US3516937A - Sustained action detergent product containing encapsulated sodium tripolyphosphate - Google Patents

Sustained action detergent product containing encapsulated sodium tripolyphosphate Download PDF

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US3516937A
US3516937A US638566A US3516937DA US3516937A US 3516937 A US3516937 A US 3516937A US 638566 A US638566 A US 638566A US 3516937D A US3516937D A US 3516937DA US 3516937 A US3516937 A US 3516937A
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detergent
sodium
tripolyphosphate
weight
water
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Julian R Story
Aaron B Herrick
Eric Jungermann
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Armour and Co
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Armour and Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/65Mixtures of anionic with cationic compounds
    • C11D1/655Mixtures of sulfonated products with alkylolamides of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2989Microcapsule with solid core [includes liposome]

Definitions

  • a light duty detergent composition in the form of granules or a tablet, providing a lotion-like feel when dissolved in water and having sustained cleaning action.
  • the composition includes an anionic or non-ionic detergent, a fatty alkanolamide or amine oxide suds booster, and sodium tripolyphosphate, a portion of the tripolyphosphate being encapsulated by a polymeric film forming material relatively insoluble to water.
  • This invention relates to a detergent composition in the form of discrete granules or a tablet, and particularly to a detergent product for use in hand dishwashing, or other manual washing where the hands of the person doing the washing may be in prolonged contact with the detergent-containing water.
  • This invention also relates to self-disintegrating detergent tablets which are adapted, when introduced into water, to breakup readily and to promote the dissolution of the ingredients therein without the need for substantial mechanical agitation. Addi tionally, the detergent product of this invention has good cleaning action over an extended period of time.
  • Heavy duty detergent tablets containing non-foaming nonionic surfactant have heretofore been used in mechanical washing operations, such as in household automatic washing machines.
  • the mechanical agitation causes the rapid disintegration of the tablet and the solubilization of the ingredients.
  • the hands of the person using the detergent tablet normally are not in contact with the wash water for any extended period of time.
  • the situation is quite different, however, for manual washing applications, such as hand dishwashing.
  • Mechanical agitation is not available to breakup and dissolve the tablet, and the hands of the dishwasher are in contact with the wash solution for considerable periods of time. Further, washing operations may extend over a greater period of time; and the detergent becomes progressively inactivated as the soils such as grease are concurrently removed from the dishes.
  • the present invention is based in part on the discovery that unexpected mildness can be obtained in the Wash solution by employing a detergent which contains a fatty ethanolamide or an amine oxide suds booster together with sodium tripolyphosphate builder to cut 'ice greases.
  • a detergent which contains a fatty ethanolamide or an amine oxide suds booster together with sodium tripolyphosphate builder to cut 'ice greases.
  • These ingredients when employed as hereinafter described, provide an unctuous or lotion-like feel when the detergent tablet is dissolved in water. This feel is pleasant and is very desirable in dishwashing detergent products which come in contact with the hands for relatively long periods of time.
  • the unctuous feel obtained by the present invention has the particular advantage that it can be produced even though the detergent tablet results in a solution having a substantially neutral pH.
  • the present invention is based in part, further on the discovery that the cleaning action of such a product can be sustained over an extended period of time by encapsulating at least a portion of the sodium tripolyphosphate.
  • Encapsulating the tripolyphosphate as hereafter described provides for adequate initial grease and dirt emulsification, yet a portion of such cleaning power is reserved and released at later times when greasy pots and pans are normally washed.
  • the reserved release of cleaning action obtained by the present invention has the particular advantage of providing a uniform cleaning throughout the entire washing operation.
  • our invention may be exemplified by a detergent tablet composition
  • a detergent tablet composition comprising, by weight, from 5 to 20% of an anionic or nonionic surface active agent; from 0.5 to 10% of a fatty ethanolamide or amine oxide suds booster; and the balance of the product consisting of inorganic builders and fillers such as sodium tripolyphosphate, Na SO and NaHCO with about 10 to 60% being tripoly hosphate, preferably in the form of its sodium salt, about 20 to by weight of said tripolyphosphate being in the form of discrete particles coated with a slowly water-soluble polymeric film.
  • inorganic builders and fillers such as sodium tripolyphosphate, Na SO and NaHCO with about 10 to 60% being tripoly hosphate, preferably in the form of its sodium salt, about 20 to by weight of said tripolyphosphate being in the form of discrete particles coated with a slowly water-soluble polymeric film.
  • Detersive surface active agents which are suitable for use in this invention, include conventional soaps, synthetic detergents of the anionic and nonionic types, and mixtures thereof.
  • the conventional soaps can be described as the water-soluble, amonium, alkali metal, or organic base salts of various fatty acids having from 12 to 18 carbon atoms.
  • Suitable anionic type synthetics can be described as those detergents having pronounced cleansing power and including in their molecular structure an alkyl radical containing from 6 to 18 carbon atoms and a sulfonic acid or sulfuric acid ester radical.
  • Organic base, ammonium, sodium, or potassium salts of the anionic type detergents can be used.
  • the main types of detergents falling within this class are the alkylaryl sulfonates, such as sodium or potassium dodecylbenzene sulfonate, sodium or potassium octylnaphthalene sulfonate; the alkyl sulfates such as sodium or potassium salts of dodecyl, hexadecyl, and octadecyl sulfates; the sulfonated fatty acid amides, such as sodium or potassium salts of the oleic acid amide of methyltaurine; and the sulfonated mono glycerides, such as the mono-coconut oil fatty acid ester of l,Z-hydroxypropane-3-sodium sulfonate.
  • alkylaryl sulfonates such as sodium or potassium dodecylbenzene sulfonate, sodium or potassium octylnaphthalene sulfonate
  • linear alkyl groups are especially desirable because of their biodegradable features; and preferably they contain 12 to 14 carbon atoms in their alkyl group, such as dodecylbenzene sulfonate or tridecylbenzene sulfonate. Since ammonium soaps and synthetic detergents will give off an ammonia odor in the presence of alkaline salts, they are generally not desirable in this type of product unless an ammonia image is desired. From the standpoint of detergent properties, the tridecylbenzene sulfonate is preferred.
  • the alkylbenzene sulfonate detergent can be used either in granular form or in flake form, although the granular form is preferred.
  • the detergent is produced in admixture with sodium sulfate.
  • spray-dried beads or granules of sodium tridecylbenzene sulfonate may contain as much as two parts by weight of sodium sulfate per part of active detergent.
  • Alkylbenzene sulfonate detergents in flake form will contain a lesser proportion of sodium sulfate.
  • the detergent can be incorporated into our product without the removal of the sodium sulfate.
  • the nonionic type synthetic detergents which are useful in this invention can be described as those detergents which do not ionize in solution, but owe their watersolubility to nonionizing polar groups such as hydroxyl or ether linkages.
