US3332874A - Detergent composition - Google Patents

Detergent composition Download PDF

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US3332874A
US3332874A US51582665A US3332874A US 3332874 A US3332874 A US 3332874A US 51582665 A US51582665 A US 51582665A US 3332874 A US3332874 A US 3332874A
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United States
Prior art keywords
detergent
sulfonate
carbon atoms
carbon atom
component
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Todd L Coward
Barker Carl
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to CA796280A priority Critical patent/CA796280A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US51582665 priority patent/US3332874A/en
Priority to US3475490D priority patent/US3475490A/en
Priority to DE1617185A priority patent/DE1617185B2/de
Priority to BE691617D priority patent/BE691617A/xx
Priority to FR88567A priority patent/FR1516056A/fr
Priority to NL6618079A priority patent/NL6618079A/xx
Priority to BE691932D priority patent/BE691932A/xx
Priority to FR89420A priority patent/FR1506964A/fr
Priority to DE19661593294 priority patent/DE1593294A1/de
Priority to GB5840966A priority patent/GB1164664A/en
Priority to NL6618459A priority patent/NL6618459A/xx
Priority to CH328567A priority patent/CH490488A/de
Application granted granted Critical
Publication of US3332874A publication Critical patent/US3332874A/en
Priority to US3553129D priority patent/US3553129A/en
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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
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/535—Organo-phosphoranes
    • C07F9/5355—Phosphoranes containing the structure P=N-
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5463—Compounds of the type "quasi-phosphonium", e.g. (C)a-P-(Y)b wherein a+b=4, b>=1 and Y=heteroatom, generally N or O
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/60—Sulfonium or phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • 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
    • 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
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • 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
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/07—Organic amine, amide, or n-base containing
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2352—Coating or impregnation functions to soften the feel of or improve the "hand" of the fabric

Definitions

  • This invention relates to a novel detergent compositron. It also relates to a detergent composition which embodies a synergistic mixture of surface active compounds.
  • compositions described herein are useful for both light-duty and heavy-duty applications. They have special usefulness, however, in connection with detergent com-positions designed for light-duty cleaning situations.
  • the terms light-duty and heavy-duty as applied to detergency have acquired fairly definite meanings in the art.
  • the term light-duty is used in the description of this invention in its usually accepted context, i.e., namely, as a semi-specialty product designed for dish-washing and laundering fine fabrics by hand.
  • the term is also used to difierentiate between this class of products and the heavy-duty laundering products used in standard and automatic washing machines which depend substantially for their satisfactory performance on the use of large amounts of various types of additives such as suds boosters, detergency' builders, sequestering agents and other similar functional ingredients.
  • Light-duty applications include the hand washing of dishes and lightly soiled fine fabrics which fabrics cannot as a rule withstand the vigorous treatment of machine laundering. Also, light-duty washing situations are those which generally call for a gentle washing action in cool or lukewarm water. It is well known by those skilled in the art that compositions designed for such uses must have certain performance properties which distinguish them from heavy-duty cleaning composition-s. For instance, they must be mild to the skin, possess high sudsing properties, and also possess cleaning power in water sol1't(1)1(1)0n; having cool or lukewarm temperatures, e.g. below -On the other hand, heavy-duty applications are those cleaning situations which involve heavily soiled fabrics and clothing.
  • a detergent compo- SllIlOIhShOuld serve as a wetting agent to solubilize and emulsify greasy soils and help remove them from soiled articles, especially from dishes.
  • the composition should be able'to disperse and suspend soil once it is removed from the articles being washed so that the soil does not redeposit on the articles.
  • a light-duty dishwashing compos tion moreover, should be able to provide quickly a copious amount of stable suds that will form a long lasting suds layer over the washing solution.
  • the blanket of suds produced should be so stable that it will last throughout the entire washing operation.
  • the cleaning capability of a dishwashing solution is frequently gauged by the amount of suds present during the washing process.
  • the detergent composition should perform these functions efficiently over the wide range of washing conditions normally encountered in dishwashing and fine fabric laundering processes (water temperature, wa-
  • a liquid detergent composition which ofiers synergistic sudsing performance characteristics which make it especially valuable for dishwashing and fine fabric laundering.
  • a light-duty liquid composition which consists essentially of an aqueous vehicle and a synergistic mixture of the hereinafter described active detergent compounds.
