US3178370A - Milled detergent bar - Google Patents
Milled detergent bar Download PDFInfo
- Publication number
- US3178370A US3178370A US261506A US26150663A US3178370A US 3178370 A US3178370 A US 3178370A US 261506 A US261506 A US 261506A US 26150663 A US26150663 A US 26150663A US 3178370 A US3178370 A US 3178370A
- Authority
- US
- United States
- Prior art keywords
- bar
- weight
- sodium
- alkyl
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0069—Laundry bars
-
- 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
- C11D3/10—Carbonates ; Bicarbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/14—Soil treatment digest, polyelectrolytes
Definitions
- This invention relates to detergent compositions and processes for preparing said compositions. Specifically, this invention relates to a detergent laundry bar which has acceptable sudsing characteristics in warm and cool, hard and soft water; which has an acceptable wear rate; which has acceptable feel, and which has a pleasing appearance. This invention also relates to a process for preparing said detergent laundry bar and a process for neutralizing a detergent material by a dry-mix method, the neutralized detergent material being useful, for example, in the preparation of said detergent laundry bar.
- An object of this invention is to provide a synthetic detergent laundry bar which will be inexpensive and have the acceptable features hereinbefore enumerated, and a process for preparing said bar.
- a further object of this invention is to provide a process for dry neutralization of detergent materials.
- the first object of this invention can be achieved by formulating a homogeneous mechanically worked synthetic detergent bar consisting essentially of: (A) from about 12% to about 30% by weight of detergent surfactant selected from the group consisting of alkali and alkaline earth metal alkyl aryl sulfonates, alkyl sulfonates, alkyl ethylene oxide ether sulfates, acyl N-methyl taurides, alkyl sulfates, and acyl monoglyceride sulfates; (B) from about 10% to about 25% by weight of sodium tripolyphosphate; (C) from about 25% to about 55% by weight of sodium bicarbonate; (D) from about 2% to about 15% by weight of trisodium orthophosphate; (E) from to about by weight of :amide selected from the group consisting of ammonia amides, monoethanol amides, and diethanol amides of fatty acids having an acyl chain of from about 8 to about 18 carbon atoms
- Ingredients (A) through (D) and (G) in the above formulation are essential to the preparation of an effective and acceptable laundry detergent bar.
- the detergent surfactant (active) is essential to provide cleaning and sudsing and to act as a plasticizer to hold the formulaice tion in the shape of a bar.
- the bar When less than about 12% by weight of the bar is detergent surfactant, the bar will not give acceptable cleaning and sudsing. Also, the bar will not have satisfactory strength since it will be diflicult to weld the bar together during extrusion.
- detergent surfactants examples include:
- the alkyl group can be derived from alcohol derivatives, e.g., halides, prepared from naturally occurring glycerides such as coconut oil, palm oil, etc., or from petroleum or olefins such as the propylene trimer, tetramer, and pentamer.
- the aryl group can be either benzene or naphthalene. Examples of these detergent surfactants include sodium tetrapropylene benzene sulfonate and sodium n-dodecyl benzene sulfonate.
- alkyl sulfates (a) alkyl sulfates, (b) alkyl sulfonates, and (0) alkyl ethylene oxide ether sulfates wherein said alkyl groups contain from about 8 to about 20 carbon atoms and wherein said alkyl ethylene oxide ether sulfates contain from one to about nine moles of ethylene oxide per molecule.
- Said alkyl groups can be derived from alkyl derivatives such as halides or from fatty alcohols which are normally derived from naturally occurring glycerides (e.g., tallow, coconut oil, palm oil, soybean oil, lard, etc.), but which can also be derived synthetically (e.g., from fatty acids prepared by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process).
- the alkyl groups can also be derived from other sources (e.g., olefins).
- detergent surfactants include sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, sodium lauryl sulfate, sodium dodecyl sulfonate, and the sodium salt of the sulfated condensation product between one mole of coconut alcohol and three moles of ethylene oxide.
- acyl N- methyl taurides and acyl monoglyceride sulfates wherein said acyl groups contain from about 8 to about 20 carbon atoms.