  • the main types of detergents falling within this category are the polyoxyethylene ethersof the higher fatty alcohols and alkyl phenols; the polyethylene glycols of fatty acids; fatty alkylol amide condensation products; fatty acid ethylene oxide condensation products; condensation products of ethylene oxide and a fatty acid ester of a polyhydric alcohol or sugar; and the detergents prepared by heating together a higher fatty acid with diethanol amine.
  • Suitable synthetic non'ionics include ethylene oxide-fatty alcohol fatty acid reaction products; iso-octylphenol-ethylene oxide reaction products; and combinations of iso-octylphenol-ethylene oxide with coconut oil fatty acid-ethylene oxide reaction products.
  • the anionic detergents are preferred because of their high sudsing or high foaming characteristics. However, it may be desired to use a nonionic detergent because of its sustained grease removal characteristics. Concentration of the detergent ingredient in the product is variable and generally to 20% by weight based on the total weight of the product is completely satisfactory.
  • the fatty ethanolamide ingredient can be either a monoethanolamide or a diethanolamide, but the diethanolamides are preferred.
  • the amide can be lauric mono-ethanolamide, myristic monoethanolamide, lauric diethanolamide, myristic diethanolamide, or mixtures thereof.
  • coco monoethanolamide or coco diethanolamide which contain mixed lauric and myristic amides in the proportion of the coconut oil generally used as the fatty source.
  • Suitable amine oxide ingredients can be described as those having pronounced suds boosting power and being chemically characterized as the reaction product of hydrogen peroxide and either a tertiary alkyl amine wherein at least one alkyl radical contains from 6 to 18 carbon atoms or a heterocyclic amine of the morpholine type containing at least one alkyl radical having from 6 to 18 carbon atoms.
  • Exemplary amine oxides within this class include dimethylhexadecylamine oxide, hydrogenated tallow amine oxide, dimethyl myristiccetylamine oxide, dodecylamine oxide, phenylstearyldimethylamine oxide, and N-dodecylmorpholine oxide and N-cocomorpholine oxide. Dimethyldodecylamine oxide and N-cocomorpholine oxide are preferred.
  • the tablets can contain a quantity of ethanolamide or amine oxide coming within the range from 0.5 to 16% by weight based on the total composition of the tablet.
  • the ethanolamide or amine oxide is incorporated in the tablet in an amount ranging from 1 to 5% by weight. Good results have been achieved when employing about 2 to 5% by weight of these suds Iboosters.
  • the tripolyphosphate will usually be in the form of a sodium salt.
  • a sodium salt for example, from to 60% by weight of sodium tripolyphosphate based on the total weight of the tablet ingredients can be employed.
  • the amount of tripolyphosphate will usually range from to 50% by weight, for example, about to 40% by weight.
  • On the basis of the amide usually from 5 to 10 parts by weight of the tripolyphosphate will be employed per part of the fatty ethanolamide.
  • high temperature rise sodium tripolyphosphate is also sometimes referred to as Phase I or Form 1 tripolyphosphate. High temperature rise sodium tripolyphosphate is available commercially.
  • tripolyphosphate when introduced into water undergoes a substantial temperature rise and tends to swell or enlarge in volume due to the heat generated. This aids the rapid breakup of the detergent tablet and dissolution of the active ingredients into the wash solution.
  • Suitable film forming materials are those which will form a slowly water-soluble film upon codried particles of the tripolyphosphate.
  • Gelatin, polyvinyl alcohol, polyvinyl acetate, carboxymethylcellulose and hydroxyethylcellulose are preferred; and gelatin is especially desirable.
  • These materials may be sorbed onto the tripolyphosphate by any suitable means such as by a plating technique involving: forming a 25% gelatin solution, permitting it to cool to about F., mixing into the solution the sodium tripolyphosphate granules in about a 3 :1 phosphate to gelatin ratio for a short period of time (about 5 to 15 minutes), and then drying the encapsulated sodium tripolyphosphate at about F. for about 16 hours.
  • the dried sodium tripolyphosphate particles remain as discrete particles, coated with a slowly water-soluble film which provides a delay for up to about 15 minutes in the dissolution of these particles in water.
  • proportions of 25 to 100 parts of solid gel encapsulating material per 100 parts of sodium tripolyphosphate may be used.
  • Different times for release of the encapsulated tripolyphosphate may be achieved by the use of encapsulating materials having different rates of dissolution, such as the gelatin above, which by the above-described method, will provide a delayed release up to about 10 minutes and thicker coating which will provide a delay of about 15 to 30 minutes.
  • Different immersion times in the encapsulating material solution for different portions of tripolyphosphate will also provide coatings of different thickness on the different portions, and thereby provide timed dissolution of the coated tripolyphosphate; viz immersing one-third of the total tripolyphosphate in the above gelatin solution for 5 minutes, another one-third for 10 minutes, and the final one-third for 15 minutes.
  • Varying the bloom of the gelatin applied to the tripolyphosphate will also provide difiering times of release.
  • the proportion of total polyphosphate ingredient in the tablet which is encapsulated may vary widely, depending generally upon the quantity of tripolyphosphate present in the tablet, whether gradients of sustained action are desired, and the degree of cleaning power to be reserved. It is desirable that about 20 to 75% of the total tripolyphosphate be encapsulated; a preferred proportion for a single later release is 50%.
  • an effervescent composition or mixture can be incorporated.
  • the tablets can contain from 25 to 60% by weight of the effervescent composition.
  • the effervescent composition can be formulated in a similar manner to that used for other kinds of self-disintegrating tablets. More specifically, the effervescent composition will be composed of at least one water-soluble carbonate salt releasing carbon dioxide in acidic aqueous solution and at least one watersoluble acidic carbon dioxide releasing agent.
  • the carbonate salt is sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, or mixtures of two or more of these carbonate salts may also be used.
  • the carbon dioxide releasing agent is preferably an inorganic acid salt, such as sodium dihydrogen phosphate, or sodium acid pyrophosphate.
  • Organic acids can also be used instead of or in addition to the inorganic acid salt. Examples of suitable organic acids are citric acid, tartaric acid, or fumaric acid.
  • the detergent tablets of this invention can also contain other ingredients of the kind which have heretofore been used in detergent compositions.
  • the tablets can contain brighteners, pigments, and perfumes.
  • the use of the combination of the fatty ethanolamide and the tripolyphosphate provides a further advantage.
  • the amide is diificult to incorporate in the detergent product, and there is a further difiiculty in distributing the amide in a tablet product in such a way that it dissolves readily when the tablet disintegrates in the water. It has been found that these problems can be substantially solved by a procedure wherein the amide is first mixed or combined with the other ingredients of the detergent tablet.
  • the amide can be mixed with the tripolyphosphate, and the mixture granulated in the presence of sufiicient water to promote the formation of granules.
