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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
  • C11D3/062—Special methods concerning phosphates
• • 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
  • C11D3/43—Solvents

Definitions

• This invention relates to a novel built liquid detergent composition and a process for making the same. More particularly, it relates to a substantially non-aqueous built liquid detergent composition and process for producing the same, in which the composition contains a nonionic detergent surfactant and colloidal polyphosphate salts in suspension in the nonionic detergent surfactant.
• liquid detergent compositions both built and unbuilt, have become increasingly popular with the housewives and other consumers because they are easy to store, dispense and measure, and they do not cake as some granulated detergent products have a tendency to do when stored for lengthy periods of time or when they become damp.
• the chief disadvantage of liquid detergent compositions has been their cost as compared to the corresponding granular products. Cost of liquid products has been excessive because the package is expensive, hydrotropes are usually required to prevent phase separation of the organic and inorganic components, the ingredients are often more critical and hence more expensive, and in the case of water based compositions shipping costs are greater because of the high Water content which does not contribute toward detergency.
• colloidal tripolyphosphate salts can be incorporated into a non-water based detergent composition. This is achieved by adding hydrated sodium tripolyphosphate (STP6H O) into a glycol, glycerin or higher alcohol solution and under controlled conditions precipitating the colloidal sodium tripolyphosphate and pyrophosphate (there is some reversion) in the glycol medium in the absence of substantial amounts of water. See US. Patent No. 2,940,938 to Joseph Bl-inka. After the colloidal tripolyphosphates are formed in the glycol or organic water absorbing medium, an active detergent agent is then admixed and other inmor additives added to form the complete detergent composition.
• STP6H O hydrated sodium tripolyphosphate
• pyrophosphate pyrophosphate
• a disadvantage of this composition is that it contains substantial amounts of inert material (glycol or other similar compound) which is expensive and which adds nothing to the detergency effectiveness of the composition. It is, however, possible by the method for preparing this composition to use the desirable alklali metal tripolyphosphate builder salts.
• the process of the present invention can be carried out with a number of variations so long as the essential step of distilling off the dehydrating vehicle, in which the colloidal anhydrous polyphosphate builder salt has been precipitated, is carried out in the presence of the colloidal anhydrous polyphosphate salt and the liquid nonionic surfactant which is desired as the active ingredient in the final product thereby leaving the colloidal anhydrous polyphosphate salts in suspension in the liquid nonionic surfactant.
• the conditions of heat, vacuum, etc. will vary as hereinafter more fully described.
• the detergent composition produced by the process de scribed herein consists essentially of a colloidal dispersion of a polyphosphate salt, e.g., sodium tripolyphosphate or sodium pyrophosphate in a liquid nonionic detergent surfactant.
• a surfactant is preferably one constituted of a water solubilizing polyoxyethylene group in chemical combination with an organic hydrophobic compound, i.g., polyoxypropylene, alkyl phenol in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkyl phenols in which each alkyl group contains from 6 to 12 carbon atoms, the reaction product of an excess of propylene oxide and ethylene diamine, and aliphatic alcohols having from about 8 to about 18 carbon atoms, said nonionic detergent desirably having a molecular weight of from about 300 to about 11,000.
• the nonionic is preferably present in an amount ranging from about .5 to
• composition has a viscosity ranging from about 500 cp. to about 15,000 cp.
• the colloidal suspension of polyphosphate salts can be produced in a liquid nonionic detergent surfactant vehicleby means of the following variations of the process of this invention.
• One variation comprisesprecipitating colloidal anhy drous alkali metal tripolyphosphate. or pyrophosphate builder salts in a glycol or similar hydroxylated vehicle, as is described in US. Patent 2,940,938, to Joseph Bliuka, then taking. the resultant colloidal suspension, ad- V process without. affecting the process.
• the end product is a highly concentrated and effective built liquid detergent which on a usageibasis can be more efiiciently used than commonly used Water-based detergent compositions.
• iAnother variation of the process ofthis invention is to prepare a mixture containing the liquid nonionic detergent surfactant, dehydrating agent (any of those mentioned in the Blinka patent) .or monoethanol amine and hydrated sodium tripolyphosphote (STP-6H O) or other hydrated polyphosphate builder salt and proceed with the dehydrating. steps as outlined in the Blinka patent, and then distill off'the dehydrating agent leaving; a dispersion of colloidal polyphosphate salts in the liquid-nonionie detergent surfactant vehicle.
• dehydrating agent any of those mentioned in the Blinka patent
• STP-6H O hydrated sodium tripolyphosphote
• the Blinka process comprises removing the water of hydration of polyphosphate builder salts by means of a dehydrating vehicle and thereby effecting precipitation of colloidal sized polyphosphate salts in thedehydrating vehicle. This is accomplished by suspending the crystalline hydrated saltsinthe dehydrating vehicle, feeding the suspension into a reaction zone or otherwise agitating it and saturating the vehicle with respect to the-hydrated-salts and maintaining the temperature .of the suspension Within a range of about 70. F. to about. 180 F. and under an absolute pressurefrom about 6 mm. of mercury to atmospheric pressure, wheredratedpolyphosphate salts are not of colloidaldimension at that point.
• a colloidal suspension is formed only after the water of hydration of the. hydrated polyphosphate salt is removed during the dehydration step and as a result ofdehydration the colloidal particles are precipitated in the. dehydrating vehicle. It is only after a colloidal. suspension is formed that a stable suspension results.
• the preferred builder foruse in this invention is anhydrous sodiumtripolyphosphate because of its greater whiteness. maintenance characteristics in laundering;.
• hydrolyzable polyphosphates can be used to good advantage.
• suitable anhydrous builder salts are, for example,-those derived from the hydrates of tetrasodium pyrophosphate.
• the size of the colloidal polyphosphatesalt precipitate left in the nonionic detergent surfactant by the dis-- tilling oil of the dehydrating vehicle will be approximately the same size as that oroginally precipitated in the vehicle, ranging from about 0.015 to aboutSO microns. Usually the particle size distribution is such'that about 95% is below 10 microns and about is below 1.0 micron.
• Mechanically produced fine particles of inorganic polyphosphate builder may be added to the mixture or to the nonionic within limits,,and will-be prevented from settling by the line colloidal dispersion of dehydrated polyphosphate. These. added builders can be of commercial grind, about 25 to 30 microns in size and can be incorporated in the composition in an amount up to 50% of the total polyphosphate builder.
• the upper limit of the percent of colloidal polyphosphate builder salts in the mixture of the nonionic and the dehydrating vehicle is set by the condition that it must be stirrable and be sufliciently fluid that it will pass through the ap paratus used to make the product, particularly after re moval of the dehydrating vehicle.
• About two parts of the colloidal polyphosphates to onepart of the liquid nonionie detergent surfactant in the final product is about as high in solids .as can be handled easily.
• the. ratio of anhydrous sodium tripolyphosphate to the nonionic should be no lower than about 1:1, although a light duty detergent could be made.
• the ratio of anhydrous polyphosphate builder to nonionic synthetic detergent surfactant should be on the order of about 1:99-toabout 2:1, depending upon the type of composition desired.
• polyphosphate levels can be loW and nonionic high.
• 10-20% polyphosphate builder salt and 80-90% nonionic can be employed.
• higher phosphate levels are desirable so that or more polyphosphate and 40% or less liquid nonionic can be employed.
• the finished product viscosity will vary.- When more than about 50-60% phosphate builder salts are present in the composition, processingv difficulties are often encountered and the .viscosity of the product is so high. that thinning materialis usually required. Desire ably, the end productviscosity should be within the range I pyleneglycol, butylene glycol, trimethylene glycol, glycerine, l-octanol, and monoethanol amine.
• the glycols above 4 carbon atoms are not good solvents for the hydrated polyphosphates, hence'the glycols usable are those described as saturatedhydrocarbons of-2 to 4 carbon atoms, two of the carbons having hydroxyl constituents.