- Said acyl groups are normally derived from naturally occurring glycerides (e.g., tallow, coconut oil, palm oil, soybean oil, lard, etc.), but can also be derived synthetically (e.g., by oxidation of petroleum, or by hydrogenation of carbon monoxide by theFischer-Tropsch process).
- these detergent surfactants include sodium N-metyhl N-coconut oil acid taurate and sodium coconut monoglyceride sulfate.
- the alkyli metals preferred herein are sodium and potassium.
- the preferred alkaline earth metals are calcium and magnesium.
- the sodium tripolyphosphate is added to the bar formulation as a cleaning aid (detergency builder), a pH buffer, and to bind water. If less than about 10% by weight of the bar is sodium tripolyphosphate (anhydrous basis), the result is an unacceptable loss in cleaning ability of the bar, and if more than about 25% by weight of the bar is used, there is no improvement in cleaning advantage over 25%. About 18% by weight of the bar is preferred. If desired, sodium tripolyphosphate can be hydrated (preferably before the bar is formed) to prevent frosting of the bar wherein crystals of sodium tripolyphosphate hexahydrate are formed on the surface of the bar in the presence of moisture. Sodium tripolyphosphate is selected rather than pyroor meta-phosphates because of better cleaning performance. Frosting does not affect the eflicacy of the bar, but merely presents an unusual appearance.
- the sodium bicarbonate serves several functions. It is a pH buffer which keeps the pH of the bar within an acceptable range for contact with the skin, i.e., from about 8 to about 11, and provides bulk for the bar without adversely affecting other properties. For example, it does not cause frosting of the bar and the solubility characteristics are suitable. It is also inexpensive and has cleansing properties of its own. From about 25% to about 55% and preferably about 32% by weight of the bar gives acceptable bulk to the bar without adversely diluting the effects of the other ingredients.
- the trisodium orthophosphate aids in forming an acceptable bar.
- the trisodium orthophosphate is a pH buffer and is a cleaning aid (detergency builder) in much the same way that sodium tripolyphosphate is.
- the trisodium orthophosphate is primarily added for the purpose of modifying the processing characteristics of the formula and the feel of the bar. It has been found surprisingly that trisodium orthophosphate modifies the normally sticky nature of the active, especially sodium alkyl benzene sulfonate, to permit working the formulation. From about 2% to about 15% and preferably about 5% by weight gives proper processing characteristics. With less the product is too sticky to process easily and with more it is too dry to process easily.
- the total of the active, the sodium tripolyphosphate, the sodium bicarbonate, and the trisodium orthophosphate should be at least about 75% by weight of the bar, preferably from about 85% to about 92% by weight.
- the amide is added optionally to the bar as a suds builder for the active. It is normally preferred to use about 2% by weight of the bar, but from to about by weight of the bar can be used. Sudsing is poorer with smaller amounts of amide and when too much amide is used, the product becomes too sticky.
- the amide is also very useful in that it acts in the above proportions as a processing aid in forming the bar.
- the amide softens the composition during processing which aids the mechanical working necessary to form a bar.
- the amide also helps to weld the bar together. Although a bar can be prepared without amide, it is somewhat more diflicult to do so and sudsing qualities are considerably improved by the addition of amide.
- the amides which can be used in this invention are the ammonia, monoethanol, and diethanol amides of fatty acids having an acyl chain of from about 8 to about 18 carbon atoms.
- These acyl chains are normally derived from naturally occurring glycerides (e.g., coconut oil, palm oil, soybean oil, and tallow), but can be derived synthetically (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process).
- the silicate solids are added optionally as a detergency builder, as an aid in processing the bar when sodium alkyl benzene sulfonate flakes are used, as a raw material, and as a corrosion inhibitor. From about 0% to about 5%, and preferably 3%, by weight of silicate solids having an Na O:SiO ratio of from about 1.0:0.90 to about l.0:3.25 is used when silicate is a part of the formulation. As will hereinafter be discussed more fully, whether the silicate solids are added as liquid (aqueous) silicate or as powdered silicate depends upon the processing used in forming the bar.
