CA1081080A - Pyrophosphate and silica-containing composition - Google Patents
Pyrophosphate and silica-containing compositionInfo
- Publication number
- CA1081080A CA1081080A CA245,225A CA245225A CA1081080A CA 1081080 A CA1081080 A CA 1081080A CA 245225 A CA245225 A CA 245225A CA 1081080 A CA1081080 A CA 1081080A
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- composition
- detergent
- weight
- silica
- alkali metal
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
-
- 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
-
- 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
- C11D3/08—Silicates
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
PYROPHOSPHATE AND SILICA
CONTAINING COMPOSITION
Steven D. Cherney and Thomas J. Hau ABSTRACT
The present invention relates to detergent additive and detergent compositions containing an alkali metal pyro-phosphate and silicas which are particularly effective in cleaning ability and in controlling water hardness.
CONTAINING COMPOSITION
Steven D. Cherney and Thomas J. Hau ABSTRACT
The present invention relates to detergent additive and detergent compositions containing an alkali metal pyro-phosphate and silicas which are particularly effective in cleaning ability and in controlling water hardness.
Description
BAC~GROUND OF THE INVE~TION
The present invention relates to detergent additives and detergent compositions. A detergent additive is a prod~ct designed to supplement the consumer's ordi~ary ~detersent product to ~oost the latter~s effectiven~ss.
The detergent composition aspect of the present invention encompasses the detergent additi~e aspect with the additional feature of having present a surface active agent in the composition.
Those skilled in the detergency arts ha~e for many years equated the alkali metal pyrophosphates with the alXali metal tripolyphosphates in detergent compositions. It is known that pyrophosphates and tripolyphosphates when used as builders will each sequester one mole of calcium or magnesi~m water hardness per mole of the phosphate species. Pyrophosphate detergency builders, however, unlike tripolyphosph2tes will under . .
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certain conditions form minor amounts of dicalcium pyro-phosphate a completely neutralized insoluble salt. These precipitates of the pyrophospnates discussed above have been known to deposit on the fabrics being cleansed or upon the sur-faces of the washing machine. Such buildup of the calcium pyrophosphate salt is undesirable in that the precipitates have a tendency to remain on the fabrics through several wash cycles and continue to builup thus causing harsh fabric. Similarly, the calcium pyrophosphate will after -~
several cycles in a wasning machine cause deposition or scale on the exposed surfaces. This precipitation phenome-non of the pyrophosphates has led many detergent manufacturers to avoid pyrophosphates and to instead use tripolyp;losphates.
It has been suggested in U.S. Patent 2,3~1,960 to Johnson issued August 14, 1945 that the effectiveness of sodium pyrophosphate in reducing water hardness could be obtained by adding the pyrophosphate to the solution of nard water after an alkaline material had been first added to the water. The alkaline materials taught by Johnson were sodium orthophosphate, sodium and potassium hydroxide, sodium and potassium carbonates, and sesqui-carbonates, soap and sodium silicate having an SiO2:;~a2O
weight ratio greater than 1.5. The point of addition of the tetrasodium pyrophosphate to the solution is after the alkaline material but prior to the formation of a macroscopic precipitate of the hardness ions and the aforementione~ alkaline naterials.
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In U.S. Patent 2,326,9~0 issued August 17, 1943 to Kepfer, it is taught that tetrasodium pyrophosphate is used more efficiently to control water hardness when it is used in conjunction with an alkaline material whicn is added to tne solution after the pyrophosphate but before a macroscopic precipitate of the hardness ions and the pyrophosphate is formed. The alkaline materials taught by Kepfer are sodium borate, sodium metasilicate (SiO2:Na2O 1:1) and disodium hydrogen phosphate. The processes of controlling water hardness by somehow increasing the effectiveness of sodium pyrophosphate taught by Kepfer and Johnson, herein incorpo-rated by reference, suffer from the defect that the compo-sition could not be effectively prepared without going to the trouble of positively insuring the delay of the pyrophospnate relative to the alkaline materials or vice versa. Thus Kepfer and Johnson could only with great difficult~ be adapted for use in granular or liquid pkoducts which - are favored by the consumer today.
U.S. Patent 3,708,428 issued January 2, 19~3, to McDonald discusses the neutralizing of organic detergent acids such as alkyl benzene sulfonic acid with sodium silicates having an SiO2:Na2O ratio of from about 1:2 to about 4:1 to form an in situ silica having an SiO2:Na2O ratio of from about 4:1 to about 2000:1 or greater. An essential condition `
to the compositions taught in McDonald is that the inclusion of water soluble alkali builders, illustrated by sodium or potassium orthophosphates, or complex phosphates (i.e. pyrophosphates), alkali carbonates, borates, . , . . : - . .
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silicates, or neutral salts, such as sodium chloride or sodium sulfate, or magnesium sulfate, be restricted to levels of concentration of the order of 4~ by weight or lower. l~cDonald goes on to state the desired advantages of the in situ formed colloidal silicas on the removal of soils will be found to be appreciably impaired if the foregoing limits are not strictly adhered to.
It is thus an object of the present invention to utilize an alkali metal pyrophosphate more efficiently in the control of water hardness.
It is a further object of the present invention to utilize an alkali metal pyrophosphate such that the deposition product of water hardness and the pyrophosphate ions is diminished on washing machine surfaces.
It is a further object of the present invention to prepare a composition utilizing ah alkali metal pyro-phosphate as a detergency builder that minimizes the buildup on fabrcis of water insoluble pyrophosphate.
` It is yet a further object of the present invention to provide a detergent additive product or a complete detergent composition built with an alkali metal pyro : ' phosphate which is particularly effective in cleaning.
It has now been found that by preparing a detergent additive comprising an alkali metal pyrophosphate and silica ~ ~
or a complete detergent composition comprising tAe alkali -j metal pyrophosphate, silica and an organic detergent component that the objects of the invention may be achievd.
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- . . . - . . -~0~:11D80 Moreover, the use of the alkali metal pyrophospnate with the silica of the present invention in an additive or detergent composition substantially decreases the amount of calcium ion in the wash solution. While not wishing to be bound by any par-ticular theory it is believed that silica in some manner encourages the precipitation of calcium ions in the wash solution as insoluble dicalcium pyrophospnate. Thus in prior art compositions pyrop~osphate salts were only able to effectively sequester on a 1:1 mole basis witn calcium hardness, the present invent~on allows the pyrophosphate to effectively control twice the amount of calcium which is possible by sequestration. The precipitation of the dicalcium pyrophosphate takes place with the aid of the silica such that the precipitated salt is less likely to form an unsiyhtly scum on tne exposed surfaces of the washing machine or deposit on fabrics to cause a harsh feel. The more , effective control of calcium ion in the wash solution means ` that the detergent components are not as likely to be interfered with by tne water hardness in the wash thus providing better cleaning of the fabrics. ~ ~, Soluble silicates are often added to detergent or addi-t.ive products to protect exposed machine surfaces from corrosion.
; It has been found, however, that soluble silicates interfere ! with the precipitation of calcium hardness as dicalcium pyro-phosphate. Other componen-ts found in detergent products have also been found to interfere with dicalcium pyrophosphate precipitation, namely the detergent active.
It has now been found that the addition of silicas to the additive or detergent product diminishes the tendency of soluble silicates and other components such as the deter-gent to interfere with the precipitation of calcium by pyro-phosphate.
~08~013~) Throughout the specifica-tion and claims percentages and ratios are by weight and temperatures are in degrees Fahrenheit unless otherwise indicated.
SUM~IARY OF_ THE INVENTION
A detergent additive comprising:
~a) an alkali metal pyrophospllate; and (b) silica ~aving a mean particle diameter less than 20 microns;
in a weight ratio of the alkali metal pyrophosphate to the silica of Erom about 25:1 to about 1:2.
A detergent composition comprising:
(a) from about 5% to about 60% by weight of an -alkali metal pyrophosphate; ;
(b) from about 1% to abo~t 40% by weight of silica having a ~ean particle diameter less than 20 microns; and (c) an organic detergent at from about 1% to about ,, 50% by weight oE the composition.
, DETAILED DESC~IPTION OF THE INVENTION
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The present invention has two aspects. The first aspect is a detergent additive product and the second is a . .
complete detergent composition. T'ne deterge~t ad~itiv~
products are formulated such that they may be used compatibly with other commercially available detergent products. The detergent additives ordiharily do not have organic detergents within their composition. The detergent additive product is intended for use as a presoak product wherein the ~108~
clothes to be washed are placed in a wash tub or the washing machine and allowed to soak in water containing the additive product for a period of time before the consumer's regular detergent product is added. Alternatively, a detergent additive product may be added simultaneously to the wash solution with the consumer's regular detergent product. In either event the detergent additive product of the present invention boosts the cleaning of the consumer's regular detergent.
When formulated as a detergent composition the present invention is utilized for cleaning in the conventional manner.
The detergent additive or detergent composition of the present invention may be formulated to be in a solid or liquid form. When formulated as a solid the compositions of the present invention may be formed into a single granule such as by spray drying or the components may be separately admixed with one another in any order.
The alkali metal pyrophosphates of the present invention are commercially available from several sources.
The alkall metal pyrophosphate such as the sodium or potassium~`
salt, preferably the sodium salt may be dehydrated or anhydrous.
The silica component of the present invention is also widely available from commercial sources such as those products marketed under the trade mark Zeosyl sold by the Huber Chemicàl Company and Ludox marketed by E. I.
duPont de Nemours & Company~ The silicas useful in the present invention have a mean particle diameter of less than 20 microns, such as from about 1 x 10 3 to about 5 microns more preferably from about 2 x 10 3 to about Ool micron, most preferably from about 3 x 10 3 to about 0.05 micron. The surface area is given as an aggregate per unlt of weight of ~0~1~80 the silica. As the surface area of the silica increases the performance advantage of the compositions of the invention increases. The specific surface area in square meters per gram of the silicas of the present invention should be greater than 0.2 square meter per gra~,preferably greater tnan 1 square meter per gram, and more preferably greater than 40 square meters per gram, and most preferably greater than 200 square meters per gram.
