US2734870A - Rnon-soap synthetic-detergent - Google Patents
Rnon-soap synthetic-detergent Download PDFInfo
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- US2734870A US2734870A US2734870DA US2734870A US 2734870 A US2734870 A US 2734870A US 2734870D A US2734870D A US 2734870DA US 2734870 A US2734870 A US 2734870A
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- wax
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- detergent
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- 239000000271 synthetic detergent Substances 0.000 title description 11
- 239000000344 soap Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 45
- 239000003599 detergent Substances 0.000 claims description 30
- 239000012188 paraffin wax Substances 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001993 wax Substances 0.000 description 44
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 14
- -1 polypropylene Polymers 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 235000019809 paraffin wax Nutrition 0.000 description 10
- 235000019271 petrolatum Nutrition 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 235000021314 Palmitic acid Nutrition 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
Definitions
- the invention t relates to a new and useful detergent composition. More particularly, it relates-to a "detergent composition which can the cast, "molded, or framed in conventionalmanner to-produce a detergent bar having superior properties.
- detergent bar is that of finding a binder which would hold the active detergent components together and give the bar suitable physical characteristics.
- An acceptable bar should be firm, cohesive, smooth and pleasant to the -touch,'lather and suds well in hot and coldwatenand .be resistant to water in the sense that it does notbecome .soft and slimy in use or wastev away rapidly when wet,
- compositions of bothofthe'above embodiments derive theirprimary valuable.characteristicsffrom the wax and organic sulfuric reaction producttype deter- 25 .gent components.
- Thepresence of the polar-material considerably simplifiesthe process of makingthe detergent compositions and enhances the already thoroughly acceptable properties of thejp'roduct.
- the compositions of both ofthe above embodiments-have areasonable tolerance for the incorporation of inorganic builders which, although insoluble, maybe-dispersed in the .bar to improve the over-alldetersive action; operable ha'rs may contain up to, about. 25 by weight of. any: of .the usual inorganic builders such as alkali metal esulfates, alkali metal phosphates, alkali metal.
- polyphosphates and alkali metal silicates are polyphosphates and alkali metal silicates. -tlt-ispreferable, however, to.ke ep the inorganic salt content of the finished bar below about 12% of its total weightin ordernto-avoid a tendency towardfrosting, -i. .-.e., the formation -ofinorganicfsalt 40 crystals on its surface.
- Thepreferred wax for use in compoundingathe compositions of theri-nvention is. preferably -:a paraffin wax derived from";-,petroleum shaving a -melting ,-.point .above ..about .-125 -F. andhaviug a relatively. low oilcontent, desirably-below about 2% by-weight.
- the ware may-be either crystalline or amorphousand its melt-ing point may :rangeupto-about 175 F.
- Theordinaryede-oiledpetroieum waxes of commerce are entirely. satisfactory for compounding-the detergent compositions of thei-nvention. .It should be understood that modificationsof the characteristics ot, paraffin -Wax by the incorporation -,-of small amounts; of vegetable waxes -is -.not precluded.
- F. -These:prodnets are characterized by alarge. hydrophobic group con- -s-isti-ngsalmostentirely-of hydrocarbon material and the smaller hydrophilic sulfuric acid residue.
- the metal-co"mponent of a s-alt of the organist sulfuric reaction product is ordinarily :sodiurn, but otheralkalimetals and: alkaline earth metals,especially magnesium, may: beipresenttasdhe metallic component.
- -Materials ofithis general description have .the. common property-of remaining highly dispersed in .thewvax matrix when thetcompositionis coldgso th'at .the finished solid is characterized by macroscopic -zhomogeneity.
- the organic sulfuric reaction product type detergent must be soluble in hot paraffin wax.
- any particular organic sulfuric reaction product type detergent and hence its suitability for use in composing the compositions of this invention, is readily determined by melting paraffin wax, heating it to about 300 F. and stirring the detergent into the wax. Suitable detergents dissolve in the wax forming a clear transparent liquid solution at concentrations above 30% by weight.
- Organic sulfuric reaction product type detergents having a branched alkyl group containing 10 to 20 carbon atoms, especially the alkyl aryl sulfonates described in Lewis Patent 2,477,383, are highly soluble in paraffin wax.
- the Lewis detergent is prepared by polymerizing propylene, separating a polypropylene fraction boiling from about 325 to 520 F., alkylating a mononuclear aromatic hydrocarbon such as benzene, toluene or xylene with the polypropylene, sulfonating the alkyl aromatic hydrocarbon product and neutralizing the resultant sulfonic acid with an alkali metal hydroxide or with an alkaline earth metal hydroxide.
