US2692237A - Detergent compositions - Google Patents
Detergent compositions Download PDFInfo
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- US2692237A US2692237A US215641A US21564151A US2692237A US 2692237 A US2692237 A US 2692237A US 215641 A US215641 A US 215641A US 21564151 A US21564151 A US 21564151A US 2692237 A US2692237 A US 2692237A
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- detergent
- sulfonamide
- water
- soluble
- sodium
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3454—Organic compounds containing sulfur containing sulfone groups, e.g. vinyl sulfones
Definitions
- the present invention relates to new synthetic detergent compositions, and, more particularly to qompositions of the type of the anionic sulfate'd and sulfonated detergents having improved properties, and to a process of preparing same.
- alkyl sulfonamide type compounds have been employed as intermediates in the manufacture of detergents, wetting agents, textile softening agents, etc.
- the present invention relates to built detergent compositions consisting essentially of the water-soluble sulfated or sulfonated detersive salts, water-soluble polyphosphate material, and a minor proportion of a higher alkyl substituted primary sulfonamide as an organic builder to enhance the action of the detergent composition in aqueous solution.
- the enhancing additives of the present invention are characterized by their generally limited water solubility. More particularly, these additives may be represented by the formula:
- R is a higher alkyl group
- Y and Z individually are selected from the group consisting of hydrogen and lower alkyl.
- the higher alkyl substituent may be branched or straight-chain in structure; it comprises moreover such groups as octyl, decyl, dodecyl, keryl, pentadecyl, hexadecyl, mixed long-chain alkyls derived from long-chain fatty materials, cracked paraffin wax olefins, polymers of mono-olefins, etc.
- This higher alkyl substituent will generally be from about 8 to about 18 carbon atoms, and preferably from about 12 to about 16 carbon atoms.
- R has-the significance set forth above.
- Suitable examples of such compounds are octyl sulfonamide, decyl sulfonamide, dodecyl sulfonamide, cocyl sulfonamide wherein the cocyl substituent is a mixture of essentially long-chain alkyls derived from mixed coconut oil fatty acids, dodecyl sulfonamide wherein the dodecyl group is derived from a propylene tetramer, tetradecyl sulfonamide, pentadecyl sulfonamide wherein the pentadecyl group is derived from a propylene pentamer, hexadecyl sulfonaznide, etc.
- An additional suitable class is the polyalkyl substituted sulfonamides wherein one alkyl group is long-chain in structure as indicated, and the one or more remaining alkyl groups is lower alkyl in structure.
- the lower alkyl groups should have a total generally of not in excess of about six carbon atoms. It is preferred that each lower alkyl group be not in excess of about three carbon atoms each.
- suitable additives are:
- R has the significance set forth above and Y is a lower alkyl group, preferably containing from about 1 to about 3 carbon atoms.
- suitable compounds are dodecyl N-methyl sulfonamide, keryl N-methyl sulfonamide, dodecyl N-butyl sulfonamide, tetradecyl N-ethyl sulfonamide, dodecyl N-propylr sulfonamide, etc.
- R is as described above, and Y and- Z may be the same or different, each being selected from the group consisting of lower alkyl.
- this sub-class are dodecyl N.dimethyl sulfonamide, dodecyl N -diethyl sulfonamide, keryl N-diethyl sulfonamide, dedecyl' N-diisopropyl sulfonamide, dodeoyl N-dipropyl sulfonamide, etc.
- compositions-ofthe present invention contain as the active ingredient the anionic sulfated and sulfonated"v detergents, including suitable mixtures thereof; Included therein are the aliphatic suliated or sulfonatedagents, such as th aliphatic acyl containing compounds wherein the acyl radical has about 8 to about 22 carbon atoms, and, more particularly, the aliphatic carboxylic ester type, containing at least about 10 and: preferably about 12 to about 26 carbon atoms to the-molecule.v Amongthe aliphatic detersive compounds it is preferred to use the sulfated aliphaticgcompoundshaving about 1-2 to about 22 carbon atoms- Assuitable examples of aliphatic detergents.
- fatty. acids e. g. coconut oil monoglyceride monosulf-ate, tallow di-glyceride monosulfate'
- the long chain pure or mixed, higher alkyl sulfates e. g. lauryl. sulfate, cetyl sulfate
- alkylol sulfonic acids e. g. oleic acid ester of isethionic acid
- thehigher fatty acid ethanolamide sulfates the higher fatty acid amides of amino alltyl sulfonic: acids, e. g. lauric amide of taurine, and the like.
- the-effects are particularly enhanced with: thev alkyl aryl sulfonate detergents.
- These aromatic sulfonate' detergents are also known in the art. They may be mononuclear or polynuclear in structure.
- aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, naphthalene, etc.
- the alkyl substituent on the aromatic nucleus may vary widely, as long as the desired detergent power of the active ingradient is preserved; More specific examples of suitable alkyl aromatic sulfonate. detergents are the higher alkyl aromatic sulfonates.
- the higher alkylsubstituent may vary: in themanner described-for such groups in the higher alkyl sulfonamide additives.
- the alkyl group is about 8 to about 22, and preferably about 12 to about 18 carbon atoms. More particularly it is preferred to use the higher alkyl benzene sulfonates wherein the higher alkyl group averages about 12 to about 16 carbon atoms.
- propylene may be polymerized to the tetramer and condensed with benzene in the presenceof a-Friedel- Crafts catalyst to yield essentially the dodecyl benzene derivative which is suitable for sulfonation to the desired sulfonate compounds.