The mean partiQle diameter of the silica is defined as being the length of the largest axis of the particle.
The surface area is related indirectly to the mean particle diameter of the silica. That is to say that if the geometry of the silica particle is known the theoretical surface area can be calculated from the mean particle diameter.
It is noted that high surface areas of the silica are possible even when a small number of particles are present per given weight of the silica. The foregoing arises when the silica particles are porous. While high surface area for the silicas of the present invention is desirable it is preferred tnat the high surface area be accompanied by a large number of particles for thorough distribution in wash or soak solution. SiIica particles of the size descri-bed above give both high surface area and a large number of particles per unit weight.
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The silicas of the present invention to a limited extent can be thought of as being ionic ln that some of the hydrogen atoms in the silanol group (-SiOH) of the silica molecule are occupied by cations particularly sodium or potassium.
In the McDonald patent, previously metioned, the distinction was made that silicas must have an SiO2:Na2O ratio greater than 4:1 and up to 2000:1 and greater.
The foregoing definition is applicable here. All the alkali metal cations occupy silanol positions. Preferably the SiO2:
NaO2 ratio is greater than 10:1, more preferably gre'ater than 20:1 and most preferably greater than 45:1.
In the additive product the rati,o of alkali metal pyrophosphate to the silica is from abou-t 25:1 to about 1:2, preferably about 20:1 to aboutl l, and most preferably about 15:1 to about 5:1 by weight. The foregoing ratios are also satisfactory in the detergent product.
The present invention contains as an optional ingredient alkali metal silicates of the formula SiO2:M2O, ,-, wherein M is an alkali metal preferably sodium or potassium and the foregoin~ weight ratio is from about 1.6:1 to about 4:1,-preferably from about 2.0:1 to about 4:1, and most preferably about 2.4:1 to about 4:1. While it nas been found that the present invention functions as a detergent additive or complete detergent composition satisfactorily and indeed to some benefit for hardness control and cleaning -8~
in t;le absence of silicates it has been found desirable to include in the composition soluble silicates at a level of from about 1~ to abou-t 25~, preferably about 3~ to about 20~, and most preferably about 5~ to about 15~ by weight. The func-tion of the silicate is important in that it lessens the tendency of tne detergent component and the pyrophosphate to tarnisn the exposed surfaces of the wasning macnine. The soluble silicates are also desirable in detergent additive type produats and co~plete detergent compositions whicn are spray dried in that more desirable granule characteristics are obtained. such granule charac~eristics include flowability of the granules and a tendency to resist caking.
The ratio of the silica to tne silicate in the present invention should be in the range of about 10:1 to about 1:10, preferably about 6:1 to about 1:6, a~d most preferably from about 2:1 to about 1:2 by weight.
When formulated as a complete detergent composition the present invention encompasses all manner of organic detergent components. Suitable detergents include for example the following:
Detergent Component Preferably the detergent component of the present invention is a water-soluble salt of: an ethoxylated sulfated alcohol with an average degree of ethoxylation of about 1 to 4 and an alkyl chain length of about 14 to 16; tallow etnoxy : : . '' ~ ,' ., '- ,. : , ~1081080 sulfate; tallow alcohol sulfates; an alkyl benzene sulfonate with an average alkyl chain length between 11 and 13, preferably 11.2 carbon atoms; a C6-C20 ~-sulfocarboxylic acid or ester t~ereof having 1 to 14 carbon atoms in the alcohol radical;
a C8-C24 paraffin sulfona-te; a C10-C24 ~-olefin sulfonate or mixtures t;~ereof; or other anionic sulfur-containing surfactant. ~.
Such preferred detergents are discussed below.
An especially preferred alkyl ether sulfate detergent component of the present invention is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of -`
about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, preferably from about ~ to 3 moles of ethylene oxide.
Specifically, such preferred mixtures comprise ...
from about 0 to 10% by weight of mixture of Cl~ 13 compounds, from about 50 to 100% by weight of mixture of Cl~ 15 compounds, ~: and from about 0 to 45% by weight of m~xture of Cl~ 17 compounds, and from about 0 to 10% by weight of a mixture of C18_19 compounds. Further, such preferred alkyl ether sulfate mixtures comprise from about 0 to 30% by weignt of mixture of compounds having a degree of ethoxylation of 0, from about 45 to 95% by weight of mixture of compounds naving a degree of.ethoxylation from 1 to 4, from about 5 to 25~ by ~.
weight of mlxture of compounds having a degree of ethoxylation ~l081080 -::
from 5 to 8, and from about 0 to 15~ by weight of mixture of compounds having a degree of ethoxylation grea-ter than 8. ~
The sulfated condehsation products of ethoxylated alcohols of ~-8 to 24 alkyl carbons and with from 1 to 30, preferably 1 to 4 moles of ethylene oxide may be used in place of the preferred alkyl ether sulfates discussed abo~e.
Another class of detergents which may be used in the present invention includes the water-soluble salts, particu-larly the alkali metal, ammonium, and alkylolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfuric acid ester group. Examples of ~:
this group of synthetic detergents are the sodium and potassium , alkyl sulfates, especially tnose obtained by sulfating the higher alcohols (C8-C18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil.
; Preferred water-soluble organic detergent compounds herein include alkyl benzene sulfonates (preferably essentially linear although "hard" ABS may be used) containing from about 9 to 15 carbon atoms in the alkyl group. Examples of the above are sodium and potasslum alkyl benzene sulfonates in which the alkyl group contains from about 11 to about 13 carbon atoms, in straig~t chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
Especially valuable are straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 11.2 carbon atoms, abbreviated as Cll 2LAS.
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~0~10~0 Another useful detergent com2ound herein includes the water-soluble salts of esters o~ ~-sulfonated fat~y acids co~taining from about 6 to 20 carbon atoms in the fatty acid group and their esters from about 1 to 14 carbon atoms in the alcohol radical.
Preferred "olefin sulfonate" detergent mixtures utilizable herein comprise olefin sulfonates containing from about 10 to about 24 carbon atoms. Such materials can be produced by sulfonation~of ~-olefins by means of uncomplexed sulfur trioxide followed by neutralization under conditions such that any sulfones present are hydrolyzed to the corresponding hydroxy-alkane sulfonates.
The ~-olefin starting materials preferably have from 14 to 16 carbon atoms. Said preferred ~-olefin sulfonates are described in U.S. Patent 3,332,880.
The paraffin sulfonates embraced in the present invention are essentially linear and contain from 8 to 24 carbon atoms, preferably 12 to 20 and more pre-ferably 14 to 1~ carbon atoms in the alkyl radical.
Other anionic detergent compounds herein in-clude the sodium alkyl glyceryl ether sulfates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fa-tty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about 1 to about 10 units of ethylene oxide per molecule and wherein t~e alkyl groups contain about 8 to about 12 carbon atoms.
10~:1080 Water-soluble salts of the higher fatty acids, i.e. "soaps", are useful as the detergent component of the composition herein. This class of detergents in-- cludes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of ; fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow and coconut soap.
- Water-sol~ble nonionic synthetic detergents are also useful as the detergent component of the instant composition. Such nonionic detergent materials can be broadly defined as compounds produced by the condensa-; tion of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements.
For example, a well-known class of nonionic synthetic deter~ents is made available on the market under the trade mark "Pluronic" sold be Wyandotte ' 108~
Chemicals. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the eondensation of propylene oxide with propylene glycol.
Other suitable nonionic synthetic detergents include the polyethylene oxide condensates of alkyl phenols, e.g. the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 earbon atoms in either a straight ehain or branehed ehain eonfiguration, with ethylene oxide, the said etnylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
The water-soluble eondensation products of aliphatie aleohols having from 8 to 22 carbon atoms, in either straight ehain or branehed configuration, with ethylene oxide, e.g. a eoeonut aleohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut aleohol fraction having from 10 to 14 earbon atoms, are also useful nonionic detergents herein.
Semi-polar nonionic detergents include water-soluble amine oxides containing one alkyl moiety of from about 10 to 28 earbon atoms and 2 moieties seleeted from the group consisting of alkyl groups and hydroxy-alkyl groups eontaining from l to about 3 earbon atoms;
water-soluble phosphine oxide detergents containing one alkyl moiety of about 10 to 28 carbon atoms and 2 moieties selected from the group eonsisting of alkyl \
101!~08~
groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxide deter-gents containing one alkyl moiety of from about 10 to 28 carbon atoms and a moiety selected from the group con-sisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Ampholytic detergents include derivatives of aliphatic or al.phatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 ~ -.
to 13 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Zwitterionic deter~ents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium .
compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of tne aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group. .-Other useful detergents include water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing ..
from about 2 to 9 carbon atoms in the a~yl group and from about 9 to about 2i carbon atoms in the alkane moiety; ~-alkyloxy alkane sulfo.nates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety; alkyl dimethyl amine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethyl-ammonio-propane-sulfonates and alkyl-dimethyl-ammonio-hydroxy propane-sulfonates wherein the alkyl group in both ' ~:)8~ 8~
types contains from about 14 to 18 carbon atoms; soaps as hereinabove defined; the condensation product of ` tallow fatty alcohol with about 11 moles of ethylene oxide; the condensation product of a C13 (avg.) secondary alcohol w~th 9 moles of ethylene oxide; and alkyl glyceral ether sulfates with from 10 to 18 carbon atoms in the alkyl radical.
A typical listing of the classes and species of ; detergent compounds useful herein appear in U.S. Patent 10 3,852,211, to Ohren issued December 3, 1974.The foregoing list of detergent compounds and mixtures whicn can be used in the instant compositions is representative of such material3, but is not intended to be limiting.