  • the resulting granules can then be mixed and blended with the other ingredients to form the complete mixture for tableting.
  • Another suitable procedure is to liquefy or melt the amide, and then to mix or blend the molten amide with the tripolyphosphate.
  • the resulting blend or mixture can then be combined with the other detergent ingredients for tableting.
  • coco diethanolamide can be heated to a temperature within the range from 80 to 100 F., and then blended with the sodium tripolyphosphate.
  • only part of the sodium tripolyphosphate can be used for premixing with the amide, although it is preferred to use a substantially larger proportion of the tripolyphosphate in relation to amide. For example, from 5 to parts by weight of the tripolyphosphate can be used per part of amide.
  • self-disintegrating detergent tablets prepared in accordance with the present invention are as follows:
  • EXAMPLE 1 Tablets were prepared from spray-dried beads of tridecylbenzene sulfonate containing approximately 35% by weight of the active detergent together with 65% of sodium sulfate.
  • 250 lbs. of the detergent beads were mixed and blended with 230 lbs. of monosodiumphosphate, and 200 lbs. of sodium bicarbonate together with small quantities of a brightener, a red pigment dye, and a perfume, totaling 3.2 lbs. All of these ingredients were in the form of dry powders.
  • 148.4 lbs. of sodium tripolyphosphate (high temperature rise- Phase I) was mixed with 20 lbs.
  • Example 2 The procedure of Example 1 was followed except that the lauric-myristic diethanolamide was melted, and introduced into a ribbon-type mixture together with the sodium tripolyphosphate. The blending and mixing was continued until the two ingredients formed a dry free flowing mixture. The remainder of the ingredients were then mixed in to prepare the complete mixture for tableting.
  • EXAMPLE 3 Tablets were prepared from spray-dried beads of tridecylbenzene sulfonate containing approximately 35% by weight of the active detergent together with 65 of sodium sulfate. 25 parts by weight of these detergent beads were mixed and blended with 10 parts of sodium dihydrogen phosphate, parts of citric acid, parts of sodium bicarbonate, and 20 parts of sodium carbonate. All of these ingredients were in the form of dry powders or granules, 3 parts by weight of lauric-myristic diethanolamide was mixed with 4 parts by weight of sodium tripolyphosphate, and this mixture was granulated in the presence of sufficient Water to promote the formation of the granules. The resulting granules were then heated to 220 F.
  • EXAMPLE 4 The same procedure of Example 3 was followed except that 37 parts by weight of the detergent beads were mixed with 15 parts by weight of citric acid, 15 parts of sodium bicarbonate and 10 parts of sodium carbonate. 5 parts of lauric-myristic diethanolamide were mixed with 10 parts of sodium tripolyphosphate and 8 parts of tetrasodium pyrophosphate, and granulated as described in Example 3. 23 parts by weight of the resulting granules were mixed with the other ingredients (including encapsulated tripolyphosphate) prior to tableting.
  • EXAMPLE 5 A mixture comprising 12 parts by weight of tridecylbenzene sulfonate, 28 parts of sodium sulfate, 6 parts of lauric-myristic diethanolamide, and 19 parts of sodium tripolyphosphate was formed into an aqueous solution, and subjected to spray drying. Alternatively, these ingredients can be mixed in the presence of a lesser amount of water and subjected to mechanical granulation. 65 parts by weight of the resulting beads or granules are then mixed with 15 parts by weight of powdered citric acid and 20 parts by weight of anhydrous sodium sesquicarbonate. The mixture is then tableted in a tableting press at pressures ranging from 400 to 6000 p.s.i.
  • EXAMPLE 6 A mixture consisting of 3 parts by weight of lauric myristic monoethanolamide in the dry granular form and 15 parts by weight of sodium tripolyphosphate were mixed thoroughly until a uniform blend, with the monoethanolamide in a finely divided state, was formed. This mixture was blended with 25 parts by weight of spraydried sodium tridecylbenzene sulfonate (35% active-65% sodium sulfate), 22 parts by weight of sodium dihydrogen phopsate, 15 parts by weight of gelatin encapsulated tripolyphosphate (ratio of 1:1 of gelatin to tripolyphosphate) and 20 parts by weight of sodium bicarbonate. This mixture is then tableted in a tableting press at pressures ranging from 400 to 2000 p.s.i.
  • sustained action of detergent tablets prepared in accordance with the present invention are as follows:
  • the test involves generating a foam by pouring water into a sink containing the detergent composition to be tested. Dinner plates, soiled with a specified standard soil, are then washed in a definitely prescribed manner until the foam is broken. The number of plates required to reach this point is designated as the plate mileage.
  • a number of glazed 10 inch diameter dinner plates are cleansed, and 5.5 grams of soil is spread uniformly on the top surface of each of the clean plates.
  • the standard soil used is a freshly prepared mixture, by weight, of 1 8.3% lard (not hydrogenated), 9.2% Wesson Oil, 9.2% Mazola Corn Oil, 4.2% oleic acid, 0.4% salt, 0.4% gelatin, 41.6% flour and 16.7% water (135 p.p.m. hardness).
  • 6.0 grams of the detergent composition to be tested is added to a stoppered sink and 9 quarts of water (tap water of 135 p.p.m. hardness) at 115 F. is added through a funnel mounted so that the delivering tip is centered 30 inches above the bottom of the sink.
  • the soiled plates are placed two at a time into the wash solution, and washed one at a time using an 18 inch by 18 inch clean Indianhead cloth as a wash rag.
  • the plates are washed at a uniform pace using 5 circular motions on each side of the plate, while keeping the plate substantially below the surface of the wash solution. Washing, one plate at a time, is continued until all the suds disappear. This is called the suds endpoint. At this time, washing is discontinued and the number of washed plates are counted and recorded as the plate mileage for the sample at the water hardness used.
  • Standard Detergent represents a known liquid deter-gent containing a linear alkyl aryl sulfonate detergent and about 6% of an ethoxylated sulfated nonionic detergent (sodium dodecyl ether sulfate).
  • Standard Detergent represents a built liquid detergent containing 68% of an alkylaryl sulfonate and 12-14% of a tetrapotassium pyrosulfate.
  • Standard Detergent*** represents a liquid detergent containing an alkyl ether sulfate and either an amide or amine oxide suds booster in a 3:1 ratio.
  • the dye-fat mixture is prepared by melting a quantity of hydrogenated vegetable cooling fat, dispersing 1% of D&C Orange #4 in the fat, and allowing the fat, to reharden. Prior to starting the test, the fat is remelted to 60 C. and taken up in a 1 ml. pipette. One drop from the pipette is placed on each of the slides and allowed to harden for 45 minutes before tesing.
  • the slides are pretreated by washing each slide with a test tube brush in hot soapy water, rinsing, placing the slide in boiling chromic acid for 15 minutes, rinsing each slide in tap water several times and twice in deionized water, drying them in an oven, and placing then in a NaNO desiccator for at least 45 "minutes.