- the silicate is added as liquid silicate to aid in processing formulations from sodium alkyl benzene sulfonate flakes. Without the water which is part of the liquid silicate, such formulations are diflicult to process.
- the silicate is normally added to the bar ingredients in its powdered form when a preparatory dry-neutralization process is used as hereinafter described. Regardless of the processing used, the use of too little silicate can give corrosion problems both in processing equipment and in use of the bar. It is preferred to have silicate present in the formulation, however, in many cases the silicate will be left out since the presence of silicate in the bar tends to promote the formation of a surface with a rough feel.
- Water is present in the bar in an amount from about 5% to about 25% by weight of the bar.
- This water in the finished bar is primarily combined water (water of hydration). Much of the water which is present is added to the formulation as a plasticizer during the processing steps. It is very difficult to process a bar formulation containing less than 5% water. Although it is possible to substitute other plasticizers for water, it is not normally practical in view of the excellent plasticizing characeristics of water.
- soil anti-redeposition agents such as sodium carboxymethylcellulose can be included in the formula for their usual purpose in amounts up to about 3% by weight of the bar. More than 3% appears to give no additional advantage over 3 Desirable additives are slip agents which are high molecular weight polymers such as tht ones sold under the trade name Polyox WSR 301. (These Polyox" resins are ultra high molecular weight condensates of ethylene oxide. The molecular weight condensates of ethylene oxide.
- the molecular weight is in the range of a million or more.
- These slip agents can be used in amounts up to about 1%, preferably 0.1% to 0.3%, by Weight of the bar to give the bar a smoother feel.
- Another type of slip agent which can be used in the material sold under the name Carbopols and which is a carboxyvinyl polymer of extremely high molecular weight.
- the bars of this invention are formed by (A) forming a homogeneous mixture of the ingredients hereinbefore described and thereafter (B) extruding said mixture at a temperature of from about F. to about F.
- the dry active can be mixed with the inorganic components and sufiicient plasticizing agent such as water or sodium silicate solution is added to plasticize the mixture so that when it is mechanically worked it is formed into a homogeneous composition (for example, the mixture can be milled into homongeneus flakes on conventional milling equipment).
- sufiicient plasticizing agent such as water or sodium silicate solution
- the active in aqueous paste form can be mixed with the inorganic compounds to form a slurry which can then be dried by conventional methods (e.g., drying on a drum to flakes or spray drying to a granule).
- the resulting homogeneous mixture, however formed, is then extruded on conventional equipment into bar form at a temperature in the range of from about 100 F. to about 170 F., preferably from about 120 F. to about 135 F.
- a temperature in these ranges can be achieved either by mechanically working the composition and thereby changing mechanical energy into thermal energy, or by a direct application of heat to the mixture.
- the temperature must be at least about 100 F. to effect a welding action, but it must not be too hot or there is a possibility the bar will become too soft and difficult to process.
- the bar can be cut into appropriate lengths and stamped, if desired, into various shapes or stamped with various indicia.
- A- preferred method of forming a homogeneous mixture and consequently of forming a bar of the type described above or other types is by dry neutralization, (3) when the active is produced in an acid form which will permit convenient processing.
- Dry neutralization refers to neutralization which occurs under conditions such that the amount of fluid present is insuflicient to destroy the particulate nature of solid particulate alkaline material used to effect said neutralization.
- Such a method is the following one for preparing a synthetic detergent (preferably alkyl aryl sulfonate) bar.
- the method consists essentially of: (A) spraying from about-l2 parts to about 40 parts of the liquid forms of alkyl aryl sulfonic acids, alkyl sulfonic acids, alkyl sulfuric acids, acyl monoglyceride sulfuric acids, and
- alkyl ethylene oxide ether sulfuric acids as hereinafter more fully described (preferably an alkyl aryl sulfonic acid phase which is prepared by sulfonating an alkyl aryl compound having an average molecular weight of from about 190 to about 280 with a sulfonating agent such as S oleum or sulfuric acid, said alkyl aryl sulfonic acid phase having a sulfonic acidzsulfuric acid ratio in the range of from about 50:1 to about :1 on a weight basis and containing up to about 25% water), onto from about 45 parts to about 93 parts of an agitated mixture wherein (1) at least a stoichiometric amount, sufficient to neutralize said acids, of said mixture is selected from the group consisting of solid particulate alkali metal and alkaline earth metal carbonates and bicarbonates (or sesquicarbonates) and (2) the remainder of said mixture is a builder and/or filler selected from the group consisting of: solid particulate
- the amount of inorganic salts and especially carbonates and bicarbonates present in the solid particulate mixture should preferably be sufficient to formulate a detergent bar of the composition hereinbefore described.
