CA1158521A - Hard surface cleaning compositions - Google Patents
Hard surface cleaning compositionsInfo
- Publication number
- CA1158521A CA1158521A CA000368277A CA368277A CA1158521A CA 1158521 A CA1158521 A CA 1158521A CA 000368277 A CA000368277 A CA 000368277A CA 368277 A CA368277 A CA 368277A CA 1158521 A CA1158521 A CA 1158521A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- surfactant
- fluorinated hydrocarbon
- boiling point
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/004—Surface-active compounds containing F
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
Abstract
Abstract:
A composition for cleaning a wide variety of hard surfaces in a no rinse mode, comprised of a mixture of organic solvents at least one having a low boiling point and at least one having a relatively higher boiling point, an alkali-metal polyphosphate, fugitive alkaline material, a first surfactant which is a nonionic or anionic surfactant, a second surfactant which is a fluorinated hydrocarbon anionic or nonionic surfactant, and water.
A composition for cleaning a wide variety of hard surfaces in a no rinse mode, comprised of a mixture of organic solvents at least one having a low boiling point and at least one having a relatively higher boiling point, an alkali-metal polyphosphate, fugitive alkaline material, a first surfactant which is a nonionic or anionic surfactant, a second surfactant which is a fluorinated hydrocarbon anionic or nonionic surfactant, and water.
Description
~585Zl HARD SURFACE CLEANING
COMPOSITIONS
:.
I.Description:
BACKG~OUND OF THE INVENTION
This invention relates to liquid compositions for cleaning a wide variety of hard surfaces such as metal-; lic, plastic, tile, porcelain, glass and mirrored sur-faces. More specifically this invention relates to hard , surface cleaners which can be used in a no rinse mode whereby the composition is brought into contact with the surface to be cleaned and then removed therefrom by wiping the surface with a dry cloth.
In the past compositions for cleaning hard surfaces in a no rinse mode have been formulated specifically, as either glass and mirrored surface cleaners, or as general r' hard surface cleaners for cleaning a variety of surfaces other than glass or mirrored surfaces. As formulated these prior art cleaners could not be used interchange-ably. One reason for this is that the general hard sur-face cleaners, in order to be effective in removing a wide variety of soils contained rather large quantities of nonvolatile ingredients such as surfactants and builders. Due to the high content of these nonvolatile ingredients the general hard surface cleaners tended to smear or streak glass or mirrored surfaces. Conversely when a glass or mirror cleaner was used on hard surfaces f~ such as tile, metal, or porcelain, incomplete cleaning of soils such as grease resulted due to the low content of the nonvolatile ingredients in these cleaners.
"
An example of prior art compositions which were formulated primarily for cleaning glass and mirrored surfaces are those described in U.S. Pat. No. 3,463,735 ~58521 to Stonebreaker et al. These compositions contain rela-tively minor amounts of nonvolatile ingredients, a sur-factant and a builder, along with a mixture of volatile ingredients, a combination of solvents, ammonia and water. Applicant has surprisingly found that by adding as little as 0.011% by weight of a fluorinated hydrocar-bon surfactant and by adjusting the levels of the vola-tile materials in the Stonebreaker et al. compositions, a composition is achieved which is capable of function-ing equally well as both a glass and mirror cleaner andas a general hard surface cleaner.
.
SUMMARY OF THE INVENTION
Accordingly it is an object of this invention to provide a hard surface cleaner which is equally effec-tive on all types of hard surfaces or porcelain, tile, or metallic surfaces, which is capable of effectively removing a wide variety of soils, and which will not smear or leave a film on glass or mirrored surfaces. It is yet a further object of the present invention to pro-vide such a cleaning composition which can be used in a no rinse mode by applying the composition to a surface, which is to be cleaned, and then wiping it dry with a cloth. The soils on the surface are removed when the surface is wiped dry.
:
The compositions of this invention are comprised of the following ingredients (where the percentage amounts ' 30 recited below and throughout the application are on a weight basis): -a) from about 1.85% to about 10.00% of at least one lower aliphatic monohydric alcohol having a boiling point within the range of from about 75C to about 100C;
b) from about 1.15% to about 10.00% of at least one lower alkylene or polyalkylene glycol or lower alkyl 2a .
1158SZl ether thereof, having a boiling point of between about 120C to about 250C;
~ c) from about 0.1% to about 2.5% of a first surfac-: tant which is a nonionic or anionic surfactant;
~' 5 d) from about 0.011% to about 5.000% of a second surfactant which is a nonionic or anionic fluorinated hydrocarbon surfactant;
e) from about 0.02% to about 2.00% of an alkali-metal polyphosphate;
.l 10 f) from about 0.15~ to about 3.00~ of a fugitive alkaline material; and the balance being water.
,, '- DETAILED DESCRIPTION OF
THE PREFERRED EMBODIMENT
In accordance with the present invention it has been found that a significant increase in cleaning ef-ficiency can be obtained by adding minor amounts of an anionic or nonionic fluorinated hydrocarbon surfactant ,~ to a composition comprised of a combination of organic solvents, a lower aliphatic alcohol having a relatively low boiling point and a lower alkylene or polyalkylene glycol or a lower aliphatic ether thereof having a rela-tively higher boiling point; a first surfactant which is - a nonionic or anionic surfactant that is compatible with thé solvents; an alkali-metal polyphosphate; fugitive alkaline material; and water. Since only a minor amount of the fluorinated hydrocarbon surfactant (referred to herein as the second surfactant) is needed to achieve a ;~ significant increase in cleaning, the resultant composi-tion has a very low concentration of nonvolatile ingre-dlents, thereby resulting in a composition effective on all types of hard surfaces.
The lower aliphatic alcohols which are suitable for use in the compositions of the present invention are those having from two to four carbon atoms and having a . ~
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~5852~
boiling point within the range of about 75C to about 100C. Examples of these are isopropyl alcohol, n-propyl alcohol, ethyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and mixtures thereof. Lower aliphatic alcohols which do not possess the requisite boiling points are not suitable for use herein in that, those having a boiling point below 75C tend to evaporate too quickly to impart the desired effects, while those ,having boiling points in excess of 100C tend to evapor-- 10 ate too slowly. A particularly suitable lower aliphatic -~alcohol is ispropyl alcohol which has a boiling point of about 82.3C.
,~,;
These lower aliphatic alcohols may be present in ; 15 amounts which vary from about 1.85% to about 10.00%. If ~ less than 1.85% is used the desired effect of this in-: gredient, the tendency to increase the volatility of the ' total composition, will not be noticed, while using ' amounts in excess of about 10.00% will have a deleterious effect on the surfactants present. Amounts of this in-r~ gredient which are particularly suitable for use herein ,~ are from about 2.76% to about 3.5%.
