CA1293905C - Built nonaqueous liquid nonionic laundry detergent composition containing quaternary ammonium stabilizer and method of use - Google Patents
Built nonaqueous liquid nonionic laundry detergent composition containing quaternary ammonium stabilizer and method of useInfo
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- CA1293905C CA1293905C CA000516238A CA516238A CA1293905C CA 1293905 C CA1293905 C CA 1293905C CA 000516238 A CA000516238 A CA 000516238A CA 516238 A CA516238 A CA 516238A CA 1293905 C CA1293905 C CA 1293905C
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Abstract
BUILT NONAQUEOUS LIQUID NONIONIC LAUNDRY DETERGENT COMPOSITION
CONTAINING QUATERNARY AMMONIUM STABILIZER
AND METHOD OF USE
ABSTRACT OF THE DISCLOSURE
A liquid heavy duty laundry detergent composition comprising a suspension of builder salt in liquid nonionic surfactant in which the stability against settling of the composition is improved by the addition of small amounts of a higher alkyl quaternary ammonium surface active agent. The yield stress of the compositions can be improved with the same or lower plastic viscosity, especially at low concentrations of the alkyl quaternary ammonium surface active agent.
CONTAINING QUATERNARY AMMONIUM STABILIZER
AND METHOD OF USE
ABSTRACT OF THE DISCLOSURE
A liquid heavy duty laundry detergent composition comprising a suspension of builder salt in liquid nonionic surfactant in which the stability against settling of the composition is improved by the addition of small amounts of a higher alkyl quaternary ammonium surface active agent. The yield stress of the compositions can be improved with the same or lower plastic viscosity, especially at low concentrations of the alkyl quaternary ammonium surface active agent.
Description
~ ~3~30~
BACKGROUND OF THE INVFNTION
(1) ~ Field of Invention This invention relates to nonaqueous liquid abric treating compositions. More particularly, this invention relates to nonaqueous liquid laundr~ detergent compositions which are stable against phase separation and gelation and are easily pourable and to the use of these compositions for cleaning soiled fabrics.
~2) Discussion of Prior Art Liquid nonaqueous heavy duty laundry detergent compositions are well known in the art. For instance, compositions of that type may comprise a liquid nonionic surfactant in which are dispersed particles of a builder, as shown for instance in the United States Patents Nos. 4,316,812, 3,630,929 and 4,264,466 and British Patents Nos. 1,205,711, 1,270,040 and 1,600,981.
Related pending Canadian applications assigned to the common assignee are No. 498,815, filed December 31, 1985; No.
478,380, filed April 4, 1985; No. 478,379, filed April 4, 1985;
No. 502,998, filed February 28, 1986; and No. 498,735, filed December 30, 1985.
These applications are directed to liquid nonaqueous nonionic laundry detergent compositions.
Liquid deter~ents are often considered to be more convenient to employ than dry powdered or particulate products and, therefore, have found substantial favour with consumers.
They are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments ~o be laundered and are ~`
~ ~ 2 ~.f~9~6~0~
non-dusting, and they usually occupy less storage space. Adclitionally, the liquid detergents may have incorporated in their formulatlons materials which could not stand drying operations without deterioration, which materials are often desirably employed in the manufacture of particulate detergent 5 products. Although they are possessed of many advantages over unitary or particulate solid products, liquid detergents often have certain inherent disadvantages too, which have to be overcome to produce acceptable commercial detergent prod~lcts~ Thus, some such products separate out on storage and others separate out on cooling and are not readily redispersed.
In some cases the product viscosity changes and it becomes either too thick to pour or so thin as to appear watery. Some clear products become cloudy and others gel on standing.
The present inventors have been involved in studying the behavior of nonionic liquid surfactant systems with particulate matter suspended therein.
Of particular interest has been nonaqueous built laundry liquid detergent compositions and the problem of settling of the suspended builder and other laundry additives as well as the problem of gelling associated with nonionic surfactants. These considerations have an impact on, for example, product stability, pourability and dispersibility.
It is known that one OI the major problems with built liquid laundry detergents is their physical stability. This problem stems from the fact that the density of the solid particles dispersed in the nonionic liquid surfactant is higher than the density of the liquid surfactant.
Therefore, the dispersed particles tend to settle out. Two basic solutions exist to solve the settling out problem: increase nonionic liquid viscosity and reduce the dispersed solid particle size.
It is known that suspensions can be stabilized against settling by adding inorganic or organic thickening agents or dispersants, such as, for example, very high surface area inorganic materials, e. g. finely divided 3 0 silica , clays , etc ., organic thickeners , such as the cellulose ethers , acrylic ~29~'t30~
and ncrylamide polymers, polyelectrolytes I etc . However, such increases in suspension viscosity are naturally lirnited by the requirement that the liquid suspension be readily pourable and flowable, even at low temperature.
Furthermore, these additives do not contribute to the cleanin g performance of the formulation.
Grinding to reduce the particle size provides the ~ollowing advantages:
1. Specific surface area of the dispersed particles is increased, and, therefore, particle wetting by the nonaqueous vehicle (liquid nonionic) is proportionately improved.
BACKGROUND OF THE INVFNTION
(1) ~ Field of Invention This invention relates to nonaqueous liquid abric treating compositions. More particularly, this invention relates to nonaqueous liquid laundr~ detergent compositions which are stable against phase separation and gelation and are easily pourable and to the use of these compositions for cleaning soiled fabrics.
~2) Discussion of Prior Art Liquid nonaqueous heavy duty laundry detergent compositions are well known in the art. For instance, compositions of that type may comprise a liquid nonionic surfactant in which are dispersed particles of a builder, as shown for instance in the United States Patents Nos. 4,316,812, 3,630,929 and 4,264,466 and British Patents Nos. 1,205,711, 1,270,040 and 1,600,981.
Related pending Canadian applications assigned to the common assignee are No. 498,815, filed December 31, 1985; No.
478,380, filed April 4, 1985; No. 478,379, filed April 4, 1985;
No. 502,998, filed February 28, 1986; and No. 498,735, filed December 30, 1985.
These applications are directed to liquid nonaqueous nonionic laundry detergent compositions.
Liquid deter~ents are often considered to be more convenient to employ than dry powdered or particulate products and, therefore, have found substantial favour with consumers.
They are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments ~o be laundered and are ~`
~ ~ 2 ~.f~9~6~0~
non-dusting, and they usually occupy less storage space. Adclitionally, the liquid detergents may have incorporated in their formulatlons materials which could not stand drying operations without deterioration, which materials are often desirably employed in the manufacture of particulate detergent 5 products. Although they are possessed of many advantages over unitary or particulate solid products, liquid detergents often have certain inherent disadvantages too, which have to be overcome to produce acceptable commercial detergent prod~lcts~ Thus, some such products separate out on storage and others separate out on cooling and are not readily redispersed.
In some cases the product viscosity changes and it becomes either too thick to pour or so thin as to appear watery. Some clear products become cloudy and others gel on standing.
The present inventors have been involved in studying the behavior of nonionic liquid surfactant systems with particulate matter suspended therein.
Of particular interest has been nonaqueous built laundry liquid detergent compositions and the problem of settling of the suspended builder and other laundry additives as well as the problem of gelling associated with nonionic surfactants. These considerations have an impact on, for example, product stability, pourability and dispersibility.
It is known that one OI the major problems with built liquid laundry detergents is their physical stability. This problem stems from the fact that the density of the solid particles dispersed in the nonionic liquid surfactant is higher than the density of the liquid surfactant.
Therefore, the dispersed particles tend to settle out. Two basic solutions exist to solve the settling out problem: increase nonionic liquid viscosity and reduce the dispersed solid particle size.
It is known that suspensions can be stabilized against settling by adding inorganic or organic thickening agents or dispersants, such as, for example, very high surface area inorganic materials, e. g. finely divided 3 0 silica , clays , etc ., organic thickeners , such as the cellulose ethers , acrylic ~29~'t30~
and ncrylamide polymers, polyelectrolytes I etc . However, such increases in suspension viscosity are naturally lirnited by the requirement that the liquid suspension be readily pourable and flowable, even at low temperature.
Furthermore, these additives do not contribute to the cleanin g performance of the formulation.
Grinding to reduce the particle size provides the ~ollowing advantages:
1. Specific surface area of the dispersed particles is increased, and, therefore, particle wetting by the nonaqueous vehicle (liquid nonionic) is proportionately improved.
2. The average distance between dispersed particles is reduced with a proportionate increase in particle-to-particle interact;on. Each of these effects contributes to increase the rest-gel strength and the suspension yield stress while at the same time, grinding significantly reduces plastic viscosity.
The yield stress is defined as the minimum stress necessary to induce a plastic deformation (flow) of the suspension. Thus, visualizing the suspension as a loose network of dispersed particles, if the applied stress is lower than the yield stress, the suspension behaves like an elastic gel and no plastic flow will occur. Once the yield stress is overcome, the network breaks at some points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much higher than the yield stress, the pigments are partially shear-deflocculated and the apparent viscosity decreases. Finally, if the shear stress is much higher than the yield stress value, the dispersed particles are completely shear-deflocculated and the apparent viscosity is very low, as if no particle interaction were present .
Therefore, the higher the yield stress of the suspension, the higher the apparent viscosity at low shear rate and the better is the physical stability against settling of the product.
In addition to the problem of settling or phase nonaqueous Iiquid laundry detergents based Oll liquid non suffer from the drawback that the nonionics tend to gel wl~
water. This is a part;cularly important problem in the ordin~
European household automatic washing machines where the user plac~
laundry detergent compos;tion in a dispensing unit (e. g. a dispensing drawer) of the machine. During the operation of the machine the detergent in the dispenser is subjected to a stream of cold water to transfer it to the main body of wash solution. lEspecially during the winter months when the ].0 detergent composition and water fed to the dispenser are particularly cold,the detergent viscosity increases markedly and a gel forms. As a result some of the composi~ion is not flushed completely off the dispenser during operation of the machine, and a deposit of the composition builds up with repeated wash cycles, eventually requiring the user to flush the dispenser with hot water.
The gelling phonomenon can also be a problem whenever it is desired to carry out washing using cold water as may be recommended for certain synthetic and delicate fabrics or fabrics which can shrink in warm or hot water.
The tendency of concentrated detergent compositions to gel during storage is aggrevated by storing the compositions in unheated storage areas, or by shipping the compositions during winter months in unheated transportation vehicles.
Partial solutions to the gelling problem have been proposed, for example, by diluting the liquid nonionic with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see [J.S.P. 3,953,380), alkali metal formates and adipates (see U.S.P.
4,368,147), hexylene glycol, polyethylene glycol, etc. and nonionic structure modification and optimization. As an example of nonionic sur~ctant modification one particularly successful result has been achieved by ..
~935aOS
acidi~ying the hydroxyl moiety end group oE the nonionic molecule. The advantages of introducing a carhoxylic acid at the end of the nonionic include ~el inhibition upon dilution;
decreasin~ the nonionic pour point; and formation oE an anionic surfactant when neutrali~ed in the washing liquor. Nonionic structure optimization has centered on the chain length of the hydrophobic-lipophilic moiety and the number and make-up of alkylene oxide (e.g. ethylene oxide) units of the hydrophilic moiety. For example, it has been found that a C13 fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendency to gel formation.
Nevertheless, improvements are desired in both the stability and gel inhibition ofnon-aqueous liquid fabric treating compositions.
~RIEF DESCRIPTION OF THE INVENTION
In accordance with the present invention there is provided a non-aqueous, liquid, heavy-duty, built laundry detergent composition comprising of: 10-70~ by weight of at least one liquid nonionic surfactant, said liquid nonionic surfactant consisting of a polyloweralkoxylated higher alkanol, wherein said alkanol is of 9 to 18 carbon atoms and the number of moles of said lower alkylene oxide is from 3 to 12 per mole of said alkanol; 10-60% by weight of at least one particulate detergent builder salt suspended in said at least one liquid non-ionic surfactant; 0.1-5~ by weight of a cationic quaternary ammonium salt surface active anti-settling agent selected from the group consisting of II) mono-higher alkyl tri-lower alkyl ~93~ 2301-1387 quaternary ammonium salt, (II) di-higher alkyl di-lower alkyl quaternary ammonium salt, ~III) mono-higher alkyl mono~lower alkyl diethoxylated quaternary ammonium salt and ~IV) di-higher alkyl diethoxylated quaternary ammonium salt; 0~2.0% by weight of a phosphoric acid alkanol ester stabilizing agent; 0-5.0% by weight of an aluminum salt of a fatty acid stabilizing agent;
0-30% by weight of a bleaching agent; 0-15% by weight of a bleach activator; 0-3.0% by weight of a sequestering agent for metal ions; 0-5.0% by weight of an anti-redeposition agent; 0-2.0% of an optical brightener; 0-3.0% of enzymes; 0-3.0% of perfume;
0-0.10% of dye.
Such a composition may also comprise 5-30% by weight of a viscosity control and gel-inhibiting agent selected from the group consisting of alkylene glycols and alkylene glycol mono alkyl ethers.
The balance of such a composition may additionally or alternatively comprise one or more detergent adjuVantS selected from corrosion inhibitors, anti-foam agents, suds suppressors, anti-yellowing agents, bluing agenks, pH mofifiers, pH buffers, bleach stabilizers and enzyme inhibitors.
The compositions of the present invention contain as an essential ingredient a quaternary amrnonium surface active agent anti-settling stabilizing additive. The anti-settling stabilizing additives are cationic surfactants. The cationic surfactants that are useful in the present invention are those surface active compounds which contain a long chain hydrocarbon hydrophobic group in their rnolecular structure and a hydrophile group, i.e.
6a ~ 3(~5 62301-1387 water soluble salt forming anion group.
The quaternary ammonium cationic surEace active anti-settling stabilizing agents of the present invention are well known and are commercially available. The quaternary ammonium compounds have been used as fabric softeners and have been used as surface~active detergents.
The preferred quaternary ammonium compounds used in accordance with the present invention are the mono and di higher alkyl lower alkyl B 6b 33~35 quaternary ammonium salts ~nd the mono and di higher nlkyl di ethoxylated quaternary ammonium salts.
The quaternary ammonium salts are believed to interact with anionic phosphate detergent builder salts to coat the anionic phosphate with a lipophylic skin. The lipophylic coating makes the anionic phosphate detergent builùer salts more compatible with the nonionic surfactant and improves the contact between the phosphate and nonionic surfactant. The improvement in the contact between the phosphate and nonionic surPactant increases the stability of the phosphate suspension in the nonionic surfactant .
The preferred cationic quaternary ammonium surface ac$ive anti-settling stabilizing agents of the present invention are members of ~he group consisting of:
I Mono-higher alkyl tri-lower alkyl quaternary ammonium salts.
II Di-higher alkyl di-lower alkyl quaternary ammonium salts.
III Mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salts; and IV Di-higher alkyl diethoxylated quaternary ammonium salts.
The cationic quaternary ammonium compound anti-settling stabilizing agents of the present invention are briefly described as follows:
The formula I compounds are mono-higher alkyl tri-lower alkyl quaternary ammonium salts represented by the formula ~ N_I~2~ X (I) wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, the R 's are, independently, lower alkyl or hydroxy allcyl having from 1 to ~I carbon atoms, and X is a water soluble salt forming anion.
The formula II compounds are di-higher ~lkyl di-lower alkyl quaternary ~3~S ~ I
ammonium salts represented by the formula wherein Rl's are, independently, lon~ chain aliphatic radicles having from 10 to 22 carbon atoms, the R2's are, independently, lower alkyl or hydroxy alkyl having from 1 to 4 carbon atoms, and X i8 a water soluble salt forming anion .
~ The formula llI compounds are mono-higher alkyl mono-lower alkyl di-ethoxy quaternary ammonium compounds represented by the formula 1_ N--(CH2cH2) xUl X
(CH2CH20) yH
wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, R2 is a lower alkyl or hydroxy Rlkyl having from 1 to 4 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x + y is from 2 to 159 and X is a water soluble salt forming anion.
The formula IV compounds are di higher alkyl diethoxylated quaternary ammonium salts represented by the formula 1 N--( CH2 CH20 ) xH ¦ X
(CH2CH20) yH
wherein R1's are independently, Icng chain aliphatic radicles having from 10 to 22 carbon atoms, x and y are each positive numbers of st least 1 and the sum of x + y is from 2 to 15, and X is a water soluble s~lt forming anion.
In order to improve the viscosity characteristics of the composition an acid terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and the storage properties of the composition there can be added to the composition viscosity improving and anti gel agents such as alkylene glycols, poly alkylene glycols and alkylene ~
The yield stress is defined as the minimum stress necessary to induce a plastic deformation (flow) of the suspension. Thus, visualizing the suspension as a loose network of dispersed particles, if the applied stress is lower than the yield stress, the suspension behaves like an elastic gel and no plastic flow will occur. Once the yield stress is overcome, the network breaks at some points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much higher than the yield stress, the pigments are partially shear-deflocculated and the apparent viscosity decreases. Finally, if the shear stress is much higher than the yield stress value, the dispersed particles are completely shear-deflocculated and the apparent viscosity is very low, as if no particle interaction were present .
Therefore, the higher the yield stress of the suspension, the higher the apparent viscosity at low shear rate and the better is the physical stability against settling of the product.
In addition to the problem of settling or phase nonaqueous Iiquid laundry detergents based Oll liquid non suffer from the drawback that the nonionics tend to gel wl~
water. This is a part;cularly important problem in the ordin~
European household automatic washing machines where the user plac~
laundry detergent compos;tion in a dispensing unit (e. g. a dispensing drawer) of the machine. During the operation of the machine the detergent in the dispenser is subjected to a stream of cold water to transfer it to the main body of wash solution. lEspecially during the winter months when the ].0 detergent composition and water fed to the dispenser are particularly cold,the detergent viscosity increases markedly and a gel forms. As a result some of the composi~ion is not flushed completely off the dispenser during operation of the machine, and a deposit of the composition builds up with repeated wash cycles, eventually requiring the user to flush the dispenser with hot water.
The gelling phonomenon can also be a problem whenever it is desired to carry out washing using cold water as may be recommended for certain synthetic and delicate fabrics or fabrics which can shrink in warm or hot water.
The tendency of concentrated detergent compositions to gel during storage is aggrevated by storing the compositions in unheated storage areas, or by shipping the compositions during winter months in unheated transportation vehicles.
Partial solutions to the gelling problem have been proposed, for example, by diluting the liquid nonionic with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see [J.S.P. 3,953,380), alkali metal formates and adipates (see U.S.P.
4,368,147), hexylene glycol, polyethylene glycol, etc. and nonionic structure modification and optimization. As an example of nonionic sur~ctant modification one particularly successful result has been achieved by ..
~935aOS
acidi~ying the hydroxyl moiety end group oE the nonionic molecule. The advantages of introducing a carhoxylic acid at the end of the nonionic include ~el inhibition upon dilution;
decreasin~ the nonionic pour point; and formation oE an anionic surfactant when neutrali~ed in the washing liquor. Nonionic structure optimization has centered on the chain length of the hydrophobic-lipophilic moiety and the number and make-up of alkylene oxide (e.g. ethylene oxide) units of the hydrophilic moiety. For example, it has been found that a C13 fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendency to gel formation.
Nevertheless, improvements are desired in both the stability and gel inhibition ofnon-aqueous liquid fabric treating compositions.
~RIEF DESCRIPTION OF THE INVENTION
In accordance with the present invention there is provided a non-aqueous, liquid, heavy-duty, built laundry detergent composition comprising of: 10-70~ by weight of at least one liquid nonionic surfactant, said liquid nonionic surfactant consisting of a polyloweralkoxylated higher alkanol, wherein said alkanol is of 9 to 18 carbon atoms and the number of moles of said lower alkylene oxide is from 3 to 12 per mole of said alkanol; 10-60% by weight of at least one particulate detergent builder salt suspended in said at least one liquid non-ionic surfactant; 0.1-5~ by weight of a cationic quaternary ammonium salt surface active anti-settling agent selected from the group consisting of II) mono-higher alkyl tri-lower alkyl ~93~ 2301-1387 quaternary ammonium salt, (II) di-higher alkyl di-lower alkyl quaternary ammonium salt, ~III) mono-higher alkyl mono~lower alkyl diethoxylated quaternary ammonium salt and ~IV) di-higher alkyl diethoxylated quaternary ammonium salt; 0~2.0% by weight of a phosphoric acid alkanol ester stabilizing agent; 0-5.0% by weight of an aluminum salt of a fatty acid stabilizing agent;
0-30% by weight of a bleaching agent; 0-15% by weight of a bleach activator; 0-3.0% by weight of a sequestering agent for metal ions; 0-5.0% by weight of an anti-redeposition agent; 0-2.0% of an optical brightener; 0-3.0% of enzymes; 0-3.0% of perfume;
0-0.10% of dye.
Such a composition may also comprise 5-30% by weight of a viscosity control and gel-inhibiting agent selected from the group consisting of alkylene glycols and alkylene glycol mono alkyl ethers.
The balance of such a composition may additionally or alternatively comprise one or more detergent adjuVantS selected from corrosion inhibitors, anti-foam agents, suds suppressors, anti-yellowing agents, bluing agenks, pH mofifiers, pH buffers, bleach stabilizers and enzyme inhibitors.
The compositions of the present invention contain as an essential ingredient a quaternary amrnonium surface active agent anti-settling stabilizing additive. The anti-settling stabilizing additives are cationic surfactants. The cationic surfactants that are useful in the present invention are those surface active compounds which contain a long chain hydrocarbon hydrophobic group in their rnolecular structure and a hydrophile group, i.e.
6a ~ 3(~5 62301-1387 water soluble salt forming anion group.
The quaternary ammonium cationic surEace active anti-settling stabilizing agents of the present invention are well known and are commercially available. The quaternary ammonium compounds have been used as fabric softeners and have been used as surface~active detergents.
The preferred quaternary ammonium compounds used in accordance with the present invention are the mono and di higher alkyl lower alkyl B 6b 33~35 quaternary ammonium salts ~nd the mono and di higher nlkyl di ethoxylated quaternary ammonium salts.
The quaternary ammonium salts are believed to interact with anionic phosphate detergent builder salts to coat the anionic phosphate with a lipophylic skin. The lipophylic coating makes the anionic phosphate detergent builùer salts more compatible with the nonionic surfactant and improves the contact between the phosphate and nonionic surfactant. The improvement in the contact between the phosphate and nonionic surPactant increases the stability of the phosphate suspension in the nonionic surfactant .
The preferred cationic quaternary ammonium surface ac$ive anti-settling stabilizing agents of the present invention are members of ~he group consisting of:
I Mono-higher alkyl tri-lower alkyl quaternary ammonium salts.
II Di-higher alkyl di-lower alkyl quaternary ammonium salts.
III Mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salts; and IV Di-higher alkyl diethoxylated quaternary ammonium salts.
The cationic quaternary ammonium compound anti-settling stabilizing agents of the present invention are briefly described as follows:
The formula I compounds are mono-higher alkyl tri-lower alkyl quaternary ammonium salts represented by the formula ~ N_I~2~ X (I) wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, the R 's are, independently, lower alkyl or hydroxy allcyl having from 1 to ~I carbon atoms, and X is a water soluble salt forming anion.
The formula II compounds are di-higher ~lkyl di-lower alkyl quaternary ~3~S ~ I
ammonium salts represented by the formula wherein Rl's are, independently, lon~ chain aliphatic radicles having from 10 to 22 carbon atoms, the R2's are, independently, lower alkyl or hydroxy alkyl having from 1 to 4 carbon atoms, and X i8 a water soluble salt forming anion .
~ The formula llI compounds are mono-higher alkyl mono-lower alkyl di-ethoxy quaternary ammonium compounds represented by the formula 1_ N--(CH2cH2) xUl X
(CH2CH20) yH
wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, R2 is a lower alkyl or hydroxy Rlkyl having from 1 to 4 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x + y is from 2 to 159 and X is a water soluble salt forming anion.
The formula IV compounds are di higher alkyl diethoxylated quaternary ammonium salts represented by the formula 1 N--( CH2 CH20 ) xH ¦ X
(CH2CH20) yH
wherein R1's are independently, Icng chain aliphatic radicles having from 10 to 22 carbon atoms, x and y are each positive numbers of st least 1 and the sum of x + y is from 2 to 15, and X is a water soluble s~lt forming anion.
In order to improve the viscosity characteristics of the composition an acid terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and the storage properties of the composition there can be added to the composition viscosity improving and anti gel agents such as alkylene glycols, poly alkylene glycols and alkylene ~
3,.~ 35 glycol mono alkyl ethers and additional anti settling agents such as phosphoric acid ester and aluminum stearate. In an embodiment of the inventîon the detergent composition contains an acid termine~ted nonionic surfactant, an alkylene glycol mono alkyl ether and a quaternary ammonium anti settling stabilizing agent.
Sanitizing or bleaching agents and activators therefor can be added to improve the bleaching and cleansing characteristics of the composition.
In an embodiment of the invention the builder components of the composition are ground to a particle size of less than lO0 microns and to preferably less than 10 microns to further improve the stability of the suspension of the builder components in the liquid nonionic surfactant detergent .
In addition other ingredients can be added to the composition such as anti-incrustation agents, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.
The presently manufactured washing machines for home use normally operate at washing temperatures of up to 95C . About 18 . 5 gallons ( 20 liters) of water are used during the wash and rinse cycles.
About 200-250 gms of powder detergent per wash is normally used.
In accordance with the present invention where the highly concentrated liquid detergent i8 used normally only 100 gms (78 cc) of the liquid detergent composition is required to wash a full load of dirty laundry.
Accordingly, in one aspect the present invention provides a liquid heavy duty laundry composition composed of a suspension of an anionic detergent builder salt, e . g. a phosphate builder salt, in a liquid nonionic surfactant wherein the composition includes an effective amount of a quaternary ammonium surface active agent to to increase the stability of the suspension against settling.
According to another aspect, the invention provides a concentrated liquid heavy duty laundry detergent composition which is stable, non-settling 3~
62301 13~7 in storage and non-gelllny in s~orage and in use. The licluicl compositions of the present invention are easily pourable, easil~
measured and easily put in-to the washing machine.
According to another aspect, the invention provides a method for dispensing a liquid nonionic laundry detergent composition into and~or with cold water without underyoing gelation. In particular, a method is provided for filling a container with a nonaqueous liquid laundry detergent composition in which the detergent is composed, at least predomlnantly, of a liquid nonionic sur~ace ac~ive agent and for dispensing the composition from the container into an aqueous wash bath, wherein the dispensing is effected by directing a stream o~ unheated water onto the composition such that the composition is carried by the stream of water into the wash bath.
ADVANTAG~S OV_R THE PRIOR ART
The addition of the quaternary ammonium surface active agents to the detergent compositions reduce the problem of dispersed particle settling and phase separation.
The concentrated nonaqueous liquid nonionic surfactant laundry detergent composltions of the present invention have the advantages of being stable, non-settllng in storage, and non-gelling in storaye. The liquid compositions are easily pourable, easily measured and easily put into the laundry washing machines.
The present invention seeks to provide a stable liquid heavy duty nonaqueous nonionic detergent composition containing at least one quaternary ammonium anti-settling stabilizing agent and at least one anionic phosphate detergent builder salt suspended in ~3~
a nonionic sur~actank.
The invention also seeks to provide llclu:ld ~abri~
treating composltions which are suspenslons o~ insoluble inorganic particles in a nonaqueous liquid and which are storage stable, easily pourable and dispersible in cold~ warm or hot water.
B lOa ~ 3~5 62301-1387 This invention relates to highly built heavy duty non-aqueous liquid nonionic surfactant laundry detergent compositions which can be poured at all temperatures and which can be repeatedly dispersed from the dispensing unit of European style automatic laundry washing machines without fouling or plugging of the dispenser even during the winter months.
The invention seeks to provide non-gelling, stable suspensions of heavy duty built non-aqueous liquid nonionic laundry detergent composi~ion which include an effective amount of a quaternary ammonium surface active agent sufficient to increase the yield stress of the composition to thereby increase its stability, i.e. prevent settling of builder particles, etc., preferably while reducing or at least without increasing, the plastic viscosity (viscosity under shear conditions) of the composition.
The invention which will become more apparent from the following detailed description of preferred embodiments are generally provided for by preparing a detergent composition by adding to the non-aqueous liquid nonionic surfactant an effec-tive amount of a quaternary ammonium surface active anti-settling stabilizing agent sufficient to inhibit settling of the suspended particles, wherein said composition includes inorganic or organic fabric treating additives, e.g. viscosity improving agents and one or more anti-gel agents, anti-incrustation agents, pH control agents, bleaching agents, bleach activators, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.
~ 9~5 62301-1387 DETAILED DESCRIPTION OF THE INVENTION
In accordance wi-th the presen-t invention the physica.l stability of the suspension of the anionic detergent builder compound or compounds and any other suspended additive, such as bleaching agent, etc. in the liquid nonionic surfactant vehicle is substantially improved by the addition of an anti-settling stabilizing agent which is a quaternary ammonium surface active agent.
B lla ~ 9~3~i The addition of very small amounts of the quaternary ammonium surface active anti-settling stabilizing agents is sufficient to substantially improve the physical stability of the detergent compositions.
The compositions of the presen~ invention contain as an essential ingredient a quaternary ammonium surface active anti settling stabilizing agent additive. The anti-settling stabilizing additive can comp~qse one or more of the quaternsry ammonium surface active agents.
The anionic surface active agents that are useful in the present invention are those cationic surface active compounds which contain a long chain hydrocarbon hydrophobic group in their molecular structure and a hydrophile group, i.e. water soluble salt forming anion group.
The preferred cationic quaternary ammonium surface active anti-settling stabilizing agents of the present invention are members of the group consisting of:
I Mono-higher alkyl tri-lower alkyl quaternary ammonium salts.
Il Di-higher alkyl di-lower alkyl quaternary ammonium salts.
III Mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salts; and IV Di-higher alkyl diethoxylated quaternary ammonium salts.
The formula I cationic anti-settling stabilizing agents used in the present invention are the mono-higher alkyl tri-lower alkyl quaternary ammonium compounds represented by the following formula:
~ X (I) wherein Rl is a long chain aliphatic radical having from 10 to 22 carbon atoms, and the R2~s are, independently, lower alkyl or hydroxy alkyl radicals and X is a water soluble salt forming anion such as halide, i. e .
chloride, bromide, iodide; sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or similar inorganic or organic ~ 3~
so~ubilizing radical. The R1 carbon chain of the aliphatic radical containing 10 to 22 carbon atoms, especially 12 to 20, preferably 12 to 18, and especially preferably 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated. The R~ lower alkyl radicals have from 1 to 4 carbon atoms, e. g. methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl, and may contain a hydroxyl radical.
The preferred ammonium salt is a mono-higher alkyl trimethyl ammonium chloride wherein the alkyl group is derived from tallow, hydrogenated tallow or stearic acid. Specific examples of quaternary ammonium anti-settling stabilizing agents of the formula I suitable for use in the composition of the present invention include the following:
tallow trimethyl ammonium chloride hydrogenated tallow trimethyl ammonium chloride stearyl trimethyl ammonium chloride stearyl triethyl ammonium chloride cetyl trimethyl ammonium chloride soya trimethyl ammonium chloride stearyl dimethylethyl ammonium chloride tallow-diisopropylmethyl ammonium chloride The corresponding sulfate, methosulfate, ethosulfate, bromide and hydroxide salts thereof, can also be used.
The formula II ca~ionic anti-settling stabilizing agents used in the present invention are the di-higher alkyl di-lower alkyl quaternary ammonium compounds represented by the following formula:
~ R ~ X (II) wherein R1's are, independently, long chain aliphatic radicals having from 10 to 22 carbon atoms, and the R2's are, independently, lower lkyl or hydroxy .~ 05 alkyl radicals and X is a water soluble salt forming anion such as halide, i . e . chloride, bromide, iodide; sulfate, nitrate, citrnte, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or similar inorganic or organic solubilizing radics~. The R1 carbon chains of the aliphatic radicals containing 10 to 22 carbon atoms, especinlly 12 to 20, preferably 12 to 18, and esp~cially preferably 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated. The R2 lower alkyl radicals have from 1 to ~ carbon atoms, e. g. methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl, and may contain a hydroxyl radical.
Typical cationics of formula 11 include the following:
distearyl dimethyl ammonium chloride ditallow dimethyl ammonium chloride dihexadecyl dimethyl ammonium chloride distearyl dimethyl ammonium bromide di(hydrogenated tallow) dimethyl ammonium bromide ditallow isopropyl methyl ammonium chloride distearyl di(isopropyl) ammonium chloride distearyl dimethyl ammonium methosulfate.
A preferred class of cationics is of formula Il wherein two of the R1 groups are C14 to C18, one R2 is methyl, or ethyl and one R2 is methyl, ethyl, isopropyl, n-propyl, hydroxy ethyl or hydroxy propyl.