- anionic detergents are generally used inthe form of their water-soluble salts, such as the alkali metal, alkaline earth metal, ammonium, amine, and alkylolamine salts. While the sodium, potassium, ammonium and alkylolalkylolaminesalts in view of: their generalht greater solubility in aqueouasolutionss The-concentration of. these water-soluble: saltsv (including suitable mixtures. thereof): in; the: detergentv compositions of the present. iIlVBIltiOIlrlS generally at least about10% by -weightiof; totalsolidm, and preferably from.
- compositions particularly inparticula-te form,. an active ingredient content of Lil-50%, and preferably about 15-40% yields: highly. satisfactory results.
- the amount of, the sulf-onamideadditives. in the detergent, composition is; generally minor in proportion to the weight, of the: active ingredient. and effective in producing the desired improvements in detersive' capacity and/or foaming, power.
- I-n particulate-detergent composi tions the additive will usually besfrom1about /e. to about 15% by weight of the; deter-gent-com-- position. Particularly effective results. have-been. achieved wherein the additives; are presentein amounts.
- lecularly-d'ehydrated poly-phosphate salts may bewholly or partiallyneutrali'zed, such as the-al kali metal or ammonium-saltsof" tripolyphos-- phoric, tetraphosphoric, and p-yr'ophosphoric acids.
- tetrasodium pyrophosphate hexasodium hexa- Suitable example are sodium tripolyphos metaphosphate (Grahams salt), hexasodium tetraphosphate, etc.
- the synthetic detergent be about to about 50% and usually about to about 40%, and about 10 to about 80% and usually about to about 60% of these water soluble polyphospha-tes, preferably tripolyphosphate, the above percentages being by weight of total solids of the detergent compositions, with an effective amount of the organic additive described above.
- the organic additives may be incorporated with active ingredient and any other ingredients at any point during the manufacturing process at which subsequent operations will not adversely modify the properties of the detergent compositions.
- a variety of procedures which have proved to be convenient, economical, and productive of best results are: the additives may be added to a hot aqueous slurry of about 40 to 50% solids concentration comprising the active ingredient with vigorous stirring to form a smooth, uniform and homogeneous paste, the additives may be dissolved in a suitable solvent and added to the slurry of the active ingredient, or a mixture or emulsion of the additives in water with a minor proportion of the active ingredient may be incorporated into the slurry.
- compositions may be prepared in the form of solutions, pastes or as dry or partially hydrated solid products, preferably in a finely divided condition. It is preferred to prepare the products in particulate form. Accordingly, the slurry of the detergent composition may be subjected to any suitable drying operations and converted to particle form. The mixture may thus be subjected to conventional sprayclrying, roll-drying or drum-drying operations utilizing temperatures above about 212 F. to obtain homogeneous detersive particles.
- the detergent compositions of the present invention may include any of these substances employed by the art in admixture with such detergent compositions generally, provided the use of any such materials does not completely neutralize or remove the effect of the sulfonamide type additives in the relationship set forth.
- These adjuvant builders or additives may be inorganic or organic in structure and may be mixed with the active ingredient in any suitable manner.
- Such convenient inorganic builders or additives as the various alkali metal phosphates (e. g. tri-sodium phosphate), the alkali metal silicates, sulfates, carbonates, etc. may be employed in these compositions.
- Suitable organic materials such as sodium carboxymethylcellulose may also be employed herein.
- a detergent composition is prepared by mixing on a weight basis 20% sodium dodecyl benzene sulfonate (the dodecyl group being derived from a propylene tetramer), 40% sodium tripolyphospate, 3% sodium carbonate, 2% lauryl sulfonamide, and the balance essentially sodium sulfate.
- This composition in 0.25% concentration in soft water is subjected to repeated laundering and dishwashing operations in comparison with similar operations conducted with the same compo-- sition without the lauryl sulfonamide.
- the foam of the detergent composition containing the sulfonamide exhibits greater volume, stability, creaminess and consistency, in comparison to otherwise identical compositions not containing the sulfonamide.
- a detergent composition is prepared by the procedure of Example I with the modifications that the lauryl sulfonamide is 4% by weight, with a correspondingly lowered sodium sulfate content. This composition similarly exhibits improved foaming power.
- EXAMPLE III A detergent composition is prepared by the procedure of Example I with the sulfona-te detergent 25% by weight and only 24% sodium sulfate. This composition in 0.25% concentration in hard water of 300 p. p. m. hardness similarly exhibits better stability, consistency, etc. during laundering and dishwashing in comparison to a blank run without the 2 sulfonamide.
- EXAIVDPLE IV An improved detergent composition is prepared from 20% sodium dodecyl benzene sulfonate, 40% sodium tripolyphosphate, 38% sodium sulfate and 2% lauryl sulfonamide. In laundering operations, this composition exhibits improved soil removal properties, even in com.- parison to a composition having a vastly increased sulfonate detergent content.
- This improved detersive efiect may be indi cated by a soil removal test.
- the testing procedure involves the uniform soiling, washing with particular detergent compositions at F212" PK, and drying of a large number of cotton swatches.
- the whiteness of the various test swatches are measured by a Hunter refiectometer.
- the increase in reflectance due to washing may be calculated by subtracting the average reflectivity of unwashed control samples from the washed swatches.
- the following table indicates the percent increased reflectance, as a maesure of improved soil removal, on cotton swatches using the detergent composition of Example IV containing 20% sulfonate detergent and 2% lauryl sulfonamide in comparison to the use of a detergent oomposition of 35% sulfonate detergent, 40% sodium tripolyphosphate, and 25% sodium sulfate. These tests are conducted at 0.25%, 0.4% and 0.75% concentration of the detergent compositions in soft Water.