  • the detergents grease removal efficiency at various stages of the dishwashing operation is measured by determining the number of immersions required to remove a standard soil from a microscope slide under standardized conditions.
  • Plate Mileage Test it is possible to measure both the over-all efficiency of a detergent (Plate Mileage Test) and the changes in efliciency during the course of dishwashing operations (Grease Removal Test).
  • dinner plates are soiled with 5.5 grams of standard soil as per Plate Mileage Test of Example 7.
  • Solutions of the detergent to be tested are prepared in stoppered sinks as follows:
  • Table III illustrates grease removal efficiencies before any dishes are washed in the test solution and again after 6, 10, 15, 30 and 45 dishes have been washed.
  • composition of claim 1 in which said detersive surface active agent is an alkyl-aryl sulfonate wherein the alkyl radical contains from 12 to 14 carbon atoms; the suds booster is coco-ethanolamide selected from the group consisting of monoethanolamide and diethanolamide.
  • a detergent tablet consisting essentially of, by
  • An improved dry detergent composition consisting essentially of (1) 5 to 20% by weight of a detersive surface active agent selected from the group consisting of ammonium and alkali metal salts of fatty acids having from 12 to 18 carbon atoms, anionic synthetic detergents, nonionic synthetic detergents and mixtures thereof; (2) 0.5 to 16% by weight of a suds booster selected from the group consisting of fatty ethanolamides wherein said fatty source is derived from coconut oil, amine oxides having at least one alkyl radical containing from 6 to 18 carbons, and mixtures thereof; and .(3) from about 10 to 60% by weight of sodium tripolyphosphate; wherein about 20 to 75% of said tripolyphosphate being in the form of discrete particles encapsulated by a water-soluble polymeric material selected from the group consisting of gelatin, polyvinyl alcohol, polyvinyl acetate, carboxymethylcellulose and hydroxyethylcellulose.
  • a detersive surface active agent selected from the group consisting of ammonium and alkali
  • composition of claim 1 in which about 50% of said tripolyphosphate is encapsulated by said polymeric material.
  • the detergent tablet of claim 5 which additionally includes from 25 to 60% by weight of an efiervescent composition consisting essentially of (a) a water soluble carbonate salt selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and mitxures thereof and (b) a carbon dioxide releasing agent selected from the group consisting of sodium dihydrogen phosphate, sodium acid pyrophosphate, ciftric acid, tartaric acid, fumaric acid and mixtures there- 0 References Cited UNITED STATES PATENTS 3,401,123 9/1968 Brynko et al. 252-316 LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.
  • an efiervescent composition consisting essentially of (a) a water soluble carbonate salt selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and mitxures thereof and (b) a carbon dioxide releasing agent selected from the group

Description

United States Patent O 3,516,937 SUSTAINED ACTION DETERGENT PROD- UCT CONTAINING ENCAPSULATED S- DIUM TRIPOLYPHOSPHATE Julian R. Story, Wheaton, Aaron B. Herrick, La Grange,
and Eric .lungermann, Chicago, Ill., assignors to Armour and Company, Chicago, 111., a corporation of Delaware No Drawing, Filed May 15, 1967, Ser. No. 638,566 Int. Cl. Clld 9/14, 3/22, 3/066 U.S. Cl. 252110 7 Claims ABSTRACT OF THE DISCLOSURE A light duty detergent composition in the form of granules or a tablet, providing a lotion-like feel when dissolved in water and having sustained cleaning action. The composition includes an anionic or non-ionic detergent, a fatty alkanolamide or amine oxide suds booster, and sodium tripolyphosphate, a portion of the tripolyphosphate being encapsulated by a polymeric film forming material relatively insoluble to water.
This application is a continuation-in-part of our copending application Ser. No. 280,715, filed on May 15, 1963, now abandoned.
This invention relates to a detergent composition in the form of discrete granules or a tablet, and particularly to a detergent product for use in hand dishwashing, or other manual washing where the hands of the person doing the washing may be in prolonged contact with the detergent-containing water. This invention also relates to self-disintegrating detergent tablets which are adapted, when introduced into water, to breakup readily and to promote the dissolution of the ingredients therein without the need for substantial mechanical agitation. Addi tionally, the detergent product of this invention has good cleaning action over an extended period of time.
Heavy duty detergent tablets containing non-foaming nonionic surfactant have heretofore been used in mechanical washing operations, such as in household automatic washing machines. In such applications, the mechanical agitation causes the rapid disintegration of the tablet and the solubilization of the ingredients. Further, the hands of the person using the detergent tablet normally are not in contact with the wash water for any extended period of time. The situation is quite different, however, for manual washing applications, such as hand dishwashing. Mechanical agitation is not available to breakup and dissolve the tablet, and the hands of the dishwasher are in contact with the wash solution for considerable periods of time. Further, washing operations may extend over a greater period of time; and the detergent becomes progressively inactivated as the soils such as grease are concurrently removed from the dishes. Often, grease-laden utensils such as pots and pans are the last to be washed, and there is no reserve cleaning power available in the wash solution for effective cleaning of such utensils. There is therefore a need for a detergent tablet which is substantially self-disintegrating, and which upon dissolution in the wash water forms a wash solution which is mild to the hands and which has good clean ing action over an extended period of time. It is therefore the principal object of this invention to provide a detergent tablet which accomplishes these objectives.
The present invention is based in part on the discovery that unexpected mildness can be obtained in the Wash solution by employing a detergent which contains a fatty ethanolamide or an amine oxide suds booster together with sodium tripolyphosphate builder to cut 'ice greases. These ingredients, when employed as hereinafter described, provide an unctuous or lotion-like feel when the detergent tablet is dissolved in water. This feel is pleasant and is very desirable in dishwashing detergent products which come in contact with the hands for relatively long periods of time. The unctuous feel obtained by the present invention has the particular advantage that it can be produced even though the detergent tablet results in a solution having a substantially neutral pH.
The present invention is based in part, further on the discovery that the cleaning action of such a product can be sustained over an extended period of time by encapsulating at least a portion of the sodium tripolyphosphate. Encapsulating the tripolyphosphate as hereafter described provides for adequate initial grease and dirt emulsification, yet a portion of such cleaning power is reserved and released at later times when greasy pots and pans are normally washed. The reserved release of cleaning action obtained by the present invention has the particular advantage of providing a uniform cleaning throughout the entire washing operation.
In one embodiment, our invention may be exemplified by a detergent tablet composition comprising, by weight, from 5 to 20% of an anionic or nonionic surface active agent; from 0.5 to 10% of a fatty ethanolamide or amine oxide suds booster; and the balance of the product consisting of inorganic builders and fillers such as sodium tripolyphosphate, Na SO and NaHCO with about 10 to 60% being tripoly hosphate, preferably in the form of its sodium salt, about 20 to by weight of said tripolyphosphate being in the form of discrete particles coated with a slowly water-soluble polymeric film.