' A particularly useful anionic detergent mixture comprises:
(i) from about 2~ to about 15% by weight of an alkyl sulfate wherein the alkyl radical has from 10 to 20 carbon atoms and mixtures thereof the cation ~; 20 being an alkali metal preferably sodium;
(ii) from about 2% to about 15~ by weight of an alkyl , benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical and mixtures thereof the cation being an alkali metal preferably sodium.
An additional component which may be added to (i) and (ii) above is:
, ~ - 17 -(iii) from about 2% to about 15~ by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon atoms in the alkyl radical ahd from 1 to 30 ethoxy groups and mixtures tnereof having an alkali metal preferably sodium cation.
When formulating the detergent composition of the present invention the organic detergent component is present at from about 1% to about 50%, preferably from about 5%
to about 40%, and most preferably from abou-t 12% to about 30%
by weight. The ratio of the detergent to builder in the composition is preferably in the range of from about 10:1 to about 1:10, more preferably from about 3:1 to about 1:3.
Tne amount of alkali me~al pyrophosphate in tne detergent composition is from about 5% to about 60%, preferably about 8% to about 40%, most preferably about 15% to about 35~ by weight. The amount of silica in the detergent product , is from about 1% to about 4U%, preferably about 3% to about 30%, and most preferably about 5% to about 20% by weight.
The colloidal silicas of the present invention are discussed in Dupont Ludox~ technical product information ~`
A-65503 SM 7/69, Dupont Product Data Sheet Ludox~3colloidal silica A-31957 and Dupont Ludox~AM Product InEormation Bulletin A-21163. Further information on silica preparation is found in U.S. Patent 3,437,441, issued April 3, 1969 to Mayes et al .
, ~L0~0~0 and U.S. Patent 3,662,059 to Weisner et al, issued ~lay 9, 1972.
Soluble silicates are generally discussed in DuPont Product Information Bulletin A-18208, copyright 1961.
Optional Ingredients The products of the present invention as either detergent additive or complete detergent composition may ; contain all manner of ingredients normally found in detergent products such as enzymes, bleaches, stabilizers, dyes, nydro-tropes, anti-caking agents, and perfumes.
Soil suspending agents at about 0.1~ to 10~
by weight such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethylcellulose copolymers of maleic and anhydride and vinyl ether and preferably polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the detergent compositions of the present invention. Dyes, pigments, optical brighteners, and perfumes can be added in varying amounts as desired.
Other materials suc~ as fluorescers, antiseptics, germicides, enzymes in minor amounts, anti-cakiny agents such as sodium sulfosuccinate,and sodium benzoate may also be added.
Additional amounts of water-soluble detergency builders may be added to the detergent compositions of the present invention. Such inorganic detergency builder salts include alkali metal carbonates, borates, and bicarbonates. Specific examples of such salts are the sodium and potassium borates, perborates, bicarbonates, and carbonates.
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- Examples of suitable organic detergency builder -sal~s are: (1) water-soluble aminopolycarboxylates, e.g.
sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)-nitrilodi~
acetates; (2) water-soluble salts of phytic acid, e.g.
sodium and potassium phytates -- see U.S. Patent 2,739,942;
(3) water-soluble polyphosphonates, including specifically, sodium, potassium and lithium salts of ethane-l-nydroxy-l,l-diphosphonic acid, sodium, potassium and lithium salts of methylene diphosphonic acid, sodium, potassium and lithium salts of ethylène diphosphonic acid, and sodium,potassium - and lithium salts of ethane-1,1,2-triphosphonic acid.
Other examples include the alkall metal salts of ethane-2-carboxy-l,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid; and (4) water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent 3,308,067.
A useful detergent builder which may be employed in the present invention comprises a water-soluble salt i of a polymeric aliphaticpolycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possesslng the following ; - 20 -~ . . ~ .
prescribed physical cnaracteristics; (a) a minimum molecular weight of about 350 calculated as to the acid form;(b) an equivalent weight of a~out 50 to about ~0 calculated as to a~id form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the ~10 polymer chain from the site of attachment of the next carboxyl-containing radical. Specific examples of the above-described builders include polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid and citraconic acid and-copolymers with tnemselves.
In addition, other builders whicn can be used satisfactorily include water-soluble salts of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, and ~20 oxydisuccinic acid.
The detergent compositons of this invention preferably contain the water-soluble detergent in a ratio to tne total builder present in a weight ratio of from about 10:1 to about 1:10, preferably from about 3:1 to about 1:3. The amount of additional builder in the detergent compositions of tne present invention is from about 5% to about 50%, preferably from about 10% to about 25%. These additional builders may be in a single granule with the silica and the pyrophosphate are admixed as separate granules. In liquid compositions the :10~11080 additional builder is dissolved or suspended with the other components in the solvent.
Zeolites or aluminosilicates enhance the function of the silica and pyrophosphate in building. One such alumino- -silicate which is useful in the compositions of the invention is an amorphous water-insoluble hydrated compound of the formula Nax(xAl02'ySi02), wherein x is an integer of from 1 to 1.2 and y is 1, said amorphous material being further characterized by a Mg++ exchange capacity of from about -50 mg eq. CaC03/g to about 150 mg eq. CaCo3/g. This ion exchange builder is more fully described in Ireland publisned , application 1505/74 to B. H. Gedge et al filed July 16, 1974.
~ A second water-insoluble synthetic aluminosilicate ion exchange material useful herein has the formula Naz[(Al02)z.
(Si02)y]xH20, wherein z and y are integers of at least 6;
the molar ratio of z to y is in the range of from 1.0 to about . . .
0.5, and x is an integer from about 15 to about 264; said aluminosilicate ion exchange material having a particle size - diameter from about 0.1 micron to about 100 microns; a calcium ,20 ion exchange capacity of at least about 200 mg eq./g; and a calcium ion exchange rate of at least about 2 grains/gallon/
minute/gram. These materials are further discussed in Belgian 814, 874.
The above described aluminosilicates are employed at levels of from about 1~ to about 40%, preferably about 5~ to ~ about 25~ by weight.
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; - 22 -~l0~511080 The compositions of the present invention can be prepared in a liquid non-detergent solvent such as water and alcohols having from 1 to 8 carbon atoms. The alcohols useful herein may be branched or straight chained, monohydric or polyhydric. Preferred alcohols for use in forming liquid detergent or additive ¢ompositions of the present invention include ethanol, glycerin and ethylene glycol. The solvents may be used alone or as mixtures at levels of from about 10 to about 90~, preferably about 15%
to about 70~, and most preferably about 20% to about 50 by weight of the composition.
The precipitation of dicalcium pyrophosphate can be enhanced in the additive or detergent compositions by including a source of alkalinity such as the alkali metal and alkaline earth metal hydroxides at levels of from about 1% to about 30%, preferably from about 3% to 20~ by weight. Some of the additional builders such as the alkali metal carbonates discus-sed previously also provide additional alkalinity.
Composition Preparation The detergent additive or complete detergent product of the present invention may be formulated into liquid semi-solid or solid, preferably granular states.
To prepare liquid compositions of the detergent additive or complete detergent product, the individual components are prepared in the slurry or solution within the previously discussed weight limitations. To facilitate mixing the slurry or solution of the components may be heated slightly, preferably not above the flash point of any organic solvent used in the solution.
~ 1~)81080 The silicas of the present invention being colloidal ' in nature tend to support or prevent settling out of the less soluble components in tne slurry or solution. The foregoing property of the silica is particularly advantageous when the s,olvent is organic in that the alkali metal pyrophos-pnates are not particularly soluble therein. Settling o~t of the components can also be prevented by using mixtures of water and lower monohydric alcohols such as et;lanol in a ; weight ratio of from about 4:1 to about 1:4 in the liquid ^applications of the present invention.
When liquid detergent compositions are intended the detergent component may be a minor amount of the overall composition or the detergent may be the solvent for tne remainder of the components. In particular, etnoxylated alcohols naving from 1 to 30 moles of ethylene or propylene oxide and an alhyl radical naving a chain length of from about 3 to 16 carbon atoms are particularly suitable as liquid mediums for the detergent composition.
To either the additive product or the detergent composition of the present invention minor amounts on the order of from about 1 to 10~ by weight of an electrolytic material, e~g., potassium chloride or sodium acetate ma~, be added to assist in maintaining a suspension of the component in the solvent medium.
Semi-solid or pasty compositions of the present invention are formed much in the manner as the liquid compositions discussed above, however the amount of - 24 - .
, . . . . .
0~
solvent used is held to the magnitude of about 10% to about 30~ by weight or merely enough to give the composition a pasty consistency.
Solid products of the present invention are preferably in the form of laundry bars or granules having a moisture content generally less than about 12~ by weight of the finished product.
Laundry bars of the present invention are conveniently prepared by dry mixing the components and then forming the mass by pressure into nonmal~eable character in the form of the bar. The process of forming laundry bars is described in U.S. Patent~3,178,370 i~sued April 13, 1965 and British Patent 1,064,414 issued April 5, 1967 each to Okenfuss.
To form the granu~ar additive or detergent composition of the present invention, the product may be converted into a solid from the slurry with methods such as spray drying, drum drying, agglomeration, or freeze drying.
; Spray drying is a preferred method of preparing the detergent additive or detergent composition of the invention as the other stated methods of preparing the product in a solid form require an additional step of breaking up the large , bulk of dried product into granules which are acceptable to consumer aesthetics.
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~a08~0~0 When spray drying the product of the present invention, countercurrent and cocurrent drying towers may be employed.
The preferred method and apparatus for spray-drying products of the present invention are described in U.S. Patents 3,629,951 and 3,629,955, issued to R. P. Davis et al on December 28 r 1971. The granule so formed in either the additive or complete detergent product are free flowing of uniform density and not tacky.
. . ' Composition Utilization The additive or detergent products of the present invention will ordinarily be formulated for use in the wash or soak solution, preferab~y from about 0.03 to about 0.5% by weight of the wash or soak solution.