- the percentages listed in the table represent the percent change in whiteness reflectance using as a standard the above detergent composition containing 35% sulfonate detergent without organic additive. The value indicates the approximate improved whiteness reflectance as a measure of improved soil'removal using the composition of Example IV in comparison to the standard:
- aroma-s7 Ihe marked: improvement -r'e'sulting' from the use 1 of the detergent composition containing the lauryl -sulfonamide -is clearly evident from: the
- a detergent composition is prepared by forming about a60% .solids slurry containing on a solids basis about 35% 'sodium'propylene tetra- EXAMPLE VI
- the organic additive isthe myristyl sulfonamide, and the'slurry is roll dried at "about'50 lbs. steam pressure to flake form. This composition also possesses highly desirable detersive properties.
- a detergent composition is prepared accordingto the procedure of Example V from. the following ccmponents: 20% sodiumr'lauryl sulfate, 40% sodium-tripolyphosphate,r38% sodium sulfate,and 2% higherxalkyl sulfonamides wherein the higher alkyl groups correspondessentially to those inmixed coconut fatty acids.
- EXAMPLE VIII Another suitable detergent compos'itionisprepared by compounding 25% sodium coconut monoglyceride sulfate, diacid disodium pyrophosphate; 62% sodium sulfate and 3% dodecyl sulfonamide.
- Audetergent composition consisting essentially oivwater-solublei:detergent: selected :from the Iicl-assiconsisting of. ithe-"water-soluble :anionic organic sulfate .and'isulfonate detergents; and. a sulfonamideecompound in an amount. minor in proportionstorsaid. detergent and sufficient toimproverithelsaidaremoval power. thereof,- said sulfonamide represented by the formula:
- R is a higher "alkyl group and Y and Z are weacheselected from mthe: :class :consi'sting. of hydrogenzand' lowera alkyl groups.
- a detergent composition consistingzessentially -z on watere'solubleil detergent selected rfrom the classztconsisting of. the' water solubleranionic organimsulfatennd:sulfonatesidetergentsfiand a sulfonamide compound as an organic builder represented by the formula:
- R is a higher alkyl group of about 8 to 18 carbon atoms and Y and Z are each selected from the class of hydrogen and lower aikyl groups, the proportion of said detergent to sulfonamide compound being from about 50:1 to about 2:1 by weight.
- a detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
- R is a higher alkyl group.
- a detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, about to about 80% of water-soluble inorganic polyphosphate salts, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
- R is a higher alkyl group of about 8 to 18 carbon atoms.
- a detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, about 10 to about 80% of water-soluble inorganic tripolyphosphate salts, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
- R is a higher alkyl group of about 8 to 18 carbon atoms.
- a detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the Water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound as an organic builder represented by the formula:
- R is a higher alkyl group of about 8 to 13 carbon atoms, the proportion of said detergent to sulfonamide compound being from about 50:1 to about 2:1 by weight.
- a detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound in an amount minor in proportion to said detergent and from about /2 to about 15% by weight of the detergent composition, said sulfonamide compound represented by the formula:
- R is a higher alkyl group of 12 to 16 carbon atoms.
- a detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
- R-SO2--NHY wherein R is a higher alkyl group of about 8 to 18 carbon atoms and Y is a lower allryl group of up to about 3 carbon atoms.
- a detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound, in an amount minor in proportion to said detergent and suflicient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
- R-SOzN wherein R is a higher alkyl group of 8 to 18 carbon atoms and Y and Z are lower alkyl groups of up to about 3 carbon atoms each.
- a detergent composition consisting essentially of water-soluble higher alkyl aryl sulfonate detergent, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
- R is a higher alkyl group of about 8 to 13 carbon atoms.
- a detergent composition consisting essentially of water-soluble higher alkyl mononuclear aryl sulfonate detergent, and a sulfonamide compound as an organic builder represented by the formula:
- R is a higher alkyl group of about 12 to 16 carbon atoms.
- a detergent composition consisting essentially of water-soluble higher alkyl benzene sulfonate detergent, about 10 to about of watersoluble inorganic polyphosphate salts and a sulfonamide compound as an organic builder represented by the formula:
- R is a, higher alkyl group of about 8 to 18 carbon atoms, the proportion of said detergent to sulfonamide being from about 50:1 to about 2:1 by weight.
- 1 l i: 15. A detergent composition consisting lessen-"'1 tially of water-soluble aliphatic sulfate detergentz anda sulfonamide compound in an amount minor in proportion: to said: detergent :andssu-fficientxto improve thesoil removal oower'thereof,.'saidzsuisx 5 I wherein'rR is a highersalkyhgroups ofabout..,l2. to- 01/ lficarbonatoms. 7
- A.detergent.compositionconsisting 'essentially of r wateresoluble -highersfatty racid mono? glyceride monosulfate detergent, and a sulfone.
- said sulfonamide compound in an amount minor in propor- 5 tion to said detergent and from about to about 15% by weight of the detergent composition, said sulfonamide compound represented by the formula:
- R is a higher alkyligroup'ofzgabout .12t0, lficarborratoms
- 'A detergent composition 20011518171115 essentially ofi waterssoluble detergent selected fromsthe': class consisting of water solubletanioniciorganic1 sulfate and sulfonatesdetergents, and dodecyl sulfonamide in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof.
- a detergent composition consisting aessent-v tially of waterssoluble:detergentselected fromthe classsconsisting of water-soluble anionic organic:- sulfate and sulfonate-detergents; .and lauryl sulr: fonamide in an: amount minor: in proportion 1 tot.