Detersive surface active agents which are suitable for use in this invention, include conventional soaps, synthetic detergents of the anionic and nonionic types, and mixtures thereof. The conventional soaps can be described as the water-soluble, amonium, alkali metal, or organic base salts of various fatty acids having from 12 to 18 carbon atoms. Suitable anionic type synthetics can be described as those detergents having pronounced cleansing power and including in their molecular structure an alkyl radical containing from 6 to 18 carbon atoms and a sulfonic acid or sulfuric acid ester radical. Organic base, ammonium, sodium, or potassium salts of the anionic type detergents can be used. The main types of detergents falling within this class are the alkylaryl sulfonates, such as sodium or potassium dodecylbenzene sulfonate, sodium or potassium octylnaphthalene sulfonate; the alkyl sulfates such as sodium or potassium salts of dodecyl, hexadecyl, and octadecyl sulfates; the sulfonated fatty acid amides, such as sodium or potassium salts of the oleic acid amide of methyltaurine; and the sulfonated mono glycerides, such as the mono-coconut oil fatty acid ester of l,Z-hydroxypropane-3-sodium sulfonate. Of this class, linear alkyl groups are especially desirable because of their biodegradable features; and preferably they contain 12 to 14 carbon atoms in their alkyl group, such as dodecylbenzene sulfonate or tridecylbenzene sulfonate. Since ammonium soaps and synthetic detergents will give off an ammonia odor in the presence of alkaline salts, they are generally not desirable in this type of product unless an ammonia image is desired. From the standpoint of detergent properties, the tridecylbenzene sulfonate is preferred. The alkylbenzene sulfonate detergent can be used either in granular form or in flake form, although the granular form is preferred. Usually, the detergent is produced in admixture with sodium sulfate. For example, spray-dried beads or granules of sodium tridecylbenzene sulfonate, as produced for commercial sale, may contain as much as two parts by weight of sodium sulfate per part of active detergent. Alkylbenzene sulfonate detergents in flake form will contain a lesser proportion of sodium sulfate. The detergent can be incorporated into our product without the removal of the sodium sulfate.
The nonionic type synthetic detergents which are useful in this invention can be described as those detergents which do not ionize in solution, but owe their watersolubility to nonionizing polar groups such as hydroxyl or ether linkages. The main types of detergents falling within this category are the polyoxyethylene ethersof the higher fatty alcohols and alkyl phenols; the polyethylene glycols of fatty acids; fatty alkylol amide condensation products; fatty acid ethylene oxide condensation products; condensation products of ethylene oxide and a fatty acid ester of a polyhydric alcohol or sugar; and the detergents prepared by heating together a higher fatty acid with diethanol amine. Examples of suitable synthetic non'ionics include ethylene oxide-fatty alcohol fatty acid reaction products; iso-octylphenol-ethylene oxide reaction products; and combinations of iso-octylphenol-ethylene oxide with coconut oil fatty acid-ethylene oxide reaction products.
Generally, the anionic detergents are preferred because of their high sudsing or high foaming characteristics. However, it may be desired to use a nonionic detergent because of its sustained grease removal characteristics. Concentration of the detergent ingredient in the product is variable and generally to 20% by weight based on the total weight of the product is completely satisfactory.
The fatty ethanolamide ingredient can be either a monoethanolamide or a diethanolamide, but the diethanolamides are preferred. For example, the amide can be lauric mono-ethanolamide, myristic monoethanolamide, lauric diethanolamide, myristic diethanolamide, or mixtures thereof. Specifically preferred are coco monoethanolamide or coco diethanolamide, which contain mixed lauric and myristic amides in the proportion of the coconut oil generally used as the fatty source.
Suitable amine oxide ingredients can be described as those having pronounced suds boosting power and being chemically characterized as the reaction product of hydrogen peroxide and either a tertiary alkyl amine wherein at least one alkyl radical contains from 6 to 18 carbon atoms or a heterocyclic amine of the morpholine type containing at least one alkyl radical having from 6 to 18 carbon atoms. Exemplary amine oxides within this class include dimethylhexadecylamine oxide, hydrogenated tallow amine oxide, dimethyl myristiccetylamine oxide, dodecylamine oxide, phenylstearyldimethylamine oxide, and N-dodecylmorpholine oxide and N-cocomorpholine oxide. Dimethyldodecylamine oxide and N-cocomorpholine oxide are preferred.
The tablets can contain a quantity of ethanolamide or amine oxide coming within the range from 0.5 to 16% by weight based on the total composition of the tablet.
Preferably, however, the ethanolamide or amine oxide is incorporated in the tablet in an amount ranging from 1 to 5% by weight. Good results have been achieved when employing about 2 to 5% by weight of these suds Iboosters.
The tripolyphosphate will usually be in the form of a sodium salt. For example, from to 60% by weight of sodium tripolyphosphate based on the total weight of the tablet ingredients can be employed. In the preferred formulations, the amount of tripolyphosphate will usually range from to 50% by weight, for example, about to 40% by weight. On the basis of the amide, usually from 5 to 10 parts by weight of the tripolyphosphate will be employed per part of the fatty ethanolamide. For the purpose of promoting the disintegration of the tablets when introduced into water, it is preferred to employ high temperature rise sodium tripolyphosphate. This form of sodium tripolyphosphate is also sometimes referred to as Phase I or Form 1 tripolyphosphate. High temperature rise sodium tripolyphosphate is available commercially.
This form of tripolyphosphate when introduced into water undergoes a substantial temperature rise and tends to swell or enlarge in volume due to the heat generated. This aids the rapid breakup of the detergent tablet and dissolution of the active ingredients into the wash solution.
The advantage of sustained cleaning action over an extended period of time is accomplished by encapsulating a substantial portion of the tripolyphosphate with a polymeric film forming material. Suitable film forming materials are those which will form a slowly water-soluble film upon codried particles of the tripolyphosphate. Gelatin, polyvinyl alcohol, polyvinyl acetate, carboxymethylcellulose and hydroxyethylcellulose are preferred; and gelatin is especially desirable. These materials may be sorbed onto the tripolyphosphate by any suitable means such as by a plating technique involving: forming a 25% gelatin solution, permitting it to cool to about F., mixing into the solution the sodium tripolyphosphate granules in about a 3 :1 phosphate to gelatin ratio for a short period of time (about 5 to 15 minutes), and then drying the encapsulated sodium tripolyphosphate at about F. for about 16 hours. The dried sodium tripolyphosphate particles remain as discrete particles, coated with a slowly water-soluble film which provides a delay for up to about 15 minutes in the dissolution of these particles in water. In the above encapsulating procedure, we prefer to use proportions of 25 to 100 parts of solid gel encapsulating material per 100 parts of sodium tripolyphosphate; although other proportions within the range of 10 to parts of gel to 100 parts of STP, may be used.