- the alkyl aryl compound is alkyl benzene with a molecular Weight of from about 208 to about 276;
- the agitated mixture comprises salts selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium sulfate, sodium tripolyphosphate, trisodium orthophosphate, disodium orthophosphate, tetrasodium pyrophosphate, disodium acid pyrophosphate, sodium trimetaphosphate, sodium chloride, potassium carbonate, potassium sulfate, potassium tripolyphosphate, potassium chloride, calcium carbonate, calcium sulfate, calcium pyrophosphate, and calcium chloride; and
- the agitated mixture contains from 0% to about 15% sodium carbonate and other inorganic salts in amounts such that the finished bar contains: (1) from about 10% to about 25% sodium tripolyphosphate, (2) from about 2% to about 15% trisodium phosphate, and (3) from about 25% to about sodium bicarbonate.
- the dry neutralization method of preparing the bars of this invention has wide applicability and scope.
- the process is one in which any liquid acid form of an anionic detergent surfactant which is capable of reacting with a basic carbonate to achieve neutralization is brought into contact with a solid particulate alkaline material capable of reacting with said acid form to produce neutralized anionic detergent surfactant and a by-product selected from the group consisting of Water, a gas, and combinations of water and gas to effect partial neutralization and thereafter effecting homogeneity of the mixture by mechanically Working said mixture to effect complete neutralization, the amount of fluid, including water, present being insufficient to destroy the particulate nature of said solid particulate alkaline material (before the mixture is mechanically worked).
- the types of actives, the acid forms of which are adaptable to dry neutralization, include:
- Alkyl aryl sulfonic acids having an average molecular weight of from about 200 to about 380.
- the liquid acid form of these materials will normally be found as a mixture of alkyl aryl sulfonic acid water and sulfuric acid.
- Examples of the liquid acid form include tetrapropylene benzene sulfonic acid, dodecylbenzene sulfonic acid and dodecylnaphthalene sulfonic acids.
- Alkyl sulfonic acids having from about 8 to about 20 carbon atoms, as, for example, dodecyl sulfonic acid, tallow alkyl sulfonic acid, and coconut alkyl sulfonic acid. These acids will normally be associated with water and sulfuric acid to form a liquid.
- Fatty acids and acyl monoglyceride sulfuric acids the acyl containing an average of from about 8 to about 20 carbon atoms, as for example, coconut oil fatty acids, oleic acid, etc., and the corresponding acyl monoglyceride sulfuric acids.
- the inorganic alkaline material is selected from the group consisting of solid particulate alkali and alkaline earth metal (e.g., sodium, potassium, lithium, calcium, barium and magnesium) carbonates and bicarbonates. This material is present in at least a sufiicient amount to neutralize all the acid added, including inorganic acids.
- Other inorganic builder and/or filler salts having a neutral to alkaline reaction reaction can be mixed in, if desired, with the carbonates and bicarbonates including aa'rasvo alkali and alkaline earth metal salts of halides, phosphates (rtho-, meta-, pyro-, tripoly-, etc.), borates, and sulfates. These materials are all in solid particulate form.
- the type of mechanical equipment which is used to effect homogeneity is any mixer, or combination of mixers capable of imparting mechanical work by a direct shearing action.
- mixers include: Roll mills (soap or paint mills-this is the preferred type of mixer); kneaders; extruders; plodders, attrition mills; edge running mills; etc.
- the amount of mechanical working needed to complete neutralization and effect homogeneity will depend upon the extent of contact originally present between the liquid acid form of the surfactant and the particulate inorganic salt.
- completeness of the neutralization can be achieved by having a finely-divided, agitated bed of the inorganic alkaline material and spraying onto said bed a finely divided spray of said dodecyl benzene sulfonic acid.
