CA2148098C - Pseudoplastic and thixotropic cleaning compositions - Google Patents
Pseudoplastic and thixotropic cleaning compositions Download PDFInfo
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- CA2148098C CA2148098C CA002148098A CA2148098A CA2148098C CA 2148098 C CA2148098 C CA 2148098C CA 002148098 A CA002148098 A CA 002148098A CA 2148098 A CA2148098 A CA 2148098A CA 2148098 C CA2148098 C CA 2148098C
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Abstract
Cleaning compositions are disclosed which are pseudoplastic and thixotropic liquids. Such suitable compositions can be prepared in the form of aqueous emulsions of nonionic surfactants. A process for washing fabrics and surfaces is also disclosed as well as a package comprising said compositions in a squeezable container equipped with a nozzle.
Description
PSEUDOPLASTIC AND THIXOTROPIC CLEANING COMPOSITIONS
Technical Field The present invention relates to cleaning compositions, which are particularly suitable for the pretreatment of laundry or the cleaning of hard surfaces, especially inclined surfaces.
Background It is well known in the art that cleaning compositions may advantageously be more or less viscous. Indeed, viscous products do not run like thin liquids, and their use is therefore easier to control. Of course, this aspect is of a lesser importance when the product merely needs to be poured into a machine dispenser or a washing device, but it is critical when the dispensing of the product needs to be controlled, i.e. from a dispenser onto a precise area, say a fabric or a hard surface, where the product is to achieve an effect before it is eliminated. Typically such uses include laundry pretreatment and hard surface cleaning. In such uses, it is important that the product be thick enough so that it clings onto surfaces instead of freely spreading. This is even more critical for products which are to be used on inclined or even vertical surfaces such as bath tubs or toilet bowls.
However, such products also need to be easy to dispense from their container onto the surface. Thus the product also needs to be as thin as possible for an easy dispensing. This requirement is even more critical for products which are sold in containers which have a rather small dispensing orifice, and which are typically used for hard surface cleaners and particularly toilet bowl cleaners. Such small dispensing orifices are indeed needed to be able to dispense the product under the toilet rim.
This latter requirement for a thin product is clearly incompatible with the previous requirement hereinabove.
Furthermore, it is highly desirable that such products be easy to rinse off the surfaces once they have acted on them. This requirement also tends towards the formulation of a thin product, rather than thick.
Typically, manufacturers of such cleaning compositions have attempted to solve this incompatibility by adopting a middle term, i.e. formulating compositions which are thick enough to provide some cling onto surfaces, but thin enough to be more or less easily dispensed from their container, and rinsed off the surfaces on which they are used. This approach typically results in products for which neither ease of dispensing nor cling are optimum.
It is an object of the present invention to solve this major incompatibility and provide cleaning compositions which are very easy to dispense, which provide a strong cling onto the surfaces on which they are used, and which are easy to rinse off.
Technical Field The present invention relates to cleaning compositions, which are particularly suitable for the pretreatment of laundry or the cleaning of hard surfaces, especially inclined surfaces.
Background It is well known in the art that cleaning compositions may advantageously be more or less viscous. Indeed, viscous products do not run like thin liquids, and their use is therefore easier to control. Of course, this aspect is of a lesser importance when the product merely needs to be poured into a machine dispenser or a washing device, but it is critical when the dispensing of the product needs to be controlled, i.e. from a dispenser onto a precise area, say a fabric or a hard surface, where the product is to achieve an effect before it is eliminated. Typically such uses include laundry pretreatment and hard surface cleaning. In such uses, it is important that the product be thick enough so that it clings onto surfaces instead of freely spreading. This is even more critical for products which are to be used on inclined or even vertical surfaces such as bath tubs or toilet bowls.
However, such products also need to be easy to dispense from their container onto the surface. Thus the product also needs to be as thin as possible for an easy dispensing. This requirement is even more critical for products which are sold in containers which have a rather small dispensing orifice, and which are typically used for hard surface cleaners and particularly toilet bowl cleaners. Such small dispensing orifices are indeed needed to be able to dispense the product under the toilet rim.
This latter requirement for a thin product is clearly incompatible with the previous requirement hereinabove.
Furthermore, it is highly desirable that such products be easy to rinse off the surfaces once they have acted on them. This requirement also tends towards the formulation of a thin product, rather than thick.
Typically, manufacturers of such cleaning compositions have attempted to solve this incompatibility by adopting a middle term, i.e. formulating compositions which are thick enough to provide some cling onto surfaces, but thin enough to be more or less easily dispensed from their container, and rinsed off the surfaces on which they are used. This approach typically results in products for which neither ease of dispensing nor cling are optimum.
It is an object of the present invention to solve this major incompatibility and provide cleaning compositions which are very easy to dispense, which provide a strong cling onto the surfaces on which they are used, and which are easy to rinse off.
Summary of the invention We have now found that this object is achieved by formulating a pseudoplastic and thixotropic aqueous composition comprising a detergent system, said composition being in the form of an emulsion comprising at least two nonionic surfactants, said composition being formulated at pH of from about 0 to about 6, said composition having a viscosity of from about 60 cps to about 1500 cps at 12 rpm, from about 40 cps to about 800 cps at 30 rpm, and from about 20 cps to about 500 cps at 60 rpm.
The present invention further encompasses said compositions contained in a squeezable container equipped with a dispensing nozzle.
The present invention also encompasses a process of treating fabrics and surfaces, where said compositions are used.
Detailed Description of the Invention v y In its broadest aspect, the invention encompasses cleaning compositions which are pseudoplastic and thixotropic. By pseudoplastic, it is meant herein a composition which has different viscosities when different shear stresses are applied within the limits claimed herein. Different shear stresses can be applied to a given composition for instance by varying the shear rate e.g. the rotation speed of the spindle of a rotational viscometer. Unless otherwise specified, all viscosities herein are measured with a Brookfield DV II
rotational viscometer, with spindle No. 2 at 20°C. Typically, when running viscosity measurements on pseudoplastic liquids with a rotational viscometer, some fluctuation may occur in the viscosity readings at the beginning of the measurement. After a while, these fluctuations dampen and the viscosity reading becomes stable. At this stage, the system has reached its equilibrium viscosity value. The time needed to reach the 21~80~~ 4 equilibrium viscosity value increases with the viscosity of the system. The equilibrium viscosity value stays substantially constant for a period of from 5 to 30 minutes. Unless otherwise specified, all viscosities herein are equilibrium viscosity values.
The compositions herein are furthermore thixotropic, i.e.
after having reached equilibrium viscosity, which is typically maintained for a period ranging from 5 to 30 minutes, the viscosity starts to decrease and eventually reaches a second equilibrium value, lower than the first one.
The compositions according to the present invention, which comprise a detergent system, have a viscosity of from 60 cps to 1500 cps at 12 rpm, from 40 cps to 800 cps at 30 rpm, and from 2o cps to 500 cps at 60 rpm. In a preferred embodiment, the compositions herein have a viscosity of from 400 cps to 600 cps, most preferably 450 cps to 550 cps at 12 rpm, from 200 cps to 350 cps, most preferably from 300 cps to 350 cps at 30 rpm, and from 100 cps to 250 cps, most preferably from 150 cps to 250 cps at 60 rpm. The ranges mentioned hereinabove for different shear rates overlap, but it is to be undertsood that for any given composition, the viscosity at 12 rpm will be higher than the viscosity at 30 rpm which, in turn, is higher than the viscosity at 60 rpm. The preferred compositions herein have a viscosity difference between 12 rpm and 30 rpm of at least 20 cps, preferably 300-100 cps, and a viscosity difference between 30 rpm and 60 rpm of at least lOcps, preferably 30-80 cps.
According to the viscosity profiles hereinabove, the compositions according to the present invention have a higher viscosity at lower shear stresses and a lower viscosity at higher shear stresses. Such a viscosity profile allows firstly an easy and precise control of the ~.
, dispensing of the composition. Indeed, as the composition is dispensed from its container, a high shear stress is applied which contributes to decreasing the viscosity of the composition. Thus the composition according to the present invention has a lower viscosity as it is dispensed.
During the dispensing step, a higher shear stress can be applied by using squeezable containers equipped with dispensing nozzles having a smaller orifice. Indeed, in such containers, the composition is forced out of the container and a higher shear stress is applied than if the product was simply poured from the container. Accordingly, the present invention further encompasses a package comprising a composition as described herein, packaged in a squeezable container equipped with a dispensing nozzle. By squeezable container equipped with a dispensing.nozzle, it is meant herein a container wherein substantially no dispensing of the composition occurs unless said composition is squeezed out of said container. Squeezable containers are well known and are commonly used to package toilet bowl cleaning compositions and other hard surface cleaning compositions.
Once the composition has been dispensed onto a surface, no shear stress is applied anymore, .apart from a weak stress caused by gravity, and the viscosity of the composition raises. Thus the composition according to the present invention has a higher viscosity once it has been dispensed onto a surface. Accordingly, the composition is prevented from overly spreading on said surfaces, and running down said surfaces too quickly when said surfaces are inclined or even vertical. In addition, as the composition is rinsed or removed, a shear stress is applied which further reduces the viscosity of the composition, thus further easing its removal or rinsing.
Furthermore, the compositions according to the present invention are thixotropic. Accordingly, the compositions according to the present invention show a viscosity decrease of up to 60% at a constant shear rate (rotational speed), preferably from 5% to 50%, most preferably from 10%
to 40%. These percentages refer to the difference between the first and second equilibrium values. This thixotropic behavior allows the viscosity of the composition of the invention to decrease with time once it has been dispensed onto the surface where it acts, contributing to an even spreading of the composition on the surface. Furthermore, this thixotropic behavior contributes to a composition which is easier to remove or rinse off said surface.
The compositions according to the present_invention can be suitably prepared in the form of an aqueous matrix comprising an emulsion of at least two, preferably only two, nonionic surfactants. Said two nonionic surfactants must have different HLB values, and preferably the difference in value of the HLBs of said two surfactants is of at least 3, preferably at least 6.5.
Suitable nonionic surfactants for preparing compositions according to the present invention are alkoxylated alcohol nonionic surfactants which are well known in the art. By varying the chain length of the alcohol and the degree of alkoxylation, a multitude of nonionic surfactants can be obtained with a great variety of different HLBs.
Appropriately combining at least two of said nonionic surfactants, with different HLBs, in water allows to form the desired emulsion.
Such alkoxylated alcohols can be readily made by condensation processes which are well known in the art, but a great variety of such alkoxylated alcohols, especially ethoxylated and/or propoxylated alcohols is also conveniently commercially available. Surfactants catalogs are available which list a number of surfactant, including nonionics, together with their respective HLB values.
Accordingly, preferred alkoxylated alcohols for use herein are nonionic surfactants according to the formula RO(E)e(P)pH where R is a hydrocarbon chain of from 6 to 20 carbon atoms, E is ethylene oxide and P is propylene oxide, and a and p which represent the average degree of, respectively ethoxylation and propoxylation, are of from 0 to 60.
To obtain an emulsion according to the present invention, i.e. with the desired viscosity profile, it is typically required to use from 4% to 30% by weight of the total composition of said nonionic surfactants, preferably from 6% to 15%. The hydrophobic nonionic surfactant (HLB
typically from 6 to 10) should represent from 70% to 90% of the total surfactant amount, preferably from 75% to 85%.
In a preferred embodiment, however,' at least one said alkoxylated alcohols herein has an R group in the formula above which has a hydrocarbon chain with only from 8 to 13 carbon atoms, preferably from 8 to 11. The advantage of using such short chain nonionic surfactants is that a pseudoplastic and thixotropic emulsion according to the present invention can be achieved with a lower total amount of surfactant, compared to the same system using longer chain nonionic surfactants. Accordingly, when such short chain nonionic surfactants are used, the compositions according to the present invention need only comprise from 2% to 9% by weight of the total composition, preferably' from 3% to 6% by weight of the total composition of said short chain nonionic surfactants.
For appropriate physical stability, emulsions according to the present invention need to be formulated at a pH of from 0 to 6, preferably 0.5 to 4. The pH of the .emulsions 2148U9~
according to the present invention can be trimmed by all means available to the man skilled in the art. The pH of the emulsion can be trimmed by appropriate organic or inorganic acids which physically stabilize the emulsion and may build up viscosity. A preferred such acid for use herein is citric acid, typically from 1% to 20% by weight of the total composition.
Emulsions according to the present invention typically comprise from 10 % to 95 % by weight of the total composition of water, preferably from 70% to 85%.
Preferably deionized water is used.
Depending on the end use envisioned, emulsions according to the present invention may further comprise a variety of other ingredients including other surfactants of all types, bleaching agents, bleach activators, organic or inorganic alkalis, enzymes, builders, chelants, optical brighteners, dye transfer inhibiting agents, perfumes and dyes.
The compositions according to the present invention are particularly useful as laundry pretreaters, i.e.
compositions which are dispensed and left to act onto fabrics before they are washed, or as hard surface cleaners. Compositions according to the present invention find a preferred application in the, cleaning of inclined or vertical surfaces, particularly bath tubs and toilet bowls.
Accordingly, the present.invention further encompasses a process of treating fabrics or surfaces wherein a pseudoplastic and thixotropic cleaning composition as hereinbefore defined, i.e. comprising a detergent system and having a viscosity of from 60 cps to 1500 cps at 12 rpm, from 40 cps to 800 cps at 30 rpm, and from 20 cps to 500 cps at 60 rpm is dispensed from a container onto said fabrics or surfaces, then left to act onto said fabric or surface, then removed by rinsing.
WO 94/11474 ~ PCT/US93/10431 As used in the foregoing paragraph, the expression "treating" includes washing as the compositions according to the present invention comprise surfactants, but it is not exclusive, i.e. other treatments may be performed concurrently such as bleaching and/or disinfecting.
The present invention is further illustrated by the following examples.
Examples The following compositions are made by mixing the listed ingredients in the listed proportions. The compositions obtained have a viscosity profile as specified.
Example 1:
Dobanol~ 23-3 (R=C12-C13; e=3, p=0) 7.2%
Dobanol@ 45-7 (R=C14-C15; e=7, p=0) 1.8%
Hydrogen peroxide 6.0%
citric acid 6.0%
water and minors up to 100%
pH=1 Viscosity: 8o cps at 12 rpm;
55 cps at 30 rpm;
30 cps at 60 rpm.
Example 2:
Dobanol@ 23-3 7.2%
Dobanol@ 91-10 (R=C9-C11, e=10, p=0) 1.8%
Hydrogen peroxide 6.0%
citric acid 6.0%
Water and minors up to 100%
pH=1 WO 94/11474 ~ ~~ ~ ~~ PCT/US93/10431 viscosity: 430 cps at 12 rpm;
225 cps at 30 rpm;
125 cps at 60 rpm.
Example 3:
Dobanol@ 23-3 7.2%
C8E04 (R=C8, e=4, p=0) 1.8%
Hydrogen peroxide 6.0%
Citric acid 6.0%
Water and minors up to 100%
pH=1 Viscosity: 1200 cps at 12 rpm 680 cps at 30 rpm 470 cps at 60 rpm Example 4:
Dobanol@ 23-3 4.8%
C8 E04 1. 2 %
Hydrogen peroxide 6.0%
citric acid 6.0%
water and minors up to 100%
pH=1 viscosity: 470 cps at 12 rpm 300 cps at 30 rpm 234 cps at 60 rpm Example 5:
Dobanol@ 91-2.5 (R=C9-C11, e=2.5, p=0) 4.8%
Dobanol@ 91-10 1.2%
citric acid 6.0%
Water and minors up to 100%
pH=1 ~14~3U98 -Viscosity: 480 cps at 12 rpm 290 cps at 30 rpm 190 cps at 60 rpm Example 6:
Dobanol@ 91-2.5 4.8%
Dobanol@ 91-10 1.2%
Citric acid 6.0%
Hydrogen peroxide 6.0%
Water and minors up to 100%
pH=2.5 Viscosity: 1020 cps at 12 rpm 400 cps at 30 rpm 220 cps at 60 rpm Example 7:
Dobanol@ 91-2.5 48%
Dobanol@ 91-10 1.2%
Citric acid 2.0%
Hydrogen peroxide 6.0%
Water and minors up to 100%
pH=1 Viscosity: 332 cps at 12 rpm;
187 cps at 30 rpm;
13o cps at 60 rpm.
All compositions in the preceding examples are thixotropic, in that viscosities drop from 10% to 40% at constant rpm.
The present invention further encompasses said compositions contained in a squeezable container equipped with a dispensing nozzle.
The present invention also encompasses a process of treating fabrics and surfaces, where said compositions are used.
Detailed Description of the Invention v y In its broadest aspect, the invention encompasses cleaning compositions which are pseudoplastic and thixotropic. By pseudoplastic, it is meant herein a composition which has different viscosities when different shear stresses are applied within the limits claimed herein. Different shear stresses can be applied to a given composition for instance by varying the shear rate e.g. the rotation speed of the spindle of a rotational viscometer. Unless otherwise specified, all viscosities herein are measured with a Brookfield DV II
rotational viscometer, with spindle No. 2 at 20°C. Typically, when running viscosity measurements on pseudoplastic liquids with a rotational viscometer, some fluctuation may occur in the viscosity readings at the beginning of the measurement. After a while, these fluctuations dampen and the viscosity reading becomes stable. At this stage, the system has reached its equilibrium viscosity value. The time needed to reach the 21~80~~ 4 equilibrium viscosity value increases with the viscosity of the system. The equilibrium viscosity value stays substantially constant for a period of from 5 to 30 minutes. Unless otherwise specified, all viscosities herein are equilibrium viscosity values.
The compositions herein are furthermore thixotropic, i.e.
after having reached equilibrium viscosity, which is typically maintained for a period ranging from 5 to 30 minutes, the viscosity starts to decrease and eventually reaches a second equilibrium value, lower than the first one.
The compositions according to the present invention, which comprise a detergent system, have a viscosity of from 60 cps to 1500 cps at 12 rpm, from 40 cps to 800 cps at 30 rpm, and from 2o cps to 500 cps at 60 rpm. In a preferred embodiment, the compositions herein have a viscosity of from 400 cps to 600 cps, most preferably 450 cps to 550 cps at 12 rpm, from 200 cps to 350 cps, most preferably from 300 cps to 350 cps at 30 rpm, and from 100 cps to 250 cps, most preferably from 150 cps to 250 cps at 60 rpm. The ranges mentioned hereinabove for different shear rates overlap, but it is to be undertsood that for any given composition, the viscosity at 12 rpm will be higher than the viscosity at 30 rpm which, in turn, is higher than the viscosity at 60 rpm. The preferred compositions herein have a viscosity difference between 12 rpm and 30 rpm of at least 20 cps, preferably 300-100 cps, and a viscosity difference between 30 rpm and 60 rpm of at least lOcps, preferably 30-80 cps.
According to the viscosity profiles hereinabove, the compositions according to the present invention have a higher viscosity at lower shear stresses and a lower viscosity at higher shear stresses. Such a viscosity profile allows firstly an easy and precise control of the ~.
, dispensing of the composition. Indeed, as the composition is dispensed from its container, a high shear stress is applied which contributes to decreasing the viscosity of the composition. Thus the composition according to the present invention has a lower viscosity as it is dispensed.
During the dispensing step, a higher shear stress can be applied by using squeezable containers equipped with dispensing nozzles having a smaller orifice. Indeed, in such containers, the composition is forced out of the container and a higher shear stress is applied than if the product was simply poured from the container. Accordingly, the present invention further encompasses a package comprising a composition as described herein, packaged in a squeezable container equipped with a dispensing nozzle. By squeezable container equipped with a dispensing.nozzle, it is meant herein a container wherein substantially no dispensing of the composition occurs unless said composition is squeezed out of said container. Squeezable containers are well known and are commonly used to package toilet bowl cleaning compositions and other hard surface cleaning compositions.
Once the composition has been dispensed onto a surface, no shear stress is applied anymore, .apart from a weak stress caused by gravity, and the viscosity of the composition raises. Thus the composition according to the present invention has a higher viscosity once it has been dispensed onto a surface. Accordingly, the composition is prevented from overly spreading on said surfaces, and running down said surfaces too quickly when said surfaces are inclined or even vertical. In addition, as the composition is rinsed or removed, a shear stress is applied which further reduces the viscosity of the composition, thus further easing its removal or rinsing.
Furthermore, the compositions according to the present invention are thixotropic. Accordingly, the compositions according to the present invention show a viscosity decrease of up to 60% at a constant shear rate (rotational speed), preferably from 5% to 50%, most preferably from 10%
to 40%. These percentages refer to the difference between the first and second equilibrium values. This thixotropic behavior allows the viscosity of the composition of the invention to decrease with time once it has been dispensed onto the surface where it acts, contributing to an even spreading of the composition on the surface. Furthermore, this thixotropic behavior contributes to a composition which is easier to remove or rinse off said surface.
The compositions according to the present_invention can be suitably prepared in the form of an aqueous matrix comprising an emulsion of at least two, preferably only two, nonionic surfactants. Said two nonionic surfactants must have different HLB values, and preferably the difference in value of the HLBs of said two surfactants is of at least 3, preferably at least 6.5.
Suitable nonionic surfactants for preparing compositions according to the present invention are alkoxylated alcohol nonionic surfactants which are well known in the art. By varying the chain length of the alcohol and the degree of alkoxylation, a multitude of nonionic surfactants can be obtained with a great variety of different HLBs.
Appropriately combining at least two of said nonionic surfactants, with different HLBs, in water allows to form the desired emulsion.
Such alkoxylated alcohols can be readily made by condensation processes which are well known in the art, but a great variety of such alkoxylated alcohols, especially ethoxylated and/or propoxylated alcohols is also conveniently commercially available. Surfactants catalogs are available which list a number of surfactant, including nonionics, together with their respective HLB values.
Accordingly, preferred alkoxylated alcohols for use herein are nonionic surfactants according to the formula RO(E)e(P)pH where R is a hydrocarbon chain of from 6 to 20 carbon atoms, E is ethylene oxide and P is propylene oxide, and a and p which represent the average degree of, respectively ethoxylation and propoxylation, are of from 0 to 60.
To obtain an emulsion according to the present invention, i.e. with the desired viscosity profile, it is typically required to use from 4% to 30% by weight of the total composition of said nonionic surfactants, preferably from 6% to 15%. The hydrophobic nonionic surfactant (HLB
typically from 6 to 10) should represent from 70% to 90% of the total surfactant amount, preferably from 75% to 85%.
In a preferred embodiment, however,' at least one said alkoxylated alcohols herein has an R group in the formula above which has a hydrocarbon chain with only from 8 to 13 carbon atoms, preferably from 8 to 11. The advantage of using such short chain nonionic surfactants is that a pseudoplastic and thixotropic emulsion according to the present invention can be achieved with a lower total amount of surfactant, compared to the same system using longer chain nonionic surfactants. Accordingly, when such short chain nonionic surfactants are used, the compositions according to the present invention need only comprise from 2% to 9% by weight of the total composition, preferably' from 3% to 6% by weight of the total composition of said short chain nonionic surfactants.
For appropriate physical stability, emulsions according to the present invention need to be formulated at a pH of from 0 to 6, preferably 0.5 to 4. The pH of the .emulsions 2148U9~
according to the present invention can be trimmed by all means available to the man skilled in the art. The pH of the emulsion can be trimmed by appropriate organic or inorganic acids which physically stabilize the emulsion and may build up viscosity. A preferred such acid for use herein is citric acid, typically from 1% to 20% by weight of the total composition.
Emulsions according to the present invention typically comprise from 10 % to 95 % by weight of the total composition of water, preferably from 70% to 85%.
Preferably deionized water is used.
Depending on the end use envisioned, emulsions according to the present invention may further comprise a variety of other ingredients including other surfactants of all types, bleaching agents, bleach activators, organic or inorganic alkalis, enzymes, builders, chelants, optical brighteners, dye transfer inhibiting agents, perfumes and dyes.
The compositions according to the present invention are particularly useful as laundry pretreaters, i.e.
compositions which are dispensed and left to act onto fabrics before they are washed, or as hard surface cleaners. Compositions according to the present invention find a preferred application in the, cleaning of inclined or vertical surfaces, particularly bath tubs and toilet bowls.
Accordingly, the present.invention further encompasses a process of treating fabrics or surfaces wherein a pseudoplastic and thixotropic cleaning composition as hereinbefore defined, i.e. comprising a detergent system and having a viscosity of from 60 cps to 1500 cps at 12 rpm, from 40 cps to 800 cps at 30 rpm, and from 20 cps to 500 cps at 60 rpm is dispensed from a container onto said fabrics or surfaces, then left to act onto said fabric or surface, then removed by rinsing.
WO 94/11474 ~ PCT/US93/10431 As used in the foregoing paragraph, the expression "treating" includes washing as the compositions according to the present invention comprise surfactants, but it is not exclusive, i.e. other treatments may be performed concurrently such as bleaching and/or disinfecting.
The present invention is further illustrated by the following examples.
Examples The following compositions are made by mixing the listed ingredients in the listed proportions. The compositions obtained have a viscosity profile as specified.
Example 1:
Dobanol~ 23-3 (R=C12-C13; e=3, p=0) 7.2%
Dobanol@ 45-7 (R=C14-C15; e=7, p=0) 1.8%
Hydrogen peroxide 6.0%
citric acid 6.0%
water and minors up to 100%
pH=1 Viscosity: 8o cps at 12 rpm;
55 cps at 30 rpm;
30 cps at 60 rpm.
Example 2:
Dobanol@ 23-3 7.2%
Dobanol@ 91-10 (R=C9-C11, e=10, p=0) 1.8%
Hydrogen peroxide 6.0%
citric acid 6.0%
Water and minors up to 100%
pH=1 WO 94/11474 ~ ~~ ~ ~~ PCT/US93/10431 viscosity: 430 cps at 12 rpm;
225 cps at 30 rpm;
125 cps at 60 rpm.
Example 3:
Dobanol@ 23-3 7.2%
C8E04 (R=C8, e=4, p=0) 1.8%
Hydrogen peroxide 6.0%
Citric acid 6.0%
Water and minors up to 100%
pH=1 Viscosity: 1200 cps at 12 rpm 680 cps at 30 rpm 470 cps at 60 rpm Example 4:
Dobanol@ 23-3 4.8%
C8 E04 1. 2 %
Hydrogen peroxide 6.0%
citric acid 6.0%
water and minors up to 100%
pH=1 viscosity: 470 cps at 12 rpm 300 cps at 30 rpm 234 cps at 60 rpm Example 5:
Dobanol@ 91-2.5 (R=C9-C11, e=2.5, p=0) 4.8%
Dobanol@ 91-10 1.2%
citric acid 6.0%
Water and minors up to 100%
pH=1 ~14~3U98 -Viscosity: 480 cps at 12 rpm 290 cps at 30 rpm 190 cps at 60 rpm Example 6:
Dobanol@ 91-2.5 4.8%
Dobanol@ 91-10 1.2%
Citric acid 6.0%
Hydrogen peroxide 6.0%
Water and minors up to 100%
pH=2.5 Viscosity: 1020 cps at 12 rpm 400 cps at 30 rpm 220 cps at 60 rpm Example 7:
Dobanol@ 91-2.5 48%
Dobanol@ 91-10 1.2%
Citric acid 2.0%
Hydrogen peroxide 6.0%
Water and minors up to 100%
pH=1 Viscosity: 332 cps at 12 rpm;
187 cps at 30 rpm;
13o cps at 60 rpm.
All compositions in the preceding examples are thixotropic, in that viscosities drop from 10% to 40% at constant rpm.
Claims (20)
1. A pseudoplastic and thixotropic aqueous composition comprising a detergent system, said composition being in the form of an emulsion comprising at least two nonionic surfactants, said composition being formulated at pH of from about 0 to about 6, said composition having a viscosity of from about 60 cps to about 1500 cps at 12 rpm, from about 40 cps to about 800 cps at 30 rpm, and from about 20 cps to about 500 cps at 60 rpm.
2. A composition according to claim 1, said composition having a viscosity of from about 400 cps to about 600 cps at 12 rpm, from about 200 cps to about 350 cps at 30 rpm, and from about 100 cps to about 250 cps at 60 rpm.
3. A composition according to claim 2, said composition having a viscosity of from about 450 cps to about 550 cps at 12 rpm, from about 300 cps to about 350 cps at 30 rpm, and from about 150 cps to about 250 cps at 60 rpm.
4. A composition according to claim 1 wherein the viscosity between the first and second equilibrium values decreases up to about 60o at constant rpm.
5. A composition according to claim 4 wherein the viscosity between the first and second equilibrium values decreases up to from about 10% to about 40% at constant rpm.
6. A composition according to claim 1 wherein the viscosity difference between 12 rpm and 30 rpm is of at least about 20 cps.
7. A composition according to claim 6 wherein the viscosity difference between 12 rpm and 30 rpm is about 300-100 cps.
8. A composition according to claim 1 wherein the viscosity difference between 30 rpm and 60 rpm is of at least about cps.
9. A composition according to claim 8 wherein the viscosity difference between 30 rpm and 60 rpm is about 30-80 cps.
10. A composition according to claim 1 which comprises from about 1% to about 20% by weight of the total composition of citric acid.
11. A composition according to claim 1 which has a pH of from about 0.5 to about 4.
12. A composition according to claim 1 wherein said nonionic surfactants are alkoxylated alcohols of the formula RO(E)e(P)pH where R is a hydrocarbon chain of from about 6 to about 20 carbon atoms, E is ethylene oxide and P is propylene oxide, and a and p which represent the average degree of, respectively ethoxylation and propoxylation, are of from about 0 to about 60.
13. A composition according to claim 12 which comprises from about 4% to about 30% by weight of the total composition of said alkoxylated alcohol nonionic surfactants.
14. A composition according to claim 12 wherein at least one of said alkoxylated alcohol nonionic surfactants has an R
group which is a hydrocarbon chain of from about 8 to about 13 carbon atoms.
group which is a hydrocarbon chain of from about 8 to about 13 carbon atoms.
15. A composition according to claim 14 wherein both of said two alkoxylated alcohol nonionic surfactants have a R group which is hydrocarbon chain of from about 8 to about 13 carbon atoms.
16. A composition according to claims 14 or 15 wherein said nonionic surfactants represent from about 2% to about 9%
by weight of the total composition.
by weight of the total composition.
17. A composition according to claim 16 wherein said nonionic surfactants represent from about 3% to about 6% by weight of the total composition.
18. A process of treating fabrics or surfaces wherein a composition according to claim 1 is dispensed from a container onto said fabrics or surfaces, then left to act onto said fabric or surface, then removed by rinsing.
19. A package comprising a composition according to claim any one of claims 1-15 or 17 or 18 packaged in a squeezable container equipped with a dispensing nozzle.
20. A package comprising a composition according to claim 16 packaged in a squeezable container equipped with a dispensing nozzle.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92870188A EP0598170B1 (en) | 1992-11-16 | 1992-11-16 | Cleaning and bleaching compositions |
| EP92870188.7 | 1992-11-16 | ||
| EP93870091.1 | 1993-06-01 | ||
| EP93870091A EP0598692A1 (en) | 1992-11-16 | 1993-06-01 | Pseudoplastic and thixotropic cleaning compositions |
| PCT/US1993/010431 WO1994011474A1 (en) | 1992-11-16 | 1993-10-29 | Pseudoplastic and thixotropic cleaning compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2148098A1 CA2148098A1 (en) | 1994-05-26 |
| CA2148098C true CA2148098C (en) | 2000-08-01 |
Family
ID=26132641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002148098A Expired - Fee Related CA2148098C (en) | 1992-11-16 | 1993-10-29 | Pseudoplastic and thixotropic cleaning compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0598692A1 (en) |
| JP (1) | JPH08503244A (en) |
| BR (1) | BR9307291A (en) |
| CA (1) | CA2148098C (en) |
| WO (1) | WO1994011474A1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5902354A (en) * | 1994-04-12 | 1999-05-11 | The Procter & Gamble Company | Bleaching compositions |
| ATE191002T1 (en) * | 1994-06-17 | 2000-04-15 | Procter & Gamble | BLEACHING AGENT COMPOSITIONS |
| GB9425882D0 (en) * | 1994-12-21 | 1995-02-22 | Solvay Interox Ltd | Thickened peracid compositions |
| EP0742279A1 (en) * | 1995-05-10 | 1996-11-13 | The Procter & Gamble Company | Acidic aqueous liquid compositions |
| EP0745663A1 (en) * | 1995-05-31 | 1996-12-04 | The Procter & Gamble Company | Colored acidic aqueous liquid compositions comprising a peroxy-bleach |
| DE69528179T2 (en) * | 1995-12-02 | 2003-04-30 | Procter & Gamble | Liquid bleach compositions packaged in a spray dispenser and a process for pretreating fabrics therewith |
| CA2219653C (en) * | 1996-10-29 | 2001-12-25 | The Procter & Gamble Company | Non-foaming liquid hard surface detergent compositions |
| AU6255098A (en) * | 1998-01-29 | 1999-08-16 | Procter & Gamble Company, The | Method for cleaning dentures |
| US6013295A (en) | 1998-03-06 | 2000-01-11 | Townsend Engineering Company | Method for linking coextruded foodstuff |
| ATE291076T1 (en) * | 1999-01-26 | 2005-04-15 | Procter & Gamble | BLEACHING AGENT COMPOSITION CONTAINING ESSENTIALLY LINEAR NON-IONIC SURFACTANTS |
| US6620774B1 (en) | 1999-01-26 | 2003-09-16 | The Procter & Gamble Company | Bleaching composition comprising substantially linear nonionic surfactants |
| US6905276B2 (en) * | 2003-04-09 | 2005-06-14 | The Clorox Company | Method and device for delivery and confinement of surface cleaning composition |
| US9895526B2 (en) | 2006-03-08 | 2018-02-20 | Ivaxis, Llc | Anti-contamination cover for fluid connections |
| US7781388B2 (en) | 2006-05-04 | 2010-08-24 | American Sterilizer Company | Cleaning compositions for hard to remove organic material |
| US7780794B2 (en) | 2006-07-21 | 2010-08-24 | Ivera Medical Corporation | Medical implement cleaning device |
| US9259284B2 (en) | 2007-02-12 | 2016-02-16 | 3M Innovative Properties Company | Female Luer connector disinfecting cap |
| JP5980954B2 (en) * | 2012-01-18 | 2016-08-31 | ザ プロクター アンド ギャンブル カンパニー | Acid laundry detergent composition |
| US9999471B2 (en) | 2012-06-04 | 2018-06-19 | 3M Innovative Properties Company | Male medical implement cleaning device |
| US9907617B2 (en) | 2013-03-15 | 2018-03-06 | 3M Innovative Properties Company | Medical implement cleaning device |
| JP6913781B1 (en) * | 2020-03-17 | 2021-08-04 | 豊田市 | Cleaning equipment and cleaning method of the object to be cleaned |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2085009A5 (en) * | 1970-03-24 | 1971-12-17 | Ciba Geigy Ag | Thixotropic suspensions prepn |
| BE789446A (en) * | 1971-10-02 | 1973-03-29 | Ciba Geigy | TREATMENT OF OPTICAL BRIGHTENERS OF THE TRIAZOLYL-STILBENE TYPE THAT CAN BE INCORPORATED IN DETERGENTS |
| GB2134132A (en) * | 1983-01-14 | 1984-08-08 | Unilever Plc | Vehicle cleaning compositions |
| US4648987A (en) * | 1985-02-13 | 1987-03-10 | The Clorox Company | Thickened aqueous prewash composition |
| US4743395A (en) * | 1986-09-12 | 1988-05-10 | The Drackett Company | Thickened acid cleaner compositions containing quaternary ammonium germicides and having improved thermal stability |
| DE3635535C2 (en) * | 1986-10-18 | 1995-05-18 | Henkel Kgaa | Pre-treatment or soaking agent for stubbornly soiled dishes and method for cleaning such dishes |
| US4900469A (en) * | 1986-10-21 | 1990-02-13 | The Clorox Company | Thickened peracid precursor compositions |
| DE3815291A1 (en) * | 1988-05-05 | 1989-11-23 | Basf Ag | WAFER ACID CLEANSER FORMULATIONS |
-
1993
- 1993-06-01 EP EP93870091A patent/EP0598692A1/en not_active Withdrawn
- 1993-10-29 WO PCT/US1993/010431 patent/WO1994011474A1/en active Application Filing
- 1993-10-29 CA CA002148098A patent/CA2148098C/en not_active Expired - Fee Related
- 1993-10-29 JP JP6512133A patent/JPH08503244A/en active Pending
- 1993-10-29 BR BR9307291A patent/BR9307291A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08503244A (en) | 1996-04-09 |
| EP0598692A1 (en) | 1994-05-25 |
| BR9307291A (en) | 1999-06-01 |
| WO1994011474A1 (en) | 1994-05-26 |
| CA2148098A1 (en) | 1994-05-26 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |