US2589190A - Detergent composition - Google Patents

Detergent composition Download PDF

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US2589190A
US2589190A US764399A US76439947A US2589190A US 2589190 A US2589190 A US 2589190A US 764399 A US764399 A US 764399A US 76439947 A US76439947 A US 76439947A US 2589190 A US2589190 A US 2589190A
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detergent
additive
celluronic
acid
detergency
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US764399A
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John E Hanson
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California Research LLC
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California Research LLC
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Priority to NL148195D priority Critical patent/NL148195C/xx
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Priority to US764399A priority patent/US2589190A/en
Priority to US28853A priority patent/US2590613A/en
Priority to GB19766/48A priority patent/GB653702A/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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • C11D9/262—Organic compounds, e.g. vitamins containing oxygen containing carbohydrates

Definitions

  • This invention relates to improved detergent compositions and more particularly to anionic and non-ionic detergent compositions containing small amounts of a celluronic acid salt of a monovalent cation, capable of enhancing the detergent characteristics of saidcompositions. Specifically it relates to the alkaryl sulfonate-type detergent compositions containing small amounts of a celluronic acid salt of a monovalent cation.
  • celluronic acidf designates the product of selective and controlled oxidation of cellulose wherein only the primary hydroxyl group of anhydroglucose units in the cellulose molecule has undergone oxidation to a carboxyl group, as will be explained hereinafter.
  • a remarkable and unexpected improvement of the detergent properties is secured by intimately incorporating, as by dispersing or dissolving, a celluronic acid salt of a monovalent cation in a composition containing a soap or a synthetic detergent. It has been found that a much greater degree of soil removal is secured in various washing operations because of the presence of such celluronic acid salt additive in the detergent composition than is otherwise obtainable in the absence of said additive.
  • a remarkable feature of the detergent compositions improved in accordance with the present invention is the small amount of the celluronic acid salt required to effect a. significant improvement of detergency.
  • the aforementioned salts of celluronic acids responsible for the new and significant improvement of detergency are prepared by the reaction of an aqueous solution of a base, e. g., sodium hydroxide, pyridine, ammonia, upon the particular derivatives of cellulose produced by the oxidation of cellulose fibers with nitrogen dioxide (NO2-N204) gases.
  • a base e. g., sodium hydroxide, pyridine, ammonia
  • oxidized celluloses obtained in this oxidation are known under the name of celluronic acids and in contradistinction to other types of oxidized celluloses, are the products of a selective and controlled oxidation of cellulose.
  • the selectivity of the NO2N2O4 oxidant for the primary hydroxyl of the anhydroglucose unit of cellulose permits of producing distinct and reproducible species of oxidized cellulose-the celluronic acids.
  • the resulting celluronic acids represent (1) polymers of anhydroglucuronic acid units in the case where the selective oxidation of the primary hydroxyl group is substantially complete, or (2) copolymers of anhydroglucose and anhydroglucuronic acid units, in the case where only a part of anhydroglucose units have been selectively. oxidized by NO2N2O4 gases.
  • the completely oxidized celluronic acid has a theoretical carboxyl content of about 25.57% by weight based on the acid, while the celluronic acid with a carboxyl content of about 13.3% is a polymer of equimolar amounts of anhydroglucose and anhydroglucuronic acid units.
  • all of the celluronic acid with a carboxyl content of about 13.3% is a polymer of equimolar amounts of anhydroglucose and anhydroglucuronic acid units.
  • celluronic acids are characterized by a high afiinity for dyes and readily absorb, e. g., methylene blue and rosaniline acetate.
  • celluronic acids which have a carboxyl content of more than about 11.5% by weight, though not directly soluble in water, form water-soluble salts with monovalent cations.
  • carboxyl content of celluronic acids is more than about '7 but less than about 11.5% by weight, they are either insoluble or partly insoluble in dilute (1-2%) alkalies.
  • salts of celluronic acids may be prepared by reacting thereon with an aqueous solution of a monovalent base, e. g., dilute solution of sodium or potassium hydroxide. They may be also prepared by reacting celluronic acids with an aqueous solution of a salt of a weak acid, such as sodium carbonate.
  • the salt of celluronic acid in an amount of at least 0.5%, and preferably 3%, and usually not greater than about 5%, by weight of the total dry ingredients in the detergent mixture is intimately dispersed in the detergent mixture supplied in a suitable form, e. g., as a slurry or a solution. Water is added, if necessary, to obtain the desired concentration of the mixture, and the resulting composition dried, e. g., by drum-drying, and recovered as a product having dispersed therein the required amount of the celluronic acid salt additive.
  • dispersed means intimately distributed, e. g., in the form of a colloidal dispersion, solution or emulsion within the detergent mixture.
  • the remarkable improvement in detergency brought about by dispersing a small amount of a celluronic salt in a detergent composition is shown by the experimental data in the following Table I.