- the additional to of neutralization can then be achieved with a minimum amount (e.g., two passes through a 3-roll mill) of mechanical working.
- Example 1 Composition 1 2 3 Sodium tetrapropylene benzene sulfonate flakes,
- compositions were formulated into bars by mixing the detergent surfactant and inorganic materials together and then adding the other ingredients, particularly the silicate solution.
- the resulting mixture was then milled on heated rolls to form homogeneous flakes of the composition and these resulting flakes were fed to a plodder and extruded in the shape of a continuous bar at a temperature of about 135 F.
- the continuous bar was out into small bars.
- dodecyl naphthalene sulfonic acid coconut alkyl sulfonic acid, coconut alkyl sulfuric acid, coconut alkyl ethylene oxide ether sulfuric acid containing an average of three ethylene oxide groups, or coconut fatty acids are neutralized in a manner similar to that used for the dodecyl benzene sulfonic acid in this example, comparable results are obtained.
- sodium bicarbonate, potassium bicarbonate, potassium carbonate, magnesium carbonate, and calcium carbonate are substituted for the sodium carbonate in the above formula on an equivalent basis in an amount sufficient to neutralize the acid mix, comparable results are obtained in that the acid mix is neutralized.
- a homogeneous synthetic, mechanically worked, miller detergent bar consisting essentially of:
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- 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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE634272D BE634272A (fr) | 1963-02-27 | ||
US261506A US3178370A (en) | 1963-02-27 | 1963-02-27 | Milled detergent bar |
GB34749/63A GB1013992A (en) | 1963-02-27 | 1963-09-03 | Detergent composition |
FR961357A FR1422035A (fr) | 1963-02-27 | 1964-01-23 | Composition détergente |
ES296801A ES296801A1 (es) | 1963-02-27 | 1964-02-24 | Procedimiento de producción de un detergente sintético homogéneo |
OA50014A OA00061A (fr) | 1963-02-27 | 1964-02-26 | Composition détergente. |
NL6401892A NL6401892A (fr) | 1963-02-27 | 1964-02-27 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US261506A US3178370A (en) | 1963-02-27 | 1963-02-27 | Milled detergent bar |
MX7274863 | 1963-06-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3178370A true US3178370A (en) | 1965-04-13 |
Family
ID=26640856
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US261506A Expired - Lifetime US3178370A (en) | 1963-02-27 | 1963-02-27 | Milled detergent bar |
Country Status (6)
Country | Link |
---|---|
US (1) | US3178370A (fr) |
BE (1) | BE634272A (fr) |
ES (1) | ES296801A1 (fr) |
GB (1) | GB1013992A (fr) |
NL (1) | NL6401892A (fr) |
OA (1) | OA00061A (fr) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3392120A (en) * | 1964-03-19 | 1968-07-09 | Fmc Corp | Dry detergent mixtures |
US3434974A (en) * | 1965-07-02 | 1969-03-25 | Colgate Palmolive Co | Continuous manufacture of detergent laundry bars |
US3481880A (en) * | 1968-11-12 | 1969-12-02 | Colgate Palmolive Co | Detergent laundry bars |
US3639286A (en) * | 1968-05-28 | 1972-02-01 | Mario Ballestra | Synthetic detergent in bar or cake form and the method to manufacture same |
US4150001A (en) * | 1977-05-26 | 1979-04-17 | Lever Brothers Company | Detergent bars containing alkaline earth metal hydrogen orthophosphate |
US4278571A (en) * | 1980-05-28 | 1981-07-14 | The Procter & Gamble Company | Surfactant cake compositions |
US4759865A (en) * | 1986-11-06 | 1988-07-26 | Colgate-Palmolive Company | Pasty acid detergent composition |
US4935158A (en) * | 1986-10-30 | 1990-06-19 | Aszman Harry W | Solid detergent cleaning composition, reusable cleaning pad containing same and method of manufacture |