- the organic polar material which is desirably incorporated in the preferred composition of the invention is preferably a higher fatty acid, i. e., aliphatic monocarboxylic acid containing 10 to 20 carbon atoms, for example stearic acid, oleic acid, palmitic acid and lauric acid.
- the wax-synthetic detergent compositions of the invention will tolerate the addition of fairly substantial amounts of inorganic builders without too much sacrifice of their desirable bar-form properties.
- the alkali metal carbonates, phosphates, borates, and silicates which are generally known as alkaline builders can be tolerated up to a maximum amount of about by weight of the total bar.
- Neutral builders such as sodium sulfate and sodium chloride can be tolerated in similar amounts.
- perfume, coloring matter and fillers such as infusorial earth and bentonite and. the allied group of clays may be incorporated in the finished bar.
- paraffin wax was melted and heated to a temperature in the range about 250 to 325 F., and preferably in the range 275 to 300 F., and the synthetic detergent was stirred into the wax to dissolve it.
- the rate of solution and solubility of the detergent in the wax are low and the detergent-wax mixtures prepared at such temperatures tend to be macroscopically heterogeneous when cooled.
- the synthetic detergent tends to char, and color of the ultimate product is poor.
- the temperature preferably should not exceed 325 F.
- the addition of a higher fatty acid to the molten wax prior to the addition of the synthetic detergent greatly facilitated the dissolving of the detergent and brought about a marked reduction in the viscosity of the solution.
- the molten mixture may be poured into individual bar molds, or poured into a conventional frame and cooled until the mass solidifies, after which the mass is cut into bars.
- the mass may be cooled to a temeprature just below its solidification point and then extruded or pressed into bars.
- Example I 70 parts by weight of de-oiled paraffin wax having a melting point of 125 F. and an oil content below 2% by weight were heated to 310 F. 30 parts by weight of a sodium alkyl benzene sulfonate containing 12 to 15 carbon atoms in the alkyl chain were dissolved in the wax. Solution was accomplished by stirring the mixture for about 6 minutes. The fluidity of the solution was approximately that of hot molten wax. The solution was poured into a metal bar mold and cooled to room temperature. The bar separated from the mold without adhering to the metal. The bar was a light buff color and was similar to wax in consistency. The bar was smooth and pleasant to the touch, was perfectly homogeneous to visual inspection, and floated in water. When the bar was worked with the hands in the usual manner with hot or cold water, it lathered, but rather poorly.
- Example 2 60 parts by weight of the paraflin wax of Example 1 were heated to 300 F. 40 parts by weight of sodium polypropylene benzene sulfonate containing 12 to 15 carbon atoms in the polypropylene radicals were dissolved in the molten wax. The wax was cast in bar form as in Example 1. The lathering properties of this bar were considerably better than those of the bar in Example 1. The specific gravity of this bar was slightly less than 1.
- Example 3 47.5 parts by weight of the paraffin wax of Example 1 were melted and heated to 300 F. 52.5 parts by weight of a mixture of sodium polypropylene benzene sulfonate containing 12 to 15 carbon atoms in the polypropylene groups and sodium sulfate were incorporated in the molten wax. The ratio of sulfonate to sulfate in the solute was 60:40. The liquid dispersion produced had a considerably higher viscosity than the solutions of Examples 1 and 2 due to the salt content. The mixture was barely pourable at 300 F. The mixture was cast in bar form as in Example 1. The bar lathered well in hot and cold water, but frosted slightly after wetting because of the sodium sulfate content.
- Example 4 47.6 parts by weight of the wax of Example 1 were melted and heated to about 300 F. 9.6 parts by weight of palmitic acid were dissolved in the molten wax and then 42.8 parts by weight of a mixture of sodium polypropylene benzene sulfonate containing 12 to 15 carbon atoms in the polypropylene radicals and sodium sulfate were incorporated in the wax-acid solution. The ratio of sulfonate to sulfate in the latter solute was :10. The resulting dispersion was highly fluid and the apparent rate of solution of the sulfonate in the wax was rapid, the sulfonate apparently dissolving completely after 2 minutes of stirring. The resulting mixture was cast in bar form. The bar lathered well, but the foam broke more rapidly than the foams produced by the bars in Examples 1 to 3 inclusive, presumably because of the high fatty acid content of the bar.
- Example 5 52.4 parts by weight of the parafiin wax of Example 1 were melted and heated to about 300 F. 4.8 parts by weight of palmitic acid were dissolved in the molten wax and then 42.8 parts by weight of the sulfonate-sulfate mixture of Example 4 were incorporated in the wax-acid solution. The resultant mixture was cast in bar form. The resultant bar lathered well and the foam was more stable than the foam produced by the bar of Example 4, but not quite as stable as the foam produced by the bar of Example 2.