  • the tests represented by these data are launderometer tests of soil removal from hard twisted cotton, the soil uniformly applied to the sample swatches of cotton being of an oily type (a paste of oil, tallow and carbon black). These tests are effected under conditions generally applied in common laundering processes, using procedures standardized to give reliable results which would be comparable to those of the actual practice.
  • the temperature of the tests is about 140 F., though higher or lower temperatures do not afiect the action of the celluronic acid salt additive.
  • the several detergent compositions which are used to compare the effect of an addition of the celluronic acid salt thereto with the detergency effects displayed without such an addition, include: a well-known anionic detergent composition comprising the salt of a half-ester of an alkenyl dicarboxylic acid designated as detergent X, an anionic mixture comprising sodium alkyl benzene sulfonate with 12 to 15 carbon atoms in the .alkyl chain and produced by alkylating benzene with polypropene and designated as Detergent A, a non-ionic alkyl phenolpolyglycol ether composition designated as Detergent Y, and an anionic sulfate of a fatty acid monoglyceride designated as Detergent Z.
  • Sodium salt of celluronic acid with a carboxyl content of 11.5 to 18.5% in an amount of 5% .by weight of the total dry ingredients of the detergent mixture is used.
  • the uniformly soiled swatches of cotton are subjected in each instance to a series of 4 consecutive washings of 20 minutes duration, and the degree of whiteness obtained is measured in a photoelectric apparatus free of human equation.
  • the detergency ratings in Table I are computed with reference to an arbitrarily chosen standard, namely, detergency (whiteness level) obtained with a 0.4% concentration of wellknown soap D in hard water (300 parts per million). taken to be equal 100 and designated as Soap Index.
  • the alkaryl sulfonate-type detergents are found to constitute particularly suitable materials capable of a striking improvement in detergency upon the addition of small amounts of monovalent cation salts of celluronic acids.
  • alkaryl. sulfonates applicable for the preparation of the detergent compositions of the present invention contain an alkyl chain of not less than 8 and not more than 20 carbon atoms, directly linked to the aryl nucleus.
  • alkyl mononuclear aryl sulfonates such as alkyl benzene sulfonates and alkyl toluene sulfonates, containing from not less than 8 to not more than;20 carbon atoms in the alkyl chain represent suitable ingredients for the preparation of the detergent compositions of the invention, a particularly desirable material being alkyl benzene sulfonates containing from 12 to 15 carbon atoms in the alkyl chain.
  • sulfonates are obtained by alkylating benzene with polypropene, sulfonating the alkylate and neutralizing to form a water-soluble salt.
  • polypropene e. g., polybutene or chlorinated kerosene
  • alkylate e. g., polybutene or chlorinated kerosene
  • Suitable inorganic salts e. g., sodium sulfate or sodium chloride, may be used to improve the sulfonate mixture, to enhance solubility and to insure a non-hygroscopic, non-caking detergent product.
  • the proportion of sodium sulfate in the detergent mixture depending on the particular intended application of the detergent. varies from 0 to 90% based on the total weight of the dry sulfonate and sulfate ingredi ents, but preferably is greater than 50% and less than 80% by weight.
  • the proportion of alkyl benzene sulfonate in the dry detergent mixture may be from 10% to 100% by weight of the total dry sulfonate-sulfate mixture (on additive-free basis, i. e., in the absence of the celluronic acid salt additive), and preferably less than 50% and at least by weight.
  • suitable inorganic alkali metal or ammonium salts such as borates, phosphates, silicate, carbonates, and the like, may be incorporated as detergent extenders or builders.
  • the alkali metal polyphosphates, such as tetrasodium pyrophosphate and sodium tetraphosphate are particularly effective builders.
  • an aqueous slurry e. g., of sodium alkyl benzene sulfonate and sodium sulfate ingredients in a desired proportion is first prepared. Then at least 0.5%, and preferably 3%, and usually not more than about 5%, by weight based on the total dry ingredients of the detergent mixture of a sodium salt of celluronic acid is dispersed in this slurry in the required amount, and water is subsequently added, if necessary, to bring the concentration of the mixture to about 70% of water, whereupon the dry detergent is recovered by drum-drying.
  • the dried product represents an intimate mixture of sodium alkyl benzene sulfonate and sodium sulfate, having dispersed therein a small amount of a sodium salt of celluronic acid.
  • compositions of the present invention and particularly of the preferred alkaryl sulfonate-type compositions are brought to light by the examination of experimental data presented hereinafter in the form of tables and graphs.
  • the tests illustrated by these data are effected under conditions similar to those used in tests of Tables I and II.
  • the amount of the sodium salt of celluronic acids added to improve detergency is equal to 3% by weight, unless otherwise indicated.
  • the preferred alkyl benzene sulfonate detergent of the invention containing from 12 to 15 carbon atoms in the alkyl chain and produced by alkylating the benzene ring with polypropene, comprises parts of sodium alkyl benzene sulfonate to parts of sodium sulfate on additive-free basis and similarly in Tables I and II is designated as Detergent A. Other designations of the various compositions tested are also the same as in Tables I and II.
  • the detergency ratings for various detergents are computed either in terms of the percentage of soil removal or with reference to one of the two arbitrarily chosen standards: (1 detergency obtained with a 0.2% concentration of Detergent B in hard water (300 parts per million) ⁇ assumed to be equal and designated as Detergent Index; and (2) detergency obtained with a 0.4% concentration of soap D in hard water (300 parts per million), which has been used as a standard in Tables I and II hereinbefore.
  • Table III shows the differences in the improve Table III [97% Detergent A+3% additive] Carboxyl Content in Per cent by Weight 53%; 'ig gi The data on soil removal assembled in Table IV again clearly show the existence of an optimum range of carboxylcontent between about 11.5% 11) 18.5
  • Table VI contains the results of launderometer tests for varying total concentration of the improved detergent mixture and shows the increase in detergency resulting from the introduction of celluronic acid additive upon increasing the total concentration of the detergent. mixture.
  • Table VI Per cent Concentration Soap 97% Detergent A+3% additive
  • Table VII illustrates the effect of salts of celluronic acids on the detergency of various commercial products in hard water. All of the compositions tested show an improvement in detergency in the presence of the new additive of the invention. However, a truly remarkable improvement is observed only for alkyl benzene sulfonate Detergents A and C.
  • Table VII Per cent Soap Composition Concentration Index Detergent A .2 44 Detergent A+3% additive .2 63 Deter ent B .2 42 Detergent 3+3 2 54 Detergent O 2 37 Detergent (D+3% additive. 2 61 Soap D (.4% concentration) .l- 4 62 Soap D+3% additive 4 68
  • Table VIII contains additional data from similar tests with various commercial detergents, the detergency being evaluated in this instance in terms of the Soap Index mentioned hereinbefore.
  • Table [X Per Cent Sample Soil Removal 60 (97% sulfonate+3% additive) +40% Na SOl 59 50% (97% sulionate+3% additive) +50% N 32304 57 40% sulfonate (no additive) +00% N3ZsO-4 30 40% (97% sulf0nate+3% additive) +60% NQZSQA 57 30%sulionate -(no additive) +70% NazS 04 38 30% (07% sulfonate+3% additive) +70% Na1SO 51
  • TableiX showsthe improving effect of the salts of celluronic acids on sulfonate/sulfate detergent :mixtures containing a-minor amount of an inorganic builder, such as tetrasodium pyrophosphate.
  • Fig. 1 graphically represents the data of Table III, while Fig. 2 corresponds to the data in Table V.
  • the most effective detergency improvers are those salts of a celluronic acid with a monovalent cation base, which have a carboxyl content from about 11.5 to about 18.5% by weight of the acid, though salts having a lower or a higher carboxyl content are also found to improve detergency;
  • alkaryl sulfonate type detergents and, in particular, those containing not less than 8 and not more than 20 carbon atoms, and preferably from 12 to 15 carbon atoms; in the alkyl chain, and obtained by alkylating benzene with polypropene, sulfonating the alkylate and neutralizing, are found to be exceptionally improved by the addition of small amounts of the aforementioned salts of celluronic acids;
  • alkali metal salts of celluronic acids in deter ent compositions.
  • Other wholly or partly soluble salts of celluronic acids produced, for instance, by dissolving them in dilute ammonia, warm aqueous pyridine.
  • aqueous solutions of quaternary ammonium hydroxides, sodium carbonate or sodium acetate possess a like property of improving detergency.
  • the valuable improved deter ent compositions of this invention are capable of numerous applications, namely, in laundering of textile fabrics and similar materials, in washing automobiles, various painted and metal surfaces, glass ware, ceramic ware, in dishwashing, window-washing and various other domestic and industrial uses.
  • a detergent composition comprising an alkaryl sulfonate detergent containing from 8 to 20 carbon atoms in the alkyl chain and a minor amount of a water-soluble, alkali metal salt of a cellurcnic acid, sufficient to enhance the detergency characteristics of said sulfonate deter ent and being from at least 0.5% to less than 50% by weight of the solid constituents thereof, the carboxyl content of said celluronic acid salt being from about 7 to about 20% by weight based on the acid.
  • a detergent composition comprising an alkyl monoaryl sulfonate detergent containing from 8 to 20 carbon atoms in the alkyl chain and a minor amount of a water-soluble, alkali metal salt of a celluronic acid, sufiicient to enhance the detergency characteristics of said sulfonate detergent and being from at least 0.5% to less than 50% by weight of the solid constituents 11 thereof, the: carboxyl contentof said celluronic acid, saltbeing fromabout'? to about 20% by weightzbased on the acid.
  • Adetergent composition as defined in claim 2, wherein said alkyl monoaryl sulfonate contains fromlZ to 15 carbonatoms in the alkyl chain, and-said celluronic acid salt has a carboxyl content from about 11.5 to about 18.5% by weight based: on the acid.
  • A. detergent composition comprising a monoalkylbenzene sulfonate containing from 8 to 20 carbon atoms in the alkyl chain and a minor amount of analkalimetal salt of a celluronic acid suflicient to enhance the detergency characteristics of said sulfonate and being from at least 0.5% to less than150% by weight of the. solid constituentsvthereof, the carboxyl content of said celluronic acid salt being from. about 7 to about 20% by; weight based on theacld,
  • Adetergent composition comprisinga monoalkyl benzene. sulfonate' containing from 12 to 15 carbonatoms in the alkyl chain and a. minor amount of an. alkali metal salt of a celluronic acidsuflicient to enhancethe-detergency charamount of a sodium salt: of a celluronic acid, suflicient to enhance the detergency characteristics of said sulfonate and being from at least 0.5% to less than 50% by weight of the solid constituents thereof, the carboxyl content of said celluronic acid salt being from about 11.5 to about 18.5% by weight based on the acid.
  • Adetergent composition comprising a polypropyl benzene sulfonatercontaining from 12 to 15. carbon atoms in the polypropyl chain and a minor-amount of a sodium salt of a celluronic acid, sufiicient to enhance the detergency characteristics of said sulfonate and being from at least 0.5% to less than 50% by weight of the. solid constituents thereof, the'carboxyl content of said sodium salt of celluronic acid being from about 7 to about 20% by weight based on the acid.

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  • Health & Medical Sciences (AREA)
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US764399A 1947-07-29 1947-07-29 Detergent composition Expired - Lifetime US2589190A (en)

Priority Applications (4)

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NL148195D NL148195C (enrdf_load_stackoverflow) 1947-07-29
US764399A US2589190A (en) 1947-07-29 1947-07-29 Detergent composition
US28853A US2590613A (en) 1947-07-29 1948-05-24 Detergent composition
GB19766/48A GB653702A (en) 1947-07-29 1948-07-23 Detergent compositions

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB211294A (en) * 1922-12-21 1924-02-21 Grigori Petroff Process for the manufacture of detergent compositions
US2201741A (en) * 1938-10-03 1940-05-21 Du Pont Polymeric materials
US2232990A (en) * 1938-07-15 1941-02-25 Eastman Kodak Co Preparation of oxycellulose
US2347336A (en) * 1939-01-04 1944-04-25 Allied Chem & Dye Corp Detergent composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB211294A (en) * 1922-12-21 1924-02-21 Grigori Petroff Process for the manufacture of detergent compositions
US2232990A (en) * 1938-07-15 1941-02-25 Eastman Kodak Co Preparation of oxycellulose
US2201741A (en) * 1938-10-03 1940-05-21 Du Pont Polymeric materials
US2347336A (en) * 1939-01-04 1944-04-25 Allied Chem & Dye Corp Detergent composition

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GB653702A (en) 1951-05-23

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