CA1319874C - Heavy duty hard surface liquid detergent - Google Patents
Heavy duty hard surface liquid detergentInfo
- Publication number
- CA1319874C CA1319874C CA000596421A CA596421A CA1319874C CA 1319874 C CA1319874 C CA 1319874C CA 000596421 A CA000596421 A CA 000596421A CA 596421 A CA596421 A CA 596421A CA 1319874 C CA1319874 C CA 1319874C
- Authority
- CA
- Canada
- Prior art keywords
- group
- detergent
- surfactant
- water
- alcohol ethoxylates
- 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 - Fee Related
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- 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
- C11D3/30—Amines; Substituted amines ; Quaternized amines
Abstract
ABSTRACT OF THE INVENTION
A single phase, highly alkaline, liquid detergent composition particularly effective in removing airborne kitchen grease from hard surfaces is provided which comprises, by weight:
a. from about 1 to 5% of a surfactant selected from the group consisting of nonionic surfactants (including alcohol ethoxylates and amine oxides, wherein the alcohol ethoxylate is selected from the group consisting of linear primary alcohol ethoxylates, random secondary alcohol ethoxylates) and amphoteric surfactants (comprising water-soluble betaines) and mixtures thereof;
b. about 2% of a builder selected from the group consisting of tetrapotassium pyrophosphate (TKPP), sodium tripolyphosphate (STPP), sodium metasilicate, sodium carbonate, sodium bicarbonate, and potassium hydroxide;
c. about 2% of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine;
d. from about 2 to 8% of at least one water miscible, preferably polar organic solvent selected from the group consisting of water soluble glycol ethers (including diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether) and alkyl acetates; and e. water.
A single phase, highly alkaline, liquid detergent composition particularly effective in removing airborne kitchen grease from hard surfaces is provided which comprises, by weight:
a. from about 1 to 5% of a surfactant selected from the group consisting of nonionic surfactants (including alcohol ethoxylates and amine oxides, wherein the alcohol ethoxylate is selected from the group consisting of linear primary alcohol ethoxylates, random secondary alcohol ethoxylates) and amphoteric surfactants (comprising water-soluble betaines) and mixtures thereof;
b. about 2% of a builder selected from the group consisting of tetrapotassium pyrophosphate (TKPP), sodium tripolyphosphate (STPP), sodium metasilicate, sodium carbonate, sodium bicarbonate, and potassium hydroxide;
c. about 2% of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine;
d. from about 2 to 8% of at least one water miscible, preferably polar organic solvent selected from the group consisting of water soluble glycol ethers (including diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether) and alkyl acetates; and e. water.
Description
'.
~IEA~Y DlJTY ILARD SURFAC~.I.IQUID DETERGENT
~AC~GRO~ND OF THE I~ENTION
Tnis invention relates to compositions, preferably in the form of clear, single phase liquids, that are particularly useful in removing aero.so1ized, polymerized, or airborne hardened grease from kitchen surfaces.
Airborne grease, polymerized grease, or aerosolized grease are names applied to the type of greasy soil whicll results from the deposition of oil particles on kitchen surfaces during various cooking processes involving edible fats and oils, i.e., deep frying, grill frying, etc. During such ~ryillg of foods, particles of fats and oils spatter and splash and eventually deposit on various kitchen sur~aces s~lch as countertops, floors.
walls and appliance surfaces. This type of greasy soil or "aerosolized grease," upon contact with the substrate undergoes a number of chemical reactions and forms a semi-solid gel structure, which strongly adheres to the substrate. The result is a difficult to remove greasy soil that contains a significant amount of insoluble and polar fractions.
The following are the major changes that have been found to occur in the physical and chemical properties of cooking oils as the oils are treated under deep frying conditions and aged on kitchen surfaces:
Initially the oil is a liquid (at room temperature), and it is composed of a mixture of low molecular weight unsaturated triglycerides with no significant polar compounds (free fatty acids). This oil has a viscosity of about 60 cps and adheres weakly to the substrate.
As the oil is exposed to high temperature, air, and moisture during deep frying (and following aging at room temperature), various chemical reactions, including polymerization, hydrolysis, and oxidation take place.
The rate and extent of these reactions depend on the nature of the oil, the temperature and the operating conditions. Key physical and chemical changes I
in oil properties which take place upon this treatment can be summarized as follows:
1. Substantial reduction in the level of unsaturated fractions and formation of dimers alld trimers, as the oil undergoes thermal and oxidative polymerization. This results in a major increase in oil viscosity as the oil transforms from a liquid to a gel (or solid, in the case of linseed o i 1 ) .
~IEA~Y DlJTY ILARD SURFAC~.I.IQUID DETERGENT
~AC~GRO~ND OF THE I~ENTION
Tnis invention relates to compositions, preferably in the form of clear, single phase liquids, that are particularly useful in removing aero.so1ized, polymerized, or airborne hardened grease from kitchen surfaces.
Airborne grease, polymerized grease, or aerosolized grease are names applied to the type of greasy soil whicll results from the deposition of oil particles on kitchen surfaces during various cooking processes involving edible fats and oils, i.e., deep frying, grill frying, etc. During such ~ryillg of foods, particles of fats and oils spatter and splash and eventually deposit on various kitchen sur~aces s~lch as countertops, floors.
walls and appliance surfaces. This type of greasy soil or "aerosolized grease," upon contact with the substrate undergoes a number of chemical reactions and forms a semi-solid gel structure, which strongly adheres to the substrate. The result is a difficult to remove greasy soil that contains a significant amount of insoluble and polar fractions.
The following are the major changes that have been found to occur in the physical and chemical properties of cooking oils as the oils are treated under deep frying conditions and aged on kitchen surfaces:
Initially the oil is a liquid (at room temperature), and it is composed of a mixture of low molecular weight unsaturated triglycerides with no significant polar compounds (free fatty acids). This oil has a viscosity of about 60 cps and adheres weakly to the substrate.
As the oil is exposed to high temperature, air, and moisture during deep frying (and following aging at room temperature), various chemical reactions, including polymerization, hydrolysis, and oxidation take place.
The rate and extent of these reactions depend on the nature of the oil, the temperature and the operating conditions. Key physical and chemical changes I
in oil properties which take place upon this treatment can be summarized as follows:
1. Substantial reduction in the level of unsaturated fractions and formation of dimers alld trimers, as the oil undergoes thermal and oxidative polymerization. This results in a major increase in oil viscosity as the oil transforms from a liquid to a gel (or solid, in the case of linseed o i 1 ) .
2. Significant tncrease in the free fatty acid content of the oil.
This results in increased tackiness and greater adhesion to the substrate, particularly glass and metal surfaces via polar bonds.
Co~nercial ~ultipurpose cleaners containing mixtures of surfactant and salt are not effective in removing such greasy soil. It has now been :liscovered, though, that it is possible to formulate a nonabrasive, liquid cleaning composition which effectively removes such greasy soil. The proposed composition utilizes high alkalinity to neutralize the polar groups of the soil to aid detachment, a solvent to penetrate and to swell the soil, and a surfactant to wet and disperse the soil.
BRIEF DESCRIPTION OF THE IN~E~rION
Cenerally, the compositions of this invention consist of the following essential ingredients:
1. A water miscible, preferably polar, organic solvent which provides penetration into and swelling of the soil.
2. A short chain, nonionic surfactant of low molecular weight with optimum hydrophilic/hydrophobic balance to provide wetting and to enhance detachment from the substrate. Amphoteric surfactants and combinations of nonionic and amphoteric surfactants may also be used.
This results in increased tackiness and greater adhesion to the substrate, particularly glass and metal surfaces via polar bonds.
Co~nercial ~ultipurpose cleaners containing mixtures of surfactant and salt are not effective in removing such greasy soil. It has now been :liscovered, though, that it is possible to formulate a nonabrasive, liquid cleaning composition which effectively removes such greasy soil. The proposed composition utilizes high alkalinity to neutralize the polar groups of the soil to aid detachment, a solvent to penetrate and to swell the soil, and a surfactant to wet and disperse the soil.
BRIEF DESCRIPTION OF THE IN~E~rION
Cenerally, the compositions of this invention consist of the following essential ingredients:
1. A water miscible, preferably polar, organic solvent which provides penetration into and swelling of the soil.
2. A short chain, nonionic surfactant of low molecular weight with optimum hydrophilic/hydrophobic balance to provide wetting and to enhance detachment from the substrate. Amphoteric surfactants and combinations of nonionic and amphoteric surfactants may also be used.
3. A builder/buffer agent to provide a high pH alkaline environment for saponification and hydrolysis of the grease so that the polar groups of the residue are neutralized.
~ . An alkanolamine to serve as a protein denaturant, which extends the efficacy on other types of food soils including egg and meat residue.
5. Water.
The compositions of the present invention are formulated as clear, single phase liquids, but they may be provided in other forms such as gels and aerosols, and they may be dispensed from pump sprayers, trigger spray or foamer bottles, aerosol cans, and the Like.
Specifically, formulations according to the present invention are highly alkaline (having a pH ranging from 9-13) and comprise:
a. from about 1 to 5% of a surfactant selected from the group consisting of nonionic surfactants (low molecular weight, short chain), amphoteric surfactants and mixtures thereof;
r pref~ bl~
b. about~2 to 6% of a builder salt selected from the group consisting of polyphosphates, pyrophosphates, silicates, metasilicates, and carbonates;
c. from about 1 to 5% of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine and triethanolamine;
d. water; and e. about 2 to 8% of at least one water miscible, preferably polar organic solvent selected from the group consisting of water soluble glycol ethers (including diethylene glycol monobutyl ether, ethylene glycolmonobutyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether) and Cf>-CI 3 alkyl acetates.
It has now been found that aerosolized grease residues can be effectively removed from hard surfaces by: contacting such soiled surfaces with an effective amount of the above-identified liquid detergent co~positions; allowing an effective amount of time for the composition to soak through the soil; and then wiping the affected soiled surfaces to remove the detergent composition and the solubilized greasy residue.
~3~987 4 6~01-1549 These composltlons provlde superlor efflcacy on hard-to-remove aerosollzed grease, when compared to commercially avallable, spray products. Moreover, they are mlld to human skln; can be easlly packaged ln a trlgger spray or trigger foamer bottle; and have a mlld odor, whlch can easlly be masked by perfume.
KEY TO INGREDIENTS HEREIN
Alfonlc 610-50 ls the trade-mark for prlmary alcohol ethoxylate (C6-C10 wlth 50~ EO) made by Vista Chemlcal.
~3arlox-14 ls the trade-mark for alkyl (C10-C14) dlmethyl amlne oxlde made by Lonza.
Betaine BL-158 ls the trade-mark for alkyl dlmethyl betalne (C12-C14) made by 5Oldschmldt Chemlcal Corp.
Butoxydlglycol ~CTFA name) - dlethylene glycol monobutyl ether-Butyl Carbltol - Vnion Carblde.
Butoxyethanol (CTFA name) - ethylene glycol mono`outyl ether-Butyl Cellosolve - Union Carbide.
Cocamlde DEA (CTFA name) - Coconut dlethanolamlde -Monoamld 150 ADD - Mona.
Cocoamldopropyl Betalne - Surco Coco Betalne - Onyx.
DEA - dlethanolamlne.
EDTA - Ethylene dlamlne tetra acetlc acld.
Exxate 600 is trade-mark for hexyl acetate made by Exxon Chemlcals.
Laurlc/Myristlc Dlethanolamlde - The fatty acld of the amlde ls a mlxture of laurlc and myrlstlc aclds, usually ln a proportlon of 1:3 to 3:1 and preferably about 1;1. Thus, such materlal ls really a mlxture of two dlfferent dlethanolamldes but ls generally named for convenlence as laurlc/myrlstlc dlethanolamlde or LMDEA.
MEA - monoethanolamlne.
Tra~le-rrlar~. 4 ,1 ~na~
Neodol ~3-6.5 is the trade namc for primary alcohol ethoxylate (C,,-Cll, 6.5 EO) made by Shell.
Pareth 25-9 (CTFA name) - polyethylene glycol ether mixture of synthetic C~ 7 fatty alcohols with any average of moles of ethylene oxide - Neodol 25-9(Shell).
Tergitol 15-S-9 is the brand name for secondary alcohol ethoxylate (C,~-CI.,,9EO) made by Union Carbide Corp.
TEA - triethanolamine.
TKPP - tetrapotassium pyrophosphate.
DETAILED DESCRIPTION OF THE IN~ENTION
Tlle grease removing compositions of this invention are essentially comprised of the following components: surfactant, builder, alkanolamine, water, and solvent. In addition to the above ingredients, the compositions of this invention may contain other substances generally present in "
j detergent compositions. For example, the composition may be thickened if desired by the addition of known viscosity increasing agents. Foam I¦ stabilising agents may also be incorporated, and other ingredients which may ¦I normally be present include preservatives, humectants, foam boosters, 'I anti-foaming agents, dispersants, pH modifiers, colorants, and perfumes.
,1 According to a first embodiment of the invention, the surfactant, which is present in the amount of 1-5% of the composition, is selected from the group consisting of nonionic surfactants, amphoteric surfactants, and their combinations. Preferably, the surfactant is present in the amount of lZ.
The nonionic surfactant, preferably, is comprised of one or a mixture ,1 of short chain, low molecular weight linear primary alcohol ethoxylates, Ij random secondary alcohol ethoxylates, and polar compounds, such as amine 11 oxides. The primary alcohols ethoxylates are represented by the general formula:
~-O-(CN,-CH,-O)~-~
r~,-~ K
13~987 ~
62:~01 `- 1 5~1 wheL eln E~ lS an alkyl ra~ical hav~ng f rGm 9 to 16 carbon atoms and the r,umber of ethoxylate groups, n, ls from 1 to 7. Com-merclally available nonlonlc surfactants of this type are sGld by Shell Chemical Company under the tradename Neodol and by Unlon Carbide Corporatlon under the tradename Tergitol.
The secondary alcohol ethoxylates are represented by the general formula:
CH3-(CH2)x-lcH-(cHz)y-cH3 o (cH2-cH2-o)n-H
Whereln x+y ls from 6 to 15 and the number of ethoxy-late groups, n, is from 1 to 9. Commercially avallable surfac-tants of thls type are sold by Union Carblde Corporation under the trade-mark Tergitol S series surfactants, with Tergitol 15-S-9(T 15-S-9) being preferred for use herein.
The useful amine oxldes are represented by the gener-al formula:
l2 R1-N-o wherein R1 ls an alkyl radlcal contalnlng from 12 to 18 carbon atoms, and R2 and R3 are methyl, ethyl or hydroxyethyl. Com-merclally avallable surfactants of thls type are sold by Armak under the trade-mark Aromox surfactant, such as, for example, Aromox DMMC-W the trade-mark for dlmethyl cocoamlne oxlde.
Other useful surfactant systems lnclude:
comblnatlons of hlgh EO-low EO alcohol ethoxylates and comblna-tlons of mono or dialkyl quaternary compounds and the nonlonlc surfactants mentloned above.
Preferable ethoxylate mlxtures comprlse C12-C15 alcohol ethoxylates having 9 to 12 ethoxy gro~ps ln comblnation wlth C12-C15 alcohol ethoxylates havlng 3 to 6 ethoxy groups.
131987~
The quaternary compounds ;uitable for use irl combination with the above mentioned nonionics are represented by the general formula:
CH, i R~ - N~ -- CH,X
R-, wherein Rl is CH, or an alkyl radical containing from 10 to 14 carbon atoms and R. is an alkyl radical containing from 10 to 14 carbon atoms and X is a halogen such as bromide or chloride. Preferably the quaternary compound used in combination with nonionic surfactant is tetradecyltrimethylammonium bromide.
The amphoteric surfactant is preferably comprised of water-soluble betaine surfactants having the following structure CH-~
R, - Nt - R2 ~ C00~
CH~
wherein R, is an alkyl radical containing from 8 to 18 carbon atoms, or the amido radical:
R C - N - (CH~)a-wherein R is an alkyl group having about 8 to 18 carbon atoms and a is the integer 1 to 4; R~ is an alkylene group having frcm 1 to 4 carbon atoms.
Suitable betaines include dodecyl dimethyl betaine and cocoamidopropyl betaine.
The composition also contains from 2 to 870 of a builder salt or electrolyte, which is comprised of phosphates, such as tetrapotassium pyrophosphate, sodium tripolyphosphate; carbonates, such as sodium carbonate, sodium sesquicarbonate and sodium bicarbonate; silicates and metasilicates, such as sodium metasilicate; and mixtures thereof. The preferred amount of the builder in the composition is 27..
, 131~874 About l-5% of an alkanolamine is also present, which comprises monoethanolamine, diethanolamine or triethanolamine. About 2.0% of the alkanolamine in the composition is preferred.
The solvent comprises about 2-8~ of the composition. The solvent is selected from the group consisting of C~-c~3 alkyl acetates, such as hexyl acetate; and water soluble glycol ethers such as diethylene glycol monobutyl ether (Butyl Carbitol), ethylene glycol monobutyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether.
Water completes the balance of the composition (from about 74-96%), the pH of which ranges from 9 to 13.
In order to easily prepare a soil to be applied to test surfaces when comparing the efficacy of different detergent compositions, a "model soil"
having the properties of "polymerized grease" was developed. This eliminated the need to run a control each time a test was run. It comprised a partially polymerized corn oil (the most frequently used frying oil) pigment and solvent. The pigment is included to improve the resolution of reflectance data, and the solvent provides ease of application.
The "model soil" was applied to a substrate by using a mohair piece or , a brush as a thin film and placed at room temperature for 1 to 3 days depending on the type of substrate and the tenacity of the soil required.
QUANTITATIVE EVALUATION OF SOIL REMOVAL
, This involved mechanical scrubbing of the soiled panels using a Gardner Instrument equipped with two pads with mohair surfaces. The mohair surface was initially soaked in the cleaning solution. After soil removal was performed at the specified number of strokes, a quantitative estimate , of the relative cleaning efficiency was determined photometrically.
Il The compositions of the present invention are particularly adapted to ¦1 be utilized by being sprayed onto the soiled surface from a trigger spray package and thereafter wiped off. It has been found that a spray cleaner that shows superior performance in removing "polymerized grease" comprises:
Water miscihle solvent Butyl Carbitol 5 Nonionic Surfactant Ethoxylated alcohol (NEODOL 23-6.5) Builder/Buffer TKPP 2 Alkanolamine TEA 2 pH 12 A comparison oF the above composition with a commercially available spray cleaner indicates the use of the nonionic surfactant instead of the linear alkyl benzene sulfonate (LAS) anionic surfactant used in the commercial spray cleaner had a major effect in cleaning efficiency of the spray cleaner.
Results of the performance assessment of this formula (FORMULA B) on both the "polymerized grease" is illustrated in the following table.
TABLE I
Percent Soil Removal --Current prototype (Formula B) 75 --Commercial All Purpose Cleaner 10 --Commercial Spray Cleaner (a) 40 --Commercial Spray Cleaner (b) 60 Soil: Polymerized Corn Oil Substrate: Latex Painted Wallboard Conditions: Gardner Test 10 Strokes , A series of s~rfactants, solvents and builders were screened in an attempt to optimize the performance of the formulations of this invention against the model greasy soil "polymerized grease". The composition of this formulation was:
BUILDER / SURFACTANT ¦ SOLVENT / TEA : 2 / 1 ¦ 4 / 2 Table II shows the results from the evaluation of a series of surfactants. All surfactants were used at lZ level. The concentrations of ~he builder (TKPP at 27~) and the solvent (Butyl Carbitol at 4%) were kept constant in all cases.
TABLE II
Type of Surfactant Percent Soil Removal Na paraffin sulfonate 20 Na Cl-~ alkylbenzene sulfonate 40 Tergitol l5-S-9 80 Alfollic 610-50 82 ~eodol 23-6 5 83 'I'ego Betaine BL-158 82 Barlox-14 85 No Surfactant 20 As shown in Table II, nonionic and amphoteric surfactants perform significantly better than the anionics.
Table III shows the result of the evaluation of a series of solvents including glycol ethers and alkyl acetates. All solvents were used at a 4%
level. The concentrations of the surfactant (Neodol 23-6.5 at 1%) and builder (TKPP at 2%) were kept constant in all cases. Exxate 600 and 700 are mixed isomers of hexyl and heptyl acetates respectively (manufactured by Exxon).
TABLE III
,I Solvent Percent Soil Removal 'I Butyl Cellosolve 78 Butyl Carbitol 78 ! i Exxate 700 80 ¦ Ethyl Acetate 82 Exxate 600 85 No Solvent 70 Results in removing polymerized grease are shown in Table I It can be seen that the prototype formula resulted in 75% soil removal which was .significantly better than the ~arket leader among the spray cleaner products. The prototype formula also outperformed another commercially available spray cleaner.
Liquid all purpose cleaners (APCs), which do not contain solvent, are generally poor in removing polymerized grease, as will be noted by the results for product nos 3-5.
The result of the evaluation of a series of builder salts is shown in Table IV.
Builder/Buffer Percent Soil Removal NaOH 72 ~a Silicate 70 TKPP
Na Carbonate 72 Na~ F~TA 70 ' No Bui].der 30 As will be noted, although the presence of builder makes significant impact on performance among different builders, no significant difference in performance is observed.
The detergent compositions of the present invention, as well as their efficacy, will now be illustrated by the following examples, wherein all parts and percentages are by weight and all temperatures in degrees Celsius unless otherwise indicated.
I ~
TABLE V
Examples Ingredient ~1 J~2 ~3 #4 #5 #6 1~7 Commercial ~ommercial Spray Clnr Lemon APC
Tergitol 15-S-9 1.0 1.0 1.0 Neodol 23-6.5 1.0 Alfonic 610-~0 1.0 Amine Oxide (Barlox-14) 1.0 ~etaine BI,-1S8 1.0 .~utyl Carbitol 5.0 5.0 5.0 5.0 5.0 5.0 ~xxate 600 5.0 TKPP 2.0~.0 2.0 2.0 2.0 2.0 Sodium Carbonate 2.0 TF,A 2.02.0 2.0 2.0 2.0 2.0 2.0 ~1 i il NaOH
(adjust to pH=12) -----------------------------------Water (Balance) -------------------------------~--~
¦ Soil Removal 81 82 82 88 82 77 87 i (polymerized grease on wallboard) Gardner: 10 strokes 12.6 g¦cm' soil load As previously indicated, the compositions of the present invention are preferably formulated as clear, single phase liquids. However~ it is within the ambit of this invention to formulate these compositions as gels and aerosols, and they may be dispensed from both pump sprayers and aerosol ~I cans. Preparation of compositions suitable to be dispensed by aerosol or 'I pump spray is within the ordinary skill in the art.
Il When it is desired to use a thickening agent with the compositions of ¦ the invention, for example when the organic matter to be removed is on a ! non-horizontal surface and it is desirable to maintain contact between these onposieions and ehe soilei surEace, any such agent, or mixture oE two or more thereot, which is compatible with the ingredients of these formulations may be used. Useful organic thickening agents include starch, sodium carboxymethylcellulose, hydroxyethyl cellulose, methocel, and water-soluble polymers such as carboxy vinyl polymer (Carbopols - B.F. Goodrich Chemical Company), sodium polyacrylate, polyacrylic acid, gums including Xanthan gums such as Keltrol, - Kelco Company. Inorganic colloidal materials lclays]
including Veegum (magnesium aluminum silicate - R.T. Vanderbilt), are also effective. When used, the thickening agent will typically vary between 0.1 to 6% by weight of the composition. Generally, it is desired to maintain the viscosity of these formulations between 100 and 150 cps. If the viscosity is too low, the compositions do not adhere well to the soiled surfaces. If too high, it has been found that the efficacy of these compositions is diminished.
Suitable foam boosters and foam stabilizers include cocomonoethanolamide, lauryl diethanolamide, lauryl/myristyl monoethanolamide, cocobetaine, and lauryl/myristyl diethanolamide.
rr~d~ r~
~ . An alkanolamine to serve as a protein denaturant, which extends the efficacy on other types of food soils including egg and meat residue.
5. Water.
The compositions of the present invention are formulated as clear, single phase liquids, but they may be provided in other forms such as gels and aerosols, and they may be dispensed from pump sprayers, trigger spray or foamer bottles, aerosol cans, and the Like.
Specifically, formulations according to the present invention are highly alkaline (having a pH ranging from 9-13) and comprise:
a. from about 1 to 5% of a surfactant selected from the group consisting of nonionic surfactants (low molecular weight, short chain), amphoteric surfactants and mixtures thereof;
r pref~ bl~
b. about~2 to 6% of a builder salt selected from the group consisting of polyphosphates, pyrophosphates, silicates, metasilicates, and carbonates;
c. from about 1 to 5% of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine and triethanolamine;
d. water; and e. about 2 to 8% of at least one water miscible, preferably polar organic solvent selected from the group consisting of water soluble glycol ethers (including diethylene glycol monobutyl ether, ethylene glycolmonobutyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether) and Cf>-CI 3 alkyl acetates.
It has now been found that aerosolized grease residues can be effectively removed from hard surfaces by: contacting such soiled surfaces with an effective amount of the above-identified liquid detergent co~positions; allowing an effective amount of time for the composition to soak through the soil; and then wiping the affected soiled surfaces to remove the detergent composition and the solubilized greasy residue.
~3~987 4 6~01-1549 These composltlons provlde superlor efflcacy on hard-to-remove aerosollzed grease, when compared to commercially avallable, spray products. Moreover, they are mlld to human skln; can be easlly packaged ln a trlgger spray or trigger foamer bottle; and have a mlld odor, whlch can easlly be masked by perfume.
KEY TO INGREDIENTS HEREIN
Alfonlc 610-50 ls the trade-mark for prlmary alcohol ethoxylate (C6-C10 wlth 50~ EO) made by Vista Chemlcal.
~3arlox-14 ls the trade-mark for alkyl (C10-C14) dlmethyl amlne oxlde made by Lonza.
Betaine BL-158 ls the trade-mark for alkyl dlmethyl betalne (C12-C14) made by 5Oldschmldt Chemlcal Corp.
Butoxydlglycol ~CTFA name) - dlethylene glycol monobutyl ether-Butyl Carbltol - Vnion Carblde.
Butoxyethanol (CTFA name) - ethylene glycol mono`outyl ether-Butyl Cellosolve - Union Carbide.
Cocamlde DEA (CTFA name) - Coconut dlethanolamlde -Monoamld 150 ADD - Mona.
Cocoamldopropyl Betalne - Surco Coco Betalne - Onyx.
DEA - dlethanolamlne.
EDTA - Ethylene dlamlne tetra acetlc acld.
Exxate 600 is trade-mark for hexyl acetate made by Exxon Chemlcals.
Laurlc/Myristlc Dlethanolamlde - The fatty acld of the amlde ls a mlxture of laurlc and myrlstlc aclds, usually ln a proportlon of 1:3 to 3:1 and preferably about 1;1. Thus, such materlal ls really a mlxture of two dlfferent dlethanolamldes but ls generally named for convenlence as laurlc/myrlstlc dlethanolamlde or LMDEA.
MEA - monoethanolamlne.
Tra~le-rrlar~. 4 ,1 ~na~
Neodol ~3-6.5 is the trade namc for primary alcohol ethoxylate (C,,-Cll, 6.5 EO) made by Shell.
Pareth 25-9 (CTFA name) - polyethylene glycol ether mixture of synthetic C~ 7 fatty alcohols with any average of moles of ethylene oxide - Neodol 25-9(Shell).
Tergitol 15-S-9 is the brand name for secondary alcohol ethoxylate (C,~-CI.,,9EO) made by Union Carbide Corp.
TEA - triethanolamine.
TKPP - tetrapotassium pyrophosphate.
DETAILED DESCRIPTION OF THE IN~ENTION
Tlle grease removing compositions of this invention are essentially comprised of the following components: surfactant, builder, alkanolamine, water, and solvent. In addition to the above ingredients, the compositions of this invention may contain other substances generally present in "
j detergent compositions. For example, the composition may be thickened if desired by the addition of known viscosity increasing agents. Foam I¦ stabilising agents may also be incorporated, and other ingredients which may ¦I normally be present include preservatives, humectants, foam boosters, 'I anti-foaming agents, dispersants, pH modifiers, colorants, and perfumes.
,1 According to a first embodiment of the invention, the surfactant, which is present in the amount of 1-5% of the composition, is selected from the group consisting of nonionic surfactants, amphoteric surfactants, and their combinations. Preferably, the surfactant is present in the amount of lZ.
The nonionic surfactant, preferably, is comprised of one or a mixture ,1 of short chain, low molecular weight linear primary alcohol ethoxylates, Ij random secondary alcohol ethoxylates, and polar compounds, such as amine 11 oxides. The primary alcohols ethoxylates are represented by the general formula:
~-O-(CN,-CH,-O)~-~
r~,-~ K
13~987 ~
62:~01 `- 1 5~1 wheL eln E~ lS an alkyl ra~ical hav~ng f rGm 9 to 16 carbon atoms and the r,umber of ethoxylate groups, n, ls from 1 to 7. Com-merclally available nonlonlc surfactants of this type are sGld by Shell Chemical Company under the tradename Neodol and by Unlon Carbide Corporatlon under the tradename Tergitol.
The secondary alcohol ethoxylates are represented by the general formula:
CH3-(CH2)x-lcH-(cHz)y-cH3 o (cH2-cH2-o)n-H
Whereln x+y ls from 6 to 15 and the number of ethoxy-late groups, n, is from 1 to 9. Commercially avallable surfac-tants of thls type are sold by Union Carblde Corporation under the trade-mark Tergitol S series surfactants, with Tergitol 15-S-9(T 15-S-9) being preferred for use herein.
The useful amine oxldes are represented by the gener-al formula:
l2 R1-N-o wherein R1 ls an alkyl radlcal contalnlng from 12 to 18 carbon atoms, and R2 and R3 are methyl, ethyl or hydroxyethyl. Com-merclally avallable surfactants of thls type are sold by Armak under the trade-mark Aromox surfactant, such as, for example, Aromox DMMC-W the trade-mark for dlmethyl cocoamlne oxlde.
Other useful surfactant systems lnclude:
comblnatlons of hlgh EO-low EO alcohol ethoxylates and comblna-tlons of mono or dialkyl quaternary compounds and the nonlonlc surfactants mentloned above.
Preferable ethoxylate mlxtures comprlse C12-C15 alcohol ethoxylates having 9 to 12 ethoxy gro~ps ln comblnation wlth C12-C15 alcohol ethoxylates havlng 3 to 6 ethoxy groups.
131987~
The quaternary compounds ;uitable for use irl combination with the above mentioned nonionics are represented by the general formula:
CH, i R~ - N~ -- CH,X
R-, wherein Rl is CH, or an alkyl radical containing from 10 to 14 carbon atoms and R. is an alkyl radical containing from 10 to 14 carbon atoms and X is a halogen such as bromide or chloride. Preferably the quaternary compound used in combination with nonionic surfactant is tetradecyltrimethylammonium bromide.
The amphoteric surfactant is preferably comprised of water-soluble betaine surfactants having the following structure CH-~
R, - Nt - R2 ~ C00~
CH~
wherein R, is an alkyl radical containing from 8 to 18 carbon atoms, or the amido radical:
R C - N - (CH~)a-wherein R is an alkyl group having about 8 to 18 carbon atoms and a is the integer 1 to 4; R~ is an alkylene group having frcm 1 to 4 carbon atoms.
Suitable betaines include dodecyl dimethyl betaine and cocoamidopropyl betaine.
The composition also contains from 2 to 870 of a builder salt or electrolyte, which is comprised of phosphates, such as tetrapotassium pyrophosphate, sodium tripolyphosphate; carbonates, such as sodium carbonate, sodium sesquicarbonate and sodium bicarbonate; silicates and metasilicates, such as sodium metasilicate; and mixtures thereof. The preferred amount of the builder in the composition is 27..
, 131~874 About l-5% of an alkanolamine is also present, which comprises monoethanolamine, diethanolamine or triethanolamine. About 2.0% of the alkanolamine in the composition is preferred.
The solvent comprises about 2-8~ of the composition. The solvent is selected from the group consisting of C~-c~3 alkyl acetates, such as hexyl acetate; and water soluble glycol ethers such as diethylene glycol monobutyl ether (Butyl Carbitol), ethylene glycol monobutyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether.
Water completes the balance of the composition (from about 74-96%), the pH of which ranges from 9 to 13.
In order to easily prepare a soil to be applied to test surfaces when comparing the efficacy of different detergent compositions, a "model soil"
having the properties of "polymerized grease" was developed. This eliminated the need to run a control each time a test was run. It comprised a partially polymerized corn oil (the most frequently used frying oil) pigment and solvent. The pigment is included to improve the resolution of reflectance data, and the solvent provides ease of application.
The "model soil" was applied to a substrate by using a mohair piece or , a brush as a thin film and placed at room temperature for 1 to 3 days depending on the type of substrate and the tenacity of the soil required.
QUANTITATIVE EVALUATION OF SOIL REMOVAL
, This involved mechanical scrubbing of the soiled panels using a Gardner Instrument equipped with two pads with mohair surfaces. The mohair surface was initially soaked in the cleaning solution. After soil removal was performed at the specified number of strokes, a quantitative estimate , of the relative cleaning efficiency was determined photometrically.
Il The compositions of the present invention are particularly adapted to ¦1 be utilized by being sprayed onto the soiled surface from a trigger spray package and thereafter wiped off. It has been found that a spray cleaner that shows superior performance in removing "polymerized grease" comprises:
Water miscihle solvent Butyl Carbitol 5 Nonionic Surfactant Ethoxylated alcohol (NEODOL 23-6.5) Builder/Buffer TKPP 2 Alkanolamine TEA 2 pH 12 A comparison oF the above composition with a commercially available spray cleaner indicates the use of the nonionic surfactant instead of the linear alkyl benzene sulfonate (LAS) anionic surfactant used in the commercial spray cleaner had a major effect in cleaning efficiency of the spray cleaner.
Results of the performance assessment of this formula (FORMULA B) on both the "polymerized grease" is illustrated in the following table.
TABLE I
Percent Soil Removal --Current prototype (Formula B) 75 --Commercial All Purpose Cleaner 10 --Commercial Spray Cleaner (a) 40 --Commercial Spray Cleaner (b) 60 Soil: Polymerized Corn Oil Substrate: Latex Painted Wallboard Conditions: Gardner Test 10 Strokes , A series of s~rfactants, solvents and builders were screened in an attempt to optimize the performance of the formulations of this invention against the model greasy soil "polymerized grease". The composition of this formulation was:
BUILDER / SURFACTANT ¦ SOLVENT / TEA : 2 / 1 ¦ 4 / 2 Table II shows the results from the evaluation of a series of surfactants. All surfactants were used at lZ level. The concentrations of ~he builder (TKPP at 27~) and the solvent (Butyl Carbitol at 4%) were kept constant in all cases.
TABLE II
Type of Surfactant Percent Soil Removal Na paraffin sulfonate 20 Na Cl-~ alkylbenzene sulfonate 40 Tergitol l5-S-9 80 Alfollic 610-50 82 ~eodol 23-6 5 83 'I'ego Betaine BL-158 82 Barlox-14 85 No Surfactant 20 As shown in Table II, nonionic and amphoteric surfactants perform significantly better than the anionics.
Table III shows the result of the evaluation of a series of solvents including glycol ethers and alkyl acetates. All solvents were used at a 4%
level. The concentrations of the surfactant (Neodol 23-6.5 at 1%) and builder (TKPP at 2%) were kept constant in all cases. Exxate 600 and 700 are mixed isomers of hexyl and heptyl acetates respectively (manufactured by Exxon).
TABLE III
,I Solvent Percent Soil Removal 'I Butyl Cellosolve 78 Butyl Carbitol 78 ! i Exxate 700 80 ¦ Ethyl Acetate 82 Exxate 600 85 No Solvent 70 Results in removing polymerized grease are shown in Table I It can be seen that the prototype formula resulted in 75% soil removal which was .significantly better than the ~arket leader among the spray cleaner products. The prototype formula also outperformed another commercially available spray cleaner.
Liquid all purpose cleaners (APCs), which do not contain solvent, are generally poor in removing polymerized grease, as will be noted by the results for product nos 3-5.
The result of the evaluation of a series of builder salts is shown in Table IV.
Builder/Buffer Percent Soil Removal NaOH 72 ~a Silicate 70 TKPP
Na Carbonate 72 Na~ F~TA 70 ' No Bui].der 30 As will be noted, although the presence of builder makes significant impact on performance among different builders, no significant difference in performance is observed.
The detergent compositions of the present invention, as well as their efficacy, will now be illustrated by the following examples, wherein all parts and percentages are by weight and all temperatures in degrees Celsius unless otherwise indicated.
I ~
TABLE V
Examples Ingredient ~1 J~2 ~3 #4 #5 #6 1~7 Commercial ~ommercial Spray Clnr Lemon APC
Tergitol 15-S-9 1.0 1.0 1.0 Neodol 23-6.5 1.0 Alfonic 610-~0 1.0 Amine Oxide (Barlox-14) 1.0 ~etaine BI,-1S8 1.0 .~utyl Carbitol 5.0 5.0 5.0 5.0 5.0 5.0 ~xxate 600 5.0 TKPP 2.0~.0 2.0 2.0 2.0 2.0 Sodium Carbonate 2.0 TF,A 2.02.0 2.0 2.0 2.0 2.0 2.0 ~1 i il NaOH
(adjust to pH=12) -----------------------------------Water (Balance) -------------------------------~--~
¦ Soil Removal 81 82 82 88 82 77 87 i (polymerized grease on wallboard) Gardner: 10 strokes 12.6 g¦cm' soil load As previously indicated, the compositions of the present invention are preferably formulated as clear, single phase liquids. However~ it is within the ambit of this invention to formulate these compositions as gels and aerosols, and they may be dispensed from both pump sprayers and aerosol ~I cans. Preparation of compositions suitable to be dispensed by aerosol or 'I pump spray is within the ordinary skill in the art.
Il When it is desired to use a thickening agent with the compositions of ¦ the invention, for example when the organic matter to be removed is on a ! non-horizontal surface and it is desirable to maintain contact between these onposieions and ehe soilei surEace, any such agent, or mixture oE two or more thereot, which is compatible with the ingredients of these formulations may be used. Useful organic thickening agents include starch, sodium carboxymethylcellulose, hydroxyethyl cellulose, methocel, and water-soluble polymers such as carboxy vinyl polymer (Carbopols - B.F. Goodrich Chemical Company), sodium polyacrylate, polyacrylic acid, gums including Xanthan gums such as Keltrol, - Kelco Company. Inorganic colloidal materials lclays]
including Veegum (magnesium aluminum silicate - R.T. Vanderbilt), are also effective. When used, the thickening agent will typically vary between 0.1 to 6% by weight of the composition. Generally, it is desired to maintain the viscosity of these formulations between 100 and 150 cps. If the viscosity is too low, the compositions do not adhere well to the soiled surfaces. If too high, it has been found that the efficacy of these compositions is diminished.
Suitable foam boosters and foam stabilizers include cocomonoethanolamide, lauryl diethanolamide, lauryl/myristyl monoethanolamide, cocobetaine, and lauryl/myristyl diethanolamide.
rr~d~ r~
Claims (8)
1. A single phase, non-caustic, liquid detergent composition especially effective in removing greasy soils from hard surfaces comprising a mixture of:
a. from about 1 to 5% of at least one surfactant selected from the group consisting of nonionic, polar nonionic, and amphoteric surfactants or mixtures thereof;
b. about 1-6% of a builder;
c. from about 1-5% of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine;
d. from about 2 to 8% of at least one organic solvent, said solvent selected from the group consisting of water soluble glycol ethers and alkyl acetates; and e. water, wherein the pH of the composition ranges from 9 to 13.
a. from about 1 to 5% of at least one surfactant selected from the group consisting of nonionic, polar nonionic, and amphoteric surfactants or mixtures thereof;
b. about 1-6% of a builder;
c. from about 1-5% of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine;
d. from about 2 to 8% of at least one organic solvent, said solvent selected from the group consisting of water soluble glycol ethers and alkyl acetates; and e. water, wherein the pH of the composition ranges from 9 to 13.
2. The detergent of Claim 1 wherein the nonionic surfactant is selected from the group consisting of alcohol ethoxylates and amine oxides.
3. The detergent of Claim 2 wherein the alcohol ethoxylate is selected from the group consisting of linear primary alcohol ethoxylates, random secondary alcohol ethoxylates.
4. The detergent of Claim 3 wherein the surfactant is selected from the group consisting of combinations of high EO - low EO alcohol ethoxylates and combinations of mono or di alkylquaternary compounds.
5. The detergent of Claim 1 wherein the amphoteric surfactant is selected from the group consisting of water-soluble betaines.
6. The detergent of Claim 5 wherein the betaine surfactant is dodecyl dimethylammonium acetate.
7. The detergent of Claim 1 wherein the builder is selected from the group consisting of tetrapotassium pyrophosphate (TKPP), sodium tripolyphosphate (STPP), sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium hydroxide, and mixtures thereof.
8. The detergent of Claim 1 wherein the water soluble glycol ether solvent is selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US181,022 | 1988-04-13 | ||
| US07/181,022 US4921629A (en) | 1988-04-13 | 1988-04-13 | Heavy duty hard surface liquid detergent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1319874C true CA1319874C (en) | 1993-07-06 |
Family
ID=22662572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000596421A Expired - Fee Related CA1319874C (en) | 1988-04-13 | 1989-04-12 | Heavy duty hard surface liquid detergent |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4921629A (en) |
| EP (1) | EP0337576A3 (en) |
| AU (1) | AU633814B2 (en) |
| BR (1) | BR8901693A (en) |
| CA (1) | CA1319874C (en) |
| DK (1) | DK166889A (en) |
| FI (1) | FI891743A (en) |
| MX (1) | MX163332A (en) |
| MY (1) | MY103867A (en) |
| NO (1) | NO891511L (en) |
| PH (1) | PH25688A (en) |
| PT (1) | PT90247B (en) |
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- 1988-04-13 US US07/181,022 patent/US4921629A/en not_active Expired - Fee Related
-
1989
- 1989-04-05 MY MYPI89000434A patent/MY103867A/en unknown
- 1989-04-06 DK DK166889A patent/DK166889A/en not_active IP Right Cessation
- 1989-04-07 AU AU32575/89A patent/AU633814B2/en not_active Ceased
- 1989-04-10 BR BR898901693A patent/BR8901693A/en not_active Application Discontinuation
- 1989-04-11 PT PT90247A patent/PT90247B/en active IP Right Grant
- 1989-04-12 EP EP89200918A patent/EP0337576A3/en not_active Withdrawn
- 1989-04-12 PH PH38498A patent/PH25688A/en unknown
- 1989-04-12 NO NO89891511A patent/NO891511L/en unknown
- 1989-04-12 MX MX15633A patent/MX163332A/en unknown
- 1989-04-12 CA CA000596421A patent/CA1319874C/en not_active Expired - Fee Related
- 1989-04-12 FI FI891743A patent/FI891743A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BR8901693A (en) | 1989-11-21 |
| FI891743A0 (en) | 1989-04-12 |
| DK166889D0 (en) | 1989-04-06 |
| MY103867A (en) | 1993-09-30 |
| DK166889A (en) | 1989-10-14 |
| PH25688A (en) | 1991-09-04 |
| MX163332A (en) | 1992-04-22 |
| EP0337576A2 (en) | 1989-10-18 |
| NO891511D0 (en) | 1989-04-12 |
| US4921629A (en) | 1990-05-01 |
| NO891511L (en) | 1989-10-16 |
| PT90247A (en) | 1989-11-10 |
| PT90247B (en) | 1994-07-29 |
| AU633814B2 (en) | 1993-02-11 |
| AU3257589A (en) | 1989-10-19 |
| FI891743A (en) | 1989-10-14 |
| EP0337576A3 (en) | 1990-05-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |