Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • 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
  • C11D1/34—Derivatives of acids of phosphorus
  • C11D1/342—Phosphonates; Phosphinates or phosphonites

Definitions

• a phosphate-free detergent composition is described.
• the present invention relates to a novel built detergent composition having general utility as a laundering agent and which is phosphate-free.
• Detergent actives such as polypropylene benzene sulfonates, however, are not the only materials present in detergent formulations.
• an effective detergent composition can be formulated consisting essentially of (a) from about 4% to about 85% by weight of a water-soluble salt of a dianionic detergent compound of the general formula Y X A (r%) (t.
• Y is selected from the class consisting of unsubstituted, mono-methyl substituted and mono-hydroxy substituted straight-chain hydrocarbon groups containing from 15 to 20 carbon atoms
• a detergent formulation which is as effective as a formulation based on the heretofore generally accepted alkylbenzene sulfonate detergents and built with phosphates.
• the dianionic detergent may be selected from biodegradable actives and the like, and since the amount of heavy-metal salt needed is relatively slight, no significant contamination of surface and ground waters results from detergents of the present formulation.
• a composition according to the invention also has an advantage over a phosphate-built composition in that there is a much reduced tendency for separation of particulate matter to occur if the composition is formulated as a liquid.
• a detergent formulation employing the present invention consists essentially of from about 4% to about 85% of said dianionic detergent and from about 1%. to about 80% of said heavy-metal salt, the balance being water or any of the other usual detergent adjuvants. It Will be understood that for the primary advantage of the present invention to be obtained, the composition must be phosphate-free. In particular, the composition must not contain any phosphate builder.
• the compounds of the above general formula can be described as dianionic detergents because they contain two anionic functional groups, i.e., sulfate, sulfonate or phosphonate groups. This is not to be confused with the valency of the anionic functional groups.
• Typical detergents which may be used in accordance with the present invention are the salts with water-solubilizing cations of dianionic sulfates, sulfonates and phosphonates.
• the water-solubilizing cations include the customary cations known in the detergent art, i.e., the alkali metals, (i.e., Li, Na, K, Rb and Cs), ammonium and substituted ammonium, and the alkaline earth metals, as well as other metals in Groups II-A, II-B, III-A, IV-A, and IV-B of the Periodic Table except for boron.
• the alkali metals i.e., Li, Na, K, Rb and Cs
• ammonium and substituted ammonium i.e., Li, Na, K, Rb and Cs
• the alkaline earth metals as well as other metals in Groups II-A, II-B, III-A, IV-A, and IV-B of the Periodic Table except for boron.
• a class of simple compounds that are preferably used in compositions according to the invention because of their convenience are disulfonates and disulfates represented by the formulas:
• Illustrative disulfonates and disulfates are the C to C disodium 1,2-alkyl-disulfates, C -C dipotassium-l, Z-alkyldisulfonates and disulfates, C C diammonium 1,8-alkyldisulfates, disodium 1,9-hexadecyl disulfates, C C disodium-1,2-alkyldisulfonates, disodium 1,9- stearyldisulfates, and the like.
• Many compounds analogous to the foregoing and falling within the scope of the above general formulas will be immediately apparent to those skilled in the art.
• M of the above formulas
• the cations most widely used commercially are sodium, potassium and ammonium.
• M may be any of the alkali metals, ammonium or a substituted ammonium compound.
• substituted ammonium compounds triethanol ammonium and morpholinium salts are particularly common.
• the cation M may also be selected from the water-soluble alkaline earth salts, i.e., the calcium, magnesium, strontium or barium salts of the disulfates and disulfonates.
• the disulfates and disulfonates typically being prepared by adding a sulfate or sulfonate group to an unsaturated linkage, the disulfate and disulfonate detergents are typically substantially saturated. It should be understood, however, that substantial saturation is not an essential element of the present invention.
• Significant saturation is not an essential element of the present invention.