Different times for release of the encapsulated tripolyphosphate may be achieved by the use of encapsulating materials having different rates of dissolution, such as the gelatin above, which by the above-described method, will provide a delayed release up to about 10 minutes and thicker coating which will provide a delay of about 15 to 30 minutes. Different immersion times in the encapsulating material solution for different portions of tripolyphosphate will also provide coatings of different thickness on the different portions, and thereby provide timed dissolution of the coated tripolyphosphate; viz immersing one-third of the total tripolyphosphate in the above gelatin solution for 5 minutes, another one-third for 10 minutes, and the final one-third for 15 minutes. Varying the bloom of the gelatin applied to the tripolyphosphate will also provide difiering times of release. The proportion of total polyphosphate ingredient in the tablet which is encapsulated may vary widely, depending generally upon the quantity of tripolyphosphate present in the tablet, whether gradients of sustained action are desired, and the degree of cleaning power to be reserved. It is desirable that about 20 to 75% of the total tripolyphosphate be encapsulated; a preferred proportion for a single later release is 50%.
Where a fully self-disintegrating detergent tablet is desired, as for hand washing applications, an effervescent composition or mixture can be incorporated. For example, the tablets can contain from 25 to 60% by weight of the effervescent composition. The effervescent composition can be formulated in a similar manner to that used for other kinds of self-disintegrating tablets. More specifically, the effervescent composition will be composed of at least one water-soluble carbonate salt releasing carbon dioxide in acidic aqueous solution and at least one watersoluble acidic carbon dioxide releasing agent. Preferably, the carbonate salt is sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, or mixtures of two or more of these carbonate salts may also be used. The carbon dioxide releasing agent is preferably an inorganic acid salt, such as sodium dihydrogen phosphate, or sodium acid pyrophosphate. Organic acids can also be used instead of or in addition to the inorganic acid salt. Examples of suitable organic acids are citric acid, tartaric acid, or fumaric acid.
The detergent tablets of this invention can also contain other ingredients of the kind which have heretofore been used in detergent compositions. For example, the tablets can contain brighteners, pigments, and perfumes.
The use of the combination of the fatty ethanolamide and the tripolyphosphate provides a further advantage. The amide is diificult to incorporate in the detergent product, and there is a further difiiculty in distributing the amide in a tablet product in such a way that it dissolves readily when the tablet disintegrates in the water. It has been found that these problems can be substantially solved by a procedure wherein the amide is first mixed or combined with the other ingredients of the detergent tablet. For example, the amide can be mixed with the tripolyphosphate, and the mixture granulated in the presence of sufiicient water to promote the formation of granules. After drying the granules to remove any excess water, the resulting granules can then be mixed and blended with the other ingredients to form the complete mixture for tableting. Another suitable procedure is to liquefy or melt the amide, and then to mix or blend the molten amide with the tripolyphosphate. The resulting blend or mixture can then be combined with the other detergent ingredients for tableting. For example, coco diethanolamide can be heated to a temperature within the range from 80 to 100 F., and then blended with the sodium tripolyphosphate. If desired, only part of the sodium tripolyphosphate can be used for premixing with the amide, although it is preferred to use a substantially larger proportion of the tripolyphosphate in relation to amide. For example, from 5 to parts by weight of the tripolyphosphate can be used per part of amide.
Specific examples of self-disintegrating detergent tablets prepared in accordance with the present invention are as follows:
EXAMPLE 1 Tablets were prepared from spray-dried beads of tridecylbenzene sulfonate containing approximately 35% by weight of the active detergent together with 65% of sodium sulfate. In preparing approximately 1,000 lbs. of material for tableting, 250 lbs. of the detergent beads were mixed and blended with 230 lbs. of monosodiumphosphate, and 200 lbs. of sodium bicarbonate together with small quantities of a brightener, a red pigment dye, and a perfume, totaling 3.2 lbs. All of these ingredients were in the form of dry powders. In a separate operation, 148.4 lbs. of sodium tripolyphosphate (high temperature rise- Phase I) was mixed with 20 lbs. of lauric-myristic diethanolamide, and this mixture was granulated in the presence of suflicient water to promote the formation of the granules. The resulting granules were then heated to remove all the moisture. In another separate operation, 148.4 lbs. of sodium tripolyphosphate (high temperature risePhase I) was plated out with a 25% gelatin solution in a 1:4 ratio of gelatin to sodium tripolyphosphate. Thereafter the granulated material was mixed and blended with the other ingredients (including the gelatin encapsulated sodium tripolyphosphate) to form the complete mixture for tableting. The mixture was formed into tablets in a tableting press.
EXAMPLE 2 The procedure of Example 1 was followed except that the lauric-myristic diethanolamide was melted, and introduced into a ribbon-type mixture together with the sodium tripolyphosphate. The blending and mixing was continued until the two ingredients formed a dry free flowing mixture. The remainder of the ingredients were then mixed in to prepare the complete mixture for tableting.
EXAMPLE 3 Tablets were prepared from spray-dried beads of tridecylbenzene sulfonate containing approximately 35% by weight of the active detergent together with 65 of sodium sulfate. 25 parts by weight of these detergent beads were mixed and blended with 10 parts of sodium dihydrogen phosphate, parts of citric acid, parts of sodium bicarbonate, and 20 parts of sodium carbonate. All of these ingredients were in the form of dry powders or granules, 3 parts by weight of lauric-myristic diethanolamide was mixed with 4 parts by weight of sodium tripolyphosphate, and this mixture was granulated in the presence of sufficient Water to promote the formation of the granules. The resulting granules were then heated to 220 F. to remove all the moisture. To 7 parts by weight of the resulting granules was added 3 parts of gelatin encapsulated sodium tripolyphosphate (plated out with a 25 gelatin solution in a 1:1 ratio of gelatin to tripolyphosphate). 10 parts by weight of the resulting granules including the encapsulated tripolyphosphate was then mixed and blended with the other ingredients to form the complete mixture for tableting. The mixture was formed into tablets in a press at pressures ranging from 400 to 2000 p.s.i. The resulting tablets were found to have a substantially greater density than water, and to be sufiiciently firm to permit packaging and shipment. The tablets disintegrated rapidly in water, and remained submerged during the disintegration. The unencapsulated portion of tripolyphosphate was found to have dissolved almost immediately; the encapsulated portion began to dissolve effectively 10 to 15 minutes later.
EXAMPLE 4 The same procedure of Example 3 was followed except that 37 parts by weight of the detergent beads were mixed with 15 parts by weight of citric acid, 15 parts of sodium bicarbonate and 10 parts of sodium carbonate. 5 parts of lauric-myristic diethanolamide were mixed with 10 parts of sodium tripolyphosphate and 8 parts of tetrasodium pyrophosphate, and granulated as described in Example 3. 23 parts by weight of the resulting granules were mixed with the other ingredients (including encapsulated tripolyphosphate) prior to tableting.