  • FIGURE 1 is a drawing of a graph presenting data showing the surprising synergistic sudsing results made possible by the detergent compositions of the present invention.
  • a detergent composition having superior sudsing performance characteristics can be prepared which consists essentially of a synergistic mixture of Detergent A and Detergent B wherein Detergent A is an ingredient which comprises from about 30% to about 70% of Component A, from about 20% to about 70% of Component B and from about 2% to about 15% of Component C, wherein:
  • Said Component A is a mixture of double-bond positional isomers of water-soluble salts of alke-ne-l-sulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including by weight about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a betagamma unsaturated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;
  • Said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attache-d to a carbon atom at least two carbon atoms removed from the terminal carbon atom; and
  • Said Component C is a mixture comprising from 30-95% water-soluble salts of alkene disulfonates containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom,
  • the synergistic sudsing results are obtained when Detergent A and Detergent B are present in admixture at a ratio of Detergent A to Detergent B of from about 10:1 to about 1:7, by weight. Outstanding results are obtained within a narrower preferred ratio of Detergent A to Detergent B of 6:1 to 1:4, by Weight. The amount of suds produced and the stability thereof drops off markedly when the 10:1 and 1:7 by weight ratios are exceeded. Within this range and especially within the preferred range, the benefits of synergism are best obtained.
  • Detergent A is itself a mixture of certain compounds. As noted above it is basically a mixture of three components each of which has a specific composition. A detailed discussion of the makeup of Detergent A is presented below.
  • a preferred percentage range by weight for Component A is from about 35% to about 65%, for Component B it is from about 25% to about 60%, and for Component C it is from about 3% to about 12%.
  • Component A is comprised essentially of the prescribed ranges of the following compounds.
  • x is an integer in the range from about 6 to about 10, preferably about 8 to 10
  • M represents any cation that forms a water-soluble salt such as alkali metals, e.g. sodium and potassium, and ammonium, and substituted ammonium compounds, e.g. trialkylammonium and trialkylolammonium compounds.
  • alkali metals e.g. sodium and potassium
  • substituted ammonium compounds e.g. trialkylammonium and trialkylolammonium compounds.
  • substituted ammonium compounds are triethylammonium, triethylamm-onium, and triethanolammonium.
  • composition is prepared by the sulfonation of alpha olefins with uncomplexed sulfur trioxide.
  • minor amounts i.e. less than 10% by weight, do not materially alter the excellent detergent properties of the composition.
  • Component A is a blend or mixture of certain unsaturated isomeric aliphatic compounds
  • Component B consists of a mixture of certain saturated aliphatic corn-pounds. A minor amount of unsaturation can be included in this mixture but preponderantly the compounds are saturated.
  • the bifunctionality of these alkane compounds is due to the presence of a hydroxyl group and a sulfonate radical on the same molecule. It has been discovered that the sulfonate radical must be located on the terminal carbon atom. It also has been discovered that the situs' of the hydroxyl group is an especially important factor in the compounds that can comprise Component B.
  • the valuable detergent properties of the Component B compounds are substantially decreased. This is especially true when the alpha and beta carbons are the two sites of attachment.
  • the critical structural arrangement which must exist in order for the compounds to be detergents is that the sulfonate radical must be in the alpha position and the hydroxyl radical must be attached to a carbon atom at least two carbons removed, for example, to the third, fourth or fifth carbons, i.e. on the gamma, delta, or epsilon carbons.
  • the carbon to which the hydroxyl group is attached should be separated from the carbon bearing the sulfonate radical by at least one methylene group along the aliphatic chain.
  • Component B consists of a mixture of the following bifunctionally-substituted saturated aliphatic compounds.
  • Component B can also include minor quantities, for example, less than about 10% of compounds wherein the hydroxyl group is attached elsewhere along the carbon chain, e.g. on the sixth carbon atom, without materially altering the overall detergent properties of the compositions.
  • the 3-, 4-, and 5-hydroxy n-alkyl sulfonate compounds, illustrated above, are preferred ingredients in Component B and at least of the hydroxy radical substitution must be in the 3, 4, and 5 positions.
  • beta-hydroxy n-alkyl sulfonate compounds are relatively poor detergent compounds. Not only are they comparatively poor detergent, but it has been discovered also that such compounds constitute an actual load on the present detergency system. For this reason, the level of such compounds should be held to a minimum. It is noted though, that minor amounts of betahydroxy n-alkyl sulfonate compounds can be tolerated in the synergistic compositions of this invention provided that Components A, B, and C of Detergent A otherwise contain the essential ingredients herein described in the proportions and percentages specified.
  • the alkene disulfonates should preferably comprise from about 40% to about 80% of the highly polar polyfunctionally substituted aliphatic compounds which make up Component C. These alkene disulfonates should preferably contain from about 12 to about 16 carbon atoms. As mentioned above, one sulfonate group is attached to the terminal carbon atom. The second sulfonate group is attached to an internal carbon atom that is not more than about six carbon atoms removed from the terminal carbon. In other words, the second sulfonate functional group can be attached to the second through about the seventh carbon atom.
  • Component C can also include minor amounts of compounds in which the second sulfonate is located more internally than the seventh carbon, such as, for example, on the eighth carbon, etc. There is no apparent advantage in having these latter compounds present in the composition, however. According to a preferred embodiment, the major portion, that is from about 60% to about of the alkene disulfonates, should be 1,2 and 1,3 disulfonates.
  • the alkene double bond can be distributed between the terminal carbon and about the seventh carbon atom; such unsaturation includes, for instance, alpha-beta, betagamma, gamma-delta, delta epsilon, epsilon-zeta, and zeta-eta unsaturation.
  • the double bond should be distributed between the second to the sixth carbon atom. It should be noted that the alkene double bond can be even more internally located than between the zeta-eta carbons, but again no apparent advantage is gained thereby.
  • the alkene disulfonates of Component C contain the polyfunctional combination of a double bond and two sulfonate groups in an important structural relationship.
  • the preferred compounds as ingredients of the alkene disulfonate portion of Component C are 2-alkene-1,2-disulfonate; 3-alkene-1,2-disulfonate; and 4-alkene-1,2-disulfonate of the 1,2 disulfonate species; and 3-alkene-1,3-disulfonate; 4-alkene-1,3-disulfonate; and 5-alkene-1,3-disulfonate of the 1,3 disulfonate species.
  • the alkene group can contain from about 12 to about 16 carbon atoms and preferably about 14 to 16 carbon atoms. The sodium and potassium salts of these compounds are preferred.
  • alkene disulfonate compounds are the following in which a carbon chain length of 16 was selected as being representative, having sulfonate attachment sites of 1,2 and 1,3;
  • Component C contains the aforementioned and illustrated alkene disulfonates. It also contains from about 5% to about 70%, and preferably about 20% to about 60%, water-soluble salts of hydroxy disulfonates containing from about 12m about 16 carbon atoms.
  • the terminal carbon atom has attached to it one of the sulfonate groups.
  • the second sulfonate group can be attached to an internal carbon atom not more than about six carbon atoms removed fromsaid terminal carbon atom.
  • the required hydroxy group is attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.
  • the preferred sites of attachment for the hydroxy group on the 1,2 disulfonate species are the fourth and fifth carbon atoms to yield 4-hydroxyalkane-1,2-disulfonates and S-hydroxyalkane-1,2-disulfonates.
  • the preferred sites of attachment for the hydroxy group are the fifth and the sixth carbon atoms to yield S-hydroxyalkane-1,3-disulfonates and 6-hydroxyalkane-1,3-disu1fonates.
  • the alkane hydrocarbons as before are those having 12 to 16 carbon atoms and preferably about 14 to 16 carbon atoms. According to a preferred embodiment, the major portion, that is, from about 60% to about 95% of the hydroxy disulfonates should be 1,2 and 1,3 disulfonates.
  • a second polar group, as in Components B and C, spaced a critical distance from a terminally attached polar group in a detergent molecule modifies the crystalline latice structure in such a way as to improve markedly the solubility characteristics of the compound. While this is not known for certain, it is offered as one possible explanation for the exceptional detergent properties of the compositions of the present invention.
  • Detergent A as described herein can be prepared in any suitable manner so long as the above teachings are adhered to. For instance, each of the ingredients can be synthesized separately and then mixed according to the stated proportions. On the other hand, it is possible to prepare the compositions of the present invention according to a novel process describedin copending patent application Ser. No. 423,292 filed J an. 4, 1965, by Adriaan Kessler and Phillip F. Pfiaumer, and another patent application being filed concurrently herewith.
  • R represents an aliphatic hydrocarbon radical that would allow for a total of carbon atoms in the molecule between about 12 and about 16.
  • the alpha-beta unsaturated sulfonate containing aliphatic compounds of Component A can be prepared readily by dehydrochlorinating a 2-chlorosulfonic acid derivative.
  • the starting step for this synthesis is a reaction between a long chain epoxide and sodium bisulfite to produce a 2-hydroxy-1-sulfonate derivative of the particular long chain epoxide used.
  • This reaction product is condensed with PCl to prepare the aforementioned 2-chlorosulfonic acid derivative which in turn is reacted with sodium carbonate to yield an alpha-beta unsaturated compound.
  • the other preferred double-bond positional isomers of Component A i.e., the beta-gamma, gamma-delta, and delta-epsilon can be prepared by the thermal dehydration of hydroxy-sulfonates. According to the following reaction, the thermal dehydration of the sodium salt of 7 3-hydroxy-sulfonate results in the preparation of a reaction mixture containing the beta-gamma isomer and the gamma-delta isomer.
  • a reaction mixture of a gamma-delta and a delta-epsilon double-bond isomer compound can be prepared by using a 4-hydroxysulfonate as a starting material:
  • reaction product can be formulated directly into a detergent composition according to the present invention. If, for some reason, it is desired to work with pure ingredients, they can be separated into pure forms.
  • hydroxy sulfonates of Component B such as the preferred 3-, 4-, and 5-hydroxy compounds can be prepared by the free radical addition of sodium bisulfite to the corresponding 3-, 4-, or 5-hydroxy-l-olefin, respectively:
  • the alkene disulfonates and the hydroxy disulfonates which comprise Component C may also be prepared separately by any known manner.
  • the -hydroxy disulfonates may be prepared by epoxidizing olefin sulfonic acid isomers, and then opening the epoxide ring with sodium bisu-lfite by standard reaction techniques.
  • the hydroxy disulfonates may then be dehydrated by reactions known to those skilled in the art to yield the corresponding isomeric alkene disulfonates.
  • the Detergent A components should contain from about 12 to about 16 carbon atoms. It is preferred, however, to have the compounds contain from 14 to 16 carbon atoms. It is not necessary that each of the compounds contain the same number of carbon atoms. Mixtures of different chain lengths within the prescribed ranges can be used.
  • compositions are illustrative of the make up of Detergent A according to the present invention wherein the percentages are by weight and wherein Components A, B and C total up to of Detergent A.
  • the percentages listed for each ingredient are by weight of that particular ingredient in Detergent A.
  • Detergent A can be comprised as follows with a chain length of 16 carbons being representative:
  • Total Component C 10 This Detergent A composition listed above has excellent detergent and synergistic sudsing properties when mixed with Detergent B according to the proportions described herein.
  • Detergent A Another illustrative example of Detergent A is as follows:
  • This detergent A composition also offers excellent detergent properties of cleaning and synergistic sudsing in admixture with Detergent B as described herein.
  • the alkyl group is derived from coconut alcohol and especially the middlecut coconut alcohol containing 2% C 66% C 23% C and 9% C This preferred compound is, at times, referred to hereinafter as CnAGS.
  • a preferred range for the carbon chain length is 12 to 16 carbon atoms.
  • alkyl glyceryl ether sulfonates useful in the present invention and methods for their preparation are described in US. Patent 3,024,273 issued to D. D. Whyte et al. and dated March 6, 1962.
  • compositions of the present invention were standardized to include a total of 30% by weight of an active deter-gent ingredient with the balance, 70%, being an aqueous vehicle.
  • Detergent A and Detergent B were each first tested separately and then in certain prescribed mixtures. Thus, for example, a composition was prepared consisting of 30% of just Detergent A and 70% water. Another composition was prepared consisting of 30% of just Detergent B and 70% water. Then mixed compositions were prepared consisting of 25% Detergent A and 5% Detergent B, and 15% Detergent A and 15% Detergent B.
  • Detergent B was the sodium salt of middle-cut coconut alkyl glyoeral ether sulfonate containing 2% C10, 66% C 23% C and 9% C It is referred to as CnAGS.
  • a dishpan was prepared containing one gallon of water with a hardness of 7 grains, a temperature of F. and a pH of 7. To this was added in separate tests 7.25 cc. of each of the detergent compositions being tested.
  • the wash-ing solution containing the detergent composition was mechanically agitated to produce the maximum suds level which was measured. This is referred to as the original suds level. Agitation was by means of a mechanical stirrer.
  • FIGURE 1 it can be seen that the average values obtained for Detergent A and Detergent B when each was used as the sole detergent are markedly lower than for mixtures of these two detergent compounds. It should be emphasized that the demonstrated synergistic sudsing performance was totally unexpected. There is no known criteria by which it is possible to predict this type of behavior. It can be seen from FIGURE 1 that an equal weight mixture or a 1:1 mixture by parts or by weight resulted in an average percent suds during washing of 43%. This can be compared with an average percent of only 34% for Detergent A alone and 36% for Detergent B alone. A 5:1 ratio (see 25:5 figure in FIG- URE 1) gave an ave-rage percentage of 39%.
  • the syntergistic detergent mixtures of the present invention consisting of the critically proportioned ingredients can be prepared readily into liquid detergent compositions.
  • the essential ingredients for such compositions are the novel synergistic mixture and a liquid vehicle therefor.
  • the detergent composition can consist of from about 5% to about 50% of the detergent mixture and the balance of 50%95% being water.
  • the detergent synergistic mixtures can range from about to about 35% by weight of the composition with the remaining 65%90% being water.
  • detergent mixtures of the present invention can be used with other materials to form complete detergent formulations.
  • Such complete compositions can contain the detergent mixtures of this invention in admixture, for example, with water soluble inorganic alkaline builder salts, organic sequestering agents, or mixtures thereof, hydrotropes, solubilizing agents, antitarnishing agents and water.
  • the builders and sequestrants can be employed at levels of from about 4% to about 30% by weight of the composition and preferably from about 8% to Water soluble inorganic alkaline builder salts which can be used alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium and potassium, tripolyphosphate, sodium and potassium carbonate, sodium and potassium tetraborate, sodium and potassium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and 'diortho phosphate and potassium bicarbonate.
  • Such inorganic builder salts enhance the overall cleaning characteristic of the novel synergistic mixtures of the present invention.
  • potassium salts of these compounds are preferred for reasons of solubility.
  • Potassium pyrophosphate is the single preferred builder. for use in the present invention.
  • organic alkaline builder salts which can be used alone or in admixture are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g., sodium and potassium N-(Z-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium nitrilotn'acetates and sodium, potassium and triethanolarnmonium- N-(2-hydroxyethyl)-nit-rilodiacetates.
  • Mixed salts of these polycarboxylates are also suitable.
  • Other valuable polycarboxylate builder compounds are the sodium and potassium salts of polymaleate, polyitaconate, and polyacrylate.
  • the alkali metal salts of phytic acid e.g., sodium phytate, are also suitable as organic alkaline builder salts (see U.S. Patent 2,739,942).
  • Polyphosphonates are also valuable builders in terms of the present invention including specifically sodium and potassium salts of ethane-l-hydroxy-l, l-diphosphonate, sodium and potassium salts of methylene diphosphonate, sodium and potassium salts of ethylene diphosphonate, and sodium and potassium salts of ethane-1,1,2-triphosphonate.
  • Hydrotropes can be added if desired to increase the compatibility of the ingredients of the formulations of this invention.
  • Preferred hydrotrope anions are benzene sulfonate, xylene sulfonate, and toluene sulfonate. They are preferably used as their soluble salts such as: ethanolammonium, diethanolammonium, and triethanolammonium, and especially as the alkali metal, potassium, or sodium salts. Sodium or potassium toluene sulfonate is especially preferred.
  • the hydrotrope is added at levels of from about 0% to about 10% by weight of the composition. Levels of from about 2% to 8% are preferred.
  • the upper limit of about 10% is set by increasing dilution of the product by an ingredient substantially inert so far as sudsing and detergency are concerned.
  • the lower limit is the amount required to achieve a homogeneous solution. It will be appreciated that it is necessary that the formulations of this invention should be liquid at somewhat higher and at somewhat lower temperatures than usual room temperature.
  • the amount of hydrotrope salt used is preferably the minimum amount which will hold the ingredients in solution at the temperature to which it is desired that the formula can be cooled without phase separation.
  • Solubilizing agents also can be added, if necessary, and those preferred are lower alcohols such as methyl, ethyl and propyl alcohols. They are generally employed at a level of from about 0% to about 25% by weight of the composition and preferably between about 5% to 15% by weight.
  • various minor ingredients can also be added to the compositions of the present invention.
  • Such normal and desirable additives include perfumes, viscosity central agents, opacifiers, and pigments.
  • inert materials such as water soluble inorganic salts can also be present in minor amounts, generally as impurities from the various ingredients or as opacifier stabilizers.
  • ethylene glycol distearate or polysytrene can be used as opacifiers in amounts of up to 3% by weight of the composition.
  • Excellent performing light-duty compositions can be prepared having by weight ratios given in Table I in the active detergent ingredient.
  • the compositions prepared accordingly rapidly produce a synergistically high level of suds volume which is stable over a prolonged period.
  • These compositions are especially useful for dishwashing and the laundering of fine and delicate fabrics as well as the washing of woolens, i.e. sweaters, carpets, etc., where copious amounts of stable suds are desirable.
  • the Detergent A represented in the following examples as Detergent A containing 12 Carbon Atoms has the following composition.
  • Total Component C 103 13 The Detergent A represented in the following examples as Detergent A Containing 14 Carbon Atoms has the following composition.
  • Component A Percent CIZHZCHZCHSO3NG.
  • Component C: Percent C H CH CHCH(SO Na)CH (SO Na) 4.5
  • Example 20 8.0% Detergent A containing 16 carbon atoms 17.0% Sodium tetradecyl glyceryl ether sulfonate 8.0% Tripotassium salt of nitrilotriacetate 67.0% Water.
  • Example 21 f 1 0 12.0% Detergent A consisting of one part C and one 2 2( 3 a) part C compounds 3.0% Ammonium coconut alkyl glyceryl ether sulfonate Total Component C ""7 25 6.0% Potassium pyrophosphate
  • the Detergent A represented in the following examples Tripotassillm Salt of y yp as Detergent A Containing 16 Carbon Atoms has the P1101!ate following composition. 50% Ethyl alcohol 68.0% Water.
  • Such solid C H CH(OH)CH CH(SO Na) formulations can also contain the synergistic combination CH CH (SO Na) 1.0 of the herein-described detergent compounds in admixture with the builders also described herein ranging from Total Component C 10.0 lightly built compositions to heavily built detergent com- TABLE I Examples DETERGENT A Detergent A Containing 12 Carbon Atoms Detergent A Containing 14 Carbon Atoms Detergent A Containing 16 Carbon Atoms Detergent A Containing a mixture of 10 parts C12,
  • a typical example of a heavy duty or heavily built granular detergent composition can contain about 17.5% of an active detergent mixture described herein, about 50% sodium tripolyphosphate, about 24% sodium sulfate, and about 8.5% sodium silicate.
  • the synergistic sudsing properties of the novel binary detergent composition described herein can be even further enhanced, by adding to said composition from about 0.1% to about 0.3% by weight of a water hardness salt such as magnesium sulfate, magnesium chloride, calcium sulfate and calcium chloride, or mixtures thereof.
  • a water hardness salt such as magnesium sulfate, magnesium chloride, calcium sulfate and calcium chloride, or mixtures thereof.
  • Other well-known water hardness salts can also be used such as iron salts and the like.
  • the suds building effect is more pronounced in relatively soft water but it is also effective in so-called medium hard water or hard water.
  • a surprising aspect of this discovery is that the marked improvement in sudsing is not obtained if the equivalent amount of water hardness salts is added to the water solution instead of being present in the detergent product.
  • a detergent composition having superior sudsing performance characteristics consisting essentially of a synergistic mixture of Detergent A and Detergent B wherein Detergent A is a mixture of from about 30% to about 70% of Component A, from about 20% to about 70% of Component B and from about 2% to about 15% of Component C, wherein:
  • said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-lsulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25 of a gamma-delta unsaturated isomer, and about 5% to about of a delta-epsilon unsaturated isomer;
  • said Component B is a mixture 'of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon "atoms removed from the terminal carbon atom with at least 90% of the hydroxy radical substitution being in the 3, 4, and 5 positions; and
  • said Component C is a mixture comprising from 30- 95% water-soluble salts of alkene disulfonate containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from
  • the ratio of Detergent A to Detergent B being from about 10:1 to about 1:7 by weight.
  • a liquid detergent composition consisting essentially of from about 5% to about 50% of the composition described in claim 1, and from about 50% to about 95% water.
  • a liquid detergent composition consisting essentially of from about 5% to about 50% of the detergent composition described in claim 1, Water and from about 4% to about 30% of a detergency builder selected from the group consisting of water soluble inorganic alkaline builder salts, organic sequestering agents and mixtures thereof.
  • a liquid detergent composition of claim 7 wherein the detergency builder is trisodium ethane-l-hydroxy-l, l-diphosphonate.
  • a liquid detergent composition having synergistic sudsing properties consisting essentially of from about 10% to about 35% of the detergent composition described in claim 1; and from about 8% to about 25 of a detergency builder selected from the group consisting of water soluble inorganic alkaline builder salts, organic sequestering agents and mixtures thereof; from about 2% to about 8% of a hydrotrope selected from the group consisting of sodium, potassium, ethan'olammonium, diethanolammonium, and triethanolammonium salts of benzene sulfonate, xylene sulfonate and toluene sulfonate; from about 5% to about 15% of a solubilizing agent selected from the group consisting of methyl, ethyl and propyl alcohols, with the balance being water.
  • a detergency builder selected from the group consisting of water soluble inorganic alkaline builder salts, organic sequestering agents and mixtures thereof
  • a detergent composition according to claim 1 which also contains from about 0.1% to about 0.3% by weight of a Water hardness salt selected from the group consisting of magnesium sulfate, magnesium chloride, calcium sulfate and calcium chloride.

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US51582665 1965-12-23 1965-12-23 Detergent composition Expired - Lifetime US3332874A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
CA796280A CA796280A (en) 1965-12-23 Detergent composition
US51582665 US3332874A (en) 1965-12-23 1965-12-23 Detergent composition
US3475490D US3475490A (en) 1965-12-23 1965-12-30 Emulsifying and textile softening phosphonium compounds,processes for preparing the same
DE1617185A DE1617185B2 (de) 1965-12-23 1966-12-21 Waschmittel
FR88567A FR1516056A (fr) 1965-12-23 1966-12-22 Composition détergente fortement moussante
BE691617D BE691617A (fr) 1965-12-23 1966-12-22
NL6618079A NL6618079A (fr) 1965-12-23 1966-12-23
BE691932D BE691932A (fr) 1965-12-23 1966-12-29
FR89420A FR1506964A (fr) 1965-12-23 1966-12-29 Composés phosphonium adoucissants des textiles et émulsifiants et procédés de préparation de ces composés et de compositions en contenant
DE19661593294 DE1593294A1 (de) 1965-12-23 1966-12-29 Avivier- und Reinigungsmittel
GB5840966A GB1164664A (en) 1965-12-23 1966-12-30 Emulsifying and Textile Softening Phosphonium Compounds, processes for preparing the same and other Compounds and Reactive Intermediates therefor
NL6618459A NL6618459A (fr) 1965-12-23 1966-12-30
CH328567A CH490488A (de) 1965-12-23 1967-03-07 Weichmachungs- und Reinigungsmittel
US3553129D US3553129A (en) 1965-12-23 1968-08-21 Emulsifying and textile softening phosphonium compounds, process for preparing the same and other compounds, reactive intermediates

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US51582665 US3332874A (en) 1965-12-23 1965-12-23 Detergent composition
US51782665A 1965-12-30 1965-12-30
CH328567A CH490488A (de) 1965-12-23 1967-03-07 Weichmachungs- und Reinigungsmittel
US75447868A 1968-08-21 1968-08-21

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US3475490D Expired - Lifetime US3475490A (en) 1965-12-23 1965-12-30 Emulsifying and textile softening phosphonium compounds,processes for preparing the same
US3553129D Expired - Lifetime US3553129A (en) 1965-12-23 1968-08-21 Emulsifying and textile softening phosphonium compounds, process for preparing the same and other compounds, reactive intermediates

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US3475490D Expired - Lifetime US3475490A (en) 1965-12-23 1965-12-30 Emulsifying and textile softening phosphonium compounds,processes for preparing the same
US3553129D Expired - Lifetime US3553129A (en) 1965-12-23 1968-08-21 Emulsifying and textile softening phosphonium compounds, process for preparing the same and other compounds, reactive intermediates

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US (3) US3332874A (fr)
BE (2) BE691617A (fr)
CA (1) CA796280A (fr)
CH (1) CH490488A (fr)
DE (2) DE1617185B2 (fr)
FR (2) FR1516056A (fr)
GB (1) GB1164664A (fr)
NL (2) NL6618079A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625910A (en) * 1968-07-29 1971-12-07 Chevron Res Hydrogenated olefin sulfonate detergent bars
US3819538A (en) * 1972-05-15 1974-06-25 Dow Chemical Co Environmentally compatible laundry detergent
US4601844A (en) * 1984-08-31 1986-07-22 The Procter & Gamble Company Granular automatic dishwasher detergent with alkyl phosphate and calcium ion source
US5078916A (en) * 1989-01-03 1992-01-07 Shell Oil Company Detergent composition containing an internal olefin sulfonate component having an enhanced content of beta-hydroxy alkane sulfonate compounds
US20110152571A1 (en) * 2009-12-22 2011-06-23 Chevron Oronite Company Llc Isomerized alpha olefin sulfonate and method of making the same
WO2022106413A1 (fr) * 2020-11-19 2022-05-27 Unilever Ip Holdings B.V. Composition de nettoyage de surface dure

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5300123B2 (ja) * 2008-03-24 2013-09-25 広栄化学工業株式会社 アンモニウム塩及びそれを用いた帯電防止剤

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2061620A (en) * 1936-11-24 Sulphonated derivatives of aliphat
US2061618A (en) * 1936-11-24 Sulphonated hydrocarbon
US2061617A (en) * 1936-11-24 Stllphonic acid derivatives of aii
US3267040A (en) * 1960-08-02 1966-08-16 Lever Brothers Ltd Synergistic combinations of alkane sulfonates and alkoxy hydroxy propane sulfonates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2061620A (en) * 1936-11-24 Sulphonated derivatives of aliphat
US2061618A (en) * 1936-11-24 Sulphonated hydrocarbon
US2061617A (en) * 1936-11-24 Stllphonic acid derivatives of aii
US3267040A (en) * 1960-08-02 1966-08-16 Lever Brothers Ltd Synergistic combinations of alkane sulfonates and alkoxy hydroxy propane sulfonates

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625910A (en) * 1968-07-29 1971-12-07 Chevron Res Hydrogenated olefin sulfonate detergent bars
US3819538A (en) * 1972-05-15 1974-06-25 Dow Chemical Co Environmentally compatible laundry detergent
US4601844A (en) * 1984-08-31 1986-07-22 The Procter & Gamble Company Granular automatic dishwasher detergent with alkyl phosphate and calcium ion source
US5078916A (en) * 1989-01-03 1992-01-07 Shell Oil Company Detergent composition containing an internal olefin sulfonate component having an enhanced content of beta-hydroxy alkane sulfonate compounds
US20110152571A1 (en) * 2009-12-22 2011-06-23 Chevron Oronite Company Llc Isomerized alpha olefin sulfonate and method of making the same
US8993798B2 (en) * 2009-12-22 2015-03-31 Chevron Oronite Company Llc Isomerized alpha olefin sulfonate and method of making the same
US9249092B2 (en) 2009-12-22 2016-02-02 Chevron Oronite Company Llc Isomerized alpha olefin sulfonate and method of making the same
WO2022106413A1 (fr) * 2020-11-19 2022-05-27 Unilever Ip Holdings B.V. Composition de nettoyage de surface dure

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FR1506964A (fr) 1967-12-22
CA796280A (en) 1968-10-08
US3475490A (en) 1969-10-28
NL6618079A (fr) 1967-06-26
CH490488A (de) 1970-05-15
NL6618459A (fr) 1967-07-03
GB1164664A (en) 1969-09-17
BE691932A (fr) 1967-06-29
DE1617185B2 (de) 1975-02-27
DE1617185A1 (de) 1971-02-25
DE1593294A1 (de) 1970-07-30
US3553129A (en) 1971-01-05
FR1516056A (fr) 1968-03-08
BE691617A (fr) 1967-06-22

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