• Favorable response to the presence of said heavy-metal ions occurs when using unsaturated disulfates or disulfonates as well as when using saturated compounds.
• a still further modification which should be mentioned, is the possibility of using mixed anionic detergents, e.g., compounds of the Formulas Y(SO (SO )M and Y(SO M)(PO M which also behave similarly to the compounds mentioned above.
• dianionic detergents are compounds in which one of the anionic groups is attached to the hydrocarbon group by a low molecular weight linking group.
• X is the linking group.
• One of the sulfonate, sulfate or phosphonate groups is attached to the linking group.
• the other is attached to the linking group or to Y.
• linking groups have been Widely used in the detergent art. Typical such groups which can be used in the present invention include the oxyalkylene, amidoalkylene, aminoalkylene, carboxylic ester, phenylene, phenylenealkylene, phenyleneoxy and phenyleneoxyalkylene.
• Oxyalkylene linkages can be prepared by reacting an unsubstituted or mono-methyl substituted alcohol containing from 15 to 20 carbon atoms with a C C alkylene oxide.
• the commercially most significant alkylene oxide is ethylene oxide. Reaction of ethylene oxide with an alcohol increases the hydrophilic character of the alcohol. This is in contrast to reaction of other alkylene oxides, such as propylene oxide, with an alcohol when hydrophilic character is increased.
• X can be Compounds containing an ether linkage, i.e., oxyalkylene link, can also be derived from glycerol ethers. In such compounds the two free hydroxy groups of glyceryl moiety can be converted to sulfate, sulfonate or phosphonate.
• Compounds containing an ether linkage can also be prepared by reacting a suitable alcohol with chlorhydrin.
• the product can be converted to a sulfate, sulfonate or phosphonate or can be reacted with ethylene oxide, as above this can involve reaction with up to 5 moles of ethylene oxide, and then converted to a sulfate, sulfonate or phosphonate.
• the amido linkage (i.e., CONH) which can be used in combination with a C -C alkylene group can be prepared by sulfating a monoethanol amide.
• the second nitrogen-attached hydrogen can also be substituted (i.e., -CO-NR where R is an alkyl group) but the total number of carbon atoms in the linking group should not be more than 6.
• Compounds of the general class can be prepared by reacting a B-amino-sulfate or a taurine (i.e., a fi-aminosulfonate) with C -C fatty acids containing a sulfatable, sulfonatable or phosphonatable group.
• compounds of the same general type may be prepared by reacting higher molecular weight fatty amines with lower molecular weight carboxylic acids.
• appropriate compounds may be prepared by reacting a hydroxy fatty amine with a hydroxy carboxylic acid (for example, lactic acid).
• the resulting lactyl amide can then be converted to a disulfate by reaction with a sulfating agent.
• the amino linkage which should contain from 1 to 6 carbon atoms, can be prepared similarly, for example, by reaction of a B-amino-sulfate with C -C fatt halide containing a sulfatable, sulfonatable or phosphontable group.
• C -C fatt halide containing a sulfatable, sulfonatable or phosphontable group.
• stand- 6 ard organic chemistry methods can be used for their preparation.
• the ester linkage can be formed, for example, by reacting isethionates (i.e., fi-hydroxyethyl sulfonates) with a fatty carboxylic acid.
• Still another class of ester linking groups are formed by using partial glycerides, for example, C monoglycerides.
• One of the free hydroxy groups of the glycerine residue may be sulfated, and, additionally, a sulfate or sulfonate group may be added to the C moiety.
• Many other linking groups containing a carboxylic ester moiety i.e., COO--
• from 1 to 5 carbon atoms will be readily apparent to those skilled in the art.
• the linking group can also be a phenylene group.
• An example of a class of compounds Where X is a phenylene group are alkylbenzene disulfonates.
• the phenylene group can be connected to the hydrocarbon group containing from 15 to 20 carbon atoms by an oxygen link.
• the linking group is then an oxyphenylene group.
• Analogous linking groups to the phenylene and oxyphenylene groups are phenylenealkylene and oxyphenylenealkylene groups. Such groups should not contain more than 7 carbon atoms.
• Typical compounds of the foregoing general classes include but are not limited to compounds of the following formulas:
• hydrocarbon group contains from 16 to 18 carbon atoms.
• Formulas 1 and 2 above are exemplary.
• Formula 3 above is exemplary.
• Formula 4 above is exemplary.