- said detergent and from about to about ..15%
- composition ⁇ by ,weight of thedetergent.
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Description
Patented Oct. 19, 1954 UNITED STATES TENT OFFICE DETERGENT COMPOSITION S No Drawing. Application March 14, 1951, Serial No. 215,641
20 Claims.
The present invention relates to new synthetic detergent compositions, and, more particularly to qompositions of the type of the anionic sulfate'd and sulfonated detergents having improved properties, and to a process of preparing same.
There has been a considerable amount of research to discover substances or additives which aid the efliciency of detergent compositions. The problem is exceedingly complex, however, in view of the various physico-chemical mechanisms or properties and the like involved in the action of a detergent composition including suspension, interfacial tension, micellar structure, dispersion, foam stability, etc. and the general difiiculty usually in determining the particular mechanism which is being altered by changes in the formulation of detergent compositions.
During recent years, synthetic detergents of the type of the organic sulfates and sulfonates have been developed which have properties which render them highly advantageous for certain uses. In general, the exploration for suitable additives or builders for synthetic detergent compositions of the type of the anionic sulfates and sulfonates has been directed by the requirements of increased foaming and/or detersive power. While the exact relationship, if any, between foaming and detergency is not known, it is highly desirable that these detergent compositions exhibit excellent foaming properties, in addition to a high level of detersive efficiency, particularly for consumer appeal and certain home and industrial uses. In view of the complex nature of both the foam and detergency phenomena, the character of such non-soap synthetic detergents,
-;,and the many other variables in detergent compositions, additives in general exhibit a certain degree of specificity of action.
The alkyl sulfonamide type compounds have been employed as intermediates in the manufacture of detergents, wetting agents, textile softening agents, etc.
It has now been discovered that the presence of a minor proportion of a higher alkyl sulfonamide in detergent compositions consisting essentially of the anionic sulfated and sulfonated detergents is effective in achieving a significant and synergistic enhancement in surface-active properties such as detergency and foaming. In a more specific aspect, the present invention relates to built detergent compositions consisting essentially of the water-soluble sulfated or sulfonated detersive salts, water-soluble polyphosphate material, and a minor proportion of a higher alkyl substituted primary sulfonamide as an organic builder to enhance the action of the detergent composition in aqueous solution. These improvements are unique since such sulfonamides by themselves have poor foaming or deterging properties, and thus are of little value as cleansing agents per se.
The enhancing additives of the present invention are characterized by their generally limited water solubility. More particularly, these additives may be represented by the formula:
wherein R, is a higher alkyl group, and Y and Z individually are selected from the group consisting of hydrogen and lower alkyl.
The higher alkyl substituent may be branched or straight-chain in structure; it comprises moreover such groups as octyl, decyl, dodecyl, keryl, pentadecyl, hexadecyl, mixed long-chain alkyls derived from long-chain fatty materials, cracked paraffin wax olefins, polymers of mono-olefins, etc. This higher alkyl substituent will generally be from about 8 to about 18 carbon atoms, and preferably from about 12 to about 16 carbon atoms.
Included within the ambit of the invention is the following preferred class of compounds suitable as additives which may be represented by the structural formula:
wherein R has-the significance set forth above. Suitable examples of such compounds are octyl sulfonamide, decyl sulfonamide, dodecyl sulfonamide, cocyl sulfonamide wherein the cocyl substituent is a mixture of essentially long-chain alkyls derived from mixed coconut oil fatty acids, dodecyl sulfonamide wherein the dodecyl group is derived from a propylene tetramer, tetradecyl sulfonamide, pentadecyl sulfonamide wherein the pentadecyl group is derived from a propylene pentamer, hexadecyl sulfonaznide, etc.
An additional suitable class is the polyalkyl substituted sulfonamides wherein one alkyl group is long-chain in structure as indicated, and the one or more remaining alkyl groups is lower alkyl in structure. The lower alkyl groups should have a total generally of not in excess of about six carbon atoms. It is preferred that each lower alkyl group be not in excess of about three carbon atoms each. Thus other suitable additives are:
wherein R has the significance set forth above and Y is a lower alkyl group, preferably containing from about 1 to about 3 carbon atoms. Examples of suitable compounds are dodecyl N-methyl sulfonamide, keryl N-methyl sulfonamide, dodecyl N-butyl sulfonamide, tetradecyl N-ethyl sulfonamide, dodecyl N-propylr sulfonamide, etc.
wherein R, is as described above, and Y and- Z may be the same or different, each being selected from the group consisting of lower alkyl. As exemplary of this sub-class are dodecyl N.dimethyl sulfonamide, dodecyl N -diethyl sulfonamide, keryl N-diethyl sulfonamide, dedecyl' N-diisopropyl sulfonamide, dodeoyl N-dipropyl sulfonamide, etc.
These various sulfonamide derivati e's'may be prepared in any suitablemanner and numerous processes for their production are' wellknown: in the art.