• nonionic detergent surfactants used in this invention have vapor pressures, in the range of the processing. temperatures, which are considerably less than thatv of the glycol or' other dehydrating vehicle, thus there is' no serious problem of volatilization of the liquid nonionic detergent surfactant during the process and the vehicle comes oif in substantiallypure form.
• the operating temperature of the process describedv herein will vary according to the pressure employed, the time of the reaction, andthe particular ingredients used to make the composition.
• the temperature at which this process can be practiced ranges from about F. to about 400- F., although the preferred temperature range is from about FQto about 220 F. It is Within ,this range that theeomposition while being processed has a gre ses desirable fluidity and therefore is more easily transferred through the various apparatuses used without the necessity of adding unduly large quantities of thinner or finished product to reduce viscosity.
• the preferred vacuum is that which can be obtained without the use of special equipment. Actually any amount of vacuum could be used, even down to as low as .1 mm. pressure.
• the operating temperature will vary with the amount of vacuum being applied.
• the vacuum tends to become lower stepwise as processing continues.
• it might be about 14 mm. of mercury while water is being removed and as low as 23 mm. mercury as the last traces of glycol pass oif.
• glycol or other dehydrating vehicle to polyphosphate salt in this process as is used in the process of the Blinka patent.
• the glycol is present in the mixture at a ratio of 1 part glycol to 2 parts of polyphosphate salt or less.
• the lower limit is that some polyphosphate be present, e.g., 99 parts glycol to 1 part polyphosphate.
• liquid nonionic synthetic organic detergent surfactants which are used in process and compositions in this invention are broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with organic hydrophobic compounds, which can be aliphatic or alkyl aromatic in nature and which are liquid at room temperatures.
• alkylene oxide groups hydrophilic in nature
• organic hydrophobic compounds which can be aliphatic or alkyl aromatic in nature and which are liquid at room temperatures.
• the length of the hydrophilic or polyoxyalkylene radical required for condensation with any particular hydrophobic group can readily be adjusted to yield a liquid water soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
• Tweens are fatty acid esters of anhydrosorbitols which have been solubilized by etherifying the free hydroxyl groups with ethylene oxide.
• Such compounds are, for example, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate and others. These compounds can be made in the manner described in US. Patent 2,322,820.
• nonionics for use in this invention are also the polyethylene oxide condensates of alkyl phenols and dialkyl phenols having about 6 to 12 carbon atoms in the alkyl group, either straight chain or branch chain, with ethylene oxide in amounts equal to 4 to 30 moles of ethylene oxide per mole of alkyl phenol.
• the alkyl substituent in such compounds may be derived from polymerized propylene diisobutylene, octane, or nonane, for example.
• Suitable nonionics we derived by the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine.
• a series of compounds can be produced, depending on the desired balance between hydrophobic and hydrophilic elements.
• nonionics are the condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, either straight chain or branched chain, with ethylene oxide with the condensate having from 4 to 30 moles of ethylene oxide per mole of aliphatic alcohol; a preferred alcohol is distilled coconut alcohol ranging from 10 to 16 carbon atoms, with the chain length distribution being about 2% C 66% C 23% C and 9% C.
• aliphatic alcohols having from 8 to 18 carbon atoms, either straight chain or branched chain, with ethylene oxide with the condensate having from 4 to 30 moles of ethylene oxide per mole of aliphatic alcohol
• a preferred alcohol is distilled coconut alcohol ranging from 10 to 16 carbon atoms, with the chain length distribution being about 2% C 66% C 23% C and 9% C
• the followng examples are illustrative of the process aspects of this invention but should not be considered as limiting.
• Example I 41.4 pounds of powdered sodium tripolyphosphate hexahydrate were suspended in a mixture of 16 pounds of ethylene glycol and 32 pounds of the condensation product of nonylphenol with about 9 moles of ethylene oxide. The mixture was well agitated in an open mixing tank at a temperature of about F. for 30 minutes. It was then transferred to a vessel equipped to heat and recirculate the mixture. Vacuum was slowly applied and free water (water of hydration given up by the tripolyphosphate) removed. The temperature was then increased to about F. at an absolute pressure of about 5 mm. Hg. At this point, ethylene glycol was removed rapidly. condensed and collected in a receiver beside the stripping vessel.
• the composition has excellent heavyduty detergency characteristics and finds utility in washing clothes and other fabrics. It had good stability upon standing.
• Example 11 Fine particle size polyphosphate was prepared by the method described in US. Patent 2,940,938.
• a mixture containing about 44% anhydrous colloidal form 11 sodium tripolyphosphate and 56% ethylene glycol was employed. 1500 grams of this mixture were added to a glass flask equipped with a stirring device, and 600 grams of the liquid anhydrous nonyl phenol ethylene oxide condensate of Example I were stirred in. The flask was sealed and a vacuum of about 2 mm. Hg applied. The temperature was raised by means of a heating mantle until the glycol passed off at a fairly rapid rate.
• the mixture was maintained at a temperature of about 75 C. for about 35 minutes. At this time, 2.2 grams of CMC (sodiumcarbox ymethyl cellulose) were added, and the agitation continued for another 10 minutes. The mixture was then transferred to a glass flask. equipped with a stirring device and heating mantle, and vacuum was slowly applied. Water (from the STP-6H O) was removed by distillation followed by removal of about 99.5%
• Nonyl phenol ethylene oxide condensate 37.18 Anhydrous colloidal sodium tripolyphosphate 55.31 Sodium silicate 6.39 Sodium carboxymethyl cellulose 0.27 Methoxy triglycol 0.50 Water and miscellaneous -a 0.35
• the final homogeneous liquid detergent product had a viscosity inexcess of 10,000 pp.
• the addition of about 4% ethyl alcohol to this composition gave a viscosity of 1400 cp. It had excellent detergency and whiteness maintenance characteristics when used to launder soiled clothes and other fabrics; .it did not settle out upon standing.
• nonionic detergent compounds which can be substituted with equivalent results include, for example, the condensation product of 6 molesethylene oxide and 1 mole coconut alcohol, andthe condensation product of 12 moles ethylene oxide with one mole of the reaction product of propylene oxide and ethylene diamine.
• compositions are examples of the product of this invention. It will be understood, however, that the examples are not to be construed as limiting the scope of conditions claimed hereinafter. These compositions are useful in automatic washers as Well as hand Washing operations.
• compositions'listed above are homogeneous and are highly stable and have excellent detergency properties. 3000 cp- It is preferred to keep the viscosities within the above indicated ranges because if the compound has I too high a viscosity the housewife will have difiiculty pouring it from the container and if the viscosity is too low it becomes too fluid and there is a tendency for the dispersed phosphate salts to settle out.
• tive inhibitors whenaddedto the compositions of this Soluble silicates are highly effecinvention at levels from about 3.5% to about It is preferable to add dried, powdered silicate. cate remains in suspension in the composition and is supported by the colloidal polyphosphate. Less than about 3 5% of silicate solids, although usable in the present They-have viscosities in the range of 1000 cp. to I
• the compositions of this invention also tend to be The silicompositions, does not provide full protection against aluminum corrosion in heavy duty use conditions, and more than about 15% of silicate solids has an adverse effect upon the desired homogeniety of the liquid composition. At that level silicate acts as a load on the composition and does not contribute to detergency.
• Carbowax or related materials can be added if desired to stabilize the liquid composition and more particularly the sodium carboxymethyl cellulose.
