composition for cleaning or rinsing hard surfaces |
US7495031B2 (en) * | 2004-02-24 | 2009-02-24 | Kao Corporation | Process for producing an emulsion |
US20050197271A1 (en) * | 2004-02-24 | 2005-09-08 | Kao Corporation | Process for producing an emulsion |
WO2012078154A1 (en) * | 2010-12-09 | 2012-06-14 | Colgate-Palmolive Company | Cleansing composition |
EP2786744A1 (en) * | 2010-12-09 | 2014-10-08 | Colgate-Palmolive Company | Cleansing composition |
US9622943B2 (en) | 2010-12-09 | 2017-04-18 | Colgate-Palmolive Company | Cleansing compositions |
US10912725B2 (en) | 2010-12-09 | 2021-02-09 | Colgate-Palmolive Company | Cleansing composition |
EP2865740A1 (de) * | 2013-10-24 | 2015-04-29 | Werner & Mertz GmbH | Flüssiges Scheuermittel |
Also Published As
Publication number | Publication date |
---|---|
GB1167597A (en) | 1969-10-15 |
SE344471B (xx) | 1972-04-17 |
CH505198A (de) | 1971-05-14 |
BE708198A (xx) | 1968-06-19 |
FR1548948A (xx) | 1968-12-06 |
NO121800B (xx) | 1971-04-13 |
DE1617193B2 (de) | 1976-11-11 |
FI48479C (fi) | 1974-10-10 |
FI48479B (xx) | 1974-07-01 |
NL6717424A (xx) | 1968-06-21 |
DE1617193A1 (de) | 1971-02-25 |
DK128377B (da) | 1974-04-22 |
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