US5108642A (en) * | 1986-10-30 | 1992-04-28 | Colgate-Palmolive Company | Solid detergent cleaning composition, and method of manufacturing |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5527489A (en) * | 1990-10-03 | 1996-06-18 | The Procter & Gamble Company | Process for preparing high density detergent compositions containing particulate pH sensitive surfactant |
US5571287A (en) * | 1993-01-11 | 1996-11-05 | Colgate-Palmolive Company | Soap composition containing sodium pyrophosphate |
WO1997042282A1 (fr) | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Compositions detergentes a base de polymeres de type polyamine a dispersion amelioree des salissures |
WO1998053040A1 (fr) * | 1997-05-22 | 1998-11-26 | The Procter & Gamble Company | Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees |
WO1999001535A1 (fr) * | 1997-07-02 | 1999-01-14 | The Procter & Gamble Company | Compositions de pain renfermant un tensioactif a base de sulfonate d'alkylglycerylether |
US6352966B1 (en) | 2000-05-19 | 2002-03-05 | Albemarle Corporation | Cleansing bars |
US20030211955A1 (en) * | 2001-09-28 | 2003-11-13 | Unilever Home & Personal Care Usa, Division Of Conopco | Toilet bar having a latent acidifier |
US6660699B2 (en) | 2001-09-28 | 2003-12-09 | Unilever Home & Personal Care Usa | Toilet bar having a latent acidifier |
WO2018063953A1 (fr) * | 2016-09-30 | 2018-04-05 | Dow Global Technologies Llc | Pains de détergent |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0122664A3 (fr) * | 1983-04-14 | 1987-05-27 | THE PROCTER & GAMBLE COMPANY | Gâteau mélangé à sec comprenant un sel de métal alcalino-terreux/composé tensio-actif de métal alcalin pour dispenseur de dosage de plus longue durée |
GB8906572D0 (en) * | 1989-03-22 | 1989-05-04 | Unilever Plc | Detergent composition |
GB2234982A (en) * | 1989-08-10 | 1991-02-20 | Unilever Plc | Detergent laundry bars |
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US2205037A (en) * | 1937-09-30 | 1940-06-18 | Du Pont | Extrusion of higher alkyl sulphate salts |
US2412819A (en) * | 1945-07-21 | 1946-12-17 | Mathieson Alkali Works Inc | Detergent briquette |
US2678921A (en) * | 1948-08-04 | 1954-05-18 | Colgate Palmolive Co | Process of producing a milled nonsoap detergent in bar form |
US2845391A (en) * | 1958-07-29 | Synthetic detergent bar | ||
US2874123A (en) * | 1954-09-07 | 1959-02-17 | Colgate Palmolive Co | Process for the preparation of granular compositions |
CA586529A (fr) * | 1959-11-03 | Blinka Joseph | Compositions detersives | |
CA587872A (fr) * | 1959-12-01 | M. Livengood Samuel | Compositions detersives synthetiques | |
CA595701A (en) * | 1960-04-05 | J. Weaver Leo | Method of bleaching alkyl aryl sulfonic acids | |
US2982736A (en) * | 1961-05-02 | Method of preparedg washing | ||
US3081267A (en) * | 1959-12-31 | 1963-03-12 | Procter & Gamble | Detergent tablet and process for making same |
-
0
- BE BE634272D patent/BE634272A/xx unknown
-
1963
- 1963-02-27 US US261506A patent/US3178370A/en not_active Expired - Lifetime
- 1963-09-03 GB GB34749/63A patent/GB1013992A/en not_active Expired
-
1964
- 1964-02-24 ES ES296801A patent/ES296801A1/es not_active Expired
- 1964-02-26 OA OA50014A patent/OA00061A/fr unknown
- 1964-02-27 NL NL6401892A patent/NL6401892A/xx unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2845391A (en) * | 1958-07-29 | Synthetic detergent bar | ||
CA586529A (fr) * | 1959-11-03 | Blinka Joseph | Compositions detersives | |
CA587872A (fr) * | 1959-12-01 | M. Livengood Samuel | Compositions detersives synthetiques | |
CA595701A (en) * | 1960-04-05 | J. Weaver Leo | Method of bleaching alkyl aryl sulfonic acids | |