`~ The liquid detergents of the present invention are particularly effective when applied directly to the ', water in the washer soaked solution. Washing temperatures , are gen~erally in the range of from about 50%F to about 130%Fr and substantially higher under European washing ~20 Gc~nditions.
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EXAMPLE I
.
- A liquid detergent additive is prepared by thoroughly mixing: ~ `
.
. .
3.4 % Na pyrophosphate 6.6 % silica (Ludox~ HS40 14xlO
microns *) ~ H2O (solvent) .
, '' The additive product at a concentration of 0.08-~ by weight is used as a soak solution in the washing machine for ~ 1 hour on dacron polyester fabric soiled with clay.
Following the soaking period 0.08 % by weight of a detergent having the following compositionO
' - .
- ~ 2 3 18 % C12 Alkyl benzene sulfonate 18 % Sodium silicate ~Na O:SiO2 1:~.6) 2 % Na2 SO
9 ~ Minors to 100%
..
The fabrics are then washed in the soak cycle in a commercial washer. The fabrics presoaked in the additive product and then washed are substantially cleaner than control swatches presoaked in water alone and then washed with the detergent de~scribed above.
* Denotes in all examples the mean particle diameter.
O .
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The experLment is repeated using a mixture of ethanol and water in a 1:1 ratio as the solvent with similar results~ The water may be replaced by a coconut cut triethoxylated alcohol to give a complete detergent product. This product used alone under the conditions of the example compares favorably to the previous compositions.
The water content is lowered to 10% of the composition and the remainder of the formula in a paste state contains sodium pyrophosphate and the silica described above in a ~5:1 weight ratio.
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10~:108~3 Detergent Products A, B and C without silicate perform better than D, E, and F respectively. G ~ H
are further illustrations of the present invention. I is a product formulated as is A showing the advantage of pyrophosphate over tripolyphosphate at equal weights.
All tests above are conducted on clay soil stained dacron polyester swatches using the product at 0.12% by weight at 100F. The percent reflectance of the cleaned fabric is measured in Hunter Whiteness Units.
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-EXA~IPL~ III
, The following additive products are prepared by spray drying: .
Sodium pyrophosphate 15 30 40~ 25 . _ _ Silica (Ludox HS40 14mlOr3ns) . _ _ _ 50 _ Silica (Ludox ~M 25xlO microns) _ _ 30 _ _ Silica (Ludox SM 30 7xlOcron5) 30 _ _ _ _ Silica (lx10-3 microns) 5 _ _ _ Silica (20 microns) ~ = 40 _ _ _ Sodium silicate (SiO2:Na2O 1.6:1) 10 ~ _ _ . - . . . _ _ _ Sodium silicate (SlO2:Na2O 2.4:1) _ ~ _ 20 _ Sodium silicate (SiO2:Na2O 3.~:1) _ 15 _ _ _ Sodium carbonate 30 15 _ _ _ Moisture and minors 20 5 5 5 __ The additive products above are tested with commercially available products and in each case enhance the perfor~ance of the detergent.
,: ~ ~,'~- . -`` ~ 80 EXAMPLE IV
Products A, B and C are prepared as follows:
_ B C
Sodium tallow alcohol sulfate 9.9% 9.9% 9.9%
Sodium alkyl (11.8)* benzene sulfona~te 8.18.1 8.1 Silica (HS 40 Ludo ~ 14xlO
microns) 8.08.0 8.0 Sodium sulfate 43.04~.020.0 10 Sodium carbonate 3.03.0 3.0 Sodium pyrophosphate26.2 Sodium tripolyphosphate - 24.4 49.6 ~linors to 100%
. ' ~'.
A, B, C, are used to clean clay soiled dacron polyester fabric swatches at a concentration of 0.12% by weignt in 100F.
water. The hardness of the water is 9 grains (3:1 Ca#/Mg~
The results measured by a Hunter Whiteness Meter in Hunter Whiteness Units (hereafter) HWU are:
A (HWU) B (HWU) C (HWU) 24.0 -2.2 32.2 LSDo 05= 2-0 Product _ (sodium pyrophosphate) formulated in accordance with the present invention performs better in cleaning the fabrics than the same product (B) formulated with sodium tripolyphosphate. Product C performs better than Product _ but Product C contains twice as much phosphorous (12.2% versus 6.1%) in the form of sodium tripolyphosphate.
* (11.8) Denotes the mean alkyl chain length.
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-- 108:~0~Q
~ EXAMPLE v Products D, E, and F are identical to A., B, and C of Example rv but each of D, E and F has 3.2:1 -SiO~:Na20 added at 8% by weight in place of sodium sulfate. D, E and F are tested as in Example IV with the following xesults .. . ' . , '. ' ~
D (HWU) E -~HWU) F~HWU) - ~7.9 -~.5 27.7 LSDo 05 = 2-0 Product D again is better in removing clay soil from ~acon Polyester fabric then Product E. Product F at twice the phosphorous level performs better than D.
The addition of the soluble silica~es has not substantially diminished the relative performance of D over A (Example IV).
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~L081~)80 EXAMPLE VI
Products G and H have the following composition:
G H
sodium alkyl (C14_Cl6) triethoxy sulfate sodium alkyl (Cll 8) benzene 7.0 7.0 sulfonate sodium tallow alcohol sulfate 5.5 5.5 sodium pyrophosphate 26.2 26.2 lO sodium sulfate 35.0 43.0 sodium carbonate 3 3 sodium silicate 8 8 (SiO2:Na20 3.2:1) silica 8 (HS 40 LUDOX 14xlO 3 micron) minors to lO0 Compositions G and H are tested as in Examples IV and V. The results are ~ G (HWU) H(HWU) 21.2 13.5 LSD 0.05 = 4.2 Product G containing silica of the present invention performs better in clay soil removal from Dacron Polyester fabries than does Product H whieh contains silicate but no siliea. *(C14 - Cl6) indicates alkyl chain length.
10~ 8V
E ~ LE VII
A laundry bar is prepared with the following composition , . .
24~ alXyl benzene sulfonate (C13 hard) 30% ~alcium carbonate 12% sodium pyrophosphate 20~ silica (Prepared as in ~acDonald U. S. Patent 3,708,428 supra) .8~ sodium silicate ~SiO2:Na2O 1.6:1) 6% minors ,
The present invention relates to detergent additives and detergent compositions. A detergent additive is a prod~ct designed to supplement the consumer's ordi~ary ~detersent product to ~oost the latter~s effectiven~ss.
The detergent composition aspect of the present invention encompasses the detergent additi~e aspect with the additional feature of having present a surface active agent in the composition.
Those skilled in the detergency arts ha~e for many years equated the alkali metal pyrophosphates with the alXali metal tripolyphosphates in detergent compositions. It is known that pyrophosphates and tripolyphosphates when used as builders will each sequester one mole of calcium or magnesi~m water hardness per mole of the phosphate species. Pyrophosphate detergency builders, however, unlike tripolyphosph2tes will under . .
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certain conditions form minor amounts of dicalcium pyro-phosphate a completely neutralized insoluble salt. These precipitates of the pyrophospnates discussed above have been known to deposit on the fabrics being cleansed or upon the sur-faces of the washing machine. Such buildup of the calcium pyrophosphate salt is undesirable in that the precipitates have a tendency to remain on the fabrics through several wash cycles and continue to builup thus causing harsh fabric. Similarly, the calcium pyrophosphate will after -~
several cycles in a wasning machine cause deposition or scale on the exposed surfaces. This precipitation phenome-non of the pyrophosphates has led many detergent manufacturers to avoid pyrophosphates and to instead use tripolyp;losphates.
It has been suggested in U.S. Patent 2,3~1,960 to Johnson issued August 14, 1945 that the effectiveness of sodium pyrophosphate in reducing water hardness could be obtained by adding the pyrophosphate to the solution of nard water after an alkaline material had been first added to the water. The alkaline materials taught by Johnson were sodium orthophosphate, sodium and potassium hydroxide, sodium and potassium carbonates, and sesqui-carbonates, soap and sodium silicate having an SiO2:;~a2O
weight ratio greater than 1.5. The point of addition of the tetrasodium pyrophosphate to the solution is after the alkaline material but prior to the formation of a macroscopic precipitate of the hardness ions and the aforementione~ alkaline naterials.
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In U.S. Patent 2,326,9~0 issued August 17, 1943 to Kepfer, it is taught that tetrasodium pyrophosphate is used more efficiently to control water hardness when it is used in conjunction with an alkaline material whicn is added to tne solution after the pyrophosphate but before a macroscopic precipitate of the hardness ions and the pyrophosphate is formed. The alkaline materials taught by Kepfer are sodium borate, sodium metasilicate (SiO2:Na2O 1:1) and disodium hydrogen phosphate. The processes of controlling water hardness by somehow increasing the effectiveness of sodium pyrophosphate taught by Kepfer and Johnson, herein incorpo-rated by reference, suffer from the defect that the compo-sition could not be effectively prepared without going to the trouble of positively insuring the delay of the pyrophospnate relative to the alkaline materials or vice versa. Thus Kepfer and Johnson could only with great difficult~ be adapted for use in granular or liquid pkoducts which - are favored by the consumer today.
U.S. Patent 3,708,428 issued January 2, 19~3, to McDonald discusses the neutralizing of organic detergent acids such as alkyl benzene sulfonic acid with sodium silicates having an SiO2:Na2O ratio of from about 1:2 to about 4:1 to form an in situ silica having an SiO2:Na2O ratio of from about 4:1 to about 2000:1 or greater. An essential condition `
to the compositions taught in McDonald is that the inclusion of water soluble alkali builders, illustrated by sodium or potassium orthophosphates, or complex phosphates (i.e. pyrophosphates), alkali carbonates, borates, . , . . : - . .
.