- Example 6 56.2 parts by weight of the paraifin wax of Example 1 were melted and heated to about 300 F. One part by weight of palmitic acid was dissolved in the molten wax and then 42.8 parts by weight of the sulfonate-sulfate mixture of Example 4 were incorporated in the wax-acid solution. The presence of the palmitic acid in this small amount noticeably increased the apparent rate of solution of the sulfonate and lowered the viscosity of the resulting mixture. The final mixture was cast in bar form. The bar lathered well in both hot and cold water and the foam produced was apparently identical with the foam produced by the bar of Example 2 with respect to stability.
- Example 7 52.3 parts by weight of the wax of Example 1 were melted and heated to about 300 F. 1.8 parts by weight of palmitic acid were dissolved in the molten wax and then 40.6 parts by weight of the sulfonate-sulfate mixture of Example 4 were incorporated in the solution. 5.3 parts by weight of glycerine were incorporated in the resultant mixture. The final mixture was cast in bar form. This bar was similar in all of its properties to the bar produced in Example 6.
- Example 8 57.7 parts by weight of a de-oiled paraflin wax having a melting point of 143 F. were melted and heated to about 300 F. 42.3 parts by weight of the sulfonatesulfate mixture of Example 4 were incorporated in the molten wax. The mixture was cast in bar form. The bar lathered well in both hot and cold water.
- Example 9 35 parts by weight of the paraflin wax of Example 1 were melted and heated to about 300 F. 5 parts by weight of palmitic acid were dissolved in the molten wax and then 60 parts by weight of the sulfonate-sulfate mixture of Example 4 were incorporated in the solution. The final mixture was cast in bar form. This bar had excellent lathering properties, and was apparently equal in this respect to a good grade of toilet soap. During prolonged use, the bar wore away smoothly and showed no tendency to soften or crumble when exposed to the usual conditions of household use.
- Example 10 45 parts by weight of the paratfin wax of Example 1 were melted and heated to about 300 F. 5 parts by weight of stearic acid were dissolved in the molten wax and then 50 parts by weight of an alkyl aryl sulfonate prepared by alkylating benzene with a propylene polymer fraction boiling over the range about 360 to 520 F., sulfonating the alkylate, and neutralizing the resultant sulfonic acid with sodium hydroxide, were dissolved in the wax-acid mixture. The resultant solution was cast in bar form. This bar had excellent lathering properties and was durable in ordinary household use.
- the bars prepared in all of the foregoing examples were macroscopically homogeneous as they left the mold and all of them retained their homogeneous appearance throughout prolonged use, with the exception of the bar produced in Example 3 which showed a tendency to frost.
- the materials of which each of the exemplified bars are formed do not appear to wet the surfaces of metallic molds and are readily freed from the mold when cooled.
- the exemplified bars may be remelted and recast without loss of homogeneity and apparently without change in any of the physical or chemical properties of the composition.
- a firm, cohesive and macroscopically homogeneous detergent bar consisting essentially of 40 to 60 parts by weight of parafiin wax, 2 to 5 parts by weight of a fatty acid containing 10 to 20 carbon atoms per molecule and 60 to 40 parts by weight of a mixture of water-soluble alkyl aryl sulfonates, the alkyl groups being propylene polymers containing predominantly from 12 to 15 carbon atoms.
- a firm, cohesive, macroscopically homogeneous detergent bar consisting essentially of 40 to 60 parts by weight of paraffin wax, 60 to 40 parts by weight of an alkyl benzene sulfonate detergent having 10 to 20 carbon atoms in its alkyl group, 1 to 10 parts by weight of a fatty acid containing 10 to 20 carbon atoms per molecule, and from 1 to 25 parts by weight of a water-soluble inorganic builder.
- a process for producing a macroscopically homogeneous detergent bar which comprises forming a mixture of molten paraffin wax and a higher fatty acid, heating the mixture to a temperature in the range 250 to 325 F., dissolving an alkyl benzene sulfonate detergent having 10 to 20 carbon atoms in its alkyl group in the hot mixture and cooling the solution to form a macroscopically homogeneous solid, the proportions of the components in the solution being 40 to 60 parts by weight of wax, 1 to 10 parts by weight of a fatty acid containing 10 to 20 carbon atoms per molecule and 60 to 40 parts by weight of sulfonate.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
United States Patent rNON-SOAP SYNTHETIC DE'I-ERGENT? BAR AllenlH. Lewis, Berkeley, Calih, "assignor "to California Research Corporatiom sanFrancisco, can, a corpo- 'ra'tionofDelaware No Drawing. Applica'tion Mayll, 1951, Serial N 0. 227,507
3 Claims. (CL 252-161) The invention t relates to a new and useful detergent composition. More particularly, it relates-to a "detergent composition which can the cast, "molded, or framed in conventionalmanner to-produce a detergent bar having superior properties.
*Inrecent years synthetic detergents, particularly the alkylzarylsulfonate detergents of "the type described in 'Lewis' U. S.'Patent No. 2,477,383, have won wide ac- "ceptance in household applications and-very large volumes of these materials are currently manufactured and sol'd. These synthetic detergents have been prepared for the consumer in powdered or granular form andsubstantially all of these materials-have-been marketed-in that form. The desirability of producing a synthetic detergent bar has long been recognized and extensive experimental workdiasbeendirected tothis end as'evidenced, for nexample, by yMcCutcheons paper entitled .Synthetic Detergents r in Barv Form, Soap, December 1949, page 3-3ret: seq. Despite: intense "effort in this .direction by a dargemumber of skilled research workers, no satisfa'cto'ry tsynthetio detergenti-bar-has beenproduced whichhas met irvithwvide consumer" acceptance. The 1 principal. problem encountered in an 'eftort to produce asynthetic; detergent bar is that of finding a binder which would hold the active detergent components together and give the bar suitable physical characteristics. An acceptable bar should be firm, cohesive, smooth and pleasant to the -touch,'lather and suds well in hot and coldwatenand .be resistant to water in the sense that it does notbecome .soft and slimy in use or wastev away rapidly when wet,
'Tparaflin Waxand 70.to 30 parts by weightof an'organic sulfuric react-ion'product type-detergent which is soluble in paratfin wax at a temperature inthe range 200 350 :F. can be cast,-mol'ded,'orframed to form a synthetic'detergent bar having'excellent physicaland de'tersive prop- Thesecompositions are produced by melting paraflin wax-andhea'tingit to a ternperature in'therange 200 to 350" "F., preferably 250'to 325 F., -and I stirring the organic 'ssulfuric reaction product type detergent into the J hot Lmolten waxto form a'clear, transparent liquid solu- ;tion, and cooling the ;-solution until it solidifies.
-..In :a preferred embodiment of the invention, 1thede- .tergent .con3position .contains -40 -to 60 ;parts .by weight mt paraflin wax.andinaddition.to the 'wax .and organic sulfuric reaction product type detergentasmall amount "ice not --exceeding about 10% "by weight based on the total detergent composition of a polar organic hampo'u'rtd,
especially of a higher fatty-acid.
ln pro'ducing the'preferred composition, 1 the wax-is 5 melted'and heated to atem'peraturein therange about 250 to 325 F. as-indicated above; the higher fatty-acid is added to the hot 'molten' wax, and-the'organic'sulfuric reaction product type detergent is' then 'dissolvedidthe hot mixture.
Three" important advantages attend 'the' use of anorganicpolar'eompound in this manner. Fir'st; the organic sulfuric reaction product type detergent dissolves "in the wax much more readily and much more rapidl'ywithconsiderably less agitation toprodnce'asolution of lowered viscosity; second, any tendency of 5 the organicsulfuric reaction-productto'drop out ofsolution'during cooling of the hot mixture and'toa'gglomerate, 'formingapp'reciably large particles-of' detergentmaterial'in" the bars produced and thus to render them macroscopicallyheterogeneous, is suppressed; and, third, the solid detergent" bars produced are plasticized by thepolar material. I
The compositions of bothofthe'above embodiments derive theirprimary valuable.characteristicsffrom the wax and organic sulfuric reaction producttype deter- 25 .gent components. Thepresence of the polar-material considerably simplifiesthe process of makingthe detergent compositions and enhances the already thoroughly acceptable properties of thejp'roduct. The compositions of both ofthe above embodiments-have areasonable tolerance for the incorporation of inorganic builders which, although insoluble, maybe-dispersed in the .bar to improve the over-alldetersive action; operable ha'rs may contain up to, about. 25 by weight of. any: of .the usual inorganic builders such as alkali metal esulfates, alkali metal phosphates, alkali metal. polyphosphates and alkali metal silicates. -tlt-ispreferable, however, to.ke ep the inorganic salt content of the finished bar below about 12% of its total weightin ordernto-avoid a tendency towardfrosting, -i. .-.e., the formation -ofinorganicfsalt 40 crystals on its surface.
.Thepreferred wax for use in compoundingathe compositions of theri-nvention is. preferably -:a paraffin wax derived from";-,petroleum shaving a -melting ,-.point .above ..about .-125 -F. andhaviug a relatively. low oilcontent, desirably-below about 2% by-weight. The ware may-be either crystalline or amorphousand its melt-ing point may :rangeupto-about 175 F. Theordinaryede-oiledpetroieum waxes of commerce are entirely. satisfactory for compounding-the detergent compositions of thei-nvention. .It should be understood that modificationsof the characteristics ot, paraffin -Wax by the incorporation -,-of small amounts; of vegetable waxes -is -.not precluded.
, -As tindi'cated ahove, theactive detersive--component=-of the lcomposition is a water-soluble salt' of ana-organic'isul- :furioreaction producbwhichis soluble in paraflin-wax -at a -temperature in the range -about- 200 350? F. =-These:prodnets are characterized by alarge. hydrophobic group con- -s-isti-ngsalmostentirely-of hydrocarbon material and the smaller hydrophilic sulfuric acid residue. The metal-co"mponent of a s-alt of the organist sulfuric reaction product is ordinarily :sodiurn, but otheralkalimetals and: alkaline earth metals,especially magnesium, may: beipresenttasdhe metallic component. -Materials ofithis general description have .the. common property-of remaining highly dispersed in .thewvax matrix when thetcompositionis coldgso th'at .the finished solid is characterized by macroscopic -zhomogeneity.
v.A very-considerable numberwof organic sulfuric-reaction .product type .-synthetic detergents .-aresdescni bedninnthe ,vliterature andvsev er-al of -.these nmaterials tare? articleswof com-mercerproduced 'incsubstantial -volume;.-tfor 'texample .alkyL-sulfates containing -1-0-.-to T20.carbon tatomsainathe alkyl group, alkyl sulfonates containing to carbon atoms in the alkyl group, sulfated monoglycerides of coconut oil fatty acids and especially alkyl aryl sulfonates containing 10 to 20 carbon atoms in the alkyl side chain. While these materials have similar physical properties in that they are water soluble and exhibit detersive and wetting properties and a structural similarity in that they are all characterized by a large hydrophobic group consisting almost entirely of hydrocarbon material and a smaller hydrophilic sulfuric acid residue, they are not all suitable for use as components of the compositions of this invention. To be useful here the organic sulfuric reaction product type detergent must be soluble in hot paraffin wax.
. Some of these materials are soluble and some are not.
Without exception it has been found that those which are soluble in the wax remain highly dispersed in the wax matrix when the solution is cooled until the wax solidifies and that the solid is macroscopically homogeneous. The solubility of any particular organic sulfuric reaction product type detergent, and hence its suitability for use in composing the compositions of this invention, is readily determined by melting paraffin wax, heating it to about 300 F. and stirring the detergent into the wax. Suitable detergents dissolve in the wax forming a clear transparent liquid solution at concentrations above 30% by weight.
Organic sulfuric reaction product type detergents having a branched alkyl group containing 10 to 20 carbon atoms, especially the alkyl aryl sulfonates described in Lewis Patent 2,477,383, are highly soluble in paraffin wax. The Lewis detergent is prepared by polymerizing propylene, separating a polypropylene fraction boiling from about 325 to 520 F., alkylating a mononuclear aromatic hydrocarbon such as benzene, toluene or xylene with the polypropylene, sulfonating the alkyl aromatic hydrocarbon product and neutralizing the resultant sulfonic acid with an alkali metal hydroxide or with an alkaline earth metal hydroxide.
The organic polar material which is desirably incorporated in the preferred composition of the invention is preferably a higher fatty acid, i. e., aliphatic monocarboxylic acid containing 10 to 20 carbon atoms, for example stearic acid, oleic acid, palmitic acid and lauric acid.
As indicated above, the wax-synthetic detergent compositions of the invention will tolerate the addition of fairly substantial amounts of inorganic builders without too much sacrifice of their desirable bar-form properties. For example, the alkali metal carbonates, phosphates, borates, and silicates which are generally known as alkaline builders can be tolerated up to a maximum amount of about by weight of the total bar. Neutral builders such as sodium sulfate and sodium chloride can be tolerated in similar amounts. Those skilled in the art will recognize that perfume, coloring matter and fillers such as infusorial earth and bentonite and. the allied group of clays may be incorporated in the finished bar. It must be recognized that the incorporation of insoluble material will proportionately increase the viscosity of the molten mix during the preparation of the product. The term consisting essentially employed in the appended claims is used in the sense that conventional fillers, builders, perfumes, etc., may be added to the waxdetergent compositions.
To prepare the compositions of the following examples paraffin wax was melted and heated to a temperature in the range about 250 to 325 F., and preferably in the range 275 to 300 F., and the synthetic detergent was stirred into the wax to dissolve it. At temperatures below 200 F. the rate of solution and solubility of the detergent in the wax are low and the detergent-wax mixtures prepared at such temperatures tend to be macroscopically heterogeneous when cooled. At temperatures much above 300 F. the synthetic detergent tends to char, and color of the ultimate product is poor. The temperature preferably should not exceed 325 F. When only wax and the synthetic detergent were employed in making the detergent composition, extensive agitation and the application of shearing force to the mixture was required to achieve homogeneity of the product. The addition of a higher fatty acid to the molten wax prior to the addition of the synthetic detergent greatly facilitated the dissolving of the detergent and brought about a marked reduction in the viscosity of the solution. After the detergent is dissolved in the wax the molten mixture may be poured into individual bar molds, or poured into a conventional frame and cooled until the mass solidifies, after which the mass is cut into bars. Alternatively, the mass may be cooled to a temeprature just below its solidification point and then extruded or pressed into bars.
Example I 70 parts by weight of de-oiled paraffin wax having a melting point of 125 F. and an oil content below 2% by weight were heated to 310 F. 30 parts by weight of a sodium alkyl benzene sulfonate containing 12 to 15 carbon atoms in the alkyl chain were dissolved in the wax. Solution was accomplished by stirring the mixture for about 6 minutes. The fluidity of the solution was approximately that of hot molten wax. The solution was poured into a metal bar mold and cooled to room temperature. The bar separated from the mold without adhering to the metal. The bar was a light buff color and was similar to wax in consistency. The bar was smooth and pleasant to the touch, was perfectly homogeneous to visual inspection, and floated in water. When the bar was worked with the hands in the usual manner with hot or cold water, it lathered, but rather poorly.
Example 2 60 parts by weight of the paraflin wax of Example 1 were heated to 300 F. 40 parts by weight of sodium polypropylene benzene sulfonate containing 12 to 15 carbon atoms in the polypropylene radicals were dissolved in the molten wax. The wax was cast in bar form as in Example 1. The lathering properties of this bar were considerably better than those of the bar in Example 1. The specific gravity of this bar was slightly less than 1.
Example 3 47.5 parts by weight of the paraffin wax of Example 1 were melted and heated to 300 F. 52.5 parts by weight of a mixture of sodium polypropylene benzene sulfonate containing 12 to 15 carbon atoms in the polypropylene groups and sodium sulfate were incorporated in the molten wax. The ratio of sulfonate to sulfate in the solute was 60:40. The liquid dispersion produced had a considerably higher viscosity than the solutions of Examples 1 and 2 due to the salt content. The mixture was barely pourable at 300 F. The mixture was cast in bar form as in Example 1. The bar lathered well in hot and cold water, but frosted slightly after wetting because of the sodium sulfate content.
Example 4 47.6 parts by weight of the wax of Example 1 were melted and heated to about 300 F. 9.6 parts by weight of palmitic acid were dissolved in the molten wax and then 42.8 parts by weight of a mixture of sodium polypropylene benzene sulfonate containing 12 to 15 carbon atoms in the polypropylene radicals and sodium sulfate were incorporated in the wax-acid solution. The ratio of sulfonate to sulfate in the latter solute was :10. The resulting dispersion was highly fluid and the apparent rate of solution of the sulfonate in the wax was rapid, the sulfonate apparently dissolving completely after 2 minutes of stirring. The resulting mixture was cast in bar form. The bar lathered well, but the foam broke more rapidly than the foams produced by the bars in Examples 1 to 3 inclusive, presumably because of the high fatty acid content of the bar.
Example 5 52.4 parts by weight of the parafiin wax of Example 1 were melted and heated to about 300 F. 4.8 parts by weight of palmitic acid were dissolved in the molten wax and then 42.8 parts by weight of the sulfonate-sulfate mixture of Example 4 were incorporated in the wax-acid solution. The resultant mixture was cast in bar form. The resultant bar lathered well and the foam was more stable than the foam produced by the bar of Example 4, but not quite as stable as the foam produced by the bar of Example 2.
Example 6 56.2 parts by weight of the paraifin wax of Example 1 were melted and heated to about 300 F. One part by weight of palmitic acid was dissolved in the molten wax and then 42.8 parts by weight of the sulfonate-sulfate mixture of Example 4 were incorporated in the wax-acid solution. The presence of the palmitic acid in this small amount noticeably increased the apparent rate of solution of the sulfonate and lowered the viscosity of the resulting mixture. The final mixture was cast in bar form. The bar lathered well in both hot and cold water and the foam produced was apparently identical with the foam produced by the bar of Example 2 with respect to stability.
Example 7 52.3 parts by weight of the wax of Example 1 were melted and heated to about 300 F. 1.8 parts by weight of palmitic acid were dissolved in the molten wax and then 40.6 parts by weight of the sulfonate-sulfate mixture of Example 4 were incorporated in the solution. 5.3 parts by weight of glycerine were incorporated in the resultant mixture. The final mixture was cast in bar form. This bar was similar in all of its properties to the bar produced in Example 6.
Example 8 57.7 parts by weight of a de-oiled paraflin wax having a melting point of 143 F. were melted and heated to about 300 F. 42.3 parts by weight of the sulfonatesulfate mixture of Example 4 were incorporated in the molten wax. The mixture was cast in bar form. The bar lathered well in both hot and cold water.
Example 9 35 parts by weight of the paraflin wax of Example 1 were melted and heated to about 300 F. 5 parts by weight of palmitic acid were dissolved in the molten wax and then 60 parts by weight of the sulfonate-sulfate mixture of Example 4 were incorporated in the solution. The final mixture was cast in bar form. This bar had excellent lathering properties, and was apparently equal in this respect to a good grade of toilet soap. During prolonged use, the bar wore away smoothly and showed no tendency to soften or crumble when exposed to the usual conditions of household use.
Example 10 45 parts by weight of the paratfin wax of Example 1 were melted and heated to about 300 F. 5 parts by weight of stearic acid were dissolved in the molten wax and then 50 parts by weight of an alkyl aryl sulfonate prepared by alkylating benzene with a propylene polymer fraction boiling over the range about 360 to 520 F., sulfonating the alkylate, and neutralizing the resultant sulfonic acid with sodium hydroxide, were dissolved in the wax-acid mixture. The resultant solution was cast in bar form. This bar had excellent lathering properties and was durable in ordinary household use.
The bars prepared in all of the foregoing examples were macroscopically homogeneous as they left the mold and all of them retained their homogeneous appearance throughout prolonged use, with the exception of the bar produced in Example 3 which showed a tendency to frost. The materials of which each of the exemplified bars are formed do not appear to wet the surfaces of metallic molds and are readily freed from the mold when cooled. The exemplified bars may be remelted and recast without loss of homogeneity and apparently without change in any of the physical or chemical properties of the composition.
I claim:
1. A firm, cohesive and macroscopically homogeneous detergent bar consisting essentially of 40 to 60 parts by weight of parafiin wax, 2 to 5 parts by weight of a fatty acid containing 10 to 20 carbon atoms per molecule and 60 to 40 parts by weight of a mixture of water-soluble alkyl aryl sulfonates, the alkyl groups being propylene polymers containing predominantly from 12 to 15 carbon atoms.
2. A firm, cohesive, macroscopically homogeneous detergent bar consisting essentially of 40 to 60 parts by weight of paraffin wax, 60 to 40 parts by weight of an alkyl benzene sulfonate detergent having 10 to 20 carbon atoms in its alkyl group, 1 to 10 parts by weight of a fatty acid containing 10 to 20 carbon atoms per molecule, and from 1 to 25 parts by weight of a water-soluble inorganic builder.
3. A process for producing a macroscopically homogeneous detergent bar which comprises forming a mixture of molten paraffin wax and a higher fatty acid, heating the mixture to a temperature in the range 250 to 325 F., dissolving an alkyl benzene sulfonate detergent having 10 to 20 carbon atoms in its alkyl group in the hot mixture and cooling the solution to form a macroscopically homogeneous solid, the proportions of the components in the solution being 40 to 60 parts by weight of wax, 1 to 10 parts by weight of a fatty acid containing 10 to 20 carbon atoms per molecule and 60 to 40 parts by weight of sulfonate.
References Cited in the file of this patent UNITED STATES PATENTS 2,175,285 Duncan Oct. 10, 1939 2,356,903 Wood Aug. 29, 1944 2,462,758 Malkemus Feb. 22, 1949 2,653,913 Van Dijck Sept. 29, 1953 2,678,921 Turck May 18, 1954 FOREIGN PATENTS 583,028 Great Britain Dec. 5, 1946 592,206 Great Britain Sept. 10, 1947
Claims (1)
1. A FIRM, COHESIVE AND MACROSCOPICALLY HOMOGENEOUS DETERGENT BAR CONSISTING ESSENTIALLY OF 40 TO 60 PARTS BY WEIGHT OF PARAFFIN WAX, 2 TO 5 PARTS BY WEIGHT OF A FATTY ACID CONTAINING 10 TO 20 CARBON ATOMS PER MOLECULE AND 60 TO 40 PARTS BY WEIGHT OF A MIXTURE OF WATER-SOLUBLE ALKYL ARYL SULFONATES, THE ALKYL GROUPS BEING PROPYLENE POLYMERS CONTAINING PREDOMINANTLY FROM 12 TO 15 CARBON ATOMS.
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US2734870A true US2734870A (en) | 1956-02-14 |
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US2734870D Expired - Lifetime US2734870A (en) | Rnon-soap synthetic-detergent |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2845391A (en) * | 1958-07-29 | Synthetic detergent bar | ||
US2858569A (en) * | 1955-07-01 | 1958-11-04 | Charles F J Dupuy | Method of producing synthetic detergent cakes |
US3055837A (en) * | 1958-10-08 | 1962-09-25 | George G Wittwer | Synthetic detergent cake and process for making the same |
US3150097A (en) * | 1961-04-18 | 1964-09-22 | Lever Brothers Ltd | Soap compositions |
US4100097A (en) * | 1977-02-02 | 1978-07-11 | The Hewitt Soap Company, Inc. | Low pH detergent bar |
US5211870A (en) * | 1992-03-11 | 1993-05-18 | The Procter & Gamble Company | Malodor-free cleansing bar composition containing zeolite odor controlling agent |
US5294363A (en) * | 1991-09-23 | 1994-03-15 | The Procter & Gamble Company | Mild personal cleansing bar composition with balanced surfactants, fatty acids, and paraffin wax |
US5300249A (en) * | 1991-09-23 | 1994-04-05 | The Procter & Gamble Company | Mild personal cleansing bar composition with balanced surfactants, fatty acids, and paraffin wax |
US5496493A (en) * | 1994-05-10 | 1996-03-05 | The Procter & Gamble Company | Ultra mild personal cleansing bar containing smaller-sized particulate wax |
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US2175285A (en) * | 1936-01-25 | 1939-10-10 | Procter & Gamble | Detergent for toilet use containing incompletely esterified polyhydric alcohol |
US2356903A (en) * | 1941-02-05 | 1944-08-29 | Procter & Gamble | Soap-free detergents in bar form |
GB583028A (en) * | 1941-06-06 | 1946-12-05 | Novag Ag Zurich | Improvements in or relating to body cleansing agents |
GB592206A (en) * | 1945-08-04 | 1947-09-10 | Eileen Spafford | Improvements in and relating to washing tablets |
US2462758A (en) * | 1945-08-10 | 1949-02-22 | Colgate Palmolive Peet Co | Synthetic detergent compositions |
US2653913A (en) * | 1950-01-21 | 1953-09-29 | Shell Dev | Synthetic detergent cakes |
US2678921A (en) * | 1948-08-04 | 1954-05-18 | Colgate Palmolive Co | Process of producing a milled nonsoap detergent in bar form |
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- US US2734870D patent/US2734870A/en not_active Expired - Lifetime
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Publication number | Priority date | Publication date | Assignee | Title |
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US2175285A (en) * | 1936-01-25 | 1939-10-10 | Procter & Gamble | Detergent for toilet use containing incompletely esterified polyhydric alcohol |
US2356903A (en) * | 1941-02-05 | 1944-08-29 | Procter & Gamble | Soap-free detergents in bar form |
GB583028A (en) * | 1941-06-06 | 1946-12-05 | Novag Ag Zurich | Improvements in or relating to body cleansing agents |
GB592206A (en) * | 1945-08-04 | 1947-09-10 | Eileen Spafford | Improvements in and relating to washing tablets |
US2462758A (en) * | 1945-08-10 | 1949-02-22 | Colgate Palmolive Peet Co | Synthetic detergent compositions |
US2678921A (en) * | 1948-08-04 | 1954-05-18 | Colgate Palmolive Co | Process of producing a milled nonsoap detergent in bar form |
US2653913A (en) * | 1950-01-21 | 1953-09-29 | Shell Dev | Synthetic detergent cakes |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2845391A (en) * | 1958-07-29 | Synthetic detergent bar | ||
US2858569A (en) * | 1955-07-01 | 1958-11-04 | Charles F J Dupuy | Method of producing synthetic detergent cakes |
US3055837A (en) * | 1958-10-08 | 1962-09-25 | George G Wittwer | Synthetic detergent cake and process for making the same |
US3150097A (en) * | 1961-04-18 | 1964-09-22 | Lever Brothers Ltd | Soap compositions |
US4100097A (en) * | 1977-02-02 | 1978-07-11 | The Hewitt Soap Company, Inc. | Low pH detergent bar |
US4151105A (en) * | 1977-02-02 | 1979-04-24 | The Hewitt Soap Company Inc. | Low pH detergent bar |
US5294363A (en) * | 1991-09-23 | 1994-03-15 | The Procter & Gamble Company | Mild personal cleansing bar composition with balanced surfactants, fatty acids, and paraffin wax |
US5300249A (en) * | 1991-09-23 | 1994-04-05 | The Procter & Gamble Company | Mild personal cleansing bar composition with balanced surfactants, fatty acids, and paraffin wax |
US5211870A (en) * | 1992-03-11 | 1993-05-18 | The Procter & Gamble Company | Malodor-free cleansing bar composition containing zeolite odor controlling agent |
US5496493A (en) * | 1994-05-10 | 1996-03-05 | The Procter & Gamble Company | Ultra mild personal cleansing bar containing smaller-sized particulate wax |
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