The formula III cationic anti-settling stabili~ing agents used in the present invention are the mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium compounds represented by the following formula:
--N--(CH2CH20~ X (III) (CH2CH20) yH
wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, and the R2 is lower alkyl or hydroxy alkyl radicals, x and y are each positive numbers of at least 1 and the sum of x ~ y is from 2 to 15, and X is a water soluble salt forming anion such as halide, i.e. chloride, bromide, iodide; sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or similar inorganic or organic solubili~ing radical.
The R1 carbon chain of the aliphatic radical containing 1~ to 22 carbon atoms, especially 12 to 20, preferably 12 to 18, and especially preferably 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated. The R lower ~lkyl radicals have from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl, and may contain a hydroxyl radical.
Typical examples of cationic quaternary ammonium anti-settling stabilizing agents of the formula III suitable for use in the composition of thepresent invention include the following:
coco methyl diethoxylated (x+y=2) ammonium chloride coco methyl diethoxylated (x~y=15) ammonium chloride oleic methyl diethoxylated (x+y=2) ammonium chloride oleic methyl diethoxylated (x+y=15) ammonium chloride stearyl methyl diethoxylated (x+y=2) ammonium chloride stearyl methyl diethoxylated (x+y=15) ammonium chloride tallow methyl diethoxylated (x+y=10) ammonium chloride The formula IV cationic anti-settling stabilizing agents used in the present invention are the di-higher alkyl diethoxylated quaternary ammonium compounds represented by the following formula:
1_N--(CH2C}120~; ~ X (IV) (CH2 CH2O) yH
wherein Rl's are, independently, long chain aliphatic radical having from 10 to 22 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x~y is from 2 to 15, and X is a water solu~le sal~ forming anion such as halide, i. e . chloride, bromide, iodide; sulfate, nitrate, citrate, acetate, ~ 2~3~0~
hydroxide, methosulfate, ethosulfate, phosphate, or similur inorganic or organic solubilizing radical. The Rl carbon chains of the aliphatic radicals containing 10 to 22 carbon atoms, especially 12 to 20, preferably 12 to 18, and especinlly preferably 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated.
A specific example of a cationic quaternary ammonium anti-settling stabilizing agent of the formula IV suitable for use in the composition of the present invention is di-tallow diethoxylated (x~y=4) ammonium chloride ~Ethoquat~2T/14) .
The mono and di-higher alkyl diethoxylated compounds are stable in both acid and alkaline solutions snd possess greater water solubility and compatibility than other related compounds.
In the formula I to IY compounds, the long carbon chains are obtained from long chain fatty acids, such as those derived from tallow and soybean oil. The terms "soya," and "tallow," etc., as used herein refer to the source from which the long chain fatty alkyl chains are derived. Mixtures of the quaternary ammonium compound anti-settling stabilizing sgents can be used.
The linear higher allcyl quaternary ammonium salts are readily biodegradable and are preferred.
Although applicants do not wish to be bound by any particular theory of the manner by which the quaternary ammonium surfactants function to prevent settling of the suspended anionic phosphate detergent builder particles, it is believed that the quaternary ammonium salts interact with the anionic phosphate detergent builder salts to coat the anionic phosphate with a cationic lipophylic skin to make the phosphate more compatible with the ~ 3~
nonionic surfactant, improves the contact between the phosphate and nonionic surfactant and increase the wettability of the dispersed phosphate solid particles surfaces by the nonionic surfaetant. The improvement in the contact between the phosphate and nonionic surfactant and the improved wettability of the dispersed phosphate part;cles by the nonionic surfactant increases the stability of the phosphate suspension and allows the ~uspended phosphate to more easily remain in suspension.
The increased physical stability is manifested by an increase in the yield stress of the composition of, for example, from B5 dynes/cm2 to 260 dynes/cm and increase in the apparent viscosity of, for example, from 2350 to 3250 ~LVT, sp . 4, 60 rpm), as compared to the same composition without the quaternary ammonium sal~ stabilizing agent. As described above, the higher the yield stress, the higher the apparent viscosity at low shear rate and the better the physical stability.
Only very small amounts of the quaternary ammonium s~lt stabilizing agent is required to obtain the signi~icant improvements in physical stability.
For example, based on the total weight of the nonionie liquid surfactant composition, suitable amounts of the quaternary ammonium salt are in the range of from about 0 .1% to about 5~6, preferably from about 0 . 3% to about 2.0% and more preferably about 0.5 to 1.5%.
In addition to its action as a physical stabilizing agent, the higher alkyl quaternary ammonium salts have the additional advantages over other physical stabilizing agents that they are cationic in character and are compatible with the nonionic surfaetant eomponent.
While the quaternary ammonium salts are effeetive in their physical stabilizing aetion, there, can be added to the formulation other known physieal stabilizers, sueh as, for example, an acidic organie phosphorus compound having an acidic - POH group, such as a partial ester of phosphorous aeid and an alkanol or an aluminum salt of a fatty acid.
1293~3S
Nonionic Surfactant Deter~ent The nonionic synthetic organic detergents employed in the practice of the invention mny be any of a wide variety of known compounds.
As is well known, the nonionic synthetic organic detergerlts are characteri2ed by the presence of an org~nic hydrophobic group and un organic hydrs)philic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature~. Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydrstion product thereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxy ethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups . Typical suitable nonionic surfactants are those disclosed in U . S .
patents 4, 316, 812 and 3, 630, 929 .
Usually, the nonionic detergents are poly-lower alkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher 2 0 alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of mols of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain ~rom 5 to 8 or 5 to 9 lower alkoxy groups per mol.
Preferably, the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, often being a minor (less than 50g6) proportion.
f r~--~t,~ Exemplary of such compounds are those wherein the alkanol is of 12 to~ 15 carbon atoms and which contain about 7 ethylene oxide groups per mol, e.g. Neodol 25-7 and Neodol 23-6.5, which products are made by Shell ~ q.c.,.,~
lB
~ 3~
Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 mols of ethylene oxide and the latter is a correspc nding mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6 . 5 . The higher alcohols ,.~ are primary alkanol~.
- Other examples of such detergents include Tergitol 15-S-7 and Tergito~l)~
15-S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven mols of ethylene oxide and the latter is a similar product but with nine mols of ethylene oxide being reacted .
Also useful in the present composition as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of h;gher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mol being about llo Such products are also made by Shell Chemical Company.
Other useful nonionics are represented by the commercially well known class of nonionics sold under the trademark Plurafac. The Plurafacs are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing ~ mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include products which are (A) C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, (B) C13-C15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles èthylene oxide, (C) C13-C~5 fatty slcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, and (D) a product which is a 1:1 mixture of products (B) and {C).
~ f~ "~
~ ?d~ 3C35 Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 i5 an ethoxylated C9-Cll fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C:15 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.
In the preferred poly-lower alkoxylated higher alkEmols, to obtain the best balance of h~drophilic and lipophilic moie~ies the number of lower alkoxies will usually be from 40~ to 100% c>f the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof and the nonionic detergent will preferably contain at least 50% of such preferred poly-lower alkoxy higher alkanol. Higher molecular weight alkanols and various other normally solid nonionic detergents and surface active agents may be contributory to gelation of the liquid detergent and consequently, will preferably be omitted or limited in quantity in the present compositions, although minor proportions thereof may be employed for their cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents the alkyl groups present therein are generally linear although branching may be tolerated, such as at a carbon next to or two carbons removed from the terminal carbon of the straight chain and away from the ethoxy chain, if such branched alkyl is not more than three carbons in length. Normally, the proportion of carbon atoms in such a branchecl configuration will be minor rarely exceeding 20% of the total carbon atom content of the alkyl.
Similarly, although linear alkyls which are terminally joined to the ethylene oxide chains are highly preferred and are considered to result in the best combination of detergency, biodegrad~bility and non-gelling characteristics, medial or secondary joinder to the ethylene oxide in the chain may occur. It A is usually in only a minor proportion o~ such alk~ls, generally less than 20%
but, as is in the cases of the mentioned ~eri6to~ may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, i1 will usually be less than 20% thereof and preferably less than 10% thereof.
1~ 20 I
l~h93~05 When grenter proportions Or non-terminally alkoxylated àlkanols, propylene oxide-containing poly-lower ~lkoxylated ~lkanols and less hydrophile-lipophile balanced nonionie detergent than mentioned a~ove are employed and when other nonionic detergents are used instead of the preferred nonionics recited herein, the product resulting may not have 88 good detergency, stability, viscosity and non-gelling properties as the preferred compositions but use of the viscosity and gel controlling compounds of the invention can also improve the properties of the detergents based on such nonionics. In some cases, as when a higher molecular weight polylower alkoxylated higher alkanol is employed, often for its detergency, the proportion thereof will be regulated or limited in accordance with the results of routine experiments, to obtain the desired detergency and still have the product non-gelling and of desired viscosity. Also, it has been found that it is only rarely necessary to utilize the higher molecular weight nonionics for their deter~ent properties since the preferred nonionics described hereîn are excellent detergentæ and additionally, permit the attainment of the desired viscosity in the liquid detergent without gelation at low temperatures.
~- Another useful group of nonionic surfactants are the "Surfactant T1' ,~ /a 6/~
series of nonionics ~h~ from British Petroleum. The Surfactant T
nonionics are obtained by the ethoxylation of secondary C13 fatty alcohols having a narrow ethylene oxide distribution. The Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 an average of 7 moles of ethylene oxide; Surfactant T9 an average of 9 moles of ethylene oxide and Surfactant T12 an average of 12 moles of ethylene oxide per mole of secondary C13 fatty alcohol.
In the compositions of this invention, preferred nonionic surfactanta include the C12-C15 secondary fstty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, snd the C9 to C11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.
~ 6 ~ ~ R~< 21 ~J~3~05 Mixtures of two or more of the liquid nonionic surfactants can be used and in some cases advantages can be obtained by the use of such mixtures.
Acid Terminated Nonionic Surfactant The viscosity and gel properties of the liquid detergent compositions can be improved by including in the composition an effective amount of an acid terminated liquid nonionic surfactant. The acid terminated nonionic surfactants consist of a nonionic surfactant which has been modified to convert a free hydroxyl group thereof to a moiety having a free carboxyl group, such as an ester or a partial ester of a non-ionic surfactant and a polycarboxylic acid or anhydride.
As disclosed in the commonly assi~ned copending Canadian application No. 478,379 filed April ~, 1985, the free carboxyl group modified nonionic surfactants, which may be broadly characteri2ed as polyether carboxylic acids, function to lower the temperature at which the liquid nonionic forms a gel with water.
The addition of the acid terminated nonionic surfactants to the liquid nonionic surfactant aids in the dispensibility of the composition, i.e. pourability~ and lowers the temperature at which the liquid nonionic surfactants form a gel in water without a decrease in their stability against settling. The acid terminated nonionic surfactant reacts in the washing machine water with the alkalinit~v of the dispersed builder salt phase of the detergent composition and acts as an effective anionic surfactant.
Specific examples include the half-esters of product (A) with succinic anhydride, the ester or half ester of Dobanol 25-7 with succinic anhydride, and the ester or half-ester of Dobanol 91-5 with succinic anhydride. Instead of C~S
succinie anhydride, other polycarboxylic acids or anhydrides can be used, e.g. maleic acid, maleic acid anhydride, glutari.e acid, malonic acid, phthalic acid, phthalic anh~dride, citrie aeid and the like.
The acid terminated nonionie surfactants can be prepared as follows:
22a Acid Terminated product (A). 400g of product (A) nonionic sùrfactant which is a C13 to Cl5 alkanol which has been alkoxylated to introduce 6 ethylene oxide and 3 prl~pylene oxide units per ~lkanol unit i8 mixed with 32g of succinic anhydride and heated for 7 hours at 100C. The mixture i8 cooled and filtered to remove unreacted succinic material. Infrared analysis indicated that about one half of the nonionic surfactant has been converted to the acidic half-ester thereof.
Acid Terminated I)obanol 25-7. 522g of Dobanol 25-7 nonionic surfactant which is the product of ethoxylation of a C12 to C15 alkanol and has about 7 ethylene oxide units per molecule of alkanol is mixed with 100g of succinic anhydride and 0 .1 g of pyridine ( which acts as an esterification catalyst) and heated at 260C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the surfactant have reacted.
Acid Terminate Dobanol 91-5. 1000 of Dobanol 91-5 nonionic surfactant which is the product o ethoxylation of a Cg to Cll alkanol and has about 5 ethylene oxide units per molecule of alkanol is mixed with 265g of succinic anhydride and 0. lg of pyridine catalyst and heated at 260C for 2 hourst cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls OI the surfactant have reacted .
Other esterification catalysts, such as an alkali metal alkoxide (e. g.
sodium methoxlde) may be used in place of, or in admixture with, the pyridine .
2~ The acidic polyether compound, i.e. the acid terminated nonionic surfactant is preferably added dissolved in the nonionic surfactant.
BUILDER SALTS
The liquid nonaqueous nonionic surfactant u~ed in the compositions of ¦
the present invention has dispersed and suspended therein fine particles of ¦
inorganic andlor inorganic detergent builder salts.
~ s The invention detergent compositions include water soluble andlor wster insoluble detergent builder salts. Water soluble inorganic alkaline build~r salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, bicarbonates, borates, S phosphates, polyphosphates, and silicates. (Ammonium or substituted ammonium salts can also be used. ) Specific examples of ~uch salts are sodium tripolyphosphate, sodium carbonate, sodium tetr&borate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, and potassium bicarbonate. Sodium tripolyphosphate (TPP~ is especially preferred.
Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate~ with an auxiliary builder such as a poly lower carboxylic acid or a polymeric carboxylic acid having high calcium binding capacity to inhibit incrustation which could otherwise be caused by formation of an insoluble calcium phosphate.
A suitable lower poly carboxylic acid compri~es alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts.
Suitable lower polycarboxylic acids have two to four carboxylic acid groups.
The preferred sodium and potassium lower polycarboxylic acids salts are the citric and tartaric acid salts.
The sodium citric acid salts are the most preferred, especially the trisodium citrate. The monosodium and disodium citrates can also be used.
The monosodium and disodium tartaric acid salts can also be used. The alkali metal lower polycarboxylic acid salts are particularly good builder s~lts; because of their high calcium and magnesium binding capacity they inhibit incrustation which could otherwise be caused by ~ormation of insoluble calcium and magnesium salts.
Il 24 ~
Il ' .... . .. .
~ 62301-1387 Other organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and the alkali metal salts thereof. More specifically such builder salts can consist of a copolymer which is the reaction product of about equal moles of methacrylic acid and maleic anhydride which has been completely neutralized to form the sodium salt thereof.
The builder is co~mercially available under the trade mark of Sokalan CP5. This builder serves when used even in small amounts to inhibit incrustation.
Examples of organic alkaline sequestrant builder salts which can be used with the detergent builder salts or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetraacetate (EDTA), sodium and potassium ni-trilotriacetates (NTA), and triethanol-ammonium N-(2-hydroxyethyl)nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.
Other suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. Of special value are the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described in United States Patents Nos. 4,144,226, 4,315,092 and 4,146~495.
The alkali metal silicates are useful builder salts which also function to adjust or control the p~l and to make the composition anticorrosive to washing machine parts. Sodium silicates of Na2O/SiO2 ratios of from 1.6/1 to 1/3.2, especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the "-same ratios can also be used.
Other typical suitable builders include, for example, those disclosed in United States Patents Nos. 4,316,812, 4,264,466 and 3,630,929. The inorganic builder salts can be `~ ~ 25 6~301-~.3~7 used with the nonionic surfa~tant detergen-t compound or ln admixture with other inorganic huilder salts or Wi th Or'JalliC
builder sal-ts. U.S. Patent 2G~,466 discloses illorcJanic builder salts which :include a halicle (chloride).
The water insoluble crystalline and amorphous aluminosilica~e æeolites can be used. The zeolites generally have the formula (M20)X- (A1203~y. (SiO2)Z.WH2(:) wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from O
to 9, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is type A or similar structure, and type 4A particular-ly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400meq/lg.
Various crystalline zeolites (i.e. alumino-silicates) that can be used are described in British Patent No. 1,504,168, United States Patent No. 4,~09,136 and Canadian Patents Nos.
1,072,835 and 1,087,477. An example of amorphous zeolites useful herein can be found in Belyium Patent No. 835,351.