~1~81~8~
silicates, or neutral salts, such as sodium chloride or sodium sulfate, or magnesium sulfate, be restricted to levels of concentration of the order of 4~ by weight or lower. l~cDonald goes on to state the desired advantages of the in situ formed colloidal silicas on the removal of soils will be found to be appreciably impaired if the foregoing limits are not strictly adhered to.
It is thus an object of the present invention to utilize an alkali metal pyrophosphate more efficiently in the control of water hardness.
It is a further object of the present invention to utilize an alkali metal pyrophosphate such that the deposition product of water hardness and the pyrophosphate ions is diminished on washing machine surfaces.
It is a further object of the present invention to prepare a composition utilizing ah alkali metal pyro-phosphate as a detergency builder that minimizes the buildup on fabrcis of water insoluble pyrophosphate.
` It is yet a further object of the present invention to provide a detergent additive product or a complete detergent composition built with an alkali metal pyro : ' phosphate which is particularly effective in cleaning.
It has now been found that by preparing a detergent additive comprising an alkali metal pyrophosphate and silica ~ ~
or a complete detergent composition comprising tAe alkali -j metal pyrophosphate, silica and an organic detergent component that the objects of the invention may be achievd.
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- . . . - . . -~0~:11D80 Moreover, the use of the alkali metal pyrophospnate with the silica of the present invention in an additive or detergent composition substantially decreases the amount of calcium ion in the wash solution. While not wishing to be bound by any par-ticular theory it is believed that silica in some manner encourages the precipitation of calcium ions in the wash solution as insoluble dicalcium pyrophospnate. Thus in prior art compositions pyrop~osphate salts were only able to effectively sequester on a 1:1 mole basis witn calcium hardness, the present invent~on allows the pyrophosphate to effectively control twice the amount of calcium which is possible by sequestration. The precipitation of the dicalcium pyrophosphate takes place with the aid of the silica such that the precipitated salt is less likely to form an unsiyhtly scum on tne exposed surfaces of the washing machine or deposit on fabrics to cause a harsh feel. The more , effective control of calcium ion in the wash solution means ` that the detergent components are not as likely to be interfered with by tne water hardness in the wash thus providing better cleaning of the fabrics. ~ ~, Soluble silicates are often added to detergent or addi-t.ive products to protect exposed machine surfaces from corrosion.
; It has been found, however, that soluble silicates interfere ! with the precipitation of calcium hardness as dicalcium pyro-phosphate. Other componen-ts found in detergent products have also been found to interfere with dicalcium pyrophosphate precipitation, namely the detergent active.
It has now been found that the addition of silicas to the additive or detergent product diminishes the tendency of soluble silicates and other components such as the deter-gent to interfere with the precipitation of calcium by pyro-phosphate.
~08~013~) Throughout the specifica-tion and claims percentages and ratios are by weight and temperatures are in degrees Fahrenheit unless otherwise indicated.
SUM~IARY OF_ THE INVENTION
A detergent additive comprising:
~a) an alkali metal pyrophospllate; and (b) silica ~aving a mean particle diameter less than 20 microns;
in a weight ratio of the alkali metal pyrophosphate to the silica of Erom about 25:1 to about 1:2.
A detergent composition comprising:
(a) from about 5% to about 60% by weight of an -alkali metal pyrophosphate; ;
(b) from about 1% to abo~t 40% by weight of silica having a ~ean particle diameter less than 20 microns; and (c) an organic detergent at from about 1% to about ,, 50% by weight oE the composition.
, DETAILED DESC~IPTION OF THE INVENTION
~ ..
The present invention has two aspects. The first aspect is a detergent additive product and the second is a . .
complete detergent composition. T'ne deterge~t ad~itiv~
products are formulated such that they may be used compatibly with other commercially available detergent products. The detergent additives ordiharily do not have organic detergents within their composition. The detergent additive product is intended for use as a presoak product wherein the ~108~
clothes to be washed are placed in a wash tub or the washing machine and allowed to soak in water containing the additive product for a period of time before the consumer's regular detergent product is added. Alternatively, a detergent additive product may be added simultaneously to the wash solution with the consumer's regular detergent product. In either event the detergent additive product of the present invention boosts the cleaning of the consumer's regular detergent.
When formulated as a detergent composition the present invention is utilized for cleaning in the conventional manner.
The detergent additive or detergent composition of the present invention may be formulated to be in a solid or liquid form. When formulated as a solid the compositions of the present invention may be formed into a single granule such as by spray drying or the components may be separately admixed with one another in any order.
The alkali metal pyrophosphates of the present invention are commercially available from several sources.
The alkall metal pyrophosphate such as the sodium or potassium~`
salt, preferably the sodium salt may be dehydrated or anhydrous.
The silica component of the present invention is also widely available from commercial sources such as those products marketed under the trade mark Zeosyl sold by the Huber Chemicàl Company and Ludox marketed by E. I.
duPont de Nemours & Company~ The silicas useful in the present invention have a mean particle diameter of less than 20 microns, such as from about 1 x 10 3 to about 5 microns more preferably from about 2 x 10 3 to about Ool micron, most preferably from about 3 x 10 3 to about 0.05 micron. The surface area is given as an aggregate per unlt of weight of ~0~1~80 the silica. As the surface area of the silica increases the performance advantage of the compositions of the invention increases. The specific surface area in square meters per gram of the silicas of the present invention should be greater than 0.2 square meter per gra~,preferably greater tnan 1 square meter per gram, and more preferably greater than 40 square meters per gram, and most preferably greater than 200 square meters per gram.
The mean partiQle diameter of the silica is defined as being the length of the largest axis of the particle.
The surface area is related indirectly to the mean particle diameter of the silica. That is to say that if the geometry of the silica particle is known the theoretical surface area can be calculated from the mean particle diameter.
It is noted that high surface areas of the silica are possible even when a small number of particles are present per given weight of the silica. The foregoing arises when the silica particles are porous. While high surface area for the silicas of the present invention is desirable it is preferred tnat the high surface area be accompanied by a large number of particles for thorough distribution in wash or soak solution. SiIica particles of the size descri-bed above give both high surface area and a large number of particles per unit weight.
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~108~1aEi~
The silicas of the present invention to a limited extent can be thought of as being ionic ln that some of the hydrogen atoms in the silanol group (-SiOH) of the silica molecule are occupied by cations particularly sodium or potassium.
In the McDonald patent, previously metioned, the distinction was made that silicas must have an SiO2:Na2O ratio greater than 4:1 and up to 2000:1 and greater.
The foregoing definition is applicable here. All the alkali metal cations occupy silanol positions. Preferably the SiO2:
NaO2 ratio is greater than 10:1, more preferably gre'ater than 20:1 and most preferably greater than 45:1.
In the additive product the rati,o of alkali metal pyrophosphate to the silica is from abou-t 25:1 to about 1:2, preferably about 20:1 to aboutl l, and most preferably about 15:1 to about 5:1 by weight. The foregoing ratios are also satisfactory in the detergent product.
The present invention contains as an optional ingredient alkali metal silicates of the formula SiO2:M2O, ,-, wherein M is an alkali metal preferably sodium or potassium and the foregoin~ weight ratio is from about 1.6:1 to about 4:1,-preferably from about 2.0:1 to about 4:1, and most preferably about 2.4:1 to about 4:1. While it nas been found that the present invention functions as a detergent additive or complete detergent composition satisfactorily and indeed to some benefit for hardness control and cleaning -8~
in t;le absence of silicates it has been found desirable to include in the composition soluble silicates at a level of from about 1~ to abou-t 25~, preferably about 3~ to about 20~, and most preferably about 5~ to about 15~ by weight. The func-tion of the silicate is important in that it lessens the tendency of tne detergent component and the pyrophosphate to tarnisn the exposed surfaces of the wasning macnine. The soluble silicates are also desirable in detergent additive type produats and co~plete detergent compositions whicn are spray dried in that more desirable granule characteristics are obtained. such granule charac~eristics include flowability of the granules and a tendency to resist caking.
The ratio of the silica to tne silicate in the present invention should be in the range of about 10:1 to about 1:10, preferably about 6:1 to about 1:6, a~d most preferably from about 2:1 to about 1:2 by weight.
When formulated as a complete detergent composition the present invention encompasses all manner of organic detergent components. Suitable detergents include for example the following:
Detergent Component Preferably the detergent component of the present invention is a water-soluble salt of: an ethoxylated sulfated alcohol with an average degree of ethoxylation of about 1 to 4 and an alkyl chain length of about 14 to 16; tallow etnoxy : : . '' ~ ,' ., '- ,. : , ~1081080 sulfate; tallow alcohol sulfates; an alkyl benzene sulfonate with an average alkyl chain length between 11 and 13, preferably 11.2 carbon atoms; a C6-C20 ~-sulfocarboxylic acid or ester t~ereof having 1 to 14 carbon atoms in the alcohol radical;
a C8-C24 paraffin sulfona-te; a C10-C24 ~-olefin sulfonate or mixtures t;~ereof; or other anionic sulfur-containing surfactant. ~.
Such preferred detergents are discussed below.
An especially preferred alkyl ether sulfate detergent component of the present invention is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of -`
about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, preferably from about ~ to 3 moles of ethylene oxide.
Specifically, such preferred mixtures comprise ...
from about 0 to 10% by weight of mixture of Cl~ 13 compounds, from about 50 to 100% by weight of mixture of Cl~ 15 compounds, ~: and from about 0 to 45% by weight of m~xture of Cl~ 17 compounds, and from about 0 to 10% by weight of a mixture of C18_19 compounds. Further, such preferred alkyl ether sulfate mixtures comprise from about 0 to 30% by weignt of mixture of compounds having a degree of ethoxylation of 0, from about 45 to 95% by weight of mixture of compounds naving a degree of.ethoxylation from 1 to 4, from about 5 to 25~ by ~.
weight of mlxture of compounds having a degree of ethoxylation ~l081080 -::
from 5 to 8, and from about 0 to 15~ by weight of mixture of compounds having a degree of ethoxylation grea-ter than 8. ~
The sulfated condehsation products of ethoxylated alcohols of ~-8 to 24 alkyl carbons and with from 1 to 30, preferably 1 to 4 moles of ethylene oxide may be used in place of the preferred alkyl ether sulfates discussed abo~e.