• the heavy metal ions employed as builders in the present invention are derived from the water-soluble, innocuous salts of calcium, barium, strontium, magnesium or aluminum, i.e., their salts with innocuous acids.
• innocuous acid it will be understood that the acid portion of the salt is so selected that it is free of objectionable color or toxicity which would interfere with the intended use of the detergent composition and is free of groups which would adversely react with the other components of the detergent formulation.
• At least about 1.2 mols of the heavy metal ion should be provided for each mole of dianionic detergent.
• a portion of the heavy metal ion can, if desired, be supplied by employing the dianionic detergent in the form of its appropriate salt. This, however, will supply only approximately 1 mole of heavy metal ion for each mole of dianionic detergent. Thus, to obtain the most satisfactory results, provision must be made for supplemental water-soluble salts of suitable heavy metals.
• Detergent formulations within the present invention preferably contain up to about 16 moles of heavy metal ion per mole of dianionic detergent. Preferred compositions have from 2 to 8 moles of heavy metal ion per mole of detergent.
• the aluminum salts such as aluminum sulfate
• the pH of the washing solution is not critical for other reasons (i.e., compatability with sodium silicate, a common detergent adjuvant), the acidity resulting as a consequence of using aluminum salt is not critical.
• solubility of the salt of the dianionic detergent and the heavy metal ion will also be of importance.
• specific heavy me't-al ions enumerated above i.e., Ca, Mg, Ba, Sr and Al
• little, if any, difficulty has been encountered.
• the salts should be soluble in water to the extent of at least about 0.1% in the presence of the other ingredients which are present in the washing solution.
• hypochlorides are convenient in that they not only provide a source of a heavy metal ion, but also provide bleaching action.
• care must be taken in formulating detergent-bleach mixtures because of the tendency of the detergent and bleaching agent to react with each other.
• EXAMPLE 1 A series of formulations were prepared by combining a disodium 1,2 n-alkyl disulfate containing a mixture of C C alkyl groups with calcium chloride in proportions of 0.8 moles of calcium ion per mole disulfate, 1.6 moles of calcium ion per mole disulfate, and 3.2 moles calcium ion per mole disulfate. This series of mixtures, together with a detergent composition containing only the pure disulfate were tested for detergency on Foster D. Snell soil cloth in a Terg-O-Tometer. No other builders were employed. For comparison, alkyl benzene sulfonate was tested in the same series. Distilled water was used in all cases with the following results:
• a typical detergent formulation embodying the present invention is illustrated by the following:
• Example 2 The compounds were tested by the procedure outlined in Example 1 using water having hardness levels corresponding to between and 720 ppm. calculated as calcium carbonate. The hardness was provided by adding a mixed calcium and magnesium sulfate and the detergents were tested at a concentration of 0.03 (except as noted) DETERGENCY OF DISULFATES WITH METAL IONS l 8 Hardness p.p.m. (Ca++/Mg++) Cloth group 180 360 540 720 Compound: 3
• l Detergency is measured by the increase in reflectance on the test swatches.
• a detergent composition consisting essentially of:
• a detergent composition in accordance with claim 1 wherein said water-soluble salt of a dianionic detergent compound has the structural formula RCHCHZOSO -Nzfi- OSO;;-Na where R Il-C H 7 37.

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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)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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Cited By (21)

Families Citing this family (4)

• 1967
  • 1967-06-21 GB GB28651/67A patent/GB1151392A/en not_active Expired
  • 1967-07-06 BE BE701009D patent/BE701009A/xx unknown
  • 1967-07-10 LU LU54066D patent/LU54066A1/xx unknown
  • 1967-07-11 NO NO169000A patent/NO121687B/no unknown
  • 1967-07-11 FR FR113949A patent/FR1531012A/fr not_active Expired
  • 1967-07-11 DE DE19671617226 patent/DE1617226A1/de active Pending
  • 1967-07-12 SE SE10482/67A patent/SE313134B/xx unknown
  • 1967-07-12 NL NL6709714A patent/NL6709714A/xx unknown
• 1969
  • 1969-10-30 US US872731A patent/US3686098A/en not_active Expired - Lifetime
• 1972
  • 1972-01-14 US US00218019A patent/US3850854A/en not_active Expired - Lifetime

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