Other materials such as clays, partic~ularly of the water-insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hyclrated aluminum silicate in which about 1~6th of the aluminum atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bentonite in its more purified form (i.e.
free from any grit, sand, etc.) suitable for detergen~s con-tains at least 50~ montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq per lOOg of bentonite.
Particularly preferred bentonites are the Wyoming or Western ~ 62301-13~7 U. S. bentonites which have been sold as Thixo-jels* 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are k:nown to soften textiles as described in British Patent No. 401,413 to Marriott and British Patent No. 461,221 to Marriott and Guan.
*Trade Mark 26a ~ ~3~0~
Viscosity Co_trol and Anti Gel Agents The inclusion in the detergent composition of an effective smount of viscosity control and gel-inhibiting agents for the nonionic surf~ctant improves the storage propertie~, of the composition. The viscosity control and gel-inhibiting agents act to lower the temperature Rt which the nonionic surfactant will form a gel when added to water. Such ~iscosity control and gel-inhibiting agents can be for example, lower alkanol, e.g. ethyl alcohol (see U.S.P. 3,953,380), hexylene glycol, polyethylene glycol, for example, polyethylene glycol having a molecular weight of about 40û (PEI~ 400) and low molecular weight alkylene oxide lower mono-alkyl ether amphiphilic compounds.
Preferred viscosity control and gel-inhibiting compounds are the amphiphilic compounds. The amphiphilic compounds can be considered to be analagous in chemical structure to the ethoxylated andlor propoxylated fatty ~lcohol liquid nonionic surfactants but have relatively short hydrocarbon chain lengths (C2 to C8) and a low content of ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).
Suitable amphiphilic compounds are represented by the following general formula R30( CH2CH2)nH
where R3 i8 a C2-C8 alkyl group, and n ifi a number of from about 1 to 6, on average.
Specifically the compounds are lower (C2 to C3) alkylene glycol mono lower (C2 to C5) alkyl ethers.
More specifically the compounds are mono di- or tri lower (C2 to C3) alkylene glycol mono lower (Cl to C5) alkyl ethers.
Specific examples of 6uitable amphiphilic compounds include ethylene glycol monoethyl ether (C2H5-0-CH2CH 20H), diethylene glycol monobutyl ether ~C4Hg-O-(CH2CH20)2H), tetraethylene glycol monobutyl ether tC4Hr-0-(CH2CH20~,~H) and ~ g OS 62301-13~37 dipropylene glycol monomethyl ether (CIl3-O-(CH2CH2CH2O)2Ml.
Diethylene ~l~colmonobutyl ether is especially preferred.
The inclusion in the composition oE the low molecular weight lower alkylene glycol mono alkyl ether decreases the viscosity of the composition, such that it is more easily pourable, improves the stability against settling and improves the dispersibility of the composition on the addition to warm water or cold water.
The compositions of the present invention have improved viscosity and stability characteristics and remain stable and pourable at temperatures as low as about 5C and lower.
In an embodiment of this invention a supplemental stabilizing agent which is an alkanol ester of phosphoric acid or an aluminum salt of a higher fatty acid can be added to the formulation.
Improvements in stability of the composition may be achieved by incorporation of a small effective amount of an acidic organic phosphorus compound having an acidic - POH group, such as a partial ester of phosphorus acid and an alkanol.
As disclosed in the commonly assigned Canadian appli-cation No. 478,379, filed April 4, 1985, the acidic organic phosphorus compound having an acidic - POH group can increase the stability of the suspension of builders in the nonaqueous liquid nonionic surfactant.
The acidic organic phosphorus compound may be, for instance, a partial ester of phosphoric acid and an alcohol such as an alkanol which has a lipophilic character, having, for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon atoms.
A specific example is a partial ester of phosphoric acid and a C16 to C18 alkanol (Empiphos* 5632 from Marchon); it is made up of about 35% monoester and 65% diester.
*Trade Mark ?~
~ S 62301-1387 The inclusion of quite small amounts of the acidic organic phosphorus compound makes the suspension stab:Le against settling on standing but remains pourable, while, for the low concentration of stabilizer, e.g. below about 1%, its plastic viscosity will generally dec~ease.
Improvements in the stability and anti-settling properties of the composition may also be achieved by the addition of a small effective amount of an aluminum salt of a higher fatty acid to the composition.
The aluminum salt stabilizing agents are the subject matter of the commonl~ assigned Canadian application No. 502,998, filed February 28, 1986.
The preferred higher aliphatic fatty acids will have from about 8 to about 22 carbon atoms, more preferably from about 10 to 20 carbon a~oms, and especially preferably from about 12 to 18 carbon atoms. The aliphatic radical may be saturated or unsaturated and may be straight or branched. As in the case of the nonionic surfactants, mixtures of fatty acids may also be used, such as those derived from natural sourees, such as tallow fatty acid, coco fatty acid, etc.
Examples of the fatty acids from whieh the aluminum salt stabilizers can be formed inelude, decanoic aeid, dodeeanoie acid, palmitie aeid, myristie aeid, stearic aeid, oleic aeid, eieosanoie acid, tallow fatty acid, coco fatty aeid, mixtures of these aeids, ete. The aluminum salts of these aeids are generally eommercially available, and are preferably used in the triacid form, e.g. aluminum stearate as aluminum tristearate Al(C17H35COO)3. The monoacid salts, e.g. aluminum monostearate, Al(OH)2(C17H35COO) and diacid salts, e.g. aluminum distearate, Al(OH)(C17H35COO)2, and mixtures of two or three of the mono-, di- and triacid aluminum salts ean also be used. It is most preferred, however, that the triacid aluminum salt eomprises at ~ . ~
~.2~ S 62301-1387 least 30~, preferably at least 50P~ especially preferably at least 80% oE the total amount of aluminum fatty acid salt.
The aluminum salts, as mentioned above, are commerciall~ available and can be easily produced by, Eor example, saponifying a fatty acid, e.g. animal fat, stearic acid, etc., followed by treatment of the resulting soap with alum, alumina, etc.
Only very small amounts of the aluminum salt stabili-zing agent is required to obtain an improvement in physical stability.
Bleaching Agents The bleanching agents are classified broadl~, for convenience, as chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine)~ and trichloro-isocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by percompounds which liberate hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates, and perphosphates, and potassium monopersulfate. The perborates, particularly sodium perborate monohydrate, are especially preferred.
The peroxygen compound is preferably used in admixture with an activator therefor. Suitable activators which can lower the effective operating temperature of the peroxide bleaching agent are disclosed, for example, in United States Patent No.
4,264,466 or in colum l of United States Patent No. 4,430,244.
Polyacylated compounds are preferred activators; among these, compounds such as tetraacetyl ethylene diamine ("TAED") and pentaacetyl glucose are particularly preferred.
Other useful activators include, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts r ethylidene carboxylate acetate and its salts, ~3~ 62301-1387 ~lkyl and alkenyl succinic anhydride, tetraacetylglycouril ("T~GU"), and the derivatives of these. Other useEul classes of activators are disclosed, for example, in United States Patents Nos. 4,111,~26, 4,422,950 and 3,661,789.
The bleach activator usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water. It is preferred to include a sequestering agent of high complexing power to inhibit any undesired reaction between such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions.
Suitable sequestering agents for this purpose include the sodium salts of nitrilotriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the trade mark Dequest 2066; and ethylene diamine tetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.
In order to avoid loss of peroxide bleaching agent, e.g. sodium perborate, resulting from enzyme-induced decomposi-tion, such as by catalase enzyme, the compositions mayadditionally include an enzyme inhibitor compound, l.e. a compound capable of inhibitiny enzyme-induced decomposition of the peroxide bleaching agent. Suitable inhibitor compounds are disclosed in United States Patent No. 3l606,990.
Of special interest as the inhibitor compound, mention can be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of this invention/ suitable amounts o~ the hydroxylamine salt inhibitors can be as low as about 0.01 to 0.4%. Generally, however, suitable amounts of enzyme inhibitors are up to about 15%, for example, 0.1 to 10%, by weight of the composition.
'D ', ~ ~ ;
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~9~05 62301-1387 In addi-tion to the detergent builders, various other detergent additives or adjuvants may be present in the deteryent product to give it additional desired properties, either of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, and hydrox~-propyl methyl cellulose. A preferred 31a ~3~35 .
anti-redeposition agent is sodium carboxymethyl cellulose having a 2 :1 ratio of CM/MC which is sold under the tradename Relatin DM 4050.
There may also be included in the composition small amounts of ~ Alcosperse D107 which is sodium polyacrylate and which functions as an anti S scaling agent. The Alcosperse D107 can be included in amounts such as 0.5 to 8%3 preferably 2 to 6% and more preferubly 3 to 5% by weight of the composition.
Optical brighteners ~r cotton, polyamide and polyester fabric~ can be used. Suitable optical brighteners include stilbene, triazole and ben~idine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene , benzidene sulfone , etc ., most preferred are stilbene and triazole combinations. A preferred brightener is Stilbene Brightener N4 which is a dianilinodimorphalino stilbene polysulfonate.
Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type anzymes, lipase type enzymes, and mixtures thereof can be added. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperse SL8. Anti-foam agents, e. g. silicon compounds, such as Silicane L
7604, which is a polysiloxane and can be added in small effective amounts.
Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyee, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents, s Lach as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume, and dyes and bluing agents such as ultramarine blue can be used.
The composition may also contain small amounts of Bentone~27 which is an organic derivative of hydrous magnesium aluminum silicate. The Bentone 27 can be used in amounts such as 0.2 to 3%, preferably 0.5 to 2%, and more preferably about 1% by weight.
~_ f~
~ 3~S 62301-13~7 The composition may also contain an inorganic insoluble thickening agen-t or dispersant oE very high surface area such as finely divided silica of extremely fine particle size ~e.~. of 5-lO0 millimicrons diameters such as sold under the trade mark Aerosil) or the other highly voluminous inor~anic carrier materials disclosed in United States Patent No. 3,630,929, in proportions of 0.1-10%, e.g. l to 5%. It is preferable, however, that compositions which form peroxyacids in the wash bath (e.g. compositions containing peroxygen compound and activator therefor) be substantially fr~e of such compounds and of other silicates; it has been found, for instance, that silica and silicates promote the undesired decomposition of the peroxyacid.
In an embodiment of the invention the stability of the builder salts in the composition during storage and the dispersibility of the composition in water is improved by grinding and reducing the particle size of the solid builders to less than 100 microns, preferably less than 40 microns and more preferably to less than 10 microns. The solid builders, e.g. sodium tripolyphosphate (TPP), are generally supplied in particle sizes of about lO0, 200 or 400 microns. The nonionic liquid surfactant phase can be mixed with the solid builders prior to or after carrying out the grinding operation.
In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to less than about 10 microns, e.g. to an average particle size oF 2 to 10 microns or even lower (e.g. 1 micron3. Preferably less thanabout 10%, especially less than about 5% of all the suspended particles have particle sizes greater than lO microns. Compositions ~ ~3~5 6230l-l387 whose dispersed particles are of such small size have improved stability against separation or settling on storage. Addition of the acid terminated nonionic surfactant compound can decrease the yield stress oE such dispersions and aid in the dispersibility of the dispersions without a corresponding decrease in the dispersions stability against settling.
33a ~.
3~0~
In the gFinding operation, it is preferred that the proportion of solid ingre~ients be high enough (e. g. ~ least about 40~ such as nbout 50%) thut the solid particles are in cont~ct with each other and are not subst~ntially shielded from one another by the nonionic surfactant liquid. After the grinding step any remaining liquid nonionic surfactsnt can be added to the ground formulation. Mills which employ grinding balls ~ball mills) or ~imilar mobile grinding elements have given Yery g~od results. Thus, one may use a labor~tory batch attritor having 8 mm di~meter s~eatite gxinding balls. For larger sc~le work a continuously operating mill in which there are 1 mm or 1.5 mm dismeter grinding balls working in ~ very small gap between a stator snd a rotor operating at a relatlvely high speed (e.g. a CoBall mill) may be employed: when using such a mill, it is desirable to pass the blend of nonionic surfactant and solids fir~t through a mill which does not effect such fine grinding (e.g. a colloid mill~ to reduce the particle size to les6 than 100microns (e. g. to about 40 microns) prior to the step of grinding to an ~ver~ge particle diameter below about 10 micron~ in the continuous ball mill.
In the preferred he~vy duty liquid laundry detergent compositions of the invention, typical proportions (percent based on the total weight of composition, unles~ otherwise speclfied) of the ingredienSs are as follows:
Liquid nonionic surfactant detergent in the range of abou~ 10 to 70, such ns 20 to 60 percent, e.g. about 30 to 50 percent.
Acid terminated nonionic surfactant in an amount in the range of about 0 to 20, such as 1 ~r 2 to 15 percent, e.g. about 4 to lO.
Detergent builder, such as sodium tripolyphosphate (TPP), in the range of about 10 to 60, such as 15 to 50 percent, e.g. about 15 to 35.
Alkali metal silicate in the range of about 0 to 30, such as~5 to 25 percent, e. g. about 10 to 20.
Copolymer of polyacrylate and polymaleis anhydride alkali metal salt arlti incrustation agent in the range of sbout 0 to 10, such as 2 to 8 psrcent, e.g. about 3 to 5.
* Trade-mark ~33~05 Alkylene glycol viscosity control and gel-inhibiting agent in an amount in the range of about 5 to 30, such as 5 to 25 percent, e . g~ about 15 to 25.
The preferred viscosity control and ~el-inhibiting agent~ nre the alkylene glycol mono-alkylethers.
The quarternary ammonium salt anti-settling stabilizin~ agent in the range of 0.1 to 5, preferably 0.2 to 2.U and more preferably about 0.5 to 1.5 percent. It is an essential feature of the invention that at least one of the quarternary ammonium salts be included in the composition.
Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 2.0 or 0.1 to 2.0, such as 0.10 to 1.0 percent.
Aluminum salt of fatty acid stabili~ing agent in the range of about 0 to 5.0, such as 0.5 to 2.0 percent, e.g. about 0.1 to 1.0 percent.
Bleaching agent in the range of about 0 to 30, such as 2 to 20, e. g.
about 5 to 15 percent.
Bleach activator in the range of about 0 to 15, such as 1 to 10, e. g.
about 1 to 8 percent.
Sequestering agent for bleach in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent, e.g. about 0.75 to 1.25 percent.
Anti-redeposition agent in the range of about 0 to 5.0, preferably û .5 to 4.0 percent, e.g. 1.0 to 3.0 percent.
Optical brightener in the range of about 0 to 2.0, preferably 0.25 to ~: 1.0 percent, e.g. 0.25 to 0.75 percent.
. A ~r~e~e ra h/y Enzymes in the range of about 0 to 3.0,-preferrA~1~0.5 to 2.0 percent, e.g. 0.75 to 1.25 percent.
Perfume in the range of about 0 to 3.0, preferably 0.25 to 1.25 percent, e.g. 0.75 to 1,0 percent.
Dye in the range of about 0 to 0.10, preferably 0.0025 to 0.050, e . g.
0.0025 to 0.0100 percent.
Various of the previously mentioned additives can optionally be added to achieve the desired function of the added matelq~ls.
~ I
~ 3'~05 Mixtures of the acid terminated nonionic surfactant ~nd viscosity control and gel-inhibiting agents, e. g. the alkylene glycol alkyl ether anti-gel agents, can be used ~nd in some cases advantages can be obtained by the use of such mixtures alone, or with the addition to the mixture of the 5anti-settling stabilizing agent.
In the selection of the additives, they will be chosen to be compatible with the main cunstituents of the cletergent composition. In this application, as mentioned above, all proportions and percentages are by weight of the entire i~ormulation or composition unless otherwise indicated.
10The concentrated nonaqueous nonionic liquid detergent composition of the present invention dispenses readily in the water in the washing machine.
The liquid nonionic detergent compositions of the present invention are preferably nonaqueous, e. g. they are substantially anhydrous. Though minor amounts of water can be tolerated, it is preferred that the 15compositions contain less than 3%, preferably less than 2% snd more preferably less than 1% water.
The presently used home washing machines normally use 200-250 gms of powder detergent to wash a full load of laundry. In accordance with the present invention only 100 cc or 78 gms of the concentrated liquid nonionic 20detergen composition is needed.
.~
~ ~ .
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In an embodiment of the invention the detergent composition of à typical formulation is formulated using the below named ingredients:
Nonionic surfactant detergent or mixture thereof. 30-50 Acid terminated surfactant. 0-20 Phosphate detergent builder salt. 15-35 Copolymer of polyacrylate and polym~leic anhydride alkali 0-10 metal salt anti-encrustation agent ~Sokalan CP-5).
