Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
  • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
  • B01J39/16—Organic material
  • B01J39/18—Macromolecular compounds
  • B01J39/22—Cellulose or wood; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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
  • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups

Definitions

• the present invention relates to sequestering calcium and magnesium ions in home laundering and, more particularly to a laundering adjunct, a method of preparing said adjunct, and to a method of using said adjunct in home laundering.
• the role of the inorganic builder in improving the performance of a detergent formulation is of the highest importance, but the mode of action is still not clear.
• a number of functions have been suggested for it, including suspending of particulate soils, lowering the critical concentration of the detergent, increasing the Wetting rate, influencing the degree of adsorption of surfactant on textile fibers, effecting the electrostatic charge of soil and fabric, and others but the major effects are usually attributed to the water softening ability of the inorganic builder.
• Formulation of a detergent to take care of all of the hardness in the water used in the wash step of the laundry cycle is not diflicult except in the case of liquid detergents where it is a real problem to combine the necessary quantities of detergent, builder, and other essential ingredients into a compatible mixture occupying a reasonable final volume.
• an alternate method for achieving the benefits of a builder would be a boon to the formulator and manufacturer.
• the inorganic builder or other watersoftening agent is incorporated in the detergent, a part of the detergent formulation and water-soluble, it is available only during the wash step and not during the rinse step or steps of the laundering cycle. It has been shown that the residual-soil build-up on repeatedly laundered cotton can be removed by a rinse containing ethylene diamine tetraacetate (EDTA) which is an indication of the desirability of maintaining a useful concentration of water-softening agent during the rinse portion of the laundering cycle as well as during the wash portion thereof.
• EDTA ethylene diamine tetraacetate
• the present means of overcoming the disadvantages of the variation of the hardness of the water in various parts of the World are (1) limitation of the formulation of liquid detergents; (2) the absence of Water-softening agent in the rinse cycle; and (3) the relative complexity of the regeneration operation of home water-softening units.
• the present invention overcomes all of these disadvantages.
• the generally used water-softening agents incorporated in home laundering detergents are complex phosphates such as sodium tripolyphosphate, i.e., penta-sodium tripolyphosphate, and potassium pyrophosphate.
• the present invention provides a laundering adjunct to be used in conjunction with detergents containing inorganic builder or in conjunction with detergents substantially devoid of inorganic builder in the washing step and in the rinsing step of a home laundering cycle and in some forms for use in personal ablutions.
• the present invention provides a method of preparing phosphorylated cellulose for use as a Water-softening agent in the wash and rinse portions of a home-laundering cycle.
• a method regenerating a phosphorylated cellulose water-softening material is likewise an object of the present invention.
• alkali metal phosphates were very useful for the regeneration of ion-exchange material and particularly recommended the alkali metal pyro-, poly-, and metaphosphates and acid phosphates or mixtures of the foregoing for that purpose.
• the preferred phosphates Were the alkali metal tripolyphosphates, such as sodium tripolyphosphate, and the pyrophosphates such as sodium acid pyrophosphate.
• ion-exchange fibers having at least one small dimension of the order of one-tenth to twenty mils are described. These fibers comprise a cross-linked polymer of a linear addition polymer at least seven mol percent of the units containing ion-exchange groups such as carboxyl groups, sulfonic groups, phosphoric acid groups, and thiol groups for cation-exchange.
• ion-exchange groups such as carboxyl groups, sulfonic groups, phosphoric acid groups, and thiol groups for cation-exchange.
• a companion US. Patent No. 2,974,101 provides a description of improved ion-exchange assemblies and of methods of treating liquids particularly assemblies comprising filamentous structures. Similar to the latter patent is the disclosure of US. Patent No.
• fiber-form ion-exchange materials native fiber cellulose is reacted in a system comprising trifluoroacetic anhydride, a suitable inert non-aqueous solvent or diluent and the mono-anhydride of a tricarboxylic non-aqueous organic acid which contains one free, active carboxylic group in addition to the carboxylic groups involved in the cyclic anhydride structure.
• water-soluble phosphates of polyvinyl alcohol are produced by the reaction of polyvinyl alcohol with urea phosphate. These are capable of self-polymerization, when heated without the aid of a catalyst, to form high-capacity ion-exchange substances.
