US 3591510 A
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United States Patent @flice 3,591,510 Patented July 6, 1971 3,591,510 LIQUID HARD SURFACE CLEANING COMPOSITIONS William Edward Zenk, Cincinnati, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio N Drawing. Filed Sept. 30, 1968, Ser. No. 763,949
Int. Cl. Clld 3/066 US. Cl. 252-137 5 Claims ABSTRACT OF THE DISCLOSURE Liquid detergent hard surface cleaning compositions containing 0.25% to 4% of specific short-chain watersoluble synthetic detergent; 1% to 6% of a water-soluble builder or mixture of builders; 1% to 10% of specific organic solvents or mixture of solvents; and Water.
BACKGROUND OF THE INVENTION This invention relates to liquid detergent compositions. More particularly, this invention relates to liquid detergent compositions suitable for hard surface cleaning in a norinse method with improved cleaning and without an unacceptable filming or streaking problem.
In general, liquid detergent compositions are well known in the art and many such compositions have been used in the past for cleaning hard surfaces such as glass, painted walls, woodwork and the like. Generally when such compositions are applied to the above surfaces without a subsequent rinse, they leave a film after their cleaning function has been performed. This residual film, when it contains an organic detergent, can act almost as a trap and collects dirt. The surface thus cleaned with such a composition does not appear clean and can become dirty again even more rapidly than the same surface would become dirty in the absence of the residual film.
Many attempts have been made to produce a so-called volatile detergent composition. Theoretically, such a volatile composition when applied to a surface would perform its cleaning function and then completely evaporate, leaving the clean surface free of any residual film which would enhance the subsequent collection of dirt or soil. Volatile compositions have been prepared in the past which will substantially evaporate after use leaving the surface devoid of any noticeable residual film but, in general, such detergent compositions will not adequately or sufiiciently clean the surface as desired or present other negatives such as inflammability or noxious odor.
One of the principal objects of the present invention is to provide a novel liquid detergent composition which effectively cleans hard surfaces when used in a no-rinse method without leaving an objectionable residual film.
It is a further object of the present invention to provide liquid detergent hard surface cleaner compositions containing specific synthetic detergent and specific organic solvents which have an increased cleaning ability and which will also leave a minimum and almost invisible film deposit on the surface.
Other objects and advantages of the present invention will be readily apparent to one skilled in the art from the following description.
SUMMARY OF THE INVENTION The objects of the present invention are achieved by a liquid detergent composition consisting essentially of an aqueous medium containing specific short-chain synthetic detergents, a builder or combination of builders and an organic solvent or mixture of organic solvents which are sufficiently hydrophobic to dissolve oily soils, e.g., grease.
The present invention is a novel liquid detergent composition consisting essentially of from about 0.25% to about 4.0% by weight of a compatible short-chain watersoluble synthetic detergent selected from the group consisting of: (1) 3-[N,N'-dimethyl-N-alkylammonio]-2-hydroxypropane-l-sulfonate wherein said alkyl group contains about 10 carbon atoms, (2) 2-(N,N',N-trimethylammonio) decanoate, (3) alkali metal straight chain alkyl benzene sulfonates wherein said alkyl group contains from about 6 to about 8 carbon atoms, and (4) alkali metal straight chain alkyl sulfates wherein said alkyl group contains from about 6 to about 12 carbon atoms, from about 0.5% to about 6.0% by weight of a water-soluble builder, e.g., a builder selected from the group consisting of watersoluble polyphosphonates, tripolyphosphates, orthophos phates, borates, pyrophosphates, polymeric carboxylates and aminopolycarboxylates and mixtures thereof, from about 1.0% to about 10.0% by weight of an organic solvent or mixture of solvents selected from the group consisting of propylene glycol butoxy ether, propylene glycol isobutoxy ether, and dipropylene glycol butoxy ether and mixtures thereof; and the balance water.
Among the detergents which have been found useful as the active detergent agent in the compositions of the present invention and which are clearly within the con templation of this invention are the following examples: the alkali metal (e.g., sodium and potassium), ammonium and substituted ammonium (e.g., lower alkanol ammonium) hexyl, octyl, nonyl, decyl, undecyl and dodecyl sulfates; linear alkylbenzene sulfonates in which the alkyl radical contains from about 6 to about 8 carbon atoms, and sulfates of long chain alcohols containing from about 6 to about 12 carbon atoms.
Other suitable synthetic detergents are 3-(N,N'-dimethyl N decylammonio)-2-hydroxypropane 1 sulfonate and 2-(N,N,N"trimethylammonio) decanoate. These detergents are unique in that compositions which contain them adhere to vertical surfaces when sprayed onto said surfaces from a spray device or aerosol container and do not run down. This is very desirable since it keeps the compositions where the soil is while the vertical surface is wiped and prevents streaking on clean walls.
From the standpoint of filming, the best detergents are a C C alkyl sulfate, 3 (N,N' dimethyl N decylammonio)-2-hydroxypropane-l-sulfonate, 2 (N,N,N- trimethylammonio) decanoate, and C -C alkyl benzene sulfonates.
From the standpoint of cleaning, the best detergents are 3 (N,N' dimethyl N decylammonio) 2 hydroxypropane-l-sulfonate, C C alkyl benzene sulfonates, and 2- (N,N',N"-trimethylammonio) decanoate.
The anionic and zwitterionic detergents mentioned above can be used singly or in combination in the practice of the preset invention. The synthetic detergent comprises from about 0.25% to about 4.0% by weight of the total composition. If more than about 4.0% is used an undesired streaking and filming problem may result and if less than about 0.25% is used the desired level of cleaning will not be achieved. A preferred range of from about 0.50% to about 2.0% by weight of a synthetic detergent as described above will yield the best results of the invention.
The builders which can be utilized in the practice of the present invention to give the desired cleaning performance without attendant excessive filming and streaking problems are selected from the group consisting of watersoluble polymeric carboxylates, polyphosphonates, tripolyphosphates, orthophosphates, borates, pyrophosphates, and amino polycarboxylates.
Suitable builders include the alkali metal (e.g., sodium and potassium) and ammonium (including substituted ammoniums, e.g., triethanolammonium) amino polycarboxylates, organic polyphosphonates, polymeric carboxylates, pyrophosphates, orthophosphates, borates and tripolyphosphates. Suitable amino polycarboxylates are those described in US. Pat. 3,329,617 and 3,336,233. Suitable polyphosphonates are those described in US. Pats. 3,329,617; 3,336,233; 3,332,880; 3,213,030; 3,400,148; 3,400,176; and 3,400,151 and copending US. applications: Roy, Ser. No. 266,055, filed Mar. 18, 1963; Roy, Ser. No. 493,925, filed Mar. 18, 1963; Quirnby, Ser. No. 517,073, filed Dec. 28, 1965; Quimby and Prentice, Ser. No. 587,417, filed Oct. 18, 1966; Quimby, Ser. No. 605,606, filed Dec. 29, 1966; Curry, Ser. No. 717,999, filed Apr. 1, 1968; Nicholson and Campbell, Ser. No. 694,002, filed Dec. 27, 1967; Nicholson and Campbell, Ser. No. 694,003, filed Dec. 27, 1967; and Prentice and Quimby, Ser. No. 694,106, filed Dec. 28, 1967. Suitable polymeric carboxylates are disclosed in US. Pat. 3,308,067. All of the above patents and applications are incorporated herein by reference. Preferred builders are sodium orthophosphate, sodium nitrilotriacetate, potassium pyrophosphate, potassium tripolyphosphate and sodium or potassium ethanel-hydroxy-1,1-diphosphonate and similar derivatives.
Other suitable builders are disclosed hereinafter in the examples.
The builders or builders mixture selected from the group above comprises from about 0.5% to about 6% by weight of the total composition. If more than about 6% by weight is used, then an undesired filming and streaking problem is observed and if less than about 0.5% weight is used the desired cleaning results of the invention will not be realized. If about 0.75% to 2.5% builders by weight of the total composition is used the best cleaning and non-filming results of the invention are achieved.
The solvent which can be used, either alone or in combination, in the practice of this invention to aid in grease removal are selected from the group consisting of propylene glycol isobutoxy ether, propylene glycol butoxy ether, and dipropylene glycol butoxy ether. These solvents cause either cleaning or filming and streaking problems when used with most conventional detergents. However, in combination with the specific detergents described hereinbefore, good cleaning filming and streaking characteristics are obtained.
The solvent or solvent mixture of this invention comprises from about 1% to about by weight of the total composition. If more than about 10% by weight is used, the resulting solvent based cleaner is undesirably capable of removing paint and finishes from the surfaces it is used on. Furthermore, such large amounts of solvents present an odor problem. If less than about 1% by weight is used, then the desired cleaning function is not adequately performed. A preferred range of solvent is from about 4% to about 8% by weight.
The compositions of this invention can also contain certain hydrotropes such as sodium, potassium and ammonium toluene sulfonates, xylene sulfonates, benzene sulfonates, and cumene sulfonates in an amount ranging from about /2% to about 3% of the composition. These hydrotropes help to keep the formula in a single phase.
Miscellaneous materials such as coloring agents, aerosol propellants, perfumes, pH buffers, and other materials which are well known as constituents in liquid detergent compositions and which are compatible in the formulations of the present invention can also be present in minor amounts.
The various constituents of the liquid detergent compositions of the present invention can be admixed in any sequence to achieve the desired objects as stated above. It is preferred, however, for ease of solubility, to add the components in the following order at temperatures of between about 40 F. and about 100 F. with constant agitation: water, builder, solvents, detergent and, if any, the optional components.
The liquid detergent compositions of this invention can be utilized either full strength or in dilute solutions. A preferred method of application is in the form of a spray or aerosol for small spots and for small spot cleaning, full strength is recommended. When one wishes to apply the compositions over large surfaces utilizing a sponge, mop, or brush, then dilution is suggested although this is dependent on the individual situations requirements.
The following examples illustrate in detail the manner in which the invention can be practiced. However, the invention is not confined to the specific limitations set forth in the individual examples but, rather, to the scope of the appended claims.
PREFERRED EMBODIMENTS Example I Liquid detergent compositions were prepared according to the following general formula:
Percent Water soluble synthetic detergent 2.0 Propylene glycol butoxy ether 6.0 Trisodium orthophosphate dodeca-hydrate 2.0 Ammonium cumene sulfonate 1.5 Soft water Balance to In order to evaluate the cleaning and resulting streaking filming characteristics of this composition the following tests were conducted.
Cardboard panels, about 2 /2" x 3", were painted with three coats of paint, divided into two groups, and then the two groups were respectively soiled in a standard manner with a low fat soil and a high fat soil. Two of the soiled panels which had been soiled with the same soil are then placed in the Gardner Straight Line Washability Machine manufactured by Gardner Laboratory Inc., Bethesda, Md., which utilizes sponges as the cleaning device. Five ml. of each of the two compositions to be compared are placed on their respective sponges and the machine is run until a cleaning difference is noted or until about 75% of the said soil is cleared by both compositions. The samples are then rerun on other similarly soiled panels reversing the positions of the compositions and the sponge. The grading is done visually based on the amount of soil removed. The grades are equal, slightly better, slightly poorer, better, worse, much better and much worse.
Filming grades were determined by spraying the composition on a black ceramic tile and a mirror, wiping the tile and mirror clean with a soft dry cloth and allowing them to dry. They are graded by judges as heavy, moderate, light, trace and no filming.
The following table shows the comparison of different chain length sodium alkylbenzene sulfonates.
Cu C10 Ca C0 04 Cleaning:
High fat" Basis..." Slightly Better Much Much poorer. better. better. Low fat. do Equal Eqnal Better Equal. Filming Moderate Moderate Light Trace- Traceheavy. light. light.
C alkylbenzene sulfonate is preferred and C and C alkylbenzene sulfonates are next best.
The following table shows the comparison of different chain length sodium alkyl sulfates.
C alkyl sulfate is preferred and C and C sulfates are next best.
Similar tests with 3-[N,N'-dimethyl-N-decylammonio]- 2 hydroxypropane 1 sulfonate (C HAPS) and 2- (N,N',N"-trimethylamn1onio)decanoate (Dupont BDO) phates, polymeric carboxylates, and amino polygave the Wl g results. carboxylates and mixtures thereof;
Sodium (C) from about 1.0% to about by Weight of an .t lb OMH CHHAPS BDO 551g) e n zene 5 01 game solvent or mixture of solvents selected from 01mm U ml E 1 B the group consisting of propylene glycol butoxy ether,
' l ua 3515. Filming Heavy il Light propylene glycol isobutoxy ether, and d1propylenellghtt glycol butoxy ether, and mixtures thereof; and
Similar results are obtained when 1% detergent is used (D) the ba1anCYvateL instead f 0 2. The composition of claim 1 wherein the Water- The CIDHAPS and BBQ fo l i not i d l soluble synthetic detergent is a linear alkylbenzene sulrun down when sprayed from a mechanical sprayer onto fonate wherein the alkyl group contains from about 6 to a Vertical Surfacti about 8 carbon atoms.
EXEIITIP1e H 3. The composition of claim 1 wherein the builder is The following compositions all have the general fortrisodium orthophosphate.
mula: 4. The composition of claim 1 wherein the organic Percent solvent is propylene glycol butoxy ether. Water Soluble synihetlc detelgent 5. The composition of claim 1 wherein the water- Propylene glycol isobutoxy ether 3.0 h d 1 Dipropylene glycol butoxy ether 3'0 soluble synt etlc etergent is so ected from the group con- B ild 21) sisting of 3-(N,N'-dirnethylN-decylammonio)-2-hydroxy- Hydrotrope 2,0 propane-l-sulfonate and 2-(N,N',N"-trimethylammonio) Water Balance decanoate.
Composition Detergent Builder Hydrotrope 1 Potassium hexylbenzene sulfouate Sodium tripolyphosphate Sodium toluene sulfonate. 2. Sodium oetylbenzene sulfonate Potassium ethane-1,1.2rtriphosphonate Potassium toluene sulfonate. 3 Ammonium nonylbenzene sulionate Triethanolammonium poly(itaeonate- Ammonium toluene sulfonate.
aerylate) (4 1 on a molar basis) (specific viscosity of 1% by weight, in dimethyl forrnamide at room temperature-.40) (equivalent Weight65.8).
4 Potassium hexylbenzene sulfonate Ptgliasurnhethale-l-hYdIOxY-LLZ- Sodium xylene sulfonate.
rip osp ona e. 5 Sodium r-oetylbenzene sulfonate Artnmfiniurhn ethane-Z-hydroxy-LIJ- Potassium xylene sulionate.
rip osp ona e. 6 Sodium r-hexylbenzene sulionate Tiipoltassilum etthane-l-hydroxy-ld- Ammonium xylene sulfonate.
ip osp ona e. 7 Potassium nonyl sulfate Sodium nitri1otriaeetate Sodium benzene sulfonate.
Sodium 4-nonyl sulfate Potassium pyrophosphate Potassium benzene sulionate. Sodium olefin sulfonate- Ammonium methylene-diphosphonate. Ammonium benzene sulfonate. Potassium salt of the deter Sodium ethylene-1,l-diphosphonate Sodium eumene sulionate.
omposition 9. Sodium nonyl polyethoxylate (4 moles) Sodium N -(2-hydroxy-ethyl)- Potassium cumene sulfonate.
sulfate. ethylenediaminetriaeetate. 12 Potalsfsitum deeyl polyethoxylate (2 moles) Potassiliuu N%(2t-hydroxyethyl- Triethanolammonium cumene sulfonate.
su as. nir o iaeeaes. 13 Sodium decyl sulfate Potassium isopropylidene diphosphonate Triethanolammonium benzene sulfonate;
Potassium undecyl sulfate. Ammonium ethylidene diphosphonate Tr ethanolammon um xylene sulfonate. 16 %tassilg.m tl r idecyl s u lfa te Potassium h ydroxyr i egl anediphpsuhonate.. g g g gfigla gl i i i gt 2 1 3 sulfonate.
........... I mix ure Wei 0 so ium 1 mix ure y weig ammonium 1 l e.
hexylbenze e sult onate and sodium propane-1,l,3,3-tetraphosphonate and octyl sulfate. ammonium propane-1,2,23-
tetraphosphonate. 17 1 :1 mixture by weight of sodium Ammonium propane1,1,2,3- Morpholmrum xylene sulionate.
oetylbenzene sulfonate and sodium decyl tetraphosphonate. so a e. 18 3-[N,N-dimethyl-N-deeylammonio]-2- 1:1 mixture by weight of sodium Morpholinium toluene sultonate.
bydroxypropane-l-sulfonate. carbonyldiphosphonate and sodium hexametaphosphonate. 19 Potassium hexylbenzene sulfonate 1:1 mixture or sodium hereto and 1:1 mixture of sodium xylene sulionate potassium pyrophosphate. and sodium toluene sulfonate.
In addition to the preferred embodiments described References Cited herein, other arrangements and variations within the UNITED STATES PATENTS s irit and sco e of the invention and the a ended claims p Pp 2,466,632 3/1949 Borus et al 252-118 W111 occur to those skllled 1n the art.
2,952,637 9/1960 Bray et al. 252118 What is claimed is.
3,031,409 3/1962 Perlman et a1. 252-158 1. A novel liquid detergent hard surface no-rmse clean- 3 048 547 8/1962 vosbigian 252 102 ing composition consisting essentially of: 3239467 3/1966 Lipinski 252 144 (A) from about 0.25% to about 4.0% by weight of a 3210287 10/1965 Kelly at 252 139 compatible short-chain water-soluble synthetic deter- 3,453,144 7/1969 Morgan et a1 134 26 gent selected from the group consisting of: (1) 3,463,73 5 8/1969 stonebraker et 252 137 3-(N,N-dimethyl-N-decylammonio)-2-hydroxy propane 1 sulfonate (2) 2-(N,N',N"-trimethylam- FOREIGN PATENTS monro) decanoate, and (3) alkali metal straight 708,000 3/1954 Great Britain chain alkylbenzene sulfonates wherein said alkyl 7 group contains from about 6 to about 8 carbon atoms; LEON D. ROSDOL, Primary Examiner (B) from about 0.5% to about 6.0% by weight of a Assistant Examiner water-soluble builder selected from the group consisting of water-soluble polyphosphonates, tripoly- U. S. Cl. X.R.
phosphates, orthophosphates, borates, pyrophos- 252--138, 153
P0405) UNITED STATES PATENT OFFICE 5 as CERTIFICATE OF CORRECTION Patent No. 3,591,510 Dated July 6, 1971 Inventor(s) William Edward Zenk It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
1 At column 2, line 53, "preset" should read present At column 3, line 24, after "The" "builders" should read builder At column 3, line 24, after "or" "builders" should read builder At column 3, line 30, "builders" should read builder At column 3, line 33 "solvent" should read solvents In claim 1, column 5, lines 66 and 67, (l) 3- (N,N dimethyl-N-decylammonio) 2-hydroxy propane l sulfonate" should read (l) 3- (N,N dimethyl-N decylammonio) -2-hydroxy propane l sulfonate Signed and sealed this 11th day of January 1972.
EDWARD M.FLETCHER, JR. ROBERT GOTTSCHALK Attesting Officer Acting Commissioner of Patents l I J