US2982736A (en) * | 1961-05-02 | Method of preparedg washing | ||
US2205037A (en) * | 1937-09-30 | 1940-06-18 | Du Pont | Extrusion of higher alkyl sulphate salts |
US2412819A (en) * | 1945-07-21 | 1946-12-17 | Mathieson Alkali Works Inc | Detergent briquette |
US2678921A (en) * | 1948-08-04 | 1954-05-18 | Colgate Palmolive Co | Process of producing a milled nonsoap detergent in bar form |
US2874123A (en) * | 1954-09-07 | 1959-02-17 | Colgate Palmolive Co | Process for the preparation of granular compositions |
US3081267A (en) * | 1959-12-31 | 1963-03-12 | Procter & Gamble | Detergent tablet and process for making same |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3392120A (en) * | 1964-03-19 | 1968-07-09 | Fmc Corp | Dry detergent mixtures |
US3434974A (en) * | 1965-07-02 | 1969-03-25 | Colgate Palmolive Co | Continuous manufacture of detergent laundry bars |
US3639286A (en) * | 1968-05-28 | 1972-02-01 | Mario Ballestra | Synthetic detergent in bar or cake form and the method to manufacture same |
US3481880A (en) * | 1968-11-12 | 1969-12-02 | Colgate Palmolive Co | Detergent laundry bars |
US4150001A (en) * | 1977-05-26 | 1979-04-17 | Lever Brothers Company | Detergent bars containing alkaline earth metal hydrogen orthophosphate |
US4278571A (en) * | 1980-05-28 | 1981-07-14 | The Procter & Gamble Company | Surfactant cake compositions |
US4935158A (en) * | 1986-10-30 | 1990-06-19 | Aszman Harry W | Solid detergent cleaning composition, reusable cleaning pad containing same and method of manufacture |
US5108642A (en) * | 1986-10-30 | 1992-04-28 | Colgate-Palmolive Company | Solid detergent cleaning composition, and method of manufacturing |
US4759865A (en) * | 1986-11-06 | 1988-07-26 | Colgate-Palmolive Company | Pasty acid detergent composition |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5527489A (en) * | 1990-10-03 | 1996-06-18 | The Procter & Gamble Company | Process for preparing high density detergent compositions containing particulate pH sensitive surfactant |
US5571287A (en) * | 1993-01-11 | 1996-11-05 | Colgate-Palmolive Company | Soap composition containing sodium pyrophosphate |
WO1997042282A1 (fr) | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Compositions detergentes a base de polymeres de type polyamine a dispersion amelioree des salissures |
WO1998053040A1 (fr) * | 1997-05-22 | 1998-11-26 | The Procter & Gamble Company | Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees |
WO1999001535A1 (fr) * | 1997-07-02 | 1999-01-14 | The Procter & Gamble Company | Compositions de pain renfermant un tensioactif a base de sulfonate d'alkylglycerylether |
US6352966B1 (en) | 2000-05-19 | 2002-03-05 | Albemarle Corporation | Cleansing bars |
US20030211955A1 (en) * | 2001-09-28 | 2003-11-13 | Unilever Home & Personal Care Usa, Division Of Conopco | Toilet bar having a latent acidifier |
US6660699B2 (en) | 2001-09-28 | 2003-12-09 | Unilever Home & Personal Care Usa | Toilet bar having a latent acidifier |
US6809070B2 (en) | 2001-09-28 | 2004-10-26 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Toilet bar having a latent acidifier |
EP1900802A2 (fr) | 2001-09-28 | 2008-03-19 | Unilever Plc | Savon de toilette renfermant un acidifiant latent |
WO2018063953A1 (fr) * | 2016-09-30 | 2018-04-05 | Dow Global Technologies Llc | Pains de détergent |
US11149237B2 (en) | 2016-09-30 | 2021-10-19 | Dow Global Technologies Llc | Detergent bars |
Also Published As
Publication number | Publication date |
---|---|
GB1013992A (en) | 1965-12-22 |
BE634272A (fr) | |
OA00061A (fr) | 1966-01-15 |
ES296801A1 (es) | 1964-05-01 |
NL6401892A (fr) | 1964-08-28 |
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