• the present invention provides (1) for hanging a cation-exchange fabric in a traditional tub used for hand washing and/ or rinsing or in the modern automatic washing machine during both the wash and the rinse portions of the laundering cycle; (2) for coating in any suitable manner the periphery of the traditional tub used for hand washing and rinsing or the periphery of the tub of a modern automatic washer in a continuous or discontinuous form with cation-exchange material; (3) for coating in any suitable manner in a continuous or discontinuous fashion the exterior of the dasher of an automatic washing machine; and (4) for suspending in the traditional tub used for hand laundering or in the modern automatic washer during both the wash and rinse cycles a porous container charged with particulate cation-exchange material and for personal ablutions a wash-cloth comprising two layers of terry cloth and an interposed layer of fabric having
• Illustrative of the principles of the present invention is the preparation of phosphorylated cellulose to provide a cation-exchange material, and the use of the so-produced cation-exchange matreial to sequester calcium ions under conditions comparable to those existing in home laundering.
• the treated cloth so obtained is nearly white, but has a rougher, heavier hand than the original cloth, and, when wet, it has a slippery feel. Under agitation of a Terg-O-Tometer run the cloth frays badly at the edges.
• three ways of preventing the disintegration were employed to wit: (1) phosphorylating a sulfone-crosslinked cotton fabric instead of Indianhead cotton (Test 1); (2) painting the edges with a label varnish (Test 2) and (3) hemming the four edges (Test 3).
• Cotton crosslinked with Ganalok A-14 sulfone crosslinked cotton
• the varnished edge cloth successfully withstood the agitation of the Terg-O-Tometer machine, but its calcium capacity was reduced out of proportion to the actual area covered by the varnish. Hemming proved to be the preferable protective treatment.
• Calcium binding capacity The capacity of the so-produced phosphorylated cotton to bind calcium was measured by agitating a weighed piece of the cloth in an aqueous solution of calcium chloride of known concentration and then determining the depletion of calcium ions in the solution by titration of an aliquot with standard ethylene diamine tetraacetate solution. [Betz, Handbook of Industrial Water Conditioning, 5th Ed. Betz Laboratories Inc., (1957)].
• phosphorylated cotton sulfone-crosslinked cotton in this case
• solutions of calcium chloride varying in concentration from 0.008 to 0.013 M (-1300 p.p.m. as CaCO but in which the same total quantity of calcium was present.
• the weight of calcium bound by the cloth was the same, indicating that it is the amount of calcium which is important and not its concentration.
• soap powders contain sodium and/or potassium, e.g., in one commercial product 0.013 molal sodium and in another 0.003 molal sodium plus potassium the effect of sodium ion upon the capacity of the phosphorylated cotton to bind calcium was examined by agitating pieces of sulfone-crosslinked phosphorylated cotton weighing 300 milligrams in 25 milliliter portions of an aqueous solution containing varying amounts of sodium chloride and being 0.0126 molal to calcium chloride.
• Table III clearly shows that at concentrations if sodium in the range usually existing in commercial detergents the interference of the sodium ion is not a serious factor in practice.
• regenerability of a calcium binding cloth will depend at least in part on the kind of reactive groups that it possesses.
• ease of regeneration could be expected to vary from excellent with sulfonic acid groups to poor with carboxyls and of some intermediate character with phosphorus acid groups.
• sodium tripolyphosphate would restore all the calcium binding activity of exhausted phosphorylated cotton, but a sizable portion of the activity could be regained by the use of even 0.1% of this reagent.
• the test chosen was one in which a panel of eight persons each wiped his face and neck with four 4 /2 x 6 inch swatches of Indianhead cotton (two of these in the morning and two in the afternoon of the same day) for which instrumental reflectance readings were obtained before and after soiling. These swatches, separated into four lots drawn one from each panel member, were washed in various solutions in the four buckets of a Terg-O-Tometer for twenty minutes at 120 F. and 100 r.p.m. agitation, rinsed, pressed, and the reflectance again read.
• THIRD DETERGENCY TEST Object To determine whether a combination of all three factors found individually to improve the performance of phosphorylated cotton will give detergency building equivalent to that of sodium tripolyphosphate.
• the simplest form of a home laundering insoluble regenerable sequesterer for calcium and magnesium, i.e., a cation exchange material, is a non-ravelling cloth having an area of at least about one square foot impergnated with a water-insoluble material having alkaline earth binding groups, e.g., carboxylic and/or sulfonic and/or phosphoric acid groups.
• alkaline earth binding groups e.g., carboxylic and/or sulfonic and/or phosphoric acid groups.
• the phosphorylated cotton described and discussed herein before is illustrative of this embodiment of the present invention. Since the capacity of phosphorylated cotton containing about 5.3 percent of phosphorus is about 30 milligrams per gram and since 60 milligrams of calcium per liter is a hardness of about 150 p.p.m.
• the water used in either the wash portion or the rinse portion or in both portions of the laundering cycle is pretreated with phosphorylated cotton, of higher tahn the minimum required, in the presence of a neutral electrolyte, e.g., sodium sulfate.
• a neutral electrolyte e.g., sodium sulfate.
• wash cloth comprising a sandwich of terrycloth, for example, with cation-exchange material, for example phosphorylated cotton interposed between two layers of terrycloth and hemmed around the edges solves the problem in a simple manner.
• particulate cation-exchange material is charged to a porous container, e.g., a loosely woven bag with a draw-string closure, which charged container is attached to the water inlet of an automatic washer or suspended therein in any other suitable manner.
• a porous container e.g., a loosely woven bag with a draw-string closure
• a portion or the whole of the inner periphery of tub of a washing machine is coated with a water-insoluble adhesive and then coated with particles of cation-exchange material or with a layer of cation-exchange fabric.
• the plunger or dasher can be so treated and when desired both the dasher and the inner periphery of the tube are so treated.
• the incidence of regeneration of the Water-insoluble cation-exchange material is dependent upon (1) the hardness of the water employed, i.e., the milligrams of cation to be removed per gallon of water; (2) the volume of water employed; (3) the cation-binding capacity of the cation-exchange material per gram; and (4) the quantity or weight of cation-exchange material employed.
• Heavy duty liquid detergent formulations have always had two major drawbacks in attaining a sizeable share of the market; one is cost and the other is their failure to measure up to the performance of powdered detergents especially in hard water.
• the major factor in the failure of heavy duty liquids to achieve performance parity with powders is the difference in builder content. Solubility limits have set the builder content in liquids at about 20% while powders incorporate approximately 50% builder. Detergent raw material suppliers as well as detergent formulators have been aware of the problem.
• liquid detergent formulation provided by the conjunct use of cation-exchange material in the wash portion of the home laundering cycle can be illustrated by consideration of the formulation of a presently sold liquid detergent composition.
• part or all of the pyrophosphate could be eliminated from the detergent formulation (as well as the potassium xylenesulfonate which is present as a solubilizing or hydrotroping agent) and water softening achieved largely or solely by the adjunct cation-exchange material thus permitting a greater concentration of organic detergent to be incorporated in the detergent formulation should that be regarded as desirable; for example, the use of more compact packaging for equal effectiveness of product.
• the concentration of detergency builder can be reduced when the solid detergent formulation is used in conjunction with cation-exchange material in the wash portion of the home-laundering cycle. It is present practice to prepare built laundry detergents with a minimum of inorganic builder, such as pentasodium tripolyphosphate (NaTPP), of 25 percent and as much as 50 percent. When the cation-exchange material is used as provided in the present invention the TPP can be reduced or even eliminated.
• inorganic builder such as pentasodium tripolyphosphate (NaTPP)
• the present invention provides a method of home-laundering in which the amount of soiled cloth washed at one time does not exceed about twelve to fifteen pounds and the volume of water employed in any portion of the cycle does not exceed about 17 gallons, wherein the water employed, at least in the wash portions of the laundering cycle, is contacted with an amount of cation-exchange material effective to reduce the concentration of calcium in and, preferably, to remove substantially all of the calcium from the water employed. It is presently preferred to make the cation-exchange material available to the home-launderer in a unit requiring regeneration after use in a single laundering when using water of maximum hardness and at less frequent intervals when using water of less than said maximum hardness.
• the improvement 1 1 wherein the phosphorylated cotton has a calcium binding capacity of 30 milligrams of calcium per gram of cation exchange material.

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Citations (3)

• 0
  • ZA ZA670030D patent/ZA670030B/xx unknown
• 1966
  • 1966-03-09 US US532902A patent/US3424545A/en not_active Expired - Lifetime
• 1967
  • 1967-01-14 ES ES335663A patent/ES335663A1/es not_active Expired
  • 1967-01-18 DE DE1967C0041259 patent/DE1617058B2/de active Granted
  • 1967-01-24 FR FR92233A patent/FR1508814A/fr not_active Expired
  • 1967-01-25 SE SE6809850A patent/SE370953B/xx unknown
  • 1967-01-25 SE SE1114/67A patent/SE345883B/xx unknown
  • 1967-01-26 BE BE693206D patent/BE693206A/xx not_active IP Right Cessation
  • 1967-02-08 DK DK68667AA patent/DK128286B/da unknown
  • 1967-02-08 CH CH186467A patent/CH506444A/de not_active IP Right Cessation
  • 1967-02-24 GB GB8978/67A patent/GB1181077A/en not_active Expired
  • 1967-02-27 NL NL6703120.A patent/NL160348C/xx not_active IP Right Cessation

Patent Citations (3)

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