The novel compositions-ofthe present invention contain as the active ingredient the anionic sulfated and sulfonated"v detergents, including suitable mixtures thereof; Included therein are the aliphatic suliated or sulfonatedagents, such as th aliphatic acyl containing compounds wherein the acyl radical has about 8 to about 22 carbon atoms, and, more particularly, the aliphatic carboxylic ester type, containing at least about 10 and: preferably about 12 to about 26 carbon atoms to the-molecule.v Amongthe aliphatic detersive compounds it is preferred to use the sulfated aliphaticgcompoundshaving about 1-2 to about 22 carbon atoms- Assuitable examples of aliphatic detergents. may be found the sulfuric acid esters of polyhydric alcohol'sincompletely esterified' with, higher: fatty. acids, e. g. coconut oil monoglyceride monosulf-ate, tallow di-glyceride monosulfate'; the long chain pure or mixed, higher alkyl sulfates, e. g. lauryl. sulfate, cetyl sulfate, higher fatty alcohol sulfates derived from coconut oil; the hydroxy sulfonated higher fatty acid esters, e. g. higher fattyacid esters of 2,3 di-hydroxy propane sulfonic acid; the higher fatty acid esters. of low:- molecular weight alkylol sulfonic acids, e. g. oleic acid ester of isethionic acid; thehigher fatty acid ethanolamide sulfates; the higher fatty acid amides of amino alltyl sulfonic: acids, e. g. lauric amide of taurine, and the like.
It isa feature of this invention that the-effectsare particularly enhanced with: thev alkyl aryl sulfonate detergents. These aromatic sulfonate' detergents are also known in the art. They may be mononuclear or polynuclear in structure.
More particularly; the, aromatic nucleusmay be derived from benzene, toluene, xylene, phenol, cresols, naphthalene, etc. The alkyl substituent on the aromatic nucleus may vary widely, as long as the desired detergent power of the active ingradient is preserved; More specific examples of suitable alkyl aromatic sulfonate. detergents are the higher alkyl aromatic sulfonates. The higher alkylsubstituent may vary: in themanner described-for such groups in the higher alkyl sulfonamide additives. Thus, it may be branched or straight-chain in structure, and comprise decyl, dodecyl, keryl, mixed long-chain alkyls from polymeric; lower mono-olefins, etc. Preferred examples of this class are the higher alkylmon'onuclear aryl sul-' ionates wherein the alkyl group is about 8 to about 22, and preferably about 12 to about 18 carbon atoms. More particularly it is preferred to use the higher alkyl benzene sulfonates wherein the higher alkyl group averages about 12 to about 16 carbon atoms. For example, propylene may be polymerized to the tetramer and condensed with benzene in the presenceof a-Friedel- Crafts catalyst to yield essentially the dodecyl benzene derivative which is suitable for sulfonation to the desired sulfonate compounds.
These various anionic detergents are generally used inthe form of their water-soluble salts, such as the alkali metal, alkaline earth metal, ammonium, amine, and alkylolamine salts. While the sodium, potassium, ammonium and alkylolalkylolaminesalts in view of: their generalht greater solubility in aqueouasolutionss The-concentration of. these water-soluble: saltsv (including suitable mixtures. thereof): in; the: detergentv compositions of the present. iIlVBIltiOIlrlS generally at least about10% by -weightiof; totalsolidm, and preferably from. abo.ut;=l0,-50 With built, compositions, particularly inparticula-te form,. an active ingredient content of Lil-50%, and preferably about 15-40% yields: highly. satisfactory results. Compositions. withvery, high concentration of these active ingredientsae. g;. of= total solids, are prepared/for; specialized uses generally.
The amount of, the sulf-onamideadditives. in the detergent, composition is; generally minor in proportion to the weight, of the: active ingredient. and effective in producing the desired improvements in detersive' capacity and/or foaming, power. Generally, the: proportion by weight-of active ingredient to additive-should bei-fromabout 50:1v to about 2:1. It ispreferredthatthe-addhtive be from about 5; to about-30% of the active ingredients. I-n particulate-detergent composi tions the additive will usually besfrom1about /e. to about 15% by weight of the; deter-gent-com-- position. Particularly effective results. have-been. achieved wherein the additives; are presentein amounts. of the order of: about; l,-to=l0%, ofthe v total. detergent. composition. It, is; preferred usually to use about 1-5% of, additivehowever. The optimum amount of additive and. its, ratio to the active ingredientswillvary according to. u
lecularly-d'ehydrated poly-phosphate saltsmay bewholly or partiallyneutrali'zed, such as the-al kali metal or ammonium-saltsof" tripolyphos-- phoric, tetraphosphoric, and p-yr'ophosphoric acids. phate- (NaaPsoio), potassium tripolyphosphate,
tetrasodium pyrophosphate hexasodium hexa- Suitable example are sodium tripolyphos metaphosphate (Grahams salt), hexasodium tetraphosphate, etc.
With such compositions, it is preferred that the synthetic detergent be about to about 50% and usually about to about 40%, and about 10 to about 80% and usually about to about 60% of these water soluble polyphospha-tes, preferably tripolyphosphate, the above percentages being by weight of total solids of the detergent compositions, with an effective amount of the organic additive described above.
The organic additives may be incorporated with active ingredient and any other ingredients at any point during the manufacturing process at which subsequent operations will not adversely modify the properties of the detergent compositions. A variety of procedures which have proved to be convenient, economical, and productive of best results are: the additives may be added to a hot aqueous slurry of about 40 to 50% solids concentration comprising the active ingredient with vigorous stirring to form a smooth, uniform and homogeneous paste, the additives may be dissolved in a suitable solvent and added to the slurry of the active ingredient, or a mixture or emulsion of the additives in water with a minor proportion of the active ingredient may be incorporated into the slurry.
Thereafter, these compositions may be prepared in the form of solutions, pastes or as dry or partially hydrated solid products, preferably in a finely divided condition. It is preferred to prepare the products in particulate form. Accordingly, the slurry of the detergent composition may be subjected to any suitable drying operations and converted to particle form. The mixture may thus be subjected to conventional sprayclrying, roll-drying or drum-drying operations utilizing temperatures above about 212 F. to obtain homogeneous detersive particles.