Alkylene glycol viscosity con$rol and gel-inhibiting agent. 10-25 Quaternary ammonium salt anti-gel stabilizing agent. 0.2-2.0 Anti-redeposition agent . 0-5 . 0 Alkali metal perborate bleaching agent. 3-15 Blesch activator (TAED). 1.0-6.0 Sequestering agent. 0-3.0 Optical brightener (Stilbene Brightener N4). 0-2.0 Enzymes (Protease-Esperase SL8). 0-3.0 Perfu~s~e . 0-3 .
31~3~
The present invention is further illustrated by the followin~ exàmples.
A concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts specified.
Weight 96 Product D nonionic surfactant. 39 Acid terminated Dobanol 91-5 reaction product with 5.0 succinic anhydride.
Sodium tri polyphosphate (TPP). 30 Diethylene glycol monobutylether anti-gel agent. 10 Quaternary ammonium salt ( 1 ) . 1. 0 Sodium perborate monohydrate bleaching agent. 9.0 Tetraacetylethylene diamine (TAED) bleach activator. 4.5 Stilbene brightener. 0.5 Protease (Esperase). 1.0 (1) The quaternary amine salt anti-settling stabilizing agent used is Arosurf TA 100 (distearyl dimethyl ammonium chloride).
The addition of 1% of the quaternary ammonium salt i6 found to increase the yield stress of the formulation from about 2 Pa to about 6 Pa. The apparent viscosity of the formulation i8 found to increased from about 0 . 5 Pa.s to 0.4 Pa.s.
The formulation is ground for about 1 hour to reduce the particle size of the suspended builder salts to less than 10 m;crons. The formulated detergent eomposition is found to be stable and non-gelling in storage and to have a high detergent capaeity.
~ 3~
A concentrated nonaqueous liquid nonionic surIactant detergent composition i8 formulated from the following ingredier~ts in the amounts specified .
Weight %
Surfactant T7 18 . 7 Surfactant T9 18 . 7 Acid terminated Dobanol 91-5 reaction product with 5.0 succinic anhydride.
Sodium tri-polyphosphate (TPP~. 30 Diethylene glycol monobutylether anti-gel agent. 10 Quaternary ammonium salt ( I 3 . 1. 0 Sodium perborate monohydrate bleaching agent. 9 Tetraacetylethylene diamine (TAED) bleaching agent. 4.5 - 15 Stilbene brightener. 0 . 5 Protease (Esperase) . 1. 0 Relatin DM 4096 (CMC/MC)(2) - 1.0 Perfume. 0 . 6 (1~ The quaternary amine salt anti settling stabilizing agent used is Ethoquat 2T14 (di-tallow diethoxylated (x~y=4) ammonium chloride.
(2) A 2 :1 mixture of sodium carboxymethyl cellulose and hydroxy methyl cellulose.
The addition of 1% of the quaternary amine s~lt is ~ound to increase the yield stress of the formulation from about 3 Pa to 10 Pa. The apparent viscosity of the ~ormulation is found to increase from about 0.5 Pa.s to 0.4 Pa.s.
The formulation is ground for about 1 hour to reduce the particle size of the suspended builder salts to less than 10 micron~. The formulated detergent composition is ~ound to be stable and non-gelling in storage and to have a high detergent capacity.
~ ;?~3~C~5 EXAMPLE _3 Concentrated nonaqueous liquid nonionic surfactant detergent compositions were formulated from the following ingredients in the amounts specified .
A B
Plurafac RA50 35 35 Plurafac B26 9.0 9.0 Sodium tri-polyphosphate (TPP3 lS lB
Polyethylene glycol (Mol.Wt. 400) anti-gel agent 20 20 Quaternary Ammonium Salt(l) 1.0 ---Sodium perborate monohydrate bleaching agent 3,6 4.1 Tetra acetyl ethylene diamine (TEAD) Bleach Activator 4.5 5.0 Relatin DM4096 (CMC/MC)~2) anti-redeposition agent 3.0 3.0 EDTA Sequestering Agent ( ) 0.9 0-9 Bentone 27(4) 1.0 1.0 Alcosperse D107 (5 ) 4 . o 4 . 0 100.~ 100.0 1. Ethoquat 2T 14 which is the di-tallow diethoxy (x ~y=4) quaternary ammonium chloride.
2 . A 2 :1 mixture of sodium carboxymethyl cellulose and hydroxy methyl cellulose.
3. Ethylene diarnine tetra acetic acid.
4. Organic derivative of hydrous magnesium aluminum silic~te which functions as an antisettling agent.
5. Alcosperse D107 which is sodium polyacrylate and which functions as antiscaling agent.
The formulation was ground for aboùt fifteen minutes to redllce the particle size OI the suspended builder salts to less than 10 microns. The I
31~33~
formulated detergent composition A of the invention is found to be stable and non-gelling in storage and to have a high detergent capacity.
A comparison of the inventive composition A with anti-settling stabilizing the quaternary arnmonium salt with composition B without the quaternary ammonium salt gave the following results.
A B
Apparent viscosity (LVT, Sp.4, 60rpm~ (m Pa.6) 3250 2350 Stability after 48h: phase separation %: 1% 7%
Yield stress: (PQ) ~ 6.5 Plastic viscosity (m Pa.s) 400 510 The data obtained show that the addition to the formulation of as little as 1% quaternary ammonium salt anti-settling stabilizing agent OI the present invention substantially increased the stability of the formulation, increased the apparent viscosity, increased the yield stress and decreased the plastic viscosity.
The formulations of Examples 1, 2 and 3 can be prepared without grinding the builder salts and suspended solid particles to a small particle size, but best results are obtained by grinding the formulation to reduce the particle size of the suspended solid particles.
The builder salts can be used as provided or the builder salts and suspended solid particles can be ground or partially ground prior to mixing them with the nonionic surfactant. The grinding can be carried out in part prior to mixing and grinding completed after mixing or the entire grinding operation can be carried out after mixing with the liquid surfactant. The formulations containing suspended builder and solid particles less th~n 10 microns in size are preferred.
It is understood that thc foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention.
Sanitizing or bleaching agents and activators therefor can be added to improve the bleaching and cleansing characteristics of the composition.
In an embodiment of the invention the builder components of the composition are ground to a particle size of less than lO0 microns and to preferably less than 10 microns to further improve the stability of the suspension of the builder components in the liquid nonionic surfactant detergent .
In addition other ingredients can be added to the composition such as anti-incrustation agents, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.
The presently manufactured washing machines for home use normally operate at washing temperatures of up to 95C . About 18 . 5 gallons ( 20 liters) of water are used during the wash and rinse cycles.
About 200-250 gms of powder detergent per wash is normally used.
In accordance with the present invention where the highly concentrated liquid detergent i8 used normally only 100 gms (78 cc) of the liquid detergent composition is required to wash a full load of dirty laundry.
Accordingly, in one aspect the present invention provides a liquid heavy duty laundry composition composed of a suspension of an anionic detergent builder salt, e . g. a phosphate builder salt, in a liquid nonionic surfactant wherein the composition includes an effective amount of a quaternary ammonium surface active agent to to increase the stability of the suspension against settling.
According to another aspect, the invention provides a concentrated liquid heavy duty laundry detergent composition which is stable, non-settling 3~
62301 13~7 in storage and non-gelllny in s~orage and in use. The licluicl compositions of the present invention are easily pourable, easil~
measured and easily put in-to the washing machine.
According to another aspect, the invention provides a method for dispensing a liquid nonionic laundry detergent composition into and~or with cold water without underyoing gelation. In particular, a method is provided for filling a container with a nonaqueous liquid laundry detergent composition in which the detergent is composed, at least predomlnantly, of a liquid nonionic sur~ace ac~ive agent and for dispensing the composition from the container into an aqueous wash bath, wherein the dispensing is effected by directing a stream o~ unheated water onto the composition such that the composition is carried by the stream of water into the wash bath.
ADVANTAG~S OV_R THE PRIOR ART
The addition of the quaternary ammonium surface active agents to the detergent compositions reduce the problem of dispersed particle settling and phase separation.
The concentrated nonaqueous liquid nonionic surfactant laundry detergent composltions of the present invention have the advantages of being stable, non-settllng in storage, and non-gelling in storaye. The liquid compositions are easily pourable, easily measured and easily put into the laundry washing machines.
The present invention seeks to provide a stable liquid heavy duty nonaqueous nonionic detergent composition containing at least one quaternary ammonium anti-settling stabilizing agent and at least one anionic phosphate detergent builder salt suspended in ~3~
a nonionic sur~actank.
The invention also seeks to provide llclu:ld ~abri~
treating composltions which are suspenslons o~ insoluble inorganic particles in a nonaqueous liquid and which are storage stable, easily pourable and dispersible in cold~ warm or hot water.
B lOa ~ 3~5 62301-1387 This invention relates to highly built heavy duty non-aqueous liquid nonionic surfactant laundry detergent compositions which can be poured at all temperatures and which can be repeatedly dispersed from the dispensing unit of European style automatic laundry washing machines without fouling or plugging of the dispenser even during the winter months.
The invention seeks to provide non-gelling, stable suspensions of heavy duty built non-aqueous liquid nonionic laundry detergent composi~ion which include an effective amount of a quaternary ammonium surface active agent sufficient to increase the yield stress of the composition to thereby increase its stability, i.e. prevent settling of builder particles, etc., preferably while reducing or at least without increasing, the plastic viscosity (viscosity under shear conditions) of the composition.
The invention which will become more apparent from the following detailed description of preferred embodiments are generally provided for by preparing a detergent composition by adding to the non-aqueous liquid nonionic surfactant an effec-tive amount of a quaternary ammonium surface active anti-settling stabilizing agent sufficient to inhibit settling of the suspended particles, wherein said composition includes inorganic or organic fabric treating additives, e.g. viscosity improving agents and one or more anti-gel agents, anti-incrustation agents, pH control agents, bleaching agents, bleach activators, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.
~ 9~5 62301-1387 DETAILED DESCRIPTION OF THE INVENTION
In accordance wi-th the presen-t invention the physica.l stability of the suspension of the anionic detergent builder compound or compounds and any other suspended additive, such as bleaching agent, etc. in the liquid nonionic surfactant vehicle is substantially improved by the addition of an anti-settling stabilizing agent which is a quaternary ammonium surface active agent.
B lla ~ 9~3~i The addition of very small amounts of the quaternary ammonium surface active anti-settling stabilizing agents is sufficient to substantially improve the physical stability of the detergent compositions.
The compositions of the presen~ invention contain as an essential ingredient a quaternary ammonium surface active anti settling stabilizing agent additive. The anti-settling stabilizing additive can comp~qse one or more of the quaternsry ammonium surface active agents.
The anionic surface active agents that are useful in the present invention are those cationic surface active compounds which contain a long chain hydrocarbon hydrophobic group in their molecular structure and a hydrophile group, i.e. water soluble salt forming anion group.
The preferred cationic quaternary ammonium surface active anti-settling stabilizing agents of the present invention are members of the group consisting of:
I Mono-higher alkyl tri-lower alkyl quaternary ammonium salts.
Il Di-higher alkyl di-lower alkyl quaternary ammonium salts.
III Mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salts; and IV Di-higher alkyl diethoxylated quaternary ammonium salts.
The formula I cationic anti-settling stabilizing agents used in the present invention are the mono-higher alkyl tri-lower alkyl quaternary ammonium compounds represented by the following formula:
~ X (I) wherein Rl is a long chain aliphatic radical having from 10 to 22 carbon atoms, and the R2~s are, independently, lower alkyl or hydroxy alkyl radicals and X is a water soluble salt forming anion such as halide, i. e .
chloride, bromide, iodide; sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or similar inorganic or organic ~ 3~
so~ubilizing radical. The R1 carbon chain of the aliphatic radical containing 10 to 22 carbon atoms, especially 12 to 20, preferably 12 to 18, and especially preferably 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated. The R~ lower alkyl radicals have from 1 to 4 carbon atoms, e. g. methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl, and may contain a hydroxyl radical.
The preferred ammonium salt is a mono-higher alkyl trimethyl ammonium chloride wherein the alkyl group is derived from tallow, hydrogenated tallow or stearic acid. Specific examples of quaternary ammonium anti-settling stabilizing agents of the formula I suitable for use in the composition of the present invention include the following:
tallow trimethyl ammonium chloride hydrogenated tallow trimethyl ammonium chloride stearyl trimethyl ammonium chloride stearyl triethyl ammonium chloride cetyl trimethyl ammonium chloride soya trimethyl ammonium chloride stearyl dimethylethyl ammonium chloride tallow-diisopropylmethyl ammonium chloride The corresponding sulfate, methosulfate, ethosulfate, bromide and hydroxide salts thereof, can also be used.
The formula II ca~ionic anti-settling stabilizing agents used in the present invention are the di-higher alkyl di-lower alkyl quaternary ammonium compounds represented by the following formula:
~ R ~ X (II) wherein R1's are, independently, long chain aliphatic radicals having from 10 to 22 carbon atoms, and the R2's are, independently, lower lkyl or hydroxy .~ 05 alkyl radicals and X is a water soluble salt forming anion such as halide, i . e . chloride, bromide, iodide; sulfate, nitrate, citrnte, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or similar inorganic or organic solubilizing radics~. The R1 carbon chains of the aliphatic radicals containing 10 to 22 carbon atoms, especinlly 12 to 20, preferably 12 to 18, and esp~cially preferably 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated. The R2 lower alkyl radicals have from 1 to ~ carbon atoms, e. g. methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl, and may contain a hydroxyl radical.
Typical cationics of formula 11 include the following:
distearyl dimethyl ammonium chloride ditallow dimethyl ammonium chloride dihexadecyl dimethyl ammonium chloride distearyl dimethyl ammonium bromide di(hydrogenated tallow) dimethyl ammonium bromide ditallow isopropyl methyl ammonium chloride distearyl di(isopropyl) ammonium chloride distearyl dimethyl ammonium methosulfate.
A preferred class of cationics is of formula Il wherein two of the R1 groups are C14 to C18, one R2 is methyl, or ethyl and one R2 is methyl, ethyl, isopropyl, n-propyl, hydroxy ethyl or hydroxy propyl.
The formula III cationic anti-settling stabili~ing agents used in the present invention are the mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium compounds represented by the following formula:
--N--(CH2CH20~ X (III) (CH2CH20) yH
wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, and the R2 is lower alkyl or hydroxy alkyl radicals, x and y are each positive numbers of at least 1 and the sum of x ~ y is from 2 to 15, and X is a water soluble salt forming anion such as halide, i.e. chloride, bromide, iodide; sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or similar inorganic or organic solubili~ing radical.
The R1 carbon chain of the aliphatic radical containing 1~ to 22 carbon atoms, especially 12 to 20, preferably 12 to 18, and especially preferably 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated. The R lower ~lkyl radicals have from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl, and may contain a hydroxyl radical.
Typical examples of cationic quaternary ammonium anti-settling stabilizing agents of the formula III suitable for use in the composition of thepresent invention include the following:
coco methyl diethoxylated (x+y=2) ammonium chloride coco methyl diethoxylated (x~y=15) ammonium chloride oleic methyl diethoxylated (x+y=2) ammonium chloride oleic methyl diethoxylated (x+y=15) ammonium chloride stearyl methyl diethoxylated (x+y=2) ammonium chloride stearyl methyl diethoxylated (x+y=15) ammonium chloride tallow methyl diethoxylated (x+y=10) ammonium chloride The formula IV cationic anti-settling stabilizing agents used in the present invention are the di-higher alkyl diethoxylated quaternary ammonium compounds represented by the following formula:
1_N--(CH2C}120~; ~ X (IV) (CH2 CH2O) yH
wherein Rl's are, independently, long chain aliphatic radical having from 10 to 22 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x~y is from 2 to 15, and X is a water solu~le sal~ forming anion such as halide, i. e . chloride, bromide, iodide; sulfate, nitrate, citrate, acetate, ~ 2~3~0~
hydroxide, methosulfate, ethosulfate, phosphate, or similur inorganic or organic solubilizing radical. The Rl carbon chains of the aliphatic radicals containing 10 to 22 carbon atoms, especially 12 to 20, preferably 12 to 18, and especinlly preferably 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated.
A specific example of a cationic quaternary ammonium anti-settling stabilizing agent of the formula IV suitable for use in the composition of the present invention is di-tallow diethoxylated (x~y=4) ammonium chloride ~Ethoquat~2T/14) .
The mono and di-higher alkyl diethoxylated compounds are stable in both acid and alkaline solutions snd possess greater water solubility and compatibility than other related compounds.
In the formula I to IY compounds, the long carbon chains are obtained from long chain fatty acids, such as those derived from tallow and soybean oil. The terms "soya," and "tallow," etc., as used herein refer to the source from which the long chain fatty alkyl chains are derived. Mixtures of the quaternary ammonium compound anti-settling stabilizing sgents can be used.
The linear higher allcyl quaternary ammonium salts are readily biodegradable and are preferred.
Although applicants do not wish to be bound by any particular theory of the manner by which the quaternary ammonium surfactants function to prevent settling of the suspended anionic phosphate detergent builder particles, it is believed that the quaternary ammonium salts interact with the anionic phosphate detergent builder salts to coat the anionic phosphate with a cationic lipophylic skin to make the phosphate more compatible with the ~ 3~
nonionic surfactant, improves the contact between the phosphate and nonionic surfactant and increase the wettability of the dispersed phosphate solid particles surfaces by the nonionic surfaetant. The improvement in the contact between the phosphate and nonionic surfactant and the improved wettability of the dispersed phosphate part;cles by the nonionic surfactant increases the stability of the phosphate suspension and allows the ~uspended phosphate to more easily remain in suspension.
The increased physical stability is manifested by an increase in the yield stress of the composition of, for example, from B5 dynes/cm2 to 260 dynes/cm and increase in the apparent viscosity of, for example, from 2350 to 3250 ~LVT, sp . 4, 60 rpm), as compared to the same composition without the quaternary ammonium sal~ stabilizing agent. As described above, the higher the yield stress, the higher the apparent viscosity at low shear rate and the better the physical stability.
Only very small amounts of the quaternary ammonium s~lt stabilizing agent is required to obtain the signi~icant improvements in physical stability.
For example, based on the total weight of the nonionie liquid surfactant composition, suitable amounts of the quaternary ammonium salt are in the range of from about 0 .1% to about 5~6, preferably from about 0 . 3% to about 2.0% and more preferably about 0.5 to 1.5%.
In addition to its action as a physical stabilizing agent, the higher alkyl quaternary ammonium salts have the additional advantages over other physical stabilizing agents that they are cationic in character and are compatible with the nonionic surfaetant eomponent.
While the quaternary ammonium salts are effeetive in their physical stabilizing aetion, there, can be added to the formulation other known physieal stabilizers, sueh as, for example, an acidic organie phosphorus compound having an acidic - POH group, such as a partial ester of phosphorous aeid and an alkanol or an aluminum salt of a fatty acid.
1293~3S
Nonionic Surfactant Deter~ent The nonionic synthetic organic detergents employed in the practice of the invention mny be any of a wide variety of known compounds.
As is well known, the nonionic synthetic organic detergerlts are characteri2ed by the presence of an org~nic hydrophobic group and un organic hydrs)philic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature~. Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydrstion product thereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxy ethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups . Typical suitable nonionic surfactants are those disclosed in U . S .
patents 4, 316, 812 and 3, 630, 929 .
Usually, the nonionic detergents are poly-lower alkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher 2 0 alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of mols of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain ~rom 5 to 8 or 5 to 9 lower alkoxy groups per mol.
Preferably, the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, often being a minor (less than 50g6) proportion.
f r~--~t,~ Exemplary of such compounds are those wherein the alkanol is of 12 to~ 15 carbon atoms and which contain about 7 ethylene oxide groups per mol, e.g. Neodol 25-7 and Neodol 23-6.5, which products are made by Shell ~ q.c.,.,~
lB
~ 3~
Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 mols of ethylene oxide and the latter is a correspc nding mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6 . 5 . The higher alcohols ,.~ are primary alkanol~.
- Other examples of such detergents include Tergitol 15-S-7 and Tergito~l)~
15-S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven mols of ethylene oxide and the latter is a similar product but with nine mols of ethylene oxide being reacted .
Also useful in the present composition as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of h;gher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mol being about llo Such products are also made by Shell Chemical Company.
Other useful nonionics are represented by the commercially well known class of nonionics sold under the trademark Plurafac. The Plurafacs are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing ~ mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include products which are (A) C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, (B) C13-C15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles èthylene oxide, (C) C13-C~5 fatty slcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, and (D) a product which is a 1:1 mixture of products (B) and {C).
~ f~ "~
~ ?d~ 3C35 Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 i5 an ethoxylated C9-Cll fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C:15 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.
In the preferred poly-lower alkoxylated higher alkEmols, to obtain the best balance of h~drophilic and lipophilic moie~ies the number of lower alkoxies will usually be from 40~ to 100% c>f the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof and the nonionic detergent will preferably contain at least 50% of such preferred poly-lower alkoxy higher alkanol. Higher molecular weight alkanols and various other normally solid nonionic detergents and surface active agents may be contributory to gelation of the liquid detergent and consequently, will preferably be omitted or limited in quantity in the present compositions, although minor proportions thereof may be employed for their cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents the alkyl groups present therein are generally linear although branching may be tolerated, such as at a carbon next to or two carbons removed from the terminal carbon of the straight chain and away from the ethoxy chain, if such branched alkyl is not more than three carbons in length. Normally, the proportion of carbon atoms in such a branchecl configuration will be minor rarely exceeding 20% of the total carbon atom content of the alkyl.
Similarly, although linear alkyls which are terminally joined to the ethylene oxide chains are highly preferred and are considered to result in the best combination of detergency, biodegrad~bility and non-gelling characteristics, medial or secondary joinder to the ethylene oxide in the chain may occur. It A is usually in only a minor proportion o~ such alk~ls, generally less than 20%
but, as is in the cases of the mentioned ~eri6to~ may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, i1 will usually be less than 20% thereof and preferably less than 10% thereof.
1~ 20 I
l~h93~05 When grenter proportions Or non-terminally alkoxylated àlkanols, propylene oxide-containing poly-lower ~lkoxylated ~lkanols and less hydrophile-lipophile balanced nonionie detergent than mentioned a~ove are employed and when other nonionic detergents are used instead of the preferred nonionics recited herein, the product resulting may not have 88 good detergency, stability, viscosity and non-gelling properties as the preferred compositions but use of the viscosity and gel controlling compounds of the invention can also improve the properties of the detergents based on such nonionics. In some cases, as when a higher molecular weight polylower alkoxylated higher alkanol is employed, often for its detergency, the proportion thereof will be regulated or limited in accordance with the results of routine experiments, to obtain the desired detergency and still have the product non-gelling and of desired viscosity. Also, it has been found that it is only rarely necessary to utilize the higher molecular weight nonionics for their deter~ent properties since the preferred nonionics described hereîn are excellent detergentæ and additionally, permit the attainment of the desired viscosity in the liquid detergent without gelation at low temperatures.
~- Another useful group of nonionic surfactants are the "Surfactant T1' ,~ /a 6/~
series of nonionics ~h~ from British Petroleum. The Surfactant T
nonionics are obtained by the ethoxylation of secondary C13 fatty alcohols having a narrow ethylene oxide distribution. The Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 an average of 7 moles of ethylene oxide; Surfactant T9 an average of 9 moles of ethylene oxide and Surfactant T12 an average of 12 moles of ethylene oxide per mole of secondary C13 fatty alcohol.
In the compositions of this invention, preferred nonionic surfactanta include the C12-C15 secondary fstty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, snd the C9 to C11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.
~ 6 ~ ~ R~< 21 ~J~3~05 Mixtures of two or more of the liquid nonionic surfactants can be used and in some cases advantages can be obtained by the use of such mixtures.
Acid Terminated Nonionic Surfactant The viscosity and gel properties of the liquid detergent compositions can be improved by including in the composition an effective amount of an acid terminated liquid nonionic surfactant. The acid terminated nonionic surfactants consist of a nonionic surfactant which has been modified to convert a free hydroxyl group thereof to a moiety having a free carboxyl group, such as an ester or a partial ester of a non-ionic surfactant and a polycarboxylic acid or anhydride.
As disclosed in the commonly assi~ned copending Canadian application No. 478,379 filed April ~, 1985, the free carboxyl group modified nonionic surfactants, which may be broadly characteri2ed as polyether carboxylic acids, function to lower the temperature at which the liquid nonionic forms a gel with water.
The addition of the acid terminated nonionic surfactants to the liquid nonionic surfactant aids in the dispensibility of the composition, i.e. pourability~ and lowers the temperature at which the liquid nonionic surfactants form a gel in water without a decrease in their stability against settling. The acid terminated nonionic surfactant reacts in the washing machine water with the alkalinit~v of the dispersed builder salt phase of the detergent composition and acts as an effective anionic surfactant.
Specific examples include the half-esters of product (A) with succinic anhydride, the ester or half ester of Dobanol 25-7 with succinic anhydride, and the ester or half-ester of Dobanol 91-5 with succinic anhydride. Instead of C~S
succinie anhydride, other polycarboxylic acids or anhydrides can be used, e.g. maleic acid, maleic acid anhydride, glutari.e acid, malonic acid, phthalic acid, phthalic anh~dride, citrie aeid and the like.
The acid terminated nonionie surfactants can be prepared as follows:
22a Acid Terminated product (A). 400g of product (A) nonionic sùrfactant which is a C13 to Cl5 alkanol which has been alkoxylated to introduce 6 ethylene oxide and 3 prl~pylene oxide units per ~lkanol unit i8 mixed with 32g of succinic anhydride and heated for 7 hours at 100C. The mixture i8 cooled and filtered to remove unreacted succinic material. Infrared analysis indicated that about one half of the nonionic surfactant has been converted to the acidic half-ester thereof.
Acid Terminated I)obanol 25-7. 522g of Dobanol 25-7 nonionic surfactant which is the product of ethoxylation of a C12 to C15 alkanol and has about 7 ethylene oxide units per molecule of alkanol is mixed with 100g of succinic anhydride and 0 .1 g of pyridine ( which acts as an esterification catalyst) and heated at 260C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the surfactant have reacted.
Acid Terminate Dobanol 91-5. 1000 of Dobanol 91-5 nonionic surfactant which is the product o ethoxylation of a Cg to Cll alkanol and has about 5 ethylene oxide units per molecule of alkanol is mixed with 265g of succinic anhydride and 0. lg of pyridine catalyst and heated at 260C for 2 hourst cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls OI the surfactant have reacted .
Other esterification catalysts, such as an alkali metal alkoxide (e. g.
sodium methoxlde) may be used in place of, or in admixture with, the pyridine .
2~ The acidic polyether compound, i.e. the acid terminated nonionic surfactant is preferably added dissolved in the nonionic surfactant.
BUILDER SALTS
The liquid nonaqueous nonionic surfactant u~ed in the compositions of ¦
the present invention has dispersed and suspended therein fine particles of ¦
inorganic andlor inorganic detergent builder salts.
~ s The invention detergent compositions include water soluble andlor wster insoluble detergent builder salts. Water soluble inorganic alkaline build~r salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, bicarbonates, borates, S phosphates, polyphosphates, and silicates. (Ammonium or substituted ammonium salts can also be used. ) Specific examples of ~uch salts are sodium tripolyphosphate, sodium carbonate, sodium tetr&borate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, and potassium bicarbonate. Sodium tripolyphosphate (TPP~ is especially preferred.
Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate~ with an auxiliary builder such as a poly lower carboxylic acid or a polymeric carboxylic acid having high calcium binding capacity to inhibit incrustation which could otherwise be caused by formation of an insoluble calcium phosphate.
A suitable lower poly carboxylic acid compri~es alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts.
Suitable lower polycarboxylic acids have two to four carboxylic acid groups.
The preferred sodium and potassium lower polycarboxylic acids salts are the citric and tartaric acid salts.
The sodium citric acid salts are the most preferred, especially the trisodium citrate. The monosodium and disodium citrates can also be used.
The monosodium and disodium tartaric acid salts can also be used. The alkali metal lower polycarboxylic acid salts are particularly good builder s~lts; because of their high calcium and magnesium binding capacity they inhibit incrustation which could otherwise be caused by ~ormation of insoluble calcium and magnesium salts.
Il 24 ~
Il ' .... . .. .
~ 62301-1387 Other organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and the alkali metal salts thereof. More specifically such builder salts can consist of a copolymer which is the reaction product of about equal moles of methacrylic acid and maleic anhydride which has been completely neutralized to form the sodium salt thereof.
The builder is co~mercially available under the trade mark of Sokalan CP5. This builder serves when used even in small amounts to inhibit incrustation.
Examples of organic alkaline sequestrant builder salts which can be used with the detergent builder salts or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetraacetate (EDTA), sodium and potassium ni-trilotriacetates (NTA), and triethanol-ammonium N-(2-hydroxyethyl)nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.
Other suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. Of special value are the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described in United States Patents Nos. 4,144,226, 4,315,092 and 4,146~495.
The alkali metal silicates are useful builder salts which also function to adjust or control the p~l and to make the composition anticorrosive to washing machine parts. Sodium silicates of Na2O/SiO2 ratios of from 1.6/1 to 1/3.2, especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the "-same ratios can also be used.
Other typical suitable builders include, for example, those disclosed in United States Patents Nos. 4,316,812, 4,264,466 and 3,630,929. The inorganic builder salts can be `~ ~ 25 6~301-~.3~7 used with the nonionic surfa~tant detergen-t compound or ln admixture with other inorganic huilder salts or Wi th Or'JalliC
builder sal-ts. U.S. Patent 2G~,466 discloses illorcJanic builder salts which :include a halicle (chloride).
The water insoluble crystalline and amorphous aluminosilica~e æeolites can be used. The zeolites generally have the formula (M20)X- (A1203~y. (SiO2)Z.WH2(:) wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from O
to 9, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is type A or similar structure, and type 4A particular-ly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400meq/lg.
Various crystalline zeolites (i.e. alumino-silicates) that can be used are described in British Patent No. 1,504,168, United States Patent No. 4,~09,136 and Canadian Patents Nos.
1,072,835 and 1,087,477. An example of amorphous zeolites useful herein can be found in Belyium Patent No. 835,351.
Other materials such as clays, partic~ularly of the water-insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hyclrated aluminum silicate in which about 1~6th of the aluminum atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bentonite in its more purified form (i.e.
free from any grit, sand, etc.) suitable for detergen~s con-tains at least 50~ montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq per lOOg of bentonite.
Particularly preferred bentonites are the Wyoming or Western ~ 62301-13~7 U. S. bentonites which have been sold as Thixo-jels* 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are k:nown to soften textiles as described in British Patent No. 401,413 to Marriott and British Patent No. 461,221 to Marriott and Guan.
*Trade Mark 26a ~ ~3~0~
Viscosity Co_trol and Anti Gel Agents The inclusion in the detergent composition of an effective smount of viscosity control and gel-inhibiting agents for the nonionic surf~ctant improves the storage propertie~, of the composition. The viscosity control and gel-inhibiting agents act to lower the temperature Rt which the nonionic surfactant will form a gel when added to water. Such ~iscosity control and gel-inhibiting agents can be for example, lower alkanol, e.g. ethyl alcohol (see U.S.P. 3,953,380), hexylene glycol, polyethylene glycol, for example, polyethylene glycol having a molecular weight of about 40û (PEI~ 400) and low molecular weight alkylene oxide lower mono-alkyl ether amphiphilic compounds.
Preferred viscosity control and gel-inhibiting compounds are the amphiphilic compounds. The amphiphilic compounds can be considered to be analagous in chemical structure to the ethoxylated andlor propoxylated fatty ~lcohol liquid nonionic surfactants but have relatively short hydrocarbon chain lengths (C2 to C8) and a low content of ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).
Suitable amphiphilic compounds are represented by the following general formula R30( CH2CH2)nH
where R3 i8 a C2-C8 alkyl group, and n ifi a number of from about 1 to 6, on average.
Specifically the compounds are lower (C2 to C3) alkylene glycol mono lower (C2 to C5) alkyl ethers.
More specifically the compounds are mono di- or tri lower (C2 to C3) alkylene glycol mono lower (Cl to C5) alkyl ethers.
Specific examples of 6uitable amphiphilic compounds include ethylene glycol monoethyl ether (C2H5-0-CH2CH 20H), diethylene glycol monobutyl ether ~C4Hg-O-(CH2CH20)2H), tetraethylene glycol monobutyl ether tC4Hr-0-(CH2CH20~,~H) and ~ g OS 62301-13~37 dipropylene glycol monomethyl ether (CIl3-O-(CH2CH2CH2O)2Ml.
Diethylene ~l~colmonobutyl ether is especially preferred.
The inclusion in the composition oE the low molecular weight lower alkylene glycol mono alkyl ether decreases the viscosity of the composition, such that it is more easily pourable, improves the stability against settling and improves the dispersibility of the composition on the addition to warm water or cold water.
The compositions of the present invention have improved viscosity and stability characteristics and remain stable and pourable at temperatures as low as about 5C and lower.
In an embodiment of this invention a supplemental stabilizing agent which is an alkanol ester of phosphoric acid or an aluminum salt of a higher fatty acid can be added to the formulation.
Improvements in stability of the composition may be achieved by incorporation of a small effective amount of an acidic organic phosphorus compound having an acidic - POH group, such as a partial ester of phosphorus acid and an alkanol.
As disclosed in the commonly assigned Canadian appli-cation No. 478,379, filed April 4, 1985, the acidic organic phosphorus compound having an acidic - POH group can increase the stability of the suspension of builders in the nonaqueous liquid nonionic surfactant.
The acidic organic phosphorus compound may be, for instance, a partial ester of phosphoric acid and an alcohol such as an alkanol which has a lipophilic character, having, for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon atoms.
A specific example is a partial ester of phosphoric acid and a C16 to C18 alkanol (Empiphos* 5632 from Marchon); it is made up of about 35% monoester and 65% diester.
*Trade Mark ?~
~ S 62301-1387 The inclusion of quite small amounts of the acidic organic phosphorus compound makes the suspension stab:Le against settling on standing but remains pourable, while, for the low concentration of stabilizer, e.g. below about 1%, its plastic viscosity will generally dec~ease.
Improvements in the stability and anti-settling properties of the composition may also be achieved by the addition of a small effective amount of an aluminum salt of a higher fatty acid to the composition.
The aluminum salt stabilizing agents are the subject matter of the commonl~ assigned Canadian application No. 502,998, filed February 28, 1986.
The preferred higher aliphatic fatty acids will have from about 8 to about 22 carbon atoms, more preferably from about 10 to 20 carbon a~oms, and especially preferably from about 12 to 18 carbon atoms. The aliphatic radical may be saturated or unsaturated and may be straight or branched. As in the case of the nonionic surfactants, mixtures of fatty acids may also be used, such as those derived from natural sourees, such as tallow fatty acid, coco fatty acid, etc.
Examples of the fatty acids from whieh the aluminum salt stabilizers can be formed inelude, decanoic aeid, dodeeanoie acid, palmitie aeid, myristie aeid, stearic aeid, oleic aeid, eieosanoie acid, tallow fatty acid, coco fatty aeid, mixtures of these aeids, ete. The aluminum salts of these aeids are generally eommercially available, and are preferably used in the triacid form, e.g. aluminum stearate as aluminum tristearate Al(C17H35COO)3. The monoacid salts, e.g. aluminum monostearate, Al(OH)2(C17H35COO) and diacid salts, e.g. aluminum distearate, Al(OH)(C17H35COO)2, and mixtures of two or three of the mono-, di- and triacid aluminum salts ean also be used. It is most preferred, however, that the triacid aluminum salt eomprises at ~ . ~
~.2~ S 62301-1387 least 30~, preferably at least 50P~ especially preferably at least 80% oE the total amount of aluminum fatty acid salt.
The aluminum salts, as mentioned above, are commerciall~ available and can be easily produced by, Eor example, saponifying a fatty acid, e.g. animal fat, stearic acid, etc., followed by treatment of the resulting soap with alum, alumina, etc.
Only very small amounts of the aluminum salt stabili-zing agent is required to obtain an improvement in physical stability.
Bleaching Agents The bleanching agents are classified broadl~, for convenience, as chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine)~ and trichloro-isocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by percompounds which liberate hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates, and perphosphates, and potassium monopersulfate. The perborates, particularly sodium perborate monohydrate, are especially preferred.
The peroxygen compound is preferably used in admixture with an activator therefor. Suitable activators which can lower the effective operating temperature of the peroxide bleaching agent are disclosed, for example, in United States Patent No.
4,264,466 or in colum l of United States Patent No. 4,430,244.
Polyacylated compounds are preferred activators; among these, compounds such as tetraacetyl ethylene diamine ("TAED") and pentaacetyl glucose are particularly preferred.
Other useful activators include, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts r ethylidene carboxylate acetate and its salts, ~3~ 62301-1387 ~lkyl and alkenyl succinic anhydride, tetraacetylglycouril ("T~GU"), and the derivatives of these. Other useEul classes of activators are disclosed, for example, in United States Patents Nos. 4,111,~26, 4,422,950 and 3,661,789.
The bleach activator usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water. It is preferred to include a sequestering agent of high complexing power to inhibit any undesired reaction between such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions.
Suitable sequestering agents for this purpose include the sodium salts of nitrilotriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the trade mark Dequest 2066; and ethylene diamine tetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.
In order to avoid loss of peroxide bleaching agent, e.g. sodium perborate, resulting from enzyme-induced decomposi-tion, such as by catalase enzyme, the compositions mayadditionally include an enzyme inhibitor compound, l.e. a compound capable of inhibitiny enzyme-induced decomposition of the peroxide bleaching agent. Suitable inhibitor compounds are disclosed in United States Patent No. 3l606,990.
Of special interest as the inhibitor compound, mention can be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of this invention/ suitable amounts o~ the hydroxylamine salt inhibitors can be as low as about 0.01 to 0.4%. Generally, however, suitable amounts of enzyme inhibitors are up to about 15%, for example, 0.1 to 10%, by weight of the composition.
'D ', ~ ~ ;
''`1' `~;; ~
~9~05 62301-1387 In addi-tion to the detergent builders, various other detergent additives or adjuvants may be present in the deteryent product to give it additional desired properties, either of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, and hydrox~-propyl methyl cellulose. A preferred 31a ~3~35 .
anti-redeposition agent is sodium carboxymethyl cellulose having a 2 :1 ratio of CM/MC which is sold under the tradename Relatin DM 4050.
There may also be included in the composition small amounts of ~ Alcosperse D107 which is sodium polyacrylate and which functions as an anti S scaling agent. The Alcosperse D107 can be included in amounts such as 0.5 to 8%3 preferably 2 to 6% and more preferubly 3 to 5% by weight of the composition.
Optical brighteners ~r cotton, polyamide and polyester fabric~ can be used. Suitable optical brighteners include stilbene, triazole and ben~idine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene , benzidene sulfone , etc ., most preferred are stilbene and triazole combinations. A preferred brightener is Stilbene Brightener N4 which is a dianilinodimorphalino stilbene polysulfonate.
Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type anzymes, lipase type enzymes, and mixtures thereof can be added. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperse SL8. Anti-foam agents, e. g. silicon compounds, such as Silicane L
7604, which is a polysiloxane and can be added in small effective amounts.
Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyee, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents, s Lach as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume, and dyes and bluing agents such as ultramarine blue can be used.
The composition may also contain small amounts of Bentone~27 which is an organic derivative of hydrous magnesium aluminum silicate. The Bentone 27 can be used in amounts such as 0.2 to 3%, preferably 0.5 to 2%, and more preferably about 1% by weight.
~_ f~
~ 3~S 62301-13~7 The composition may also contain an inorganic insoluble thickening agen-t or dispersant oE very high surface area such as finely divided silica of extremely fine particle size ~e.~. of 5-lO0 millimicrons diameters such as sold under the trade mark Aerosil) or the other highly voluminous inor~anic carrier materials disclosed in United States Patent No. 3,630,929, in proportions of 0.1-10%, e.g. l to 5%. It is preferable, however, that compositions which form peroxyacids in the wash bath (e.g. compositions containing peroxygen compound and activator therefor) be substantially fr~e of such compounds and of other silicates; it has been found, for instance, that silica and silicates promote the undesired decomposition of the peroxyacid.
In an embodiment of the invention the stability of the builder salts in the composition during storage and the dispersibility of the composition in water is improved by grinding and reducing the particle size of the solid builders to less than 100 microns, preferably less than 40 microns and more preferably to less than 10 microns. The solid builders, e.g. sodium tripolyphosphate (TPP), are generally supplied in particle sizes of about lO0, 200 or 400 microns. The nonionic liquid surfactant phase can be mixed with the solid builders prior to or after carrying out the grinding operation.
In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to less than about 10 microns, e.g. to an average particle size oF 2 to 10 microns or even lower (e.g. 1 micron3. Preferably less thanabout 10%, especially less than about 5% of all the suspended particles have particle sizes greater than lO microns. Compositions ~ ~3~5 6230l-l387 whose dispersed particles are of such small size have improved stability against separation or settling on storage. Addition of the acid terminated nonionic surfactant compound can decrease the yield stress oE such dispersions and aid in the dispersibility of the dispersions without a corresponding decrease in the dispersions stability against settling.
33a ~.
3~0~
In the gFinding operation, it is preferred that the proportion of solid ingre~ients be high enough (e. g. ~ least about 40~ such as nbout 50%) thut the solid particles are in cont~ct with each other and are not subst~ntially shielded from one another by the nonionic surfactant liquid. After the grinding step any remaining liquid nonionic surfactsnt can be added to the ground formulation. Mills which employ grinding balls ~ball mills) or ~imilar mobile grinding elements have given Yery g~od results. Thus, one may use a labor~tory batch attritor having 8 mm di~meter s~eatite gxinding balls. For larger sc~le work a continuously operating mill in which there are 1 mm or 1.5 mm dismeter grinding balls working in ~ very small gap between a stator snd a rotor operating at a relatlvely high speed (e.g. a CoBall mill) may be employed: when using such a mill, it is desirable to pass the blend of nonionic surfactant and solids fir~t through a mill which does not effect such fine grinding (e.g. a colloid mill~ to reduce the particle size to les6 than 100microns (e. g. to about 40 microns) prior to the step of grinding to an ~ver~ge particle diameter below about 10 micron~ in the continuous ball mill.
In the preferred he~vy duty liquid laundry detergent compositions of the invention, typical proportions (percent based on the total weight of composition, unles~ otherwise speclfied) of the ingredienSs are as follows:
Liquid nonionic surfactant detergent in the range of abou~ 10 to 70, such ns 20 to 60 percent, e.g. about 30 to 50 percent.
Acid terminated nonionic surfactant in an amount in the range of about 0 to 20, such as 1 ~r 2 to 15 percent, e.g. about 4 to lO.
Detergent builder, such as sodium tripolyphosphate (TPP), in the range of about 10 to 60, such as 15 to 50 percent, e.g. about 15 to 35.
Alkali metal silicate in the range of about 0 to 30, such as~5 to 25 percent, e. g. about 10 to 20.
Copolymer of polyacrylate and polymaleis anhydride alkali metal salt arlti incrustation agent in the range of sbout 0 to 10, such as 2 to 8 psrcent, e.g. about 3 to 5.
* Trade-mark ~33~05 Alkylene glycol viscosity control and gel-inhibiting agent in an amount in the range of about 5 to 30, such as 5 to 25 percent, e . g~ about 15 to 25.
The preferred viscosity control and ~el-inhibiting agent~ nre the alkylene glycol mono-alkylethers.
The quarternary ammonium salt anti-settling stabilizin~ agent in the range of 0.1 to 5, preferably 0.2 to 2.U and more preferably about 0.5 to 1.5 percent. It is an essential feature of the invention that at least one of the quarternary ammonium salts be included in the composition.
Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 2.0 or 0.1 to 2.0, such as 0.10 to 1.0 percent.
Aluminum salt of fatty acid stabili~ing agent in the range of about 0 to 5.0, such as 0.5 to 2.0 percent, e.g. about 0.1 to 1.0 percent.
Bleaching agent in the range of about 0 to 30, such as 2 to 20, e. g.
about 5 to 15 percent.
Bleach activator in the range of about 0 to 15, such as 1 to 10, e. g.
about 1 to 8 percent.
Sequestering agent for bleach in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent, e.g. about 0.75 to 1.25 percent.
Anti-redeposition agent in the range of about 0 to 5.0, preferably û .5 to 4.0 percent, e.g. 1.0 to 3.0 percent.
Optical brightener in the range of about 0 to 2.0, preferably 0.25 to ~: 1.0 percent, e.g. 0.25 to 0.75 percent.
. A ~r~e~e ra h/y Enzymes in the range of about 0 to 3.0,-preferrA~1~0.5 to 2.0 percent, e.g. 0.75 to 1.25 percent.
Perfume in the range of about 0 to 3.0, preferably 0.25 to 1.25 percent, e.g. 0.75 to 1,0 percent.
Dye in the range of about 0 to 0.10, preferably 0.0025 to 0.050, e . g.
0.0025 to 0.0100 percent.
Various of the previously mentioned additives can optionally be added to achieve the desired function of the added matelq~ls.
~ I
~ 3'~05 Mixtures of the acid terminated nonionic surfactant ~nd viscosity control and gel-inhibiting agents, e. g. the alkylene glycol alkyl ether anti-gel agents, can be used ~nd in some cases advantages can be obtained by the use of such mixtures alone, or with the addition to the mixture of the 5anti-settling stabilizing agent.
In the selection of the additives, they will be chosen to be compatible with the main cunstituents of the cletergent composition. In this application, as mentioned above, all proportions and percentages are by weight of the entire i~ormulation or composition unless otherwise indicated.
10The concentrated nonaqueous nonionic liquid detergent composition of the present invention dispenses readily in the water in the washing machine.
The liquid nonionic detergent compositions of the present invention are preferably nonaqueous, e. g. they are substantially anhydrous. Though minor amounts of water can be tolerated, it is preferred that the 15compositions contain less than 3%, preferably less than 2% snd more preferably less than 1% water.
The presently used home washing machines normally use 200-250 gms of powder detergent to wash a full load of laundry. In accordance with the present invention only 100 cc or 78 gms of the concentrated liquid nonionic 20detergen composition is needed.
.~
~ ~ .
-~
~?3~0~i `
In an embodiment of the invention the detergent composition of à typical formulation is formulated using the below named ingredients:
Nonionic surfactant detergent or mixture thereof. 30-50 Acid terminated surfactant. 0-20 Phosphate detergent builder salt. 15-35 Copolymer of polyacrylate and polym~leic anhydride alkali 0-10 metal salt anti-encrustation agent ~Sokalan CP-5).
Alkylene glycol viscosity con$rol and gel-inhibiting agent. 10-25 Quaternary ammonium salt anti-gel stabilizing agent. 0.2-2.0 Anti-redeposition agent . 0-5 . 0 Alkali metal perborate bleaching agent. 3-15 Blesch activator (TAED). 1.0-6.0 Sequestering agent. 0-3.0 Optical brightener (Stilbene Brightener N4). 0-2.0 Enzymes (Protease-Esperase SL8). 0-3.0 Perfu~s~e . 0-3 .
31~3~
The present invention is further illustrated by the followin~ exàmples.
A concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts specified.
Weight 96 Product D nonionic surfactant. 39 Acid terminated Dobanol 91-5 reaction product with 5.0 succinic anhydride.
Sodium tri polyphosphate (TPP). 30 Diethylene glycol monobutylether anti-gel agent. 10 Quaternary ammonium salt ( 1 ) . 1. 0 Sodium perborate monohydrate bleaching agent. 9.0 Tetraacetylethylene diamine (TAED) bleach activator. 4.5 Stilbene brightener. 0.5 Protease (Esperase). 1.0 (1) The quaternary amine salt anti-settling stabilizing agent used is Arosurf TA 100 (distearyl dimethyl ammonium chloride).
The addition of 1% of the quaternary ammonium salt i6 found to increase the yield stress of the formulation from about 2 Pa to about 6 Pa. The apparent viscosity of the formulation i8 found to increased from about 0 . 5 Pa.s to 0.4 Pa.s.
The formulation is ground for about 1 hour to reduce the particle size of the suspended builder salts to less than 10 m;crons. The formulated detergent eomposition is found to be stable and non-gelling in storage and to have a high detergent capaeity.
~ 3~
A concentrated nonaqueous liquid nonionic surIactant detergent composition i8 formulated from the following ingredier~ts in the amounts specified .
Weight %
Surfactant T7 18 . 7 Surfactant T9 18 . 7 Acid terminated Dobanol 91-5 reaction product with 5.0 succinic anhydride.
Sodium tri-polyphosphate (TPP~. 30 Diethylene glycol monobutylether anti-gel agent. 10 Quaternary ammonium salt ( I 3 . 1. 0 Sodium perborate monohydrate bleaching agent. 9 Tetraacetylethylene diamine (TAED) bleaching agent. 4.5 - 15 Stilbene brightener. 0 . 5 Protease (Esperase) . 1. 0 Relatin DM 4096 (CMC/MC)(2) - 1.0 Perfume. 0 . 6 (1~ The quaternary amine salt anti settling stabilizing agent used is Ethoquat 2T14 (di-tallow diethoxylated (x~y=4) ammonium chloride.
(2) A 2 :1 mixture of sodium carboxymethyl cellulose and hydroxy methyl cellulose.
The addition of 1% of the quaternary amine s~lt is ~ound to increase the yield stress of the formulation from about 3 Pa to 10 Pa. The apparent viscosity of the ~ormulation is found to increase from about 0.5 Pa.s to 0.4 Pa.s.
The formulation is ground for about 1 hour to reduce the particle size of the suspended builder salts to less than 10 micron~. The formulated detergent composition is ~ound to be stable and non-gelling in storage and to have a high detergent capacity.
~ ;?~3~C~5 EXAMPLE _3 Concentrated nonaqueous liquid nonionic surfactant detergent compositions were formulated from the following ingredients in the amounts specified .
A B
Plurafac RA50 35 35 Plurafac B26 9.0 9.0 Sodium tri-polyphosphate (TPP3 lS lB
Polyethylene glycol (Mol.Wt. 400) anti-gel agent 20 20 Quaternary Ammonium Salt(l) 1.0 ---Sodium perborate monohydrate bleaching agent 3,6 4.1 Tetra acetyl ethylene diamine (TEAD) Bleach Activator 4.5 5.0 Relatin DM4096 (CMC/MC)~2) anti-redeposition agent 3.0 3.0 EDTA Sequestering Agent ( ) 0.9 0-9 Bentone 27(4) 1.0 1.0 Alcosperse D107 (5 ) 4 . o 4 . 0 100.~ 100.0 1. Ethoquat 2T 14 which is the di-tallow diethoxy (x ~y=4) quaternary ammonium chloride.
2 . A 2 :1 mixture of sodium carboxymethyl cellulose and hydroxy methyl cellulose.
3. Ethylene diarnine tetra acetic acid.
4. Organic derivative of hydrous magnesium aluminum silic~te which functions as an antisettling agent.
5. Alcosperse D107 which is sodium polyacrylate and which functions as antiscaling agent.
The formulation was ground for aboùt fifteen minutes to redllce the particle size OI the suspended builder salts to less than 10 microns. The I
31~33~
formulated detergent composition A of the invention is found to be stable and non-gelling in storage and to have a high detergent capacity.
A comparison of the inventive composition A with anti-settling stabilizing the quaternary arnmonium salt with composition B without the quaternary ammonium salt gave the following results.
A B
Apparent viscosity (LVT, Sp.4, 60rpm~ (m Pa.6) 3250 2350 Stability after 48h: phase separation %: 1% 7%
Yield stress: (PQ) ~ 6.5 Plastic viscosity (m Pa.s) 400 510 The data obtained show that the addition to the formulation of as little as 1% quaternary ammonium salt anti-settling stabilizing agent OI the present invention substantially increased the stability of the formulation, increased the apparent viscosity, increased the yield stress and decreased the plastic viscosity.
The formulations of Examples 1, 2 and 3 can be prepared without grinding the builder salts and suspended solid particles to a small particle size, but best results are obtained by grinding the formulation to reduce the particle size of the suspended solid particles.
The builder salts can be used as provided or the builder salts and suspended solid particles can be ground or partially ground prior to mixing them with the nonionic surfactant. The grinding can be carried out in part prior to mixing and grinding completed after mixing or the entire grinding operation can be carried out after mixing with the liquid surfactant. The formulations containing suspended builder and solid particles less th~n 10 microns in size are preferred.
It is understood that thc foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention.
Claims (22)
- THE EMBODIMENT OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A non-aqueous, liquid, heavy-duty, built laundry detergent composition comprising of:
10-70% by weight of at least one liquid nonionic surfactant, said liquid nonionic surfactant consisting of a polyloweralkoxylated higher alkanol, wherein said alkanol is of 9 to 18 carbon atoms and the number of moles of said lower alkylene oxide is from 3 to 12 per mole of said alkanol;
10-60% by weight of at least one particulate detergent builder salt suspended in said at least one liquid nonionic surfactant;
0.1-5% by weight of a cationic quaternary ammonium salt surface active anti-settling agent selected from the group consisting of (I) mono-higher alkyl tri-lower alkyl quaternary ammonium salt, (II) di-higher alkyl di-lower alkyl quaternary ammonium salt, (III) mono-higher alkyl mono-lower alkyl diethoxy-lated quaternary ammonium salt and (IV) di-higher alkyl diethoxy-lated quaternary ammonium salt;
0-2.0% by weight of a phosphoric acid alkanol ester stabilizing agent;
0-5.0% by weight of an aluminum salt of a fatty acid stabilizing agent;
0-30% by weight of a bleaching agent;
0-15% by weight of a bleach activator;
0-3.0% by weight of a sequestering agent for metal ions;
0-5.0% by weight of an anti-redeposition agent;
0-2.0% of an optical brightener;
0-3.0% of enzymes;
0-3.0% of perfume;
0-0.10% of dye. - 2. The composition of claim l, wherein said particulate detergent builder salt is a phosphate detergent builder salt.
- 3. The composition of claim l, wherein said cationic quaternary amine salt is represented by the formula:
( I ) wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, and the R2's are, independently, lower alkyl or hydroxy alkyl radicals and X is a water-soluble salt-forming anion. - 4. The composition of claim 1, wherein said cationic quaternary amine salt is represented by the formula:
( II ) wherein R1's are, independently, long chain aliphatic radical having from 10 to 22 carbon atoms, and the R2's are, independently, lower alkyl or hydroxy alkyl radicals and X is a water-soluble salt-forming anion. - 5. The composition of claim 1, wherein said cationic quaternary amine salt is represented by the formula:
(I I I ) wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, and the R2 is lower alkyl or hydroxy alkyl radicals, x and y are each positive numbers of at least 1 and the sum of x+y is from 2 to 15, and X is a water-soluble salt-forming anion. - 6. The composition of claim 1, wherein said cationic quaternary amine salt is represented by the formula:
( IV) wherein Rl are, independently, long chain aliphatic radical having from 10 to 22 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x+y is from 2 to 15, and X
is a water-soluble salt-forming anion. - 7. The composition of claim 1, wherein said at least one particulate detergent builder salt is a halide salt present in an amount of 10-50% by weight.
- 8. The composition of claim 7, wherein said detergent builder salt is an inorganic phosphate builder salt.
- 9. The composition of claim 8, wherein said inorganic phosphate is an alkali metal polyphosphate.
- 10. The composition of claim l, wherein said at least one particulate detergent builder salt has a particle size distribution such that no more than about 10% by weight of said particles have a particle size of more than about 10 microns.
- 11. The composition of claim l, wherein said cationic quaternary ammonium salt surface active anti-settling agent is present in an amount of 0.2-2.0% by weight.
- 12. The composition of claim 4, wherein said cationic quaternary ammonium salt is distearyl dimethyl ammonium chloride.
- 13. The composition of claim 6, wherein said cationic quaternary ammonium salt is ditallow diethoxylated ammonium chloride wherein x+y=4.
- 14. A non-aqueous, liquid, heavy-duty, built laundry detergent composition consisting of:
10-70% by weight of at least one liquid nonionic surfactant, said liquid nonionic surfactant consisting of a poly-loweralkoxylated higher alkanol, wherein said alkanol is of 9 to 18 carbon atoms and the number of moles of said lower alkylene oxide is from 3 to 12 per mole of said alkanol;
10-60% by weight of at least one particulate detergent builder salt suspended in said at least one nonionic surfactant;
0.1-5% by weight of a cationic quaternary ammonium salt surface active anti-settling agent selected from the group consisting of (I) mono-higher alkyl tri-lower alkyl quaternary ammonium salt, (II) di-higher alkyl di-lower alkyl quaternary ammonium salt, (III) mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salt and (IV) di-higher alkyl diethoxylated quaternary ammonium salt;
5-30% by weight of a viscosity control and gel-inhibiting agent selected from the group consisting of alkylene glycols and alkylene glycol mono alkyl ethers;
0-2.0% by weight of a phosphoric acid alkanol ester stabilizing agent;
0-5.0% by weight of an aluminum salt of a fatty acid stabilizing agent;
0-30% by weight of a bleaching agent;
0-15% by weight of a bleach activator;
0-3.0% by weight of a sequestering agent for metal ions;
0-5.0% by weight of an anti-redeposition agent;
0-2.0% of an optical brightener;
0-3.0% of enzymes;
0-3.0% of perfume;
0-0.10% of dye. - 15. The composition of claim 14, wherein said viscosity control and gel-inhibiting agent is polyethylene glycol.
- 16. The composition of claim 14, wherein said viscosity control and gel-inhibiting agent is diethylene glycol mono-butylether.
- 17. A non-aqueous, liquid, heavy-duty, built laundry detergent composition consisting of:
10-70% by weight of at least one liquid nonionic surfactant, said liquid nonionic surfactant consisting of a polyloweralkoxylated higher alkanol, wherein said alkanol is of 9 to 18 carbon atoms and the number of moles of said lower alkylene oxide is from 3 to 12 per mole of said alkanol;
10-60% by weight of at least one particulate detergent builder salt suspended in said at least one liquid nonionic surfactant;
0.1-5% by weight of a cationic quaternary ammonium salt surface active anti-settling agent selected from the group consisting of (I) mono-higher alkyl tri-lower alkyl quaternary ammonium salt, (II) di-higher alkyl di-lower alkyl quaternary ammonium salt, (III) mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salt and (IV) di-higher alkyl diethoxylated quaternary ammonium salt;
0-2.0% by weight of a phosphoric acid alkanol ester stabilizing agent;
0-5.0% by weight of an aluminum salt of a fatty acid stabilizing agent;
0-30% by weight of a bleaching agent;
0-15% by weight of a bleach activator;
0-3.0% by weight of a sequestering agent for metal ions;
0-5.0% by weight of an anti-redeposition agent;
0-2.0% of an optical brightener;
0-3.0% of enzymes;
0-3.0% of perfume;
0-0.10% of dye;
balance, one or more detergent adjuvants selected from corrosion inhibitors, anti-foam agents, suds suppressors, anti-yellowing agents, bluing agents, pH modifiers, pH buffers, bleach stabilizers and enzyme inhibitors. - 18. A non-aqueous, liquid, heavy-duty, built laundry detergent composition consisting of:
10-70% by weight of at least one liquid nonionic surfactant, said liquid nonionic surfactant consisting of a poly-loweralkoxylated higher alkanol, wherein said alkanol is of 9 to 18 carbon atoms and the number of moles of said lower alkylene oxide is from 3 to 12 per mole of said alkanol;
10-60% by weight of at least one particulate detergent builder salt suspended in said at least one nonionic surfactant, 0.1-5% by weight of a cationic quaternary ammonium salt surface active anti-settling agent selected from the group consisting of (I) mono-higher alkyl tri-lower alkyl quaternary ammonium salt, (II) di-higher alkyl di-lower alkyl quaternary ammonium salt, (III) mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salt and (IV) di-higher alkyl diethoxylated quaternary ammonium salt;
5-30% by weight of a viscosity control and gel-inhibit-ing agent selected from alkylene glycols and alkylene glycol mono alkyl ethers;
0-2.0% by weight of a phosphoric acid alkanol ester stabilizing agent;
0-5.0% by weight of an aluminum salt of a fatty acid stabilizing agent;
0-30% by weight of a bleaching agent;
0-15% by weight of a bleach activator;
0-3.0% by weight of a sequestering agent for metal ions;
0-5.0% by weight of an anti-redeposition agent;
0-2.0% of an optical brightener;
0-3.0% of enzymes;
0-3.0% of perfume;
0-0.10% of dye;
balance, one or more detergent adjuvants selected from the group consisting of corrosion inhibitors, anti-foam agents, suds suppressors, anti-yellowing agents, bluing agents, pH modifiers, pH buffers, bleach stabilizers and enzyme inhibitors. - 19. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with an effective cleaning agent of the laundry detergent composition of claim 1.
- 20. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with an effective cleaning amount of the laundry detergent composition of claim 14.
- 21. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with an effective cleaning amount of the laundry detergent composition of claim 17.
- 22. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with an effective cleaning amount of the laundry detergent composition of claim 18.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76756885A | 1985-08-20 | 1985-08-20 | |
| US767,568 | 1985-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1293905C true CA1293905C (en) | 1992-01-07 |
Family
ID=25079879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000516238A Expired - Lifetime CA1293905C (en) | 1985-08-20 | 1986-08-19 | Built nonaqueous liquid nonionic laundry detergent composition containing quaternary ammonium stabilizer and method of use |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS6270500A (en) |
| CA (1) | CA1293905C (en) |
| PH (1) | PH24181A (en) |
| TR (1) | TR27070A (en) |
| ZA (1) | ZA865751B (en) |
| ZM (1) | ZM6986A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11046915B2 (en) | 2018-12-21 | 2021-06-29 | Henkel IP & Holding GmbH | Use of polyglycols to control rheology of unit dose detergent compositions |
| US11118141B2 (en) | 2018-12-21 | 2021-09-14 | Henkel IP & Holding GmbH | Use of alkoxylated polyamines to control rheology of unit dose detergent compositions |
| US11242499B2 (en) | 2019-08-21 | 2022-02-08 | Henkel IP & Holding GmbH | Use of glycol ethers and alkyl alcohol blends to control surfactant composition rheology |
| US11306279B2 (en) | 2019-08-21 | 2022-04-19 | Henkel Ag & Co. Kgaa | Use of glycol ether to control rheology of unit dose detergent pack |
| US11414625B2 (en) | 2019-12-07 | 2022-08-16 | Henkel Ag & Co. Kgaa | Use of tertiary amines and alkyl alcohol blends to control surfactant composition rheology |
| US11629313B2 (en) | 2019-12-07 | 2023-04-18 | Henkel Ag & Co. Kgaa | Use of tertiary amine to control rheology of unit dose detergent pack |
| US11773261B2 (en) | 2019-08-21 | 2023-10-03 | Henkel Ag & Co. Kgaa | Use of poloxamers and alkyl alcohol blends to control surfactant composition rheology |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA974226B (en) * | 1996-05-17 | 1998-12-28 | Procter & Gamble | Detergent composition |
| JP7004537B2 (en) * | 2016-09-30 | 2022-01-21 | ライオン株式会社 | Particle dispersion detergent composition |
-
1986
- 1986-07-31 ZA ZA865751A patent/ZA865751B/en unknown
- 1986-08-06 ZM ZM6986A patent/ZM6986A1/en unknown
- 1986-08-12 PH PH34124A patent/PH24181A/en unknown
- 1986-08-19 CA CA000516238A patent/CA1293905C/en not_active Expired - Lifetime
- 1986-08-20 JP JP61195128A patent/JPS6270500A/en active Pending
- 1986-08-20 TR TR45386A patent/TR27070A/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11046915B2 (en) | 2018-12-21 | 2021-06-29 | Henkel IP & Holding GmbH | Use of polyglycols to control rheology of unit dose detergent compositions |
| US11118141B2 (en) | 2018-12-21 | 2021-09-14 | Henkel IP & Holding GmbH | Use of alkoxylated polyamines to control rheology of unit dose detergent compositions |
| US11242499B2 (en) | 2019-08-21 | 2022-02-08 | Henkel IP & Holding GmbH | Use of glycol ethers and alkyl alcohol blends to control surfactant composition rheology |
| US11306279B2 (en) | 2019-08-21 | 2022-04-19 | Henkel Ag & Co. Kgaa | Use of glycol ether to control rheology of unit dose detergent pack |
| US11773261B2 (en) | 2019-08-21 | 2023-10-03 | Henkel Ag & Co. Kgaa | Use of poloxamers and alkyl alcohol blends to control surfactant composition rheology |
| US11414625B2 (en) | 2019-12-07 | 2022-08-16 | Henkel Ag & Co. Kgaa | Use of tertiary amines and alkyl alcohol blends to control surfactant composition rheology |
| US11629313B2 (en) | 2019-12-07 | 2023-04-18 | Henkel Ag & Co. Kgaa | Use of tertiary amine to control rheology of unit dose detergent pack |
Also Published As
| Publication number | Publication date |
|---|---|
| ZM6986A1 (en) | 1988-04-29 |
| PH24181A (en) | 1990-03-22 |
| JPS6270500A (en) | 1987-03-31 |
| ZA865751B (en) | 1988-03-30 |
| TR27070A (en) | 1994-10-12 |
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