• a process of preparing a substantially non-aqueous built liquid detergent comprising the steps of (1) admixing a liquid nonionic detergent surface active agent constituted of a water solubilizing polyoxyethylene group in chemical combination with an organic hydrophobic compound selected from the group consisting of polyoxypropylene, alkyl phenol and dialkyl phenol in which the alkyl group contains from about 6 to about 12 carbon atoms, the reaction product of an excess of propylene oxide and ethylene diamine, and aliphatic alcohols having from about 8 to about 18 carbon atoms, said nonionic detergent having a molecular weight of from about 300 to about 11,000, with a colloidal suspension of dehydrated polyphosphate salts selected from the group consisting of sodium pyrophosphate, sodium tripolyphosphate, and mixtures thereof, in a dehydrating vehicle selected from the group consisting of glycols of 2 to 4 carbon glycerol, l-octanol, monoethanol amine, and mixtures thereof, said nonionic detergent agent
• nonionic detergent agent is an alkyl phenol ethylene oxide condensate having about 4-30 moles of ethylene oxide per mole of alkyl phenol.
• nonionic detergent agent is the condensation product of 6 moles of ethylene oxide and 1 mole coconut fatty alcohol.
• a process of making a substantially waterfree built liquid detergent comprising the steps (1) admixing a liquid nonionic surface active agent constituted of a water so'lubilizing polyoxyethylene group in chemical combination with an organic hydrophobic compound selected from the group consisting of polyoxypropylene, alkyl phenol in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkyl phenols in which each alkyl group contains from 6 to 12 carbon atoms, the reaction product of an excess of propylene oxide and ethylene diamine, and aliphatic alcohols having from about 8 to about 18 carbon atoms, said nonionic detergent having a molecular weight of from about 300 to about 11,000, with a suspension consisting of hydrated polyphosphate salts selected from the group consisting of sodium tripolyphosphate, sodium pyrophosphate, and mixtures thereof, and a dehydrating vehicle selected from the group consisting of glycols of 2 to 4 carbon atoms, glycerol, l-octanol,
• nonionic agent is an alkyl phenol ethylene oxide condensate having about 4-30 moles of ethylene oxide per mole of alkyl phenol.
• step (1) is sodium tripolyphosphate With six molecules of Water of hydration.
• nonionic detergent agent is the condensation product of 6 moles ethylone oxide with 1 mole coconut fatty alcohol.
• a substantially non-aqueous built liquid detergent composition consisting essentially of:
• a liquid nonionic synthetic detergent constituted of a water solubilizing polyoxyethylene group in chemical combination with an organic hydrophobic compound selected from the group consisting of polyoxypropylene, alkyl phenol and dialkyl phenol in which the alkyl group contains from about 6 to about 12 carbon atoms, the reaction product of an excess of propylene oxide and ethylene diamine, and aliphatic alcohols having from about 8 to about 18 carbon atoms, said nonionic detergent having a molecular weight of from about 300 to 11,000;
• composition of claim 9 in which the nonionic synthetic detergent compound is an alkyl phenol ethylene oxide condensate having about 4-30 moles of ethylene oxide per mole of alkyl phenol.
• composition of claim 9 in which the dehydrated polyphosphate salt is sodium tripolyphosphate.
• composition of claim 9 in which the nonionic synthetic detergent compound is present in the ratio of 1:1 to about 1:2 to the colloidal dehydrated polyphosphate builder salt.
• composition of claim 9 in which the nonionic detergent is the condensation product of 6 moles ethylene oxide with 1 mole coconut fatty alcohol.

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Cited By (16)

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Citations (3)

• 0
  • NL NL290315D patent/NL290315A/xx unknown
  • CA CA729145A patent/CA729145A/en not_active Expired
• 1962
  • 1962-03-20 US US181170A patent/US3169930A/en not_active Expired - Lifetime
• 1963
  • 1963-03-16 DE DE19631467647 patent/DE1467647A1/de active Pending
  • 1963-03-19 SE SE2994/63A patent/SE311715B/xx unknown
  • 1963-03-19 DK DK125163AA patent/DK114499B/da unknown
  • 1963-03-20 GB GB11138/63A patent/GB1008016A/en not_active Expired
• 1965
  • 1965-01-18 BE BE658450A patent/BE658450A/xx unknown

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