Another class of detergents which may be used in the present invention includes the water-soluble salts, particu-larly the alkali metal, ammonium, and alkylolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfuric acid ester group. Examples of ~:
this group of synthetic detergents are the sodium and potassium , alkyl sulfates, especially tnose obtained by sulfating the higher alcohols (C8-C18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil.
; Preferred water-soluble organic detergent compounds herein include alkyl benzene sulfonates (preferably essentially linear although "hard" ABS may be used) containing from about 9 to 15 carbon atoms in the alkyl group. Examples of the above are sodium and potasslum alkyl benzene sulfonates in which the alkyl group contains from about 11 to about 13 carbon atoms, in straig~t chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
Especially valuable are straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 11.2 carbon atoms, abbreviated as Cll 2LAS.
' ' ' .
~0~10~0 Another useful detergent com2ound herein includes the water-soluble salts of esters o~ ~-sulfonated fat~y acids co~taining from about 6 to 20 carbon atoms in the fatty acid group and their esters from about 1 to 14 carbon atoms in the alcohol radical.
Preferred "olefin sulfonate" detergent mixtures utilizable herein comprise olefin sulfonates containing from about 10 to about 24 carbon atoms. Such materials can be produced by sulfonation~of ~-olefins by means of uncomplexed sulfur trioxide followed by neutralization under conditions such that any sulfones present are hydrolyzed to the corresponding hydroxy-alkane sulfonates.
The ~-olefin starting materials preferably have from 14 to 16 carbon atoms. Said preferred ~-olefin sulfonates are described in U.S. Patent 3,332,880.
The paraffin sulfonates embraced in the present invention are essentially linear and contain from 8 to 24 carbon atoms, preferably 12 to 20 and more pre-ferably 14 to 1~ carbon atoms in the alkyl radical.
Other anionic detergent compounds herein in-clude the sodium alkyl glyceryl ether sulfates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fa-tty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about 1 to about 10 units of ethylene oxide per molecule and wherein t~e alkyl groups contain about 8 to about 12 carbon atoms.
10~:1080 Water-soluble salts of the higher fatty acids, i.e. "soaps", are useful as the detergent component of the composition herein. This class of detergents in-- cludes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of ; fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow and coconut soap.
- Water-sol~ble nonionic synthetic detergents are also useful as the detergent component of the instant composition. Such nonionic detergent materials can be broadly defined as compounds produced by the condensa-; tion of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements.
For example, a well-known class of nonionic synthetic deter~ents is made available on the market under the trade mark "Pluronic" sold be Wyandotte ' 108~
Chemicals. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the eondensation of propylene oxide with propylene glycol.
Other suitable nonionic synthetic detergents include the polyethylene oxide condensates of alkyl phenols, e.g. the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 earbon atoms in either a straight ehain or branehed ehain eonfiguration, with ethylene oxide, the said etnylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
The water-soluble eondensation products of aliphatie aleohols having from 8 to 22 carbon atoms, in either straight ehain or branehed configuration, with ethylene oxide, e.g. a eoeonut aleohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut aleohol fraction having from 10 to 14 earbon atoms, are also useful nonionic detergents herein.
Semi-polar nonionic detergents include water-soluble amine oxides containing one alkyl moiety of from about 10 to 28 earbon atoms and 2 moieties seleeted from the group consisting of alkyl groups and hydroxy-alkyl groups eontaining from l to about 3 earbon atoms;
water-soluble phosphine oxide detergents containing one alkyl moiety of about 10 to 28 carbon atoms and 2 moieties selected from the group eonsisting of alkyl \
101!~08~
groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxide deter-gents containing one alkyl moiety of from about 10 to 28 carbon atoms and a moiety selected from the group con-sisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Ampholytic detergents include derivatives of aliphatic or al.phatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 ~ -.
to 13 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Zwitterionic deter~ents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium .
compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of tne aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group. .-Other useful detergents include water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing ..
from about 2 to 9 carbon atoms in the a~yl group and from about 9 to about 2i carbon atoms in the alkane moiety; ~-alkyloxy alkane sulfo.nates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety; alkyl dimethyl amine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethyl-ammonio-propane-sulfonates and alkyl-dimethyl-ammonio-hydroxy propane-sulfonates wherein the alkyl group in both ' ~:)8~ 8~
types contains from about 14 to 18 carbon atoms; soaps as hereinabove defined; the condensation product of ` tallow fatty alcohol with about 11 moles of ethylene oxide; the condensation product of a C13 (avg.) secondary alcohol w~th 9 moles of ethylene oxide; and alkyl glyceral ether sulfates with from 10 to 18 carbon atoms in the alkyl radical.
A typical listing of the classes and species of ; detergent compounds useful herein appear in U.S. Patent 10 3,852,211, to Ohren issued December 3, 1974.The foregoing list of detergent compounds and mixtures whicn can be used in the instant compositions is representative of such material3, but is not intended to be limiting.
' A particularly useful anionic detergent mixture comprises:
(i) from about 2~ to about 15% by weight of an alkyl sulfate wherein the alkyl radical has from 10 to 20 carbon atoms and mixtures thereof the cation ~; 20 being an alkali metal preferably sodium;
(ii) from about 2% to about 15~ by weight of an alkyl , benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical and mixtures thereof the cation being an alkali metal preferably sodium.
An additional component which may be added to (i) and (ii) above is:
, ~ - 17 -(iii) from about 2% to about 15~ by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon atoms in the alkyl radical ahd from 1 to 30 ethoxy groups and mixtures tnereof having an alkali metal preferably sodium cation.
When formulating the detergent composition of the present invention the organic detergent component is present at from about 1% to about 50%, preferably from about 5%
to about 40%, and most preferably from abou-t 12% to about 30%
by weight. The ratio of the detergent to builder in the composition is preferably in the range of from about 10:1 to about 1:10, more preferably from about 3:1 to about 1:3.
Tne amount of alkali me~al pyrophosphate in tne detergent composition is from about 5% to about 60%, preferably about 8% to about 40%, most preferably about 15% to about 35~ by weight. The amount of silica in the detergent product , is from about 1% to about 4U%, preferably about 3% to about 30%, and most preferably about 5% to about 20% by weight.
The colloidal silicas of the present invention are discussed in Dupont Ludox~ technical product information ~`
A-65503 SM 7/69, Dupont Product Data Sheet Ludox~3colloidal silica A-31957 and Dupont Ludox~AM Product InEormation Bulletin A-21163. Further information on silica preparation is found in U.S. Patent 3,437,441, issued April 3, 1969 to Mayes et al .
, ~L0~0~0 and U.S. Patent 3,662,059 to Weisner et al, issued ~lay 9, 1972.
Soluble silicates are generally discussed in DuPont Product Information Bulletin A-18208, copyright 1961.
Optional Ingredients The products of the present invention as either detergent additive or complete detergent composition may ; contain all manner of ingredients normally found in detergent products such as enzymes, bleaches, stabilizers, dyes, nydro-tropes, anti-caking agents, and perfumes.
Soil suspending agents at about 0.1~ to 10~
by weight such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethylcellulose copolymers of maleic and anhydride and vinyl ether and preferably polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the detergent compositions of the present invention. Dyes, pigments, optical brighteners, and perfumes can be added in varying amounts as desired.
Other materials suc~ as fluorescers, antiseptics, germicides, enzymes in minor amounts, anti-cakiny agents such as sodium sulfosuccinate,and sodium benzoate may also be added.
Additional amounts of water-soluble detergency builders may be added to the detergent compositions of the present invention. Such inorganic detergency builder salts include alkali metal carbonates, borates, and bicarbonates. Specific examples of such salts are the sodium and potassium borates, perborates, bicarbonates, and carbonates.
, - , . . : ............................ .. ~ , - , : ~ . .
~08108~
- Examples of suitable organic detergency builder -sal~s are: (1) water-soluble aminopolycarboxylates, e.g.
sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)-nitrilodi~
acetates; (2) water-soluble salts of phytic acid, e.g.
sodium and potassium phytates -- see U.S. Patent 2,739,942;
(3) water-soluble polyphosphonates, including specifically, sodium, potassium and lithium salts of ethane-l-nydroxy-l,l-diphosphonic acid, sodium, potassium and lithium salts of methylene diphosphonic acid, sodium, potassium and lithium salts of ethylène diphosphonic acid, and sodium,potassium - and lithium salts of ethane-1,1,2-triphosphonic acid.
Other examples include the alkall metal salts of ethane-2-carboxy-l,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid; and (4) water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent 3,308,067.
A useful detergent builder which may be employed in the present invention comprises a water-soluble salt i of a polymeric aliphaticpolycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possesslng the following ; - 20 -~ . . ~ .
prescribed physical cnaracteristics; (a) a minimum molecular weight of about 350 calculated as to the acid form;(b) an equivalent weight of a~out 50 to about ~0 calculated as to a~id form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the ~10 polymer chain from the site of attachment of the next carboxyl-containing radical. Specific examples of the above-described builders include polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid and citraconic acid and-copolymers with tnemselves.
In addition, other builders whicn can be used satisfactorily include water-soluble salts of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, and ~20 oxydisuccinic acid.
The detergent compositons of this invention preferably contain the water-soluble detergent in a ratio to tne total builder present in a weight ratio of from about 10:1 to about 1:10, preferably from about 3:1 to about 1:3. The amount of additional builder in the detergent compositions of tne present invention is from about 5% to about 50%, preferably from about 10% to about 25%. These additional builders may be in a single granule with the silica and the pyrophosphate are admixed as separate granules. In liquid compositions the :10~11080 additional builder is dissolved or suspended with the other components in the solvent.