~":
The alkylene or polyalkylene glycols or the lower alkyl ethers thereof which are suitable for use in the instant compositions are those having boiling points of from about 120C to about 250C and those which are sel-ected from the group consisting of alkylene and poly-alkylene glycols containing from about 2 to 6 carbon atoms, and the lower alkyl ethers of alkylene or poly-alkylene glycols, containing a total of about 3 to 8 carbon atoms wherein the alkyl ether contains a total of from about 1 to 4 carbon atoms. Examples of these com-pounds which are suitable are ethylene glycol, proplyene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butane-diol, tetramethylene glycol, 1,2-pentanediol, 1,4-:
~58521 .. s ,.:
pentanediol, pentamethylene glycol, 2,3-hexanediol, hexa-~ethylene glycol, glycol monoethyl ether, glycol mono-butyl ether, glycol monomethyl ether, propylene glycol 'monoethyl ether, ethylene glycol monobutyl ether, di--5 ethylene glycol monoethyl ether and mixtures thereof. A
particularly suitable compound for use herein is ethyl-,;ene glycol monobutyl ether which has a boiling point of about 171C.
These higher boiling point solvents can be present , in amounts which vary from about 1.15% to about lO.O0~.
If less than 1.15% is employed this ingredient will not impart its desired effect, the increase in lubricity or ease by which the composition may be spread on a surface;
while using more than 10.00% will have a deleterious ef-~' fect on the detergency of the compositions. A particu-larly suitable amount of this ingredient for use herein is between about 1.73% to about 2.50%.
. , .
, 20 Using a combination of the organic solvents enumer-ated above, one having a relatively low boiling point and the other having a relatively higher boiling point is required in compositions of the instant type which are formulated to be used in a no rinse mode. The com-bination of these solvents in their respective concentra-tions will provide a sufficiently slow evaporation rate to promote easy spreading without rendering the evapora-tion rate so slow as to require excessive mopping for removal of these compositions.
The first surfactant is selected from the group of anionic and nonionic surfactants which are compatible with the organic solvents used herein. Examples of mem-bers of this group are the linear primary alcohol ethoxy-lates, such as the reaction product of a linear primaryalcohol having from about 9 to about 11 carbon atoms re-acted with an average of 2.5 moles of ethylene oxide;
~i ~, ..
~ ~L158521 ; 6 the alkyl aryl sulfonates; polyethylene oxide ethers of :fatty alcohols; sodium lauryl sulfate; octyl phenoxy ;polyethoxy ethanol; sodium lauryl ether sulfate; and sodium dodecyl benzene sulfonate. A particularly suit---5 able surfactant for use as the first surfactant is sodium lauryl sulfate.
The amount of this first surfactant present in the .,instant compositions can vary from about 0.1% to about , 10 2.5%. A particularly suitable amount for use herein is from about 0.20% to about 0.30%.
The second surfactant is an anionic or nonionic fluorinated hydrocarbon surfactant. Examples of suit-able second surfactants are the anionic fluorinated sur-factants having a fluorinated hydrocarbon portion which exhibits a branched chain structure and having aliphatic per-fluorocarbon groups at one end of the molecule. One such surfactant is that sold by I.C.I. Ltd. under the registered trademark of MONFLOR 31, which is the sodium salt of a branched chain perfluoroalkyenyl oxybenzene sulphonic acid of the formula: CloFlgOC6H4SO3( )Na(+).
Other examples of suitable fluorinated anionic surfac-tants are those where the fluorinated hydrocarbon por-tion exhibits a straight chain structure, having alipha-tic per-fluorocarbon groups at the end of the chain.
One such surfactant is that sold by the 3M Company under the designation of FC 128, which is the potassium salt of a fluorinated alkyl carboxylate. Examples of suit able nonionic flourinated surfactants are those where the fluorinated hydrocarbon portion exhibits a branched chain structure and which have aliphatic per-fluorocar-bon groups at both ends of the chain such as those having the formula:
Rf(OCH2CH2)nORf, where Rf is C8F15, CloFlg, or C12F23 and n is from 10 to 30. Other suitable nonionic fluor-,~,'', " . .
~ ~158521 , ,~ inated hydrocarbon surfactants are those where the fluorinated hydrocarbon portion exhibits a branched chain structure and which have an aliphatic per-fluoro-' carbon group at one end of the chain, such as those having the formula:
Rf(OCH2CH2)mOR where R is a lower alkyl, suitably CH3, m is from 2 to 20 and Rf is C8F15, CloFlg, or C12Flg , A particularly suitable fluorinated hydrocarbon surfac-tant for use herein is the anionic surfactant sold under the trademark of MONFLOR 31 having the formula:
CloFl9oc6H4 3 ..
, These fluorinated hydrocarbon surfactants can be present in the instant invention in amounts which range i 15 from 0.011% to about 5.000~. Using amounts of less than 0.011% will not provide the detergency necessary while using amounts in excess of 5.000% will increase the level of nonvolatile ingredients such that smearing will occur, additionally increasing the lev~ls of this ingre-dient to 5.000% will not increase the detergency of the resultant compositions. A particularly suitable amount of the fluorinated hydrocarbon surfactant is from about 0.011% to about 0.099%.
The alkali metal polyphosphates which are suitable for use herein include sodium tripolyphosphate, tetra-sodium pyrophosphate, and sodium hexametaphosphate. The potassium salts of any of the foregoing are equally use-ful hereln. A particularly suitable alkali metal poly-phosphate is tetra-sodium pyrophosphate. Suitable amounts of this ingredient may vary from about 0.02% to about 2.00%. Using less than the 0.02% will decrease the efficiency of the composition in removing grease soils while using in excess of 2.00% will tend to cause smearing. A particularly suitable amount of this ingre-dient for use herein is from about 0.04% to about 0.08%.
: Xl "' "'' ' : , .
.. ,- :
~1585Z~.
Fugitive alkaline materials are used herein for their ability to improve detergency without increasing the level of nonvolatile ingredients, since these materials will evaporate from the surface being cleaned.
Examples of suitable fugitive alkaline materials are ammonia and morpholine. The amount of this material which is useful herein can vary from about 0.15% to about 3.00%. Using less than about 0.15% will affect the ability of the formulation to remove greasy soils while using more than about 3.00% will result in the liberation of gases, which create an offensive odor.
Although morpholine can be used herein it is preferable to use ammonia. When ammonia is used it may be convien-iently added in the form of ammonium hydroxide, ammonium acetate and ammonium carbonate, however, if so added it should be added in quantities capable of producing suit-able amounts of ammonia. A particularly suitable amount of the fugitive alkaline material for use herein is from about 0.30% to about 1.00%.
The last of the essential ingredients is water which will make up the balance of the composition. In order to achieve a composition with a low concentration of nonvolatile ingredients, it has been found that the aqueous component should preferably be made up of de-ionized or soft water.
As optional ingredients these compositions may con-tain perfumes, dyes and solubilizing agents for the perfumes.
The compositions can be made by mixing the various ingredients in any suitable amount. In use these com-positions are applied to a surface in any conventional manner such as spraying, pouring, etc. After being left in contact with the surface the composition is re-moved by wiping the surface with a clean dry absorbent t, ,~
: 1158S21 ,f 9 material. After removal of the composition the surface is clean and requires no rinse. Due to~the high con-tent of volatile ingredients in the instant compositions no film or residue is left on the surface, thereby pre-venting the resoiling of the surface.
The following examples illustrate the present in-vention:
' 10 EXAM~?LE 1 A test was conducted to determine the effect of the fluorinated hydrocarbon surfactant in removing grease soils. In accordance with this test two compositions were prepared. Composition A and Composition B. Com-position A, in accordance with the present invention, was comprised of the following ingredients by weight:
COMPOSITIONS
:.
I.Description:
BACKG~OUND OF THE INVENTION
This invention relates to liquid compositions for cleaning a wide variety of hard surfaces such as metal-; lic, plastic, tile, porcelain, glass and mirrored sur-faces. More specifically this invention relates to hard , surface cleaners which can be used in a no rinse mode whereby the composition is brought into contact with the surface to be cleaned and then removed therefrom by wiping the surface with a dry cloth.
In the past compositions for cleaning hard surfaces in a no rinse mode have been formulated specifically, as either glass and mirrored surface cleaners, or as general r' hard surface cleaners for cleaning a variety of surfaces other than glass or mirrored surfaces. As formulated these prior art cleaners could not be used interchange-ably. One reason for this is that the general hard sur-face cleaners, in order to be effective in removing a wide variety of soils contained rather large quantities of nonvolatile ingredients such as surfactants and builders. Due to the high content of these nonvolatile ingredients the general hard surface cleaners tended to smear or streak glass or mirrored surfaces. Conversely when a glass or mirror cleaner was used on hard surfaces f~ such as tile, metal, or porcelain, incomplete cleaning of soils such as grease resulted due to the low content of the nonvolatile ingredients in these cleaners.
"
An example of prior art compositions which were formulated primarily for cleaning glass and mirrored surfaces are those described in U.S. Pat. No. 3,463,735 ~58521 to Stonebreaker et al. These compositions contain rela-tively minor amounts of nonvolatile ingredients, a sur-factant and a builder, along with a mixture of volatile ingredients, a combination of solvents, ammonia and water. Applicant has surprisingly found that by adding as little as 0.011% by weight of a fluorinated hydrocar-bon surfactant and by adjusting the levels of the vola-tile materials in the Stonebreaker et al. compositions, a composition is achieved which is capable of function-ing equally well as both a glass and mirror cleaner andas a general hard surface cleaner.
.
SUMMARY OF THE INVENTION
Accordingly it is an object of this invention to provide a hard surface cleaner which is equally effec-tive on all types of hard surfaces or porcelain, tile, or metallic surfaces, which is capable of effectively removing a wide variety of soils, and which will not smear or leave a film on glass or mirrored surfaces. It is yet a further object of the present invention to pro-vide such a cleaning composition which can be used in a no rinse mode by applying the composition to a surface, which is to be cleaned, and then wiping it dry with a cloth. The soils on the surface are removed when the surface is wiped dry.
:
The compositions of this invention are comprised of the following ingredients (where the percentage amounts ' 30 recited below and throughout the application are on a weight basis): -a) from about 1.85% to about 10.00% of at least one lower aliphatic monohydric alcohol having a boiling point within the range of from about 75C to about 100C;
b) from about 1.15% to about 10.00% of at least one lower alkylene or polyalkylene glycol or lower alkyl 2a .
1158SZl ether thereof, having a boiling point of between about 120C to about 250C;
~ c) from about 0.1% to about 2.5% of a first surfac-: tant which is a nonionic or anionic surfactant;
~' 5 d) from about 0.011% to about 5.000% of a second surfactant which is a nonionic or anionic fluorinated hydrocarbon surfactant;
e) from about 0.02% to about 2.00% of an alkali-metal polyphosphate;
.l 10 f) from about 0.15~ to about 3.00~ of a fugitive alkaline material; and the balance being water.
,, '- DETAILED DESCRIPTION OF
THE PREFERRED EMBODIMENT
In accordance with the present invention it has been found that a significant increase in cleaning ef-ficiency can be obtained by adding minor amounts of an anionic or nonionic fluorinated hydrocarbon surfactant ,~ to a composition comprised of a combination of organic solvents, a lower aliphatic alcohol having a relatively low boiling point and a lower alkylene or polyalkylene glycol or a lower aliphatic ether thereof having a rela-tively higher boiling point; a first surfactant which is - a nonionic or anionic surfactant that is compatible with thé solvents; an alkali-metal polyphosphate; fugitive alkaline material; and water. Since only a minor amount of the fluorinated hydrocarbon surfactant (referred to herein as the second surfactant) is needed to achieve a ;~ significant increase in cleaning, the resultant composi-tion has a very low concentration of nonvolatile ingre-dlents, thereby resulting in a composition effective on all types of hard surfaces.
The lower aliphatic alcohols which are suitable for use in the compositions of the present invention are those having from two to four carbon atoms and having a . ~
, :.: . . :
., ~ .
..
;-,' : ' : :
~5852~
boiling point within the range of about 75C to about 100C. Examples of these are isopropyl alcohol, n-propyl alcohol, ethyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and mixtures thereof. Lower aliphatic alcohols which do not possess the requisite boiling points are not suitable for use herein in that, those having a boiling point below 75C tend to evaporate too quickly to impart the desired effects, while those ,having boiling points in excess of 100C tend to evapor-- 10 ate too slowly. A particularly suitable lower aliphatic -~alcohol is ispropyl alcohol which has a boiling point of about 82.3C.
,~,;
These lower aliphatic alcohols may be present in ; 15 amounts which vary from about 1.85% to about 10.00%. If ~ less than 1.85% is used the desired effect of this in-: gredient, the tendency to increase the volatility of the ' total composition, will not be noticed, while using ' amounts in excess of about 10.00% will have a deleterious effect on the surfactants present. Amounts of this in-r~ gredient which are particularly suitable for use herein ,~ are from about 2.76% to about 3.5%.
~":
The alkylene or polyalkylene glycols or the lower alkyl ethers thereof which are suitable for use in the instant compositions are those having boiling points of from about 120C to about 250C and those which are sel-ected from the group consisting of alkylene and poly-alkylene glycols containing from about 2 to 6 carbon atoms, and the lower alkyl ethers of alkylene or poly-alkylene glycols, containing a total of about 3 to 8 carbon atoms wherein the alkyl ether contains a total of from about 1 to 4 carbon atoms. Examples of these com-pounds which are suitable are ethylene glycol, proplyene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butane-diol, tetramethylene glycol, 1,2-pentanediol, 1,4-:
~58521 .. s ,.:
pentanediol, pentamethylene glycol, 2,3-hexanediol, hexa-~ethylene glycol, glycol monoethyl ether, glycol mono-butyl ether, glycol monomethyl ether, propylene glycol 'monoethyl ether, ethylene glycol monobutyl ether, di--5 ethylene glycol monoethyl ether and mixtures thereof. A
particularly suitable compound for use herein is ethyl-,;ene glycol monobutyl ether which has a boiling point of about 171C.
These higher boiling point solvents can be present , in amounts which vary from about 1.15% to about lO.O0~.
If less than 1.15% is employed this ingredient will not impart its desired effect, the increase in lubricity or ease by which the composition may be spread on a surface;
while using more than 10.00% will have a deleterious ef-~' fect on the detergency of the compositions. A particu-larly suitable amount of this ingredient for use herein is between about 1.73% to about 2.50%.
. , .
, 20 Using a combination of the organic solvents enumer-ated above, one having a relatively low boiling point and the other having a relatively higher boiling point is required in compositions of the instant type which are formulated to be used in a no rinse mode. The com-bination of these solvents in their respective concentra-tions will provide a sufficiently slow evaporation rate to promote easy spreading without rendering the evapora-tion rate so slow as to require excessive mopping for removal of these compositions.
The first surfactant is selected from the group of anionic and nonionic surfactants which are compatible with the organic solvents used herein. Examples of mem-bers of this group are the linear primary alcohol ethoxy-lates, such as the reaction product of a linear primaryalcohol having from about 9 to about 11 carbon atoms re-acted with an average of 2.5 moles of ethylene oxide;
~i ~, ..
~ ~L158521 ; 6 the alkyl aryl sulfonates; polyethylene oxide ethers of :fatty alcohols; sodium lauryl sulfate; octyl phenoxy ;polyethoxy ethanol; sodium lauryl ether sulfate; and sodium dodecyl benzene sulfonate. A particularly suit---5 able surfactant for use as the first surfactant is sodium lauryl sulfate.
The amount of this first surfactant present in the .,instant compositions can vary from about 0.1% to about , 10 2.5%. A particularly suitable amount for use herein is from about 0.20% to about 0.30%.
The second surfactant is an anionic or nonionic fluorinated hydrocarbon surfactant. Examples of suit-able second surfactants are the anionic fluorinated sur-factants having a fluorinated hydrocarbon portion which exhibits a branched chain structure and having aliphatic per-fluorocarbon groups at one end of the molecule. One such surfactant is that sold by I.C.I. Ltd. under the registered trademark of MONFLOR 31, which is the sodium salt of a branched chain perfluoroalkyenyl oxybenzene sulphonic acid of the formula: CloFlgOC6H4SO3( )Na(+).
Other examples of suitable fluorinated anionic surfac-tants are those where the fluorinated hydrocarbon por-tion exhibits a straight chain structure, having alipha-tic per-fluorocarbon groups at the end of the chain.
One such surfactant is that sold by the 3M Company under the designation of FC 128, which is the potassium salt of a fluorinated alkyl carboxylate. Examples of suit able nonionic flourinated surfactants are those where the fluorinated hydrocarbon portion exhibits a branched chain structure and which have aliphatic per-fluorocar-bon groups at both ends of the chain such as those having the formula:
Rf(OCH2CH2)nORf, where Rf is C8F15, CloFlg, or C12F23 and n is from 10 to 30. Other suitable nonionic fluor-,~,'', " . .
~ ~158521 , ,~ inated hydrocarbon surfactants are those where the fluorinated hydrocarbon portion exhibits a branched chain structure and which have an aliphatic per-fluoro-' carbon group at one end of the chain, such as those having the formula:
Rf(OCH2CH2)mOR where R is a lower alkyl, suitably CH3, m is from 2 to 20 and Rf is C8F15, CloFlg, or C12Flg , A particularly suitable fluorinated hydrocarbon surfac-tant for use herein is the anionic surfactant sold under the trademark of MONFLOR 31 having the formula:
CloFl9oc6H4 3 ..
, These fluorinated hydrocarbon surfactants can be present in the instant invention in amounts which range i 15 from 0.011% to about 5.000~. Using amounts of less than 0.011% will not provide the detergency necessary while using amounts in excess of 5.000% will increase the level of nonvolatile ingredients such that smearing will occur, additionally increasing the lev~ls of this ingre-dient to 5.000% will not increase the detergency of the resultant compositions. A particularly suitable amount of the fluorinated hydrocarbon surfactant is from about 0.011% to about 0.099%.
The alkali metal polyphosphates which are suitable for use herein include sodium tripolyphosphate, tetra-sodium pyrophosphate, and sodium hexametaphosphate. The potassium salts of any of the foregoing are equally use-ful hereln. A particularly suitable alkali metal poly-phosphate is tetra-sodium pyrophosphate. Suitable amounts of this ingredient may vary from about 0.02% to about 2.00%. Using less than the 0.02% will decrease the efficiency of the composition in removing grease soils while using in excess of 2.00% will tend to cause smearing. A particularly suitable amount of this ingre-dient for use herein is from about 0.04% to about 0.08%.
: Xl "' "'' ' : , .
.. ,- :
~1585Z~.
Fugitive alkaline materials are used herein for their ability to improve detergency without increasing the level of nonvolatile ingredients, since these materials will evaporate from the surface being cleaned.
Examples of suitable fugitive alkaline materials are ammonia and morpholine. The amount of this material which is useful herein can vary from about 0.15% to about 3.00%. Using less than about 0.15% will affect the ability of the formulation to remove greasy soils while using more than about 3.00% will result in the liberation of gases, which create an offensive odor.
Although morpholine can be used herein it is preferable to use ammonia. When ammonia is used it may be convien-iently added in the form of ammonium hydroxide, ammonium acetate and ammonium carbonate, however, if so added it should be added in quantities capable of producing suit-able amounts of ammonia. A particularly suitable amount of the fugitive alkaline material for use herein is from about 0.30% to about 1.00%.
The last of the essential ingredients is water which will make up the balance of the composition. In order to achieve a composition with a low concentration of nonvolatile ingredients, it has been found that the aqueous component should preferably be made up of de-ionized or soft water.
As optional ingredients these compositions may con-tain perfumes, dyes and solubilizing agents for the perfumes.
The compositions can be made by mixing the various ingredients in any suitable amount. In use these com-positions are applied to a surface in any conventional manner such as spraying, pouring, etc. After being left in contact with the surface the composition is re-moved by wiping the surface with a clean dry absorbent t, ,~
: 1158S21 ,f 9 material. After removal of the composition the surface is clean and requires no rinse. Due to~the high con-tent of volatile ingredients in the instant compositions no film or residue is left on the surface, thereby pre-venting the resoiling of the surface.
The following examples illustrate the present in-vention:
' 10 EXAM~?LE 1 A test was conducted to determine the effect of the fluorinated hydrocarbon surfactant in removing grease soils. In accordance with this test two compositions were prepared. Composition A and Composition B. Com-position A, in accordance with the present invention, was comprised of the following ingredients by weight:
2.76% isopropyl alcohol: 1.73% ethylene glycol mono-butyl ether; 0.20% sodium lauryl sulfate; 0.066~ of MONFLOR 31, a 30% active solution of an anionic fluor-inated hydrocarbon surfactant having the formula:
CloFlgOC6H4SO3( )Na( ) in a mixture of isopropanol and ;~ water; 0.60% of ammonium hydroxide; 0.04% tetrasodium pyrophosphate; 0.04% perfume; 0.05% of a solublizing agent for the perfume, a nonionic surfactant; and the - balance being deionized water. Composition B which was not a composition of the present invention was comprised of the following ingredients by weight: 4.0% isopropyl alcohol; 2.5% of ethylene glycol monobutyl ether; 0.10%
30 ~odium lauryl sulfate; 0.60% ammonium hydroxide; 0.01%
tetrasodium pyrophosphate; 0.01% perfume; 0.01%
~olubilizing agent for perfume, a nonionic surfactant;
and the balance being deionized water. Both composi-tlons were applied to plates containing grease soils which were prepared in the manner described below.
!, 35 The plates used in this test were made of glass and were rectangular in shape having the approximate ..
' ~
dimensions of 17 3/4 inches by 6 3/4 inches. Each plate was soiled by drawing horizontal lines across the plate at 3/4 inch intervals with a Blaisdell red grease marker.
The intensity of these lines was varied after every fourth line. This was done by increasing the number of strokes per line which were made with the marker, one - extra stroke per line after every fourth line. The first four lines on the plate were made using two strokes of the marker and to increase the intensity of the lines an extra stroke was used for each line, on each succes-sive group of four lines. This resulted in the first group of four lines being made by two strokes of the marker, the second group of four lines being made by three strokes of the marker, the third group of four lines being made with four strokes of the marker and so on until the plate was completely lined.
A piece of masking tape was then placed on two plates, which were soiled in the manner described above.
The tape was placed along the center line of the plates dividing them in half lengthwise. After this was done approximately 2 grams of Composition A were applied to the right side of one plate and approximately 2 grams of this Composition were applied to the left side of the other plate. Equal amounts of Composition B were applied to the opposite sides of each of these plates.
The total number of lines removed by Composition A
on each side of the two plates was then divided by the total number of lines which were present on the plate prior to its being cleaned. This figure was then multiplied by 100% to give the percentage of cleaning for Composi-tion A. The figures thus obtained for each half of the two plates were then added and divided by two to give an ; 35 average of the percentage of cleaning. This same proce-dure was followed for the halves of the two plates which were cleaned with Composition B.
.
1~5852~
~J
The average percentage of cleaning obtained using Composition A was 98%, while the average percentage of cleaning obtained using Composition B was 20%.
From the foregoing it is apparent that the addition of a fluorocarbon surfactant significantly increases the ability of the present compositions to remove grease.
Two compositions, C and D, were prepared and tested for their relative ability to remove aged fat. Composi-tion C being the same as Composition A of the preceding example except that the level of ammonium hydroxide was increased to 1.0% from 0.60~.
Several soiled glass plates were prepared by spray-ing a fat solution, containing 3% to 5% of beef fat in hexane, onto each of the plates. After the fat was ap-plied it was smeared over the surface of the plate witha sweeping motion to insure that the fat film evenly covers the entire surface of the plate. The plates thus soiled were then aged for a period of 55 days.
A drop of Composition C was then placed on the sur-face of a soiled plate and allowed to remain in contact with the film for a predetermined number of minutes, as indicated in the table below. At the end of the prede-termined time the plate was shaken by hand to remove the composition and then flushed gently with deionized water The area of the plate in contact with the composition was then examined visually for completeness of removal of the fat film. The results of these observations are given in the table below. Following the tests conducted with Composition C the identical tests were conducted with Composition D, the results of which are also given in the table below.
~!
12 ~L~L5~35Zl .
Extent of Film Removal in %
~ Contact of Total fat Time (Min) Removed 5 Composition C 2 35%
Composition D 2 10%
Composition C 3 50%
Composition D 3 10%
Composition C 4 90%
10 Composition D 4 10%
Composition C 5 99-100~
Composition D 5 10%
From the foregoing it should be apparent that Com-position C, containing the fluorinated hydrocarbon sur-factant in accordance with the present invention, has a significantly greater ability to remove fat soils than that of Composition D which does not contain such a sur-factant.
The following numbered examples of complete specific embodiments serve to further illustrate the practise of this invention. In these examples all proportions are on a percent by weight basis.
Ingredient % by Weight Isopropyl alcohol 2.76 %
30 Ethylene glycol monobutyl ether 1.73 %
Octyl phenoxypoly ethoxy ethanol 0.20 %
Tetra-sodium pyrophosphate 0.04 %
MONFLOR 31 0.066%
Ammonium hydroxide 0.60 %
35 Perfume 0-04 %
Solubilizing agent for perfume 0.05 %
Deionized water 94.514 '`~"1 ~5852~
','' Ingredient ~ by Weight isopropyl alcohol 2.76 %
Ethylene glycol monobutyl ether 1.73 ~
5 Sodium dodecyl benzene sulfonate0.20 %
Tetra-sodium pyrophosphate 0.04 %
MONFLOR 31 0.066%
Ammonium hydroxide 0.60 %
Perfume 0.04 %
10 Solubilizing agent for perfume0.05 %
Deionized water 99.514%
Ingredient % by Weight 15 Isopropyl alcohol 4 0 %
Ethylene glycol monobutyl ether 2.5 %
Neodol 91-2.5 * 0 30 %
Tetra-sodium pyrophosphate 0 04 %
MONFLOR 31 0 099%
20 Ammonium Carbonate 1.60 %
, Perfume 0 04 %
Solubilizing agent for perfume0 05 %
Deionized water 91.371%
, * Neodol 91-2.5 - a nonionic surfactant available from the Shell Oil Company which is a linear primary alcohol ethoxylate, the reaction product of one mole of a linear primary alcohol having from 9 to 11 carbon atoms with an average of 2.5 moles of ethylene oxide.
Ingredient % by Weight -Isopropyl alcohol 3.08 %
Ethylene glycol monobutyl ether 1.92 %
Sodium Lauryl sulfate 0.20 %
35 Tetra-sodium pyrophosphate 0.04 %
MONFLOR 31 0.066%
~1 ' 115852~
EXAMPLE 6 CON'T
, ngredient % by Weight Ammonium acetate 0.01 %
Perfume 0.04 %
Solubilizing agent for perfume 0.05 %
Deionized water 93.404%
Having described some typical embodiments of this invention it is not my intent to be limited to the specific details set forth herein. Rather, I wish to reserve to myself any variations or modifications that may appear to those skilled in the art and fall within the scope of the following claims.
, ~
.
. ' ' ' , ~' ~
. ~
.
CloFlgOC6H4SO3( )Na( ) in a mixture of isopropanol and ;~ water; 0.60% of ammonium hydroxide; 0.04% tetrasodium pyrophosphate; 0.04% perfume; 0.05% of a solublizing agent for the perfume, a nonionic surfactant; and the - balance being deionized water. Composition B which was not a composition of the present invention was comprised of the following ingredients by weight: 4.0% isopropyl alcohol; 2.5% of ethylene glycol monobutyl ether; 0.10%
30 ~odium lauryl sulfate; 0.60% ammonium hydroxide; 0.01%
tetrasodium pyrophosphate; 0.01% perfume; 0.01%
~olubilizing agent for perfume, a nonionic surfactant;
and the balance being deionized water. Both composi-tlons were applied to plates containing grease soils which were prepared in the manner described below.
!, 35 The plates used in this test were made of glass and were rectangular in shape having the approximate ..
' ~
dimensions of 17 3/4 inches by 6 3/4 inches. Each plate was soiled by drawing horizontal lines across the plate at 3/4 inch intervals with a Blaisdell red grease marker.
The intensity of these lines was varied after every fourth line. This was done by increasing the number of strokes per line which were made with the marker, one - extra stroke per line after every fourth line. The first four lines on the plate were made using two strokes of the marker and to increase the intensity of the lines an extra stroke was used for each line, on each succes-sive group of four lines. This resulted in the first group of four lines being made by two strokes of the marker, the second group of four lines being made by three strokes of the marker, the third group of four lines being made with four strokes of the marker and so on until the plate was completely lined.
A piece of masking tape was then placed on two plates, which were soiled in the manner described above.
The tape was placed along the center line of the plates dividing them in half lengthwise. After this was done approximately 2 grams of Composition A were applied to the right side of one plate and approximately 2 grams of this Composition were applied to the left side of the other plate. Equal amounts of Composition B were applied to the opposite sides of each of these plates.
The total number of lines removed by Composition A
on each side of the two plates was then divided by the total number of lines which were present on the plate prior to its being cleaned. This figure was then multiplied by 100% to give the percentage of cleaning for Composi-tion A. The figures thus obtained for each half of the two plates were then added and divided by two to give an ; 35 average of the percentage of cleaning. This same proce-dure was followed for the halves of the two plates which were cleaned with Composition B.
.
1~5852~
~J
The average percentage of cleaning obtained using Composition A was 98%, while the average percentage of cleaning obtained using Composition B was 20%.
From the foregoing it is apparent that the addition of a fluorocarbon surfactant significantly increases the ability of the present compositions to remove grease.
Two compositions, C and D, were prepared and tested for their relative ability to remove aged fat. Composi-tion C being the same as Composition A of the preceding example except that the level of ammonium hydroxide was increased to 1.0% from 0.60~.
Several soiled glass plates were prepared by spray-ing a fat solution, containing 3% to 5% of beef fat in hexane, onto each of the plates. After the fat was ap-plied it was smeared over the surface of the plate witha sweeping motion to insure that the fat film evenly covers the entire surface of the plate. The plates thus soiled were then aged for a period of 55 days.
A drop of Composition C was then placed on the sur-face of a soiled plate and allowed to remain in contact with the film for a predetermined number of minutes, as indicated in the table below. At the end of the prede-termined time the plate was shaken by hand to remove the composition and then flushed gently with deionized water The area of the plate in contact with the composition was then examined visually for completeness of removal of the fat film. The results of these observations are given in the table below. Following the tests conducted with Composition C the identical tests were conducted with Composition D, the results of which are also given in the table below.
~!
12 ~L~L5~35Zl .
Extent of Film Removal in %
~ Contact of Total fat Time (Min) Removed 5 Composition C 2 35%
Composition D 2 10%
Composition C 3 50%
Composition D 3 10%
Composition C 4 90%
10 Composition D 4 10%
Composition C 5 99-100~
Composition D 5 10%
From the foregoing it should be apparent that Com-position C, containing the fluorinated hydrocarbon sur-factant in accordance with the present invention, has a significantly greater ability to remove fat soils than that of Composition D which does not contain such a sur-factant.
The following numbered examples of complete specific embodiments serve to further illustrate the practise of this invention. In these examples all proportions are on a percent by weight basis.
Ingredient % by Weight Isopropyl alcohol 2.76 %
30 Ethylene glycol monobutyl ether 1.73 %
Octyl phenoxypoly ethoxy ethanol 0.20 %
Tetra-sodium pyrophosphate 0.04 %
MONFLOR 31 0.066%
Ammonium hydroxide 0.60 %
35 Perfume 0-04 %
Solubilizing agent for perfume 0.05 %
Deionized water 94.514 '`~"1 ~5852~
','' Ingredient ~ by Weight isopropyl alcohol 2.76 %
Ethylene glycol monobutyl ether 1.73 ~
5 Sodium dodecyl benzene sulfonate0.20 %
Tetra-sodium pyrophosphate 0.04 %
MONFLOR 31 0.066%
Ammonium hydroxide 0.60 %
Perfume 0.04 %
10 Solubilizing agent for perfume0.05 %
Deionized water 99.514%
Ingredient % by Weight 15 Isopropyl alcohol 4 0 %
Ethylene glycol monobutyl ether 2.5 %
Neodol 91-2.5 * 0 30 %
Tetra-sodium pyrophosphate 0 04 %
MONFLOR 31 0 099%
20 Ammonium Carbonate 1.60 %
, Perfume 0 04 %
Solubilizing agent for perfume0 05 %
Deionized water 91.371%
, * Neodol 91-2.5 - a nonionic surfactant available from the Shell Oil Company which is a linear primary alcohol ethoxylate, the reaction product of one mole of a linear primary alcohol having from 9 to 11 carbon atoms with an average of 2.5 moles of ethylene oxide.
Ingredient % by Weight -Isopropyl alcohol 3.08 %
Ethylene glycol monobutyl ether 1.92 %
Sodium Lauryl sulfate 0.20 %
35 Tetra-sodium pyrophosphate 0.04 %
MONFLOR 31 0.066%
~1 ' 115852~
EXAMPLE 6 CON'T
, ngredient % by Weight Ammonium acetate 0.01 %
Perfume 0.04 %
Solubilizing agent for perfume 0.05 %
Deionized water 93.404%
Having described some typical embodiments of this invention it is not my intent to be limited to the specific details set forth herein. Rather, I wish to reserve to myself any variations or modifications that may appear to those skilled in the art and fall within the scope of the following claims.
, ~
.
. ' ' ' , ~' ~
. ~
.
Claims (9)
1. A cleaning composition for hard surfaces com-prised by weight of:
a) from about 1.85% to about 10.00% of at least one organic solvent which is a lower aliphatic monohydric alcohol having from about 2 to about 4 carbon atoms and having a boiling point within the range of from about 75°C to about 100°C;
b) from about 1.15% to about 10.00% of at least one organic solvent having a boiling point of between about 120°C to about 250°C and selected from the group consisting of alkylene and polyalkylene glycols having from about 2 to 6 carbon atoms, and the lower alkyl ethers, having about 1 to 4 carbon atoms, of alkylene or polyalkylene glycols containing a total of from about 3 to 8 carbon atoms;
c) from about 0.1% to about 2.5% of a first sur-factant which is an anionic or nonionic surfactant;
d) from about 0.011% to about 5.000% of a second surfactant which is an anionic or nonionic fluorinated hydrocarbon surfactant;
e) from about 0.02% to about 2.0% of an alkali-metal polyphosphate;
f) from about 0.15% to about 3.00% of a fugitive alkaline material; and the balance of said composition being water.
a) from about 1.85% to about 10.00% of at least one organic solvent which is a lower aliphatic monohydric alcohol having from about 2 to about 4 carbon atoms and having a boiling point within the range of from about 75°C to about 100°C;
b) from about 1.15% to about 10.00% of at least one organic solvent having a boiling point of between about 120°C to about 250°C and selected from the group consisting of alkylene and polyalkylene glycols having from about 2 to 6 carbon atoms, and the lower alkyl ethers, having about 1 to 4 carbon atoms, of alkylene or polyalkylene glycols containing a total of from about 3 to 8 carbon atoms;
c) from about 0.1% to about 2.5% of a first sur-factant which is an anionic or nonionic surfactant;
d) from about 0.011% to about 5.000% of a second surfactant which is an anionic or nonionic fluorinated hydrocarbon surfactant;
e) from about 0.02% to about 2.0% of an alkali-metal polyphosphate;
f) from about 0.15% to about 3.00% of a fugitive alkaline material; and the balance of said composition being water.
2. The composition of claim 1 wherein the second surfactant is selected from the group consisting of:
a) anionic fluorinated hydrocarbon surfactants wherein the fluorinated hydrocarbon portion has a branched chain structure and having aliphatic per-fluoro-carbon groups at one end thereof;
b) nonionic fluorinated hydrocarbon surfactants having a fluorinated hydrocarbon portion exhibiting a branched structure and having the formula:
Rf(OCH2CH2)nOR
wherein Rf is C8F15, C1OF19 or C12F23 and n is an in-teger from 10 to 30.
c) nonionic fluorinated hydrocarbon surfactants wherein the fluorinated hydrocarbon portion exhibits a branched structure and having the formula:
Rf(OCH2CH2)mOR
wherein Rf is as in b), R is a lower alkyl and m is an integer from 2 to 10; and d) anionic fluorinated hydrocarbon surfactants wherein the fluorinated hydrocarbon portion exhibits a straight chain structure and having aliphatic per-fluoro-carbon groups at one end of the chain thereof.
a) anionic fluorinated hydrocarbon surfactants wherein the fluorinated hydrocarbon portion has a branched chain structure and having aliphatic per-fluoro-carbon groups at one end thereof;
b) nonionic fluorinated hydrocarbon surfactants having a fluorinated hydrocarbon portion exhibiting a branched structure and having the formula:
Rf(OCH2CH2)nOR
wherein Rf is C8F15, C1OF19 or C12F23 and n is an in-teger from 10 to 30.
c) nonionic fluorinated hydrocarbon surfactants wherein the fluorinated hydrocarbon portion exhibits a branched structure and having the formula:
Rf(OCH2CH2)mOR
wherein Rf is as in b), R is a lower alkyl and m is an integer from 2 to 10; and d) anionic fluorinated hydrocarbon surfactants wherein the fluorinated hydrocarbon portion exhibits a straight chain structure and having aliphatic per-fluoro-carbon groups at one end of the chain thereof.
3. The composition of claim 2 wherein the second surfactant is the sodium salt of a branched chain per-fluoroalkyenyl oxybenzene sulphonic acid having the formula:
C10F19OC6H4SO3(-)Na(+)
C10F19OC6H4SO3(-)Na(+)
4. The composition of claim 3 wherein the organic solvent having a boiling point of between about 75°C to about 100°C is isopropyl alcohol; and wherein the organic solvent having a boiling point of between about 120°C
to about 250°C is ethylene glycol monobutyl ether.
to about 250°C is ethylene glycol monobutyl ether.
5. The composition of claim 4 wherein the fugitive alkaline material is ammonia.
6. The composition of claim 5 wherein the surfac-tant is sodium lauryl sulfate.
7. The composition of claim 6 wherein the alkali-metal polyphosphate is tetra-sodium pyrophosphate.
8. The composition of claims 1 or 7 wherein the organic solvent having a boiling point of between about 75°C to about 100°C is present from about 2.76% to about 3.50% by weight; wherein the organic solvent having a boiling point of between about 120°C to about 250°C is present from about 1.73% to about 2.50% by weight;
wherein the first surfactant is present from about 0.20 to about 0.30% by weight; wherein the second surfactant is present from about 0.011% to about 0.099% by weight;
wherein the alkali-metal polyphosphate is present from about 0.04% to about 0.08% by weight; and wherein the fugitive alkaline material is present from about 0.30%
to about 1.00% by weight.
wherein the first surfactant is present from about 0.20 to about 0.30% by weight; wherein the second surfactant is present from about 0.011% to about 0.099% by weight;
wherein the alkali-metal polyphosphate is present from about 0.04% to about 0.08% by weight; and wherein the fugitive alkaline material is present from about 0.30%
to about 1.00% by weight.
9. A process for cleaning hard surfaces which com-prises the steps of applying a composition in accordance with claim 1 to a hard surface and then removing said composition by wiping said surface with a substantially dry absorbent material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US189,986 | 1980-09-23 | ||
| US06/189,986 US4302348A (en) | 1980-09-23 | 1980-09-23 | Hard surface cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1158521A true CA1158521A (en) | 1983-12-13 |
Family
ID=22699593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000368277A Expired CA1158521A (en) | 1980-09-23 | 1981-01-12 | Hard surface cleaning compositions |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4302348A (en) |
| JP (1) | JPS5785897A (en) |
| AU (1) | AU540606B2 (en) |
| CA (1) | CA1158521A (en) |
| GB (1) | GB2084175B (en) |
| NZ (1) | NZ198119A (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4606842A (en) * | 1982-03-05 | 1986-08-19 | Drackett Company | Cleaning composition for glass and similar hard surfaces |
| US4511489A (en) * | 1983-06-01 | 1985-04-16 | The Drackett Company | Composition for cleaning and imparting antistatic properties to plastics surfaces |
| US4661436A (en) * | 1983-06-17 | 1987-04-28 | Petrarch System, Inc. | Process of forming high contrast resist pattern in positive photoagent material using alkalai developer with fluorocarbon surfactant |
| US4613340A (en) * | 1984-01-09 | 1986-09-23 | Polar Molecular Corp. | Residual oil sludge dispersant |
| US4689168A (en) * | 1984-06-08 | 1987-08-25 | The Drackett Company | Hard surface cleaning composition |
| US4670372A (en) * | 1984-10-15 | 1987-06-02 | Petrarch Systems, Inc. | Process of developing radiation imaged photoresist with alkaline developer solution including a carboxylated surfactant |
| US4613561A (en) * | 1984-10-17 | 1986-09-23 | James Marvin Lewis | Method of high contrast positive O-quinone diazide photoresist developing using pretreatment solution |
| GB2166153A (en) * | 1984-10-25 | 1986-04-30 | Procter & Gamble | No-rinse hard surface cleaning composition |
| US4670171A (en) * | 1985-02-26 | 1987-06-02 | Pennzoil Company | Surface cleaner composition |
| JPS61254922A (en) * | 1985-05-07 | 1986-11-12 | Asahi Glass Co Ltd | Cleaning material |
| US5102573A (en) * | 1987-04-10 | 1992-04-07 | Colgate Palmolive Co. | Detergent composition |
| US4822854A (en) * | 1987-09-23 | 1989-04-18 | The Drackett Company | Cleaning compositions containing a colorant stabilized against fading |
| US4921629A (en) * | 1988-04-13 | 1990-05-01 | Colgate-Palmolive Company | Heavy duty hard surface liquid detergent |
| FR2667871B1 (en) * | 1990-10-12 | 1994-06-17 | Valeo Systemes Dessuyage | CLEANING PRODUCT FOR WINDSCREEN WASHER DEVICE, PARTICULARLY FOR MOTOR VEHICLES. |
| US5415811A (en) * | 1991-04-09 | 1995-05-16 | E And R Investments | Cleaning composition and method for utilizing same |
| ZA925727B (en) * | 1991-08-09 | 1993-03-10 | Bristol Myers Squibb Co | Glass cleaning composition. |
| US5207838A (en) * | 1991-08-29 | 1993-05-04 | Martin Marietta Energy Systems, Inc. | Nonhazardous solvent composition and method for cleaning metal surfaces |
| US5213706A (en) * | 1991-11-08 | 1993-05-25 | Lever Brothers Company, Division Of Conopco, Inc. | Homogeneous detergent gel compositions for use in automatic dishwashers |
| US5523024A (en) * | 1992-02-07 | 1996-06-04 | The Clorox Company | Reduced residue hard surface cleaner |
| US5252245A (en) * | 1992-02-07 | 1993-10-12 | The Clorox Company | Reduced residue hard surface cleaner |
| US5817615A (en) * | 1992-02-07 | 1998-10-06 | The Clorox Company | Reduced residue hard surface cleaner |
| US5585342A (en) * | 1995-03-24 | 1996-12-17 | The Clorox Company | Reduced residue hard surface cleaner |
| US5468423A (en) * | 1992-02-07 | 1995-11-21 | The Clorox Company | Reduced residue hard surface cleaner |
| DE4333385C2 (en) * | 1993-09-30 | 1997-01-30 | Friedrich A Spruegel | Surface disinfectants and cleaning agents |
| US5536452A (en) * | 1993-12-07 | 1996-07-16 | Black; Robert H. | Aqueous shower rinsing composition and a method for keeping showers clean |
| JPH07216392A (en) * | 1994-01-26 | 1995-08-15 | Daikin Ind Ltd | Detergent and cleaning method |
| JP3579058B2 (en) * | 1994-09-12 | 2004-10-20 | エコラブ・インコーポレイテッド | Rinse aid for plastic tableware |
| US5603776A (en) * | 1994-09-12 | 1997-02-18 | Ecolab Inc. | Method for cleaning plasticware |
| US5910474A (en) * | 1995-05-11 | 1999-06-08 | Black; Robert H. | Method of rinsing showers clean |
| US5849681A (en) * | 1996-02-09 | 1998-12-15 | S. C. Johnson & Son, Inc. | Glass cleaner with enhanced anti-streaking properties |
| US6010539A (en) * | 1996-04-01 | 2000-01-04 | E. I. Du Pont De Nemours And Company | Cleaning formulations for textile fabrics |
| US5837664A (en) * | 1996-07-16 | 1998-11-17 | Black; Robert H. | Aqueous shower rinsing composition and a method for keeping showers clean |
| SK124499A3 (en) | 1997-03-20 | 2000-05-16 | Procter & Gamble | Detergent composition for use with a cleaning implement comprising a superabsorbent material and kits comprising both |
| DE19859778A1 (en) * | 1998-12-23 | 2000-06-29 | Henkel Kgaa | Multi-phase cleaning agent with naphthalenesulfonic acid-formaldehyde condensate |
| US20060258557A1 (en) * | 2005-05-11 | 2006-11-16 | Popplewell Lewis M | Hard surface cleaning compositions and methods for making same |
| US7618930B2 (en) * | 2006-11-17 | 2009-11-17 | Colgate-Palmolive Company | Foaming hard surface cleaner comprising a TEA alkyl sulfate and amine oxide surfactant system |
| EP3545061B1 (en) | 2016-11-28 | 2022-03-09 | S.C. Johnson & Son, Inc. | Hard surface cleaners including fluorosurfactants |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3239467A (en) * | 1962-02-15 | 1966-03-08 | Lord Corp | Metal cleaning and treating compositions |
| US3463735A (en) * | 1967-10-18 | 1969-08-26 | Drackett Co | Glass cleaning composition |
| US3882038A (en) * | 1968-06-07 | 1975-05-06 | Union Carbide Corp | Cleaner compositions |
| US3591510A (en) * | 1968-09-30 | 1971-07-06 | Procter & Gamble | Liquid hard surface cleaning compositions |
| JPS5139250B2 (en) * | 1972-04-20 | 1976-10-27 | ||
| US3887497A (en) * | 1973-03-15 | 1975-06-03 | George B Ulvild | Liquid cleansing composition and method of producing |
| US4152305A (en) * | 1974-06-20 | 1979-05-01 | Safe-Tech, Inc. | Nontoxic general purpose liquid cleaning compositions |
| IT1038373B (en) * | 1974-08-06 | 1979-11-20 | Rolls Royce Motors Ltd | FORMULATION FOR WINDOW CLEANING |
| DE2709690B1 (en) * | 1977-03-05 | 1978-05-11 | Henkel Kgaa | Liquid detergent |
| US4213873A (en) * | 1978-03-10 | 1980-07-22 | Leisure Products Corporation | Water based window, glass and chrome cleaner composition |
-
1980
- 1980-09-23 US US06/189,986 patent/US4302348A/en not_active Expired - Lifetime
-
1981
- 1981-01-12 CA CA000368277A patent/CA1158521A/en not_active Expired
- 1981-08-17 AU AU74250/81A patent/AU540606B2/en not_active Ceased
- 1981-08-21 NZ NZ198119A patent/NZ198119A/en unknown
- 1981-09-22 GB GB8128553A patent/GB2084175B/en not_active Expired
- 1981-09-22 JP JP56150480A patent/JPS5785897A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU7425081A (en) | 1982-04-01 |
| AU540606B2 (en) | 1984-11-29 |
| NZ198119A (en) | 1984-04-27 |
| GB2084175B (en) | 1983-11-16 |
| JPS5785897A (en) | 1982-05-28 |
| GB2084175A (en) | 1982-04-07 |
| US4302348A (en) | 1981-11-24 |
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