It is common to employ various adjuvant materials in synthetic detergent compositions. The detergent compositions of the present invention may include any of these substances employed by the art in admixture with such detergent compositions generally, provided the use of any such materials does not completely neutralize or remove the effect of the sulfonamide type additives in the relationship set forth. These adjuvant builders or additives may be inorganic or organic in structure and may be mixed with the active ingredient in any suitable manner. Such convenient inorganic builders or additives as the various alkali metal phosphates (e. g. tri-sodium phosphate), the alkali metal silicates, sulfates, carbonates, etc. may be employed in these compositions. Suitable organic materials such as sodium carboxymethylcellulose may also be employed herein.
The following examples are additionally illus trative of the nature of the present invention and it will be understood that the invention is not limited thereto:
EXAMPLE I A detergent composition is prepared by mixing on a weight basis 20% sodium dodecyl benzene sulfonate (the dodecyl group being derived from a propylene tetramer), 40% sodium tripolyphospate, 3% sodium carbonate, 2% lauryl sulfonamide, and the balance essentially sodium sulfate.
This composition in 0.25% concentration in soft water is subjected to repeated laundering and dishwashing operations in comparison with similar operations conducted with the same compo-- sition without the lauryl sulfonamide. In each case, it may be noted that the foam of the detergent composition containing the sulfonamide exhibits greater volume, stability, creaminess and consistency, in comparison to otherwise identical compositions not containing the sulfonamide.
EXAll/IPLE II A detergent composition is prepared by the procedure of Example I with the modifications that the lauryl sulfonamide is 4% by weight, with a correspondingly lowered sodium sulfate content. This composition similarly exhibits improved foaming power.
EXAMPLE III A detergent composition is prepared by the procedure of Example I with the sulfona-te detergent 25% by weight and only 24% sodium sulfate. This composition in 0.25% concentration in hard water of 300 p. p. m. hardness similarly exhibits better stability, consistency, etc. during laundering and dishwashing in comparison to a blank run without the 2 sulfonamide.
EXAIVDPLE IV An improved detergent composition is prepared from 20% sodium dodecyl benzene sulfonate, 40% sodium tripolyphosphate, 38% sodium sulfate and 2% lauryl sulfonamide. In laundering operations, this composition exhibits improved soil removal properties, even in com.- parison to a composition having a vastly increased sulfonate detergent content.
This improved detersive efiect may be indi cated by a soil removal test. The testing procedure involves the uniform soiling, washing with particular detergent compositions at F212" PK, and drying of a large number of cotton swatches. The whiteness of the various test swatches are measured by a Hunter refiectometer. The increase in reflectance due to washing may be calculated by subtracting the average reflectivity of unwashed control samples from the washed swatches.
The following table indicates the percent increased reflectance, as a maesure of improved soil removal, on cotton swatches using the detergent composition of Example IV containing 20% sulfonate detergent and 2% lauryl sulfonamide in comparison to the use of a detergent oomposition of 35% sulfonate detergent, 40% sodium tripolyphosphate, and 25% sodium sulfate. These tests are conducted at 0.25%, 0.4% and 0.75% concentration of the detergent compositions in soft Water. The percentages listed in the table represent the percent change in whiteness reflectance using as a standard the above detergent composition containing 35% sulfonate detergent without organic additive. The value indicates the approximate improved whiteness reflectance as a measure of improved soil'removal using the composition of Example IV in comparison to the standard:
Table Concentration of Deterg. Comp.
aroma-s7 Ihe marked: improvement -r'e'sulting' from the use 1 of the detergent composition containing the lauryl -sulfonamide -is clearly evident from: the
data. I It is ap'parentalso that the incorporation ofthese additives -also permits asharp' reduction in the concentration of: the :organic. detergent per se. "It may be further noted. that the improved results are exhibited over a wide range of washing concentrations. This feature is significantalso since itpermits economy of use'and allows a'wi'dela'titude' asto suitable quantities which may-be employed by the consumer! Furthermorethese sulfonamide additives of the =presentinvention usually achieve an-even more A detergent composition is prepared by forming about a60% .solids slurry containing on a solids basis about 35% 'sodium'propylene tetra- EXAMPLE VI A detergent composition is prepared according to theproc'edure of Example V with the-modifications that the active ingredient consists essentially of the kerylbenzene-'sulfonate=-salt.' the organic additive isthe myristyl sulfonamide, and the'slurry is roll dried at "about'50 lbs. steam pressure to flake form. This composition also possesses highly desirable detersive properties.
. EXAMPLEVII A detergent composition is prepared accordingto the procedure of Example V from. the following ccmponents: 20% sodiumr'lauryl sulfate, 40% sodium-tripolyphosphate,r38% sodium sulfate,and 2% higherxalkyl sulfonamides wherein the higher alkyl groups correspondessentially to those inmixed coconut fatty acids.
EXAMPLE VIII Another suitable detergent compos'itionisprepared by compounding 25% sodium coconut monoglyceride sulfate, diacid disodium pyrophosphate; 62% sodium sulfate and 3% dodecyl sulfonamide.
Other formulations (productive of desired results are:
EXAMPLE IX Percent Sodium :fatty alcohol sulfates derived from reduced coconut oil acids 16 Sodium ichloride 1 Sodium itripolyphosphate 38 fletrasodiumpyrophosphate Sodium lsulfate -527 Dodecyl-sulfonamide 3 @Percent -Sodium-dodecy1benzene=sulfonate 9 'sodiurndauryl sulfate -10 Dodecyl and tetradecylsulfonamide (1:1) 3 *Sodium" carboxymethylcellulose 0.5 'Sodiumcarbonate 1.5 "Sodium sulfate Sodium"tripolyphosphate 44 *Tetra-sodium'pyrophosphate '12 EXAMPLE XI Percent Higher-fatty acid amides of taurine derived "from coconut oil "sodium's'ulfate Sodium tripolyphosphate "42 DodecyPsulfonamide 3 "Certain general conclusions are apparent from the many tests-which have beenconduct'ed to determine the effectiveness 'of the additives in the relationship-set fo'rthi' 'I'hemost appropriate additive Land -itsmost efie'ctiveconcentration for each'particular sulphonated orsulphated detergent composition may suitably be determined by routine-controls. lnleach case the intended use (e. g. soft water, rug shampoos or machine washing-compositions;etc.) and the proper Washing conditions should' be taken into consideration in order to derive the maximum beneficial effects.
llheterm -consisting essentially of as used in the 'definiti'on of the ingredients present in the composition claimed is intended to exclude the presence or other materials. in such amounts as to interfere substantially with theproperties and characteristics possessed by' the composition set forthbut to permit th'e presencexof other-materials. in suchcamounts: as not substantially. to efiect said "-i properties: and lzcharacteristicsl radversely.
'JAlthou'ghftherpresent'zinventionshas sbeen =de- :scribedwithareferenc'e to particular embodiments :and examples; itzvvill beapparent'toithose skilled in: :the." artii'th at variations ands modifications 10f this invention; can :bet madefand that equivalents can. ibeizsubstituted therefor without departing from the-. 'principlesrand 'true' spirit of ...the. .invention.
Havingadescribedthe: invention what is desired to=besecuredby Letters Patent is:
. Audetergent: composition consisting essentially oivwater-solublei:detergent: selected :from the Iicl-assiconsisting of. ithe-"water-soluble :anionic organic sulfate .and'isulfonate detergents; and. a sulfonamideecompound in an amount. minor in proportionstorsaid. detergent and sufficient toimproverithelsaidaremoval power. thereof,- said sulfonamide represented by the formula:
wherein R is a higher "alkyl group and Y and Z are weacheselected from mthe: :class :consi'sting. of hydrogenzand' lowera alkyl groups.
2;-A'L detergent: compositioniin accordance with claim. l-wliich containssabout 10 to about:% by weight of wateresoluble"inorganic polyphosphateisalts.
3. A detergent composition consistingzessentially -z on watere'solubleil detergent selected rfrom the classztconsisting of. the' water solubleranionic organimsulfatennd:sulfonatesidetergentsfiand a sulfonamide compound as an organic builder represented by the formula:
wherein R is a higher alkyl group of about 8 to 18 carbon atoms and Y and Z are each selected from the class of hydrogen and lower aikyl groups, the proportion of said detergent to sulfonamide compound being from about 50:1 to about 2:1 by weight.
4. A detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
Rr-SOZ-NHZ wherein R, is a higher alkyl group.
5. A detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, about to about 80% of water-soluble inorganic polyphosphate salts, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
wherein R is a higher alkyl group of about 8 to 18 carbon atoms.
6. A detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, about 10 to about 80% of water-soluble inorganic tripolyphosphate salts, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
wherein R is a higher alkyl group of about 8 to 18 carbon atoms.
'7. A detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the Water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound as an organic builder represented by the formula:
wherein R is a higher alkyl group of about 8 to 13 carbon atoms, the proportion of said detergent to sulfonamide compound being from about 50:1 to about 2:1 by weight.
8. A detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound in an amount minor in proportion to said detergent and from about /2 to about 15% by weight of the detergent composition, said sulfonamide compound represented by the formula:
wherein R is a higher alkyl group of 12 to 16 carbon atoms.
9. A detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
R-SO2--NHY wherein R is a higher alkyl group of about 8 to 18 carbon atoms and Y is a lower allryl group of up to about 3 carbon atoms.
10. A detergent composition consisting essentially of water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide compound, in an amount minor in proportion to said detergent and suflicient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
R-SOzN wherein R is a higher alkyl group of 8 to 18 carbon atoms and Y and Z are lower alkyl groups of up to about 3 carbon atoms each.
11. A detergent composition consisting essentially of water-soluble higher alkyl aryl sulfonate detergent, and a sulfonamide compound in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof, said sulfonamide compound represented by the formula:
wherein R is a higher alkyl group of about 8 to 13 carbon atoms.
12. A detergent composition consisting essentially of water-soluble higher alkyl mononuclear aryl sulfonate detergent, and a sulfonamide compound as an organic builder represented by the formula:
wherein R is a higher alkyl group of about 12 to 16 carbon atoms.
14. A detergent composition consisting essentially of water-soluble higher alkyl benzene sulfonate detergent, about 10 to about of watersoluble inorganic polyphosphate salts and a sulfonamide compound as an organic builder represented by the formula:
wherein R is a, higher alkyl group of about 8 to 18 carbon atoms, the proportion of said detergent to sulfonamide being from about 50:1 to about 2:1 by weight.
1 l i: 15. =A detergent composition consisting lessen-"'1 tially of water-soluble aliphatic sulfate detergentz anda sulfonamide compound in an amount minor in proportion: to said: detergent :andssu-fficientxto improve thesoil removal oower'thereof,.'saidzsuisx 5 I wherein'rR is a highersalkyhgroups ofabout..,l2. to- 01/ lficarbonatoms. 7
1'7. A.detergent.compositionconsisting 'essentially of r wateresoluble -highersfatty=racid mono? glyceride monosulfate detergent, and a sulfone.
amide compound in an amount minor in propor- 5 tion to said detergent and from about to about 15% by weight of the detergent composition, said sulfonamide compound represented by the formula:
nsoi-sNrnfl wherein R is a higher alkyligroup'ofzgabout .12t0, lficarborratoms;
18. 'A detergent composition: 20011518171115 essentially ofi waterssoluble detergent selected fromsthe': class consisting of water solubletanioniciorganic1 sulfate and sulfonatesdetergents, and dodecyl sulfonamide in an amount minor in proportion to said detergent and sufficient to improve the soil removal power thereof.
19; A detergent composition consisting aessent-v tially of waterssoluble:detergentselected fromthe classsconsisting of water-soluble anionic organic:- sulfate and sulfonate-detergents; .and lauryl sulr: fonamide in an: amount minor: in proportion 1 tot.
said detergent and from about to about ..15%
by ,weight of thedetergent. composition};
20.. A detergent composition-rconsisting essem;
' tiallyv of. water-soluble higher alkyl; benzenensulr.
fonate detergent, and lauryl sulfonamide .in- .an.
amount, minoru-inr. proportion (to. said detergent.
and sufficient to improve the soil removal power thereon;
References Cited in thefile'of this'patent UNITED :STATES -PATENTS Number Name Date; 1 j 2,093,941; Albrecht; Sept.v21, 1937 2,1-918003: Henkesc -Apr;.' 23; 194% 2,341,614. 3- Hent-rich .Feb; 15; 19%;; 1486;921:- Byerly:; so- NOV: 1, 19%;
FOREIGN PATENTS Number A Country, Date; v.
413;157 GreatnBritainuunw. July, 19,1934 888,804, r
France DecH23, r1943,
Claims (2)
1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF WATER-SOLUBLE DETERGENT SELECTED FROM THE CLASS CONSISTING OF THE WATER-SOLUBLE ANIONIC ORGANIC SULFATE AND SULFONATE DETERGENTS, AND A SULFONAMIDE COMPOUND IN AN AMOUNT MINOR IN PROPORTION TO SAID DETERGENT AND SUFFICIENT TO IMPROVE THE SAID REMOVAL POWER THEREOF, SAID SULFONAMIDE REPRESENTED BY THE FORMULA:
2. A DETERGENT COMPOSITION IN ACCORDANCE WITH CLAIM 1 WHICH CONTAINS ABOUT 10 TO ABOUT 80% BY WEIGHT OF WATER-SOLUBLE INORGANIC POLYPHOSPHATE SALTS.
Priority Applications (1)
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US215641A US2692237A (en) | 1951-03-14 | 1951-03-14 | Detergent compositions |
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US215641A US2692237A (en) | 1951-03-14 | 1951-03-14 | Detergent compositions |
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US2692237A true US2692237A (en) | 1954-10-19 |
Family
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US215641A Expired - Lifetime US2692237A (en) | 1951-03-14 | 1951-03-14 | Detergent compositions |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE975289C (en) * | 1953-09-06 | 1961-11-02 | Voegele Ag J | Lubrication device |
US4260497A (en) * | 1979-11-26 | 1981-04-07 | Colgate-Palmolive Company | Methanesulfonamides as antistatic agents for laundered fabrics |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB413457A (en) * | 1932-04-20 | 1934-07-19 | Ig Farbenindustrie Ag | Manufacture of emulsifying, cleansing, wetting or softening agents |
US2093947A (en) * | 1934-11-07 | 1937-09-21 | Soc Of Chemical Ind | Sulfamides |
US2197800A (en) * | 1938-06-30 | 1940-04-23 | Du Pont | Reaction of aliphatic hydrocarbons with sulphur dioxide and chlorine and products thereof |
FR888804A (en) * | 1941-12-08 | 1943-12-23 | Ig Farbenindustrie Ag | emulsifiers |
US2341614A (en) * | 1940-02-03 | 1944-02-15 | Hentrich Winfrid | Process for preparing capillary active substances |
US2486921A (en) * | 1944-10-16 | 1949-11-01 | Procter & Gamble | Detergent composition |
-
1951
- 1951-03-14 US US215641A patent/US2692237A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB413457A (en) * | 1932-04-20 | 1934-07-19 | Ig Farbenindustrie Ag | Manufacture of emulsifying, cleansing, wetting or softening agents |
US2093947A (en) * | 1934-11-07 | 1937-09-21 | Soc Of Chemical Ind | Sulfamides |
US2197800A (en) * | 1938-06-30 | 1940-04-23 | Du Pont | Reaction of aliphatic hydrocarbons with sulphur dioxide and chlorine and products thereof |
US2341614A (en) * | 1940-02-03 | 1944-02-15 | Hentrich Winfrid | Process for preparing capillary active substances |
FR888804A (en) * | 1941-12-08 | 1943-12-23 | Ig Farbenindustrie Ag | emulsifiers |
US2486921A (en) * | 1944-10-16 | 1949-11-01 | Procter & Gamble | Detergent composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE975289C (en) * | 1953-09-06 | 1961-11-02 | Voegele Ag J | Lubrication device |
US4260497A (en) * | 1979-11-26 | 1981-04-07 | Colgate-Palmolive Company | Methanesulfonamides as antistatic agents for laundered fabrics |
FR2470120A1 (en) * | 1979-11-26 | 1981-05-29 | Colgate Palmolive Co | METHANESULFONAMIDE CLASS ANTISTATIC AGENTS, WHITENING COMPOSITIONS CONTAINING THE SAME AND METHODS THEREOF |
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