EXAMPLE 5 A mixture comprising 12 parts by weight of tridecylbenzene sulfonate, 28 parts of sodium sulfate, 6 parts of lauric-myristic diethanolamide, and 19 parts of sodium tripolyphosphate was formed into an aqueous solution, and subjected to spray drying. Alternatively, these ingredients can be mixed in the presence of a lesser amount of water and subjected to mechanical granulation. 65 parts by weight of the resulting beads or granules are then mixed with 15 parts by weight of powdered citric acid and 20 parts by weight of anhydrous sodium sesquicarbonate. The mixture is then tableted in a tableting press at pressures ranging from 400 to 6000 p.s.i.
EXAMPLE 6 A mixture consisting of 3 parts by weight of lauric myristic monoethanolamide in the dry granular form and 15 parts by weight of sodium tripolyphosphate were mixed thoroughly until a uniform blend, with the monoethanolamide in a finely divided state, was formed. This mixture was blended with 25 parts by weight of spraydried sodium tridecylbenzene sulfonate (35% active-65% sodium sulfate), 22 parts by weight of sodium dihydrogen phopsate, 15 parts by weight of gelatin encapsulated tripolyphosphate (ratio of 1:1 of gelatin to tripolyphosphate) and 20 parts by weight of sodium bicarbonate. This mixture is then tableted in a tableting press at pressures ranging from 400 to 2000 p.s.i.
Specific examples of the sustained action of detergent tablets prepared in accordance with the present invention are as follows:
EXAMPLE 7 Sudsing and suds durability performance were determined by a Plate Mileage Test as follows:
In general, the test involves generating a foam by pouring water into a sink containing the detergent composition to be tested. Dinner plates, soiled with a specified standard soil, are then washed in a definitely prescribed manner until the foam is broken. The number of plates required to reach this point is designated as the plate mileage.
Specifically, a number of glazed 10 inch diameter dinner plates are cleansed, and 5.5 grams of soil is spread uniformly on the top surface of each of the clean plates. The standard soil used is a freshly prepared mixture, by weight, of 1 8.3% lard (not hydrogenated), 9.2% Wesson Oil, 9.2% Mazola Corn Oil, 4.2% oleic acid, 0.4% salt, 0.4% gelatin, 41.6% flour and 16.7% water (135 p.p.m. hardness). Then 6.0 grams of the detergent composition to be tested is added to a stoppered sink and 9 quarts of water (tap water of 135 p.p.m. hardness) at 115 F. is added through a funnel mounted so that the delivering tip is centered 30 inches above the bottom of the sink. The soiled plates are placed two at a time into the wash solution, and washed one at a time using an 18 inch by 18 inch clean Indianhead cloth as a wash rag. The plates are washed at a uniform pace using 5 circular motions on each side of the plate, while keeping the plate substantially below the surface of the wash solution. Washing, one plate at a time, is continued until all the suds disappear. This is called the suds endpoint. At this time, washing is discontinued and the number of washed plates are counted and recorded as the plate mileage for the sample at the water hardness used.
Table I sets forth exemplary Plate Mileage Test results for various formulations of our composition as compared with 3 known light duty detergent compositions. In the table, Standard Detergent represents a known liquid deter-gent containing a linear alkyl aryl sulfonate detergent and about 6% of an ethoxylated sulfated nonionic detergent (sodium dodecyl ether sulfate). Standard Detergent represents a built liquid detergent containing 68% of an alkylaryl sulfonate and 12-14% of a tetrapotassium pyrosulfate. Standard Detergent*** represents a liquid detergent containing an alkyl ether sulfate and either an amide or amine oxide suds booster in a 3:1 ratio.
8 1 tablet (or 6 grams of a liquid detergent) in 9 liters of water. No dishes are washed in this solution.
1 tablet in 9 liters of water 6 dishes are washed in this solution.
1 tablet in 9 liters of water -1 dishes are washed in this solution.
1 tablet in 9 liters of water 30 dishes are washed in this solution.
1 tablet in 9 liters of water 45 dishes are washed in this solution.
Thereafter approximately 500 ml. of each of these detergent solutions is placed in a beaker and the beaker is placed in a constant temperature bath. The temperature of the solution is brought to 112 F. and maintained at this temperature throughout the test. A number of stainless glass microscope slides, attached to mechanical dipping machines positioned over each of the test solutions, are soiled with one drop of a dye-fat mixture and dipping is begun.
The dye-fat mixture is prepared by melting a quantity of hydrogenated vegetable cooling fat, dispersing 1% of D&C Orange #4 in the fat, and allowing the fat, to reharden. Prior to starting the test, the fat is remelted to 60 C. and taken up in a 1 ml. pipette. One drop from the pipette is placed on each of the slides and allowed to harden for 45 minutes before tesing.
Previous to use in the test, the slides are pretreated by washing each slide with a test tube brush in hot soapy water, rinsing, placing the slide in boiling chromic acid for 15 minutes, rinsing each slide in tap water several times and twice in deionized water, drying them in an oven, and placing then in a NaNO desiccator for at least 45 "minutes.
TAB LE I.PLATE MILEAGE [Sustained Cleaning Power Light Duty Detergent Tablet g.)]
Standard Standard Standard Ingredient formulation Percent of Ingredient Detergent Detergent" Detergentfi Sodium tridecyl benzene sulfonate 15 16 15 15 15 15 Ooeo-mono-ethanolamide 5 5 5 5 5 5 Unencapsulated sodium tripolyphosphate 35 20 20 15 Encapsulated sodium tripolyphcsphate (4 parts of active gelatin, 1 STP) 15 Encapsulated sodium t polyphosphate (1 part of 25% ac ve gelatin, 4 STP) 15 Insol. metaphosphate 20 NaHzPO 23 23 23 23 23 23 NaHOOa 20 20 20 20 20 20 NazSOi 2 2 2 2 2 Plate mileage tap water 48 44 44 43 45 45 26 19 26 EXAMPLE 8 Sustained cleaning power was measured by the following grease removal method:
Generally, the detergents grease removal efficiency at various stages of the dishwashing operation is measured by determining the number of immersions required to remove a standard soil from a microscope slide under standardized conditions. By combining this test with the Plate Mileage Test, it is possible to measure both the over-all efficiency of a detergent (Plate Mileage Test) and the changes in efliciency during the course of dishwashing operations (Grease Removal Test).
Specifically, dinner plates are soiled with 5.5 grams of standard soil as per Plate Mileage Test of Example 7. Solutions of the detergent to be tested are prepared in stoppered sinks as follows:
Dipping of the slides into the test detergent solution is continued until all of the red coloring matter of the dye-fat mixture is removed from the slide. The number of immersions required to remove all of the coloring is recorded. The number of immersions obtained on 4 runs for each of duplicate detergent test solutions are averaged and divided into to obtain accurate grease removal efliciencies. The higher the grease removal efliciency value, the better the grease removal characteristics of the detergent. Exemplary results comparing detergent formulations to known liquid detergents is set forth in Table II. The same Standard Detergents used in Example 7 were used in this example.
Table III illustrates grease removal efficiencies before any dishes are washed in the test solution and again after 6, 10, 15, 30 and 45 dishes have been washed.
4. The composition of claim 1 in which said detersive surface active agent is an alkyl-aryl sulfonate wherein the alkyl radical contains from 12 to 14 carbon atoms; the suds booster is coco-ethanolamide selected from the group consisting of monoethanolamide and diethanolamide.
5. A detergent tablet consisting essentially of, by
TABLE II.GREASE REMOVAL EFFICIENCIES [Sustained Cleaning Power Light Duty Detergent Tablet (20 g.)]
Standard Standard Standard Ingredient formulation Percent of Ingredient Detergent Detergent Detergent*** Sodium tridecylbenzee sulionate 15 15 15 15 15 Coco-mono-ethonolamide 5 Unencapsulated sodium tripolyphosphate Encapsulated sodium tripolyphosphate (4 gelatin, 1 STP) Encapsulated sodium tripolyphosphate (1 gelatin, 4 STP) 35 15 Insol. metaphosphate 2 2 2 2 2 2 Grease removal efiiciencies for 15 plates 7. 8 7. 5. 9 08. 5 10. 0 8. 4 6. 8 4. 8 5, 0
TABLE III.GREASE REMOVAL EFFICIENCIES [Sustained Cleaning Power Light Duty Detergent Tablet (20 g.)]
Initial 5 15 45 0 plates plates plates plates plates Standard Detergent- 6. 6 5. 7 5. 1 4. 8 4. 5 Standard Detergent* 6.0 6.0 5. 0 5. 7 5.0 Standard Detergent*** 5. 7 3. 8 4. 2 3. 4 3. 3 Tablet containing:
10% Sodium didodecylbeuzene sulfonate (NaDDBS) 8. 8 9. 8 8. 9 7. G 7 2% Coco mono-ethanol-(CMEA) amide 45% unencapsulated sodium tripolyphosphate (STP) Table containing:
10% NaDDBS 2% CMEA 20% unencapsulated STP 7. 4 8. 2 7. 8 7. 7 7 6 25% gelatin encapsulated STP While in the foregoing specification this invention has been described in relation to preferred embodiments thereof and many details have been set forth for purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to other embodiments than those specifically described herein, and that many of the details set forth in the foregoing specification can be varied considerably without departing from the basic principles of the invention.
What is claimed is:
1. An improved dry detergent composition consisting essentially of (1) 5 to 20% by weight of a detersive surface active agent selected from the group consisting of ammonium and alkali metal salts of fatty acids having from 12 to 18 carbon atoms, anionic synthetic detergents, nonionic synthetic detergents and mixtures thereof; (2) 0.5 to 16% by weight of a suds booster selected from the group consisting of fatty ethanolamides wherein said fatty source is derived from coconut oil, amine oxides having at least one alkyl radical containing from 6 to 18 carbons, and mixtures thereof; and .(3) from about 10 to 60% by weight of sodium tripolyphosphate; wherein about 20 to 75% of said tripolyphosphate being in the form of discrete particles encapsulated by a water-soluble polymeric material selected from the group consisting of gelatin, polyvinyl alcohol, polyvinyl acetate, carboxymethylcellulose and hydroxyethylcellulose.
2. The composition of claim 1 in which said polymeric material is gelatin.
3. The composition of claim 1 in which about 50% of said tripolyphosphate is encapsulated by said polymeric material.
weight, from 5 to 20% of sodium tridecylbenzene sulfonate; from 0.5 to 16% of lauric-myristic diethanolamide; and from 20 to 50% of sodium tripolyphosphate, about 20 to of said tripolyphosphate being in the form of discrete particles encapsulated by a water soluble polymeric material selected from the group consisting of gelatin, polyvinyl alcohol, polyvinyl acetate, carboxymethylcellulose and hydroxyethylcellulose.
6. The composition of claim 5 in which said polymeric material is gelatin.
7. The detergent tablet of claim 5 which additionally includes from 25 to 60% by weight of an efiervescent composition consisting essentially of (a) a water soluble carbonate salt selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and mitxures thereof and (b) a carbon dioxide releasing agent selected from the group consisting of sodium dihydrogen phosphate, sodium acid pyrophosphate, ciftric acid, tartaric acid, fumaric acid and mixtures there- 0 References Cited UNITED STATES PATENTS 3,401,123 9/1968 Brynko et al. 252-316 LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.
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US4113644A (en) * 1975-02-20 1978-09-12 Ashcraft William R Protected glassy phosphate detergent additive
US4124521A (en) * 1976-12-09 1978-11-07 Revlon, Inc. Soaps containing encapsulated oils
US4303542A (en) * 1979-04-23 1981-12-01 Heinlein Karl H Powdered detergent or soak
US4428749A (en) 1981-01-14 1984-01-31 Lever Brothers Company Fabric washing process and detergent composition for use therein
US4522738A (en) * 1983-04-26 1985-06-11 Magid David J Toilet bowl cleaner
FR2584088A1 (en) * 1985-06-27 1987-01-02 Lion Corp SOLID SOAP COMPOSITION
US4749501A (en) * 1985-06-27 1988-06-07 Lion Corporation Solid soap composition containing microencapsulated hydrophobic liquids
US4744911A (en) * 1985-08-01 1988-05-17 The Procter & Gamble Company Dispersible fabric softeners
US6035869A (en) * 1997-09-10 2000-03-14 Albemarle Corporation Dish-washing method
US20060110464A1 (en) * 2003-02-11 2006-05-25 Walls John E Material encapsulation system
US8834934B2 (en) * 2003-02-11 2014-09-16 Haviland Products Company Material encapsulation system
US20090054295A1 (en) * 2007-08-24 2009-02-26 Celanese International Corporation Chemical Delivery Product And Process For Making The Same
US8772220B2 (en) * 2007-08-24 2014-07-08 Sekisui Specialty Chemicals America, Llc Chemical delivery product and process for making the same
CN101914415A (en) * 2010-08-27 2010-12-15 郭俊华 Effervescent detergent and preparation method thereof
CN104342097A (en) * 2013-08-09 2015-02-11 中国石油天然气股份有限公司 Solid foam drainage agent applied to gas field
CN104342097B (en) * 2013-08-09 2017-08-04 中国石油天然气股份有限公司 A kind of solid foam water discharge agent for gas field

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GB1224777A (en) 1971-03-10
BE715038A (en) 1968-09-30

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