Zeolites or aluminosilicates enhance the function of the silica and pyrophosphate in building. One such alumino- -silicate which is useful in the compositions of the invention is an amorphous water-insoluble hydrated compound of the formula Nax(xAl02'ySi02), wherein x is an integer of from 1 to 1.2 and y is 1, said amorphous material being further characterized by a Mg++ exchange capacity of from about -50 mg eq. CaC03/g to about 150 mg eq. CaCo3/g. This ion exchange builder is more fully described in Ireland publisned , application 1505/74 to B. H. Gedge et al filed July 16, 1974.
~ A second water-insoluble synthetic aluminosilicate ion exchange material useful herein has the formula Naz[(Al02)z.
(Si02)y]xH20, wherein z and y are integers of at least 6;
the molar ratio of z to y is in the range of from 1.0 to about . . .
0.5, and x is an integer from about 15 to about 264; said aluminosilicate ion exchange material having a particle size - diameter from about 0.1 micron to about 100 microns; a calcium ,20 ion exchange capacity of at least about 200 mg eq./g; and a calcium ion exchange rate of at least about 2 grains/gallon/
minute/gram. These materials are further discussed in Belgian 814, 874.
The above described aluminosilicates are employed at levels of from about 1~ to about 40%, preferably about 5~ to ~ about 25~ by weight.
,, .
~' ''" ' .
; - 22 -~l0~511080 The compositions of the present invention can be prepared in a liquid non-detergent solvent such as water and alcohols having from 1 to 8 carbon atoms. The alcohols useful herein may be branched or straight chained, monohydric or polyhydric. Preferred alcohols for use in forming liquid detergent or additive ¢ompositions of the present invention include ethanol, glycerin and ethylene glycol. The solvents may be used alone or as mixtures at levels of from about 10 to about 90~, preferably about 15%
to about 70~, and most preferably about 20% to about 50 by weight of the composition.
The precipitation of dicalcium pyrophosphate can be enhanced in the additive or detergent compositions by including a source of alkalinity such as the alkali metal and alkaline earth metal hydroxides at levels of from about 1% to about 30%, preferably from about 3% to 20~ by weight. Some of the additional builders such as the alkali metal carbonates discus-sed previously also provide additional alkalinity.
Composition Preparation The detergent additive or complete detergent product of the present invention may be formulated into liquid semi-solid or solid, preferably granular states.
To prepare liquid compositions of the detergent additive or complete detergent product, the individual components are prepared in the slurry or solution within the previously discussed weight limitations. To facilitate mixing the slurry or solution of the components may be heated slightly, preferably not above the flash point of any organic solvent used in the solution.
~ 1~)81080 The silicas of the present invention being colloidal ' in nature tend to support or prevent settling out of the less soluble components in tne slurry or solution. The foregoing property of the silica is particularly advantageous when the s,olvent is organic in that the alkali metal pyrophos-pnates are not particularly soluble therein. Settling o~t of the components can also be prevented by using mixtures of water and lower monohydric alcohols such as et;lanol in a ; weight ratio of from about 4:1 to about 1:4 in the liquid ^applications of the present invention.
When liquid detergent compositions are intended the detergent component may be a minor amount of the overall composition or the detergent may be the solvent for tne remainder of the components. In particular, etnoxylated alcohols naving from 1 to 30 moles of ethylene or propylene oxide and an alhyl radical naving a chain length of from about 3 to 16 carbon atoms are particularly suitable as liquid mediums for the detergent composition.
To either the additive product or the detergent composition of the present invention minor amounts on the order of from about 1 to 10~ by weight of an electrolytic material, e~g., potassium chloride or sodium acetate ma~, be added to assist in maintaining a suspension of the component in the solvent medium.
Semi-solid or pasty compositions of the present invention are formed much in the manner as the liquid compositions discussed above, however the amount of - 24 - .
, . . . . .
0~
solvent used is held to the magnitude of about 10% to about 30~ by weight or merely enough to give the composition a pasty consistency.
Solid products of the present invention are preferably in the form of laundry bars or granules having a moisture content generally less than about 12~ by weight of the finished product.
Laundry bars of the present invention are conveniently prepared by dry mixing the components and then forming the mass by pressure into nonmal~eable character in the form of the bar. The process of forming laundry bars is described in U.S. Patent~3,178,370 i~sued April 13, 1965 and British Patent 1,064,414 issued April 5, 1967 each to Okenfuss.
To form the granu~ar additive or detergent composition of the present invention, the product may be converted into a solid from the slurry with methods such as spray drying, drum drying, agglomeration, or freeze drying.
; Spray drying is a preferred method of preparing the detergent additive or detergent composition of the invention as the other stated methods of preparing the product in a solid form require an additional step of breaking up the large , bulk of dried product into granules which are acceptable to consumer aesthetics.
', . ~
: , ~ .
.: .
i ~ :
:. .
'""
~a08~0~0 When spray drying the product of the present invention, countercurrent and cocurrent drying towers may be employed.
The preferred method and apparatus for spray-drying products of the present invention are described in U.S. Patents 3,629,951 and 3,629,955, issued to R. P. Davis et al on December 28 r 1971. The granule so formed in either the additive or complete detergent product are free flowing of uniform density and not tacky.
. . ' Composition Utilization The additive or detergent products of the present invention will ordinarily be formulated for use in the wash or soak solution, preferab~y from about 0.03 to about 0.5% by weight of the wash or soak solution.
`~ The liquid detergents of the present invention are particularly effective when applied directly to the ', water in the washer soaked solution. Washing temperatures , are gen~erally in the range of from about 50%F to about 130%Fr and substantially higher under European washing ~20 Gc~nditions.
;~ ' ' :' ., .
:i :
.~ , ., .
- 26 ~
.. . . . .
L08~ .
EXAMPLE I
.
- A liquid detergent additive is prepared by thoroughly mixing: ~ `
.
. .
3.4 % Na pyrophosphate 6.6 % silica (Ludox~ HS40 14xlO
microns *) ~ H2O (solvent) .
, '' The additive product at a concentration of 0.08-~ by weight is used as a soak solution in the washing machine for ~ 1 hour on dacron polyester fabric soiled with clay.
Following the soaking period 0.08 % by weight of a detergent having the following compositionO
' - .
- ~ 2 3 18 % C12 Alkyl benzene sulfonate 18 % Sodium silicate ~Na O:SiO2 1:~.6) 2 % Na2 SO
9 ~ Minors to 100%
..
The fabrics are then washed in the soak cycle in a commercial washer. The fabrics presoaked in the additive product and then washed are substantially cleaner than control swatches presoaked in water alone and then washed with the detergent de~scribed above.
* Denotes in all examples the mean particle diameter.
O .
.
The experLment is repeated using a mixture of ethanol and water in a 1:1 ratio as the solvent with similar results~ The water may be replaced by a coconut cut triethoxylated alcohol to give a complete detergent product. This product used alone under the conditions of the example compares favorably to the previous compositions.
The water content is lowered to 10% of the composition and the remainder of the formula in a paste state contains sodium pyrophosphate and the silica described above in a ~5:1 weight ratio.
- ~
. . : . .
.
. . .
lV~ )8~) ,. ,J, ~" o C 1-- N C C C n ~_: o c c o ~ ~ o x u~ n a n ~ ~ c~ o rl~ n t~ ~ O ~ ~ rt rt X X X .y O ~ .
. ~_ a~' tD (D tD 3 r ~ 0~ ~a ~ , ..
C ~J ~ . ; NO ~,0 O O X ~U rD n _ _ O H
V~ 5 ~ ~ ro ~ ~, l l l l o l l ~ 1~
l~ ~ t~
_ _ l _ H
Ul Ul __ 1~ 1_ l l 1_ l l 1_ l Vl ICI' ~ .' . t- to~) Ul 01 ~ ~ O ,1 l O l l î~) It~
___ _ _ ... . ~
o o .1 l o o l l 1. 1. o' l o 1~ ~4 ''.
__ __ . _ ., ~ ~ l l O l ~ l l .~ 1. l ~ lC~ ' '.
~ l l l ~- ~11 l l Ul ~Jl l l O~ 1~
1~ ~ 1~1~ L~ 11 ~
-- 2~ --. ~ .' ' '" ' ' ' - ~
10~:108~3 Detergent Products A, B and C without silicate perform better than D, E, and F respectively. G ~ H
are further illustrations of the present invention. I is a product formulated as is A showing the advantage of pyrophosphate over tripolyphosphate at equal weights.
All tests above are conducted on clay soil stained dacron polyester swatches using the product at 0.12% by weight at 100F. The percent reflectance of the cleaned fabric is measured in Hunter Whiteness Units.
, ',, " ~ - ' : : ' ' ~
," ' , ~ ': .' ~
... .
.~
-EXA~IPL~ III
, The following additive products are prepared by spray drying: .
Sodium pyrophosphate 15 30 40~ 25 . _ _ Silica (Ludox HS40 14mlOr3ns) . _ _ _ 50 _ Silica (Ludox ~M 25xlO microns) _ _ 30 _ _ Silica (Ludox SM 30 7xlOcron5) 30 _ _ _ _ Silica (lx10-3 microns) 5 _ _ _ Silica (20 microns) ~ = 40 _ _ _ Sodium silicate (SiO2:Na2O 1.6:1) 10 ~ _ _ . - . . . _ _ _ Sodium silicate (SlO2:Na2O 2.4:1) _ ~ _ 20 _ Sodium silicate (SiO2:Na2O 3.~:1) _ 15 _ _ _ Sodium carbonate 30 15 _ _ _ Moisture and minors 20 5 5 5 __ The additive products above are tested with commercially available products and in each case enhance the perfor~ance of the detergent.
,: ~ ~,'~- . -`` ~ 80 EXAMPLE IV
Products A, B and C are prepared as follows:
_ B C
Sodium tallow alcohol sulfate 9.9% 9.9% 9.9%
Sodium alkyl (11.8)* benzene sulfona~te 8.18.1 8.1 Silica (HS 40 Ludo ~ 14xlO
microns) 8.08.0 8.0 Sodium sulfate 43.04~.020.0 10 Sodium carbonate 3.03.0 3.0 Sodium pyrophosphate26.2 Sodium tripolyphosphate - 24.4 49.6 ~linors to 100%
. ' ~'.
A, B, C, are used to clean clay soiled dacron polyester fabric swatches at a concentration of 0.12% by weignt in 100F.
water. The hardness of the water is 9 grains (3:1 Ca#/Mg~
The results measured by a Hunter Whiteness Meter in Hunter Whiteness Units (hereafter) HWU are:
A (HWU) B (HWU) C (HWU) 24.0 -2.2 32.2 LSDo 05= 2-0 Product _ (sodium pyrophosphate) formulated in accordance with the present invention performs better in cleaning the fabrics than the same product (B) formulated with sodium tripolyphosphate. Product C performs better than Product _ but Product C contains twice as much phosphorous (12.2% versus 6.1%) in the form of sodium tripolyphosphate.
* (11.8) Denotes the mean alkyl chain length.
~ 32 - ;
~ ~ ..
-- 108:~0~Q
~ EXAMPLE v Products D, E, and F are identical to A., B, and C of Example rv but each of D, E and F has 3.2:1 -SiO~:Na20 added at 8% by weight in place of sodium sulfate. D, E and F are tested as in Example IV with the following xesults .. . ' . , '. ' ~
D (HWU) E -~HWU) F~HWU) - ~7.9 -~.5 27.7 LSDo 05 = 2-0 Product D again is better in removing clay soil from ~acon Polyester fabric then Product E. Product F at twice the phosphorous level performs better than D.
The addition of the soluble silica~es has not substantially diminished the relative performance of D over A (Example IV).
. ..
, ';" .:
. .. , , . . :
~L081~)80 EXAMPLE VI
Products G and H have the following composition:
G H
sodium alkyl (C14_Cl6) triethoxy sulfate sodium alkyl (Cll 8) benzene 7.0 7.0 sulfonate sodium tallow alcohol sulfate 5.5 5.5 sodium pyrophosphate 26.2 26.2 lO sodium sulfate 35.0 43.0 sodium carbonate 3 3 sodium silicate 8 8 (SiO2:Na20 3.2:1) silica 8 (HS 40 LUDOX 14xlO 3 micron) minors to lO0 Compositions G and H are tested as in Examples IV and V. The results are ~ G (HWU) H(HWU) 21.2 13.5 LSD 0.05 = 4.2 Product G containing silica of the present invention performs better in clay soil removal from Dacron Polyester fabries than does Product H whieh contains silicate but no siliea. *(C14 - Cl6) indicates alkyl chain length.
10~ 8V
E ~ LE VII
A laundry bar is prepared with the following composition , . .
24~ alXyl benzene sulfonate (C13 hard) 30% ~alcium carbonate 12% sodium pyrophosphate 20~ silica (Prepared as in ~acDonald U. S. Patent 3,708,428 supra) .8~ sodium silicate ~SiO2:Na2O 1.6:1) 6% minors ,
Claims (25)
1. A detergent additive comprising:
(a) an alkali metal pyrophosphate; and (b) silica having a mean particle diameter less than 20 microns;
in a weight ratio of the alkali metal pyrophosphate to the silica of from about 25:1 to about 1:2.
(a) an alkali metal pyrophosphate; and (b) silica having a mean particle diameter less than 20 microns;
in a weight ratio of the alkali metal pyrophosphate to the silica of from about 25:1 to about 1:2.
2. The composition of Claim 1 containing from about 1 to about 30% by weight of a supplemental alkaline material.
3. The composition of Claim 1 wherein the weight ratio of the alkali metal pyrophosphate to the silica is from about 20:1 to about 1:1.
4. The composition of Claim 3 wherein the mean particle diameter of the silica is from about 1x10-3 micron to about 5 microns.
5. The composition of Claim 4 wherein the alkali metal pyrophosphate is selected from the group consisting of sodium and potassium pyrophosphate and mixtures thereof.
6. The composition of Claim 5 wherein the alkali metal pyrophosphate is sodium pyrophosphate.
7. A composition in accordance with Claim 2 wherein the supplemental alkaline material is sodium carbonate at a level of from about 3% to about 20% by weight of the composition.
8. The composition of Claim 2 additionally comprising at from about 1% to about 25% by weight of an alkali metal silicate having an SiO2:M20 weight ratio of from about 1.6:1 to about 4:1 wherein M is selected from the group consisting of sodium and potassium.
9. The composition of Claim 8 wherein the alkali metal silicate is the sodium salt having an SiO2:Na20 weight ratio of from about 2:1 to about 4:1 at a level of from 3% to 20% by weight.
10. The composition of Claim 9 wherein the weight ratio of the silica to the silicate is from about 10:1 to about 1:10.
11. The composition of Claim 10 wherein the silica has a mean particle diameter of from about 2 x 10-3 to about 0.1 micron.
12. A detergent composition comprising:
(a) from about 5% to about 60% by weight of an alkali metal pyrophosphate;
(b) from about 1% to about 40% by weight of silica having a mean particle diameter less than 20 microns; and (c) an organic detergent at from about 1% to about 50% by weight of the composition.
(a) from about 5% to about 60% by weight of an alkali metal pyrophosphate;
(b) from about 1% to about 40% by weight of silica having a mean particle diameter less than 20 microns; and (c) an organic detergent at from about 1% to about 50% by weight of the composition.
13. The composition of Claim 12 wherein the organic detergent is selected from the group consisting of anionic and nonionic detergents and mixtures thereof.
14. The detergent composition of Claim 12 wherein the weight ratio of the alkali metal pyrophosphate to the silica is from about 25:1 to about 1:2.
15. The detergent composition of Claim 14 wherein the mean particle diameter of the silica is from about 1 x 10-3 micron to about 5 microns.
16. The composition of Claim 15 wherein the alkali metal pyrophosphate is present at from about 8% to about 40%
and the silica is present at from about 3% to about 30%
by weight.
and the silica is present at from about 3% to about 30%
by weight.
17. The detergent composition of Claim 16 wherein the detergent component is a nonionic selected from the group consisting of alkoxylated alcohols and alkoxylated alkyl phenols having from 8 to 20 carbon atoms in the alkyl radical and from 1 to 30 alkoxy units per alkyl radical and mixtures thereof.
18. The composition of Claim 17 wherein the nonionic detergent is an ethoxylated alcohol wherein the alcohol residue has from 10 to 16 carbon atoms and from 1 to 10 moles of ethylene oxide per mole of alcohol residue.
19. The composition of Claim 18 wherein the nonionic detergent is present at from about 5% to about 40% by weight.
20. The composition of Claim 13 wherein the organic detergent is anionic.
21. The composition of Claim 20 wherein the organic detergent is selected from the group consisting of the alkali metal, or substituted ammonium, alkyl ether sulfates, alpha-sulfocarboxylates, alkylbenzene sulfonates, and alkyl sulfates, and mixtures thereof.
22. The composition of Claim 21 wherein the anionic detergent is present at from about 5% to about 40% by weight.
23. The detergent composition of Claim 22 additionally comprising at from about 1% to about 25% by weight of an alkali metal silicate having an SiO2:M20 weight ratio of about 1.6:1 to about 4:1 wherein M is selected from the group consisting of sodium and potassium and mixtures thereof.
24. The detergent composition of Claim 23 wherein the alkali metal silicate is the sodium salt at a level of from about 3% to about 20% by weight in a weight ratio to the silica of from about 10:1 to about 1:10.
25. The detergent composition of Claim 16 wherein the mean particle diameter of the silica is from about 2 x 10-3 micron to about 0.1 micron.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55005475A | 1975-02-14 | 1975-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1081080A true CA1081080A (en) | 1980-07-08 |
Family
ID=24195544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA245,225A Expired CA1081080A (en) | 1975-02-14 | 1976-02-06 | Pyrophosphate and silica-containing composition |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE838547A (en) |
| CA (1) | CA1081080A (en) |
| DE (1) | DE2605023A1 (en) |
| FR (1) | FR2300797A1 (en) |
| GB (1) | GB1531433A (en) |
| IT (1) | IT1055274B (en) |
| NL (1) | NL7601484A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4299717A (en) * | 1979-03-06 | 1981-11-10 | Lever Brothers Company | Detergent compositions |
| US4339235A (en) * | 1979-12-06 | 1982-07-13 | Economics Laboratory, Inc. | Methods and compositions for bleaching of mycological stain |
| FR2613377B1 (en) * | 1987-03-30 | 1989-06-16 | Rhone Poulenc Chimie | USE IN DETERGENT COMPOSITIONS FOR WASHING MACHINES OF SILICATE-SILICA CO-GRANULES |
| EP2071017A1 (en) * | 2007-12-04 | 2009-06-17 | The Procter and Gamble Company | Detergent composition |
-
1976
- 1976-02-06 CA CA245,225A patent/CA1081080A/en not_active Expired
- 1976-02-10 DE DE19762605023 patent/DE2605023A1/en active Pending
- 1976-02-13 GB GB574576A patent/GB1531433A/en not_active Expired
- 1976-02-13 IT IT2017276A patent/IT1055274B/en active
- 1976-02-13 BE BE164303A patent/BE838547A/en unknown
- 1976-02-13 NL NL7601484A patent/NL7601484A/en not_active Application Discontinuation
- 1976-02-13 FR FR7603975A patent/FR2300797A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE2605023A1 (en) | 1976-08-26 |
| BE838547A (en) | 1976-08-13 |
| FR2300797A1 (en) | 1976-09-10 |
| GB1531433A (en) | 1978-11-08 |
| IT1055274B (en) | 1981-12-21 |
| NL7601484A (en) | 1976-08-17 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |