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CA1178160A - Liquid hard-surface cleaner - Google Patents

Liquid hard-surface cleaner

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Publication number
CA1178160A
CA1178160A CA000385586A CA385586A CA1178160A CA 1178160 A CA1178160 A CA 1178160A CA 000385586 A CA000385586 A CA 000385586A CA 385586 A CA385586 A CA 385586A CA 1178160 A CA1178160 A CA 1178160A
Authority
CA
Canada
Prior art keywords
glycol mono
composition
ether
butyl
alkyl
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
Application number
CA000385586A
Other languages
French (fr)
Inventor
Donald B. Compton
Neil D. Fraser
Ricardo Diez
Michael E. Burns
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to CA000385586A priority Critical patent/CA1178160A/en
Priority to GR69130A priority patent/GR78090B/el
Priority to AU88168/82A priority patent/AU555988B2/en
Priority to IE2215/82A priority patent/IE53499B1/en
Priority to MX194348A priority patent/MX158027A/en
Priority to SE8205171A priority patent/SE8205171L/en
Priority to EP82305211A priority patent/EP0105063B1/en
Application granted granted Critical
Publication of CA1178160A publication Critical patent/CA1178160A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3418Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

LIQUID HARD-SURFACE CLEANER

ABSTRACT

Homogeneous liquid hard surface cleaning detergents are comprised of surfactant, hydrotrope, 10.1-19% sequestering builder, and 6-15% of solvent having a molar volume below about 200 cm.3/gm.mol and Hansen's solubility parameters as follows: polarity parameter from zero to about 3.5 (cal./cm.3)1/2 and hydrogen bonding parameter from zero to about 6(cal./cm.3)1/2. For solvents whose parameters are below about 2, an auxiliary solvent is often needed for solubilization in the formula. A preferred solvent is diethylene glycol mono-n-butyl ether. Cleaning performance at these concurrent high levels of builder and solvent is outstanding, especially for bathroom surfaces such as tubs and walls.

Description

I ~7816~

LIQUID HARD-SURFACE CLEANER

Ricardo Diez Donald Brown Compton Neil David Fraser Michael Eugene Burns TECHNICAL FIELD

This invention relates to novel homogeneous aqueous liquid detergent compositions intended for general purpose household usage for cleaning hard surfaces.

Composit~ons lntended fo~r such purposes have been commercially manu~actured for many years. They have been available in both li~uid and granular form, and often haYe been ~ormula~ed ~o perform especiall~
well in accomplishing some specific household task, such as cleaning tile floors in kitchen and bath, or tile walls in the bath, or bathroom tubs, or kitchen sinks, or painted ~alls in the kitchen or elsewhere in the house, or glass and porcelain surfaces. In general, the requirements for these tasks differ sufficiently from one another that no single composition is ideal for all such usages. The compositions of the present invention are effective across an unusually broad spectrum of these tasks.

BACKGROUND ART

Pxoducts sold commercially for use in cleaning hard surfaces around the house fall into several categories. Solvent-based liquids such as Pine Sol (TM
American Cyanamid Co.~ and ~estoil ~TM Noxell Corp.) ~ . .

typically contain about 25 to 35% o~ a solvent such as pine oil together with about 10-15~ surfactant, but with little or no sequestering builders or alkaline buffers. When used full strength they are effective on greasy soils, such as spots on kitchen walls, but clean poorly on bathroom soils. They are also poor when diluted with water for cleaning surfaces having a broad area such as floors cr walls.

Built products have been formulated as both granules and llquids. The formex contain large amounts o~ se~uestering builders and alkaline buffers~ with generally low levels of surfactant and no solvent.
They are especially effective when dissolved and used on broad wall or ~loor Sux~aaes, but are somewha~ less ef~ective as compared with other types o~ formulations ln those appllcations where aoncentrated product is needed. Li~uid products o~ this type, such as Mr.
Clean CTM Procter & Gamble Inc.l, typically con~ain up to about 18~ builder, up to about 5~ surfactant, and up to about 12% hydrotrope, with little or no solvent -perhaps levels up to 2~ or thereabouts.

Other formulations such as Windex (TM Drackett Company~, Fantastik tTM Texize Chemicals, Inc.~ and ~ormula 409 (TM Clorox Co.) have been prepared for use as spray cleaners on glass ox appliances where freedom from streaking is an important advantage because xinsing is not normally done. These products may also be used ~ull strength for spots on ~alls. They typically contain from about 4~ to about 7% solvent, about l-lQ~ surfactant, and about 1-3~ sequestering builder/alkaline buffer.

~ till other formulations such as Comet CTM
Procter & Gamble IncO~ are sold as abrasive cleansers 1 ~781~0 for use on sinks, tubs and the like. They are most commonly in dry form, and contain finely ground silica as abrasive, together with relatively low levels of chlorine bleach, surfactant, calcium sequestrant, and alkaline buffer. A liquid cleanser containing suspended abrasive has also appeared commercially. These cleanser formula-tions contain no solvent.
Documents that make reference to liquid detergent compositions containing surfactants, builders and selected solvents, at levels that are high for the prior art but low as compared with these of the present invention, include Mausner, U.S. patent 3,232,880 issued February 1, 1966; Krusius, U.S. patent 3,360,476 issued December 26, 1967; Disch et al, U.S. patent 4,175,062 issued November lS 20, 1979; and copending commonly assigne~ Canadian application serial number 377,202 filed May 26, 1981 (~ofinet)~
~ he gist of the present invention is a range of compositions in convenient li~uid form which contain exceptionally high levels of both builders and of solvents specifically chosen for their superb cleaning abilities, together with surfactant and with other ingredients needed to make the compositions homogeneous and physically stable for convenient use and storage. The compositions of this invention are novel and exhibit outstanding performance characteristics that have not hitherto been achieved in a single formula: cleaning of floors as well as commercial li~uid or granular floor cleaners when both are used diluted;

~ ~'781~0 cleaning of greasy walls as well as commercial wall cleaners when both are used full strength; and cleaning of bathtub soil, when used full strength, as well as abrasive cleansers.

DISCLOSURE OF INVENTION

The detergent compositions of the present invention are homogeneous aqueous liquids comprising the following components:
a) from about 0.9% to about 10~ of a non-soap anionic, amphoteric, zwitterionic or nonionic surfactant;
b) from zero to about 5~ soap;
c) from about 10.5~ to about 19% of a polyphosphate or polyphosphonate sequestrant;
d) from zero to about 6% oE an ~lkaline pH buffer, with the proviso that the sum oE components (c) and (d) is not greater than about 21% of th~
composition;
e) Erom about 6% to about 15~ oiE a Principal Solvent having a molar volume below i~bout 2QO(cm.3/gm.
mol) and solubility paramete~s at 25C. as follows: Polarity Parameter from zero to about 3.5(cal./cm3)1/2 and Hydrogen Bonding Parameter from zero to about 6(cal./cm.3)1/2;
~5 f) from zero to about 10% of an Auxiliary Solvent having a Polarity Parameter of about 3.51 or above and/or a Hydrogen Bonding Parameter of about 6.01 or above, with the proviso that the sum of components (e) and (f) is not greater than about 22~ of the composition;

~ ~ 7816~

g) from about 3% to about 25% of a hydrotrope;
and h) the balance water;
wherein all percentages are by weight of the composition; and wherein the pH of a 1% aqueous solution of the detergent composition is from about 8.5 to about 11.

Surfactants. The surfactants of this invention are of two general types, each of which is characterized separately 10 herein. The first such type is comprised of a wide range of non-soap anionic, zwitterionic, amphoteric and nonionic surfactants. A typical listing of the classes and species of these surfactants is given in U.S. Patent 3,664,961 issued to Norris on ~ay 23, 1972. These surfactants can 15 be used singly or in combination at levels in the range from about 0.9~ to about 10%, pre~erably at levels ~rom about 2% to about 7~ by weight of the co~positions.

Non-soap suractants as herein defined contribute cleaning per~ormance to the compositions o~ this invention, 20 especially when used in d~luted form to clean broad sur-aces such as floors and walls.

Suitable anionic non-soap surfactants are water-soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy sulfates, paraffin sulfonates, alpha-25 olefin sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-acyloxy-alkane-1-sulfonate, and beta-alkyloxy alkane sulfonate.

A particularly suitable class of non-soap anionic detergents includes water-soluble salts of 1 ~81~0 organic sulfuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to - about 20, carbon atoms and a sul~onic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic detergents which form part o the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (ClQ-C18~ carbon atoms lQ produced from the glycerides of tallow or coconut oil;
and sodium ancl potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15, especially about 11 ~o about 13, carbon atoms, in stralght chain or branched chain configuration, e.g.
those of the t~pe described in USP 2,220,099 and
2,477,383 and those prepared from alkylbenæenes obtained by alk~lation with straight chain chloroparaffins ~using aluminum trichlori~e catalysis~ or straight chain olefins ~using hydrogen fluoride catalysisl.
Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as Cll 8L~S.

Other non-soap anionic detexgent compounds herein include the sodium C10-C18 alkyl glycexyl ether sulfonates, especially those ethers of higher alcohols deri~ed from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sul~onates and sulfates; and sodium or potas~ium salts of alkyl phenol ethylene oxide ether sulfate containing a~out 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.

Ot~er useful non-soap anionic detergent compounds herein include the water-soluble salts or 1 ~781BO

esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-al~ane-1-sulfonic acids containing from about 2 to 9 carbonatoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl polyethoxy sulfates containin~ from about 10 to 18, especially ahout 12 to 16, carbon atoms in the alkyl group and lQ from a~out 1 to 12, especially 1 to 6, more especially 1 to 4 moieties of ethylene oxide per fatty alcohol moiety; water-soluble salts of olefin sulfonates containin~
from about 12 to 24, preferably about 14 to 16 , carbon atoms, especially those made by react:ion ~ith sulfur trioxide ~ollowed by neu~ralizatio~ ~mder conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sul~onates; water-soluble salts of paraffin sulfonates aontaini.ng from about 8 to 24, especially 1~ to 18 carbon atoms r and beta-alkyloxy alkane sulfonates containin~ from about 1 to 3 carbon atoms in the alkyl ~roup and from a~out 8 to 2Q carbon atoms in the alkane moiety.

The alkane chains o~ the foragoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthet-ically as fox example using the Ziegler or Oxo processes.
~ater solubility can be achiaved by using alkali metal ~r alkanol-ammonium cations; or magnesium or calcium cations under circumstances described by Canadian 3Q patent 1,071,Q55 invented by Jones et al, i~sued February 5, 198Q.

Mixtures of non-soap anionic surfactants are contemplated by this inventi~n; a preferred mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkvl group and either an alkyl sulfate having 8 to 18, preferably 12 to 18, carbon atoms in the alkyl group, or an alkyl polyethoxy sulfate having 10 to 16 caxbon atoms in the alkyl group and an average degree of ethoxylation of 1 to 6.

Suitable ampholytic surfactants are water-soluble derivatives o~ aliphatic secondary and tertiary amines in which the aliphatic moiety is straight chain or branched and wherein one of the aliphatic substituents contains ~rom about 8 to 18 carbon atoms and one contains lQ an anionic water-solubilizing group/ e.~. carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Suitable zwitterionic sur~actants are water soluble derivati~es of aliphatic ~uaternary ammonium phosphonium and sul~onium catlonic compounds in which the aliphatic moieties are straight chain or branched, and wherein one of t~e aliphatic substituents contains rom about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.

Preferred amphoteric and zwitterionic su~actants have the general formula:

I
~1 N~ R2_ X
R4 n wherein X is C02 or S03 , Rl ls alkyl or alkenyl group having 8 to 22 caxbon atoms, possibly interrupted by amide, ester ~x ether linkages, R2 is a methylene, ethylene, propylene, isopropylene or iso~utylene radical, R3 and R4 are independently selected from hydrogen, Cl 3 1 ~781~0 g alkyl ox -R2-X, whereby one of the substituents R3 and R4 is hydrogen if the other one is represented by the group -R2X, n ls an integer from 1 to 6, and A is an equivalent amount of a neutralizing anion, except that amphoteric sur~actants include amine salts of the above formula and also the corresponding ~ree amines.

Highly preferred surfactants according to the above formula include N-alkyl-2-aminopropionic acid, N-alkyl-2-imino-diacetic acid, N-alkyl-2-iminodipropionic la acid, N-alkyl-2-amino-2-methyl-propionic acid, N-alkyl-propylened~amine-propionic acid, N-alkyl-dipropylene-triamine-propionic acid, N-alkyl-dipropylenetriamine dipropionlc acid, N-alkylglycine, N-alkyl-amino-succinic acid, N-amidoalkyl-N'-carboxymethyl-N',N'-dimethyl-ammonio -ethylene diamine, N-alk~l-amino-ethane-sulfonic acid, N-alkyl-N,N-dimethyl-ammonio-h~droxy-propane-sulfonic acid and salts thereo~, wherein alkyl xepresents a C8 to C18 alk~l group, e~peclally coconut alky~, lauryl and tallo~ alkyl. Speci~ic examples includ~
~rmeen~Z ~marketed ~y Armour-Dial, Inc.l, ~mphoram CPl, Diamphoram~CPl, Triamphoram~CPl, Triamphora ~C2Pl and Polyamphorams~ Pl, C2Pl and C3Pl ~markete~ by Pierrefitte-Auby S.A.~ and Deriphat~70C and Deriphat 154 ~marketed b~ General Mills, Inc.~.

Suitable nonionic surfactants are of several classe~. Suitable semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of ~rom about 10 to 28 carbon atom~ and 2 moieties selected from the group consisting of alkyl groups and
3~ hydroxyalkyl groups containing from 1 to about 3 carbon atoms, and especially alkyl dimethyl amine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; water-soluble phosphine oxide detergents containing one alk~l moiety of about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl moiety of from about 10 to 28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.

Another and especially suitable class of nonionic surfactants are alkyl mono- and di-alkanol lQ amides, the alkyl group of which contains from about 10 to about 18 car~on atoms, such as coconut monoethanol amide and oleyl diethanol amide. Particularly preferred axe the ClQ to C18, more especially C12 to C14, diethanol amides.

Alkoxylated nonionic sur~actants are another class that is suitable for use in th:ls inventio~, ;
especially when used in mixtures at levels no more than about 50% o~ the total non-soap surfactant system, pre~erably at ~evels from about 5% t~3 abou~ 35% thereo~.
2Q Alkoxylated nonionic suractant materials can be ~roadly defined as compounds produced by the condensation of alkylene oxide groups ~hydrophilic in nature~ with an organic h~drophobic compound, which may be aliphatic or alkyl aromatic in nature~ The length of the poly-oxyalkylene group which is condensed with an~ particularhydrophobic group can be readily adjusted to yield a w~ter-solu~le compound having the desired degree of balance between hydrophilic and hydrophobic elements, Examples of suitable noniontc surfactants include (a~ polyethylene oxide condensates of alkyl phenol, e.g. the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain .~

- . :

8 1 6 ~) configuration xeacted with ethylene oxide in amounts equal to from 1 to about 25 mols of ethylene oxide per mol of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerised propyLene, di-isobutylene, octene and nonene. Other S examples include dodecylphenol condensed with 3 mols of ethylene oxide per mol of phenol; dinonylphenol condensed with la mols of ethylene oxide per mol of phenol; and nonylphenol and di-isooctylphenol condensed with 20 mols of ethylene oxide; ~I The condensation products of primary or secondary allp~atic alcohols having from 8 to 24 carbon atoms, ln elther stralght chain or branched chain configuration, with from 1 to about 30 mols o~ alkylene oxide per m~l o~ alcohol. Preferably, the alip~atic alcohol comprises between 9 and 15 caxbon atoms and às ethoxylated ~ith between 2 and 12, desira~ly between 3 and 9 mols o~ ethylene oxide per mol o~ aliphatic alcohol. Pre~erred nonionic surfactants o this type aXe prepared from primary alcohols which are either li~ear (such as tho~e dexived ~rom natural ~ats or prepared by t~e Zlegler process from et~ylene, e.g. myristyl, cetyl, stearyl alcohols~, s~r partly branched such a~ the Dobanols~and Neodols~which have about 25~ 2-methyl branching tDobanol and Neodol being Trade Marks of Shell Chemical Co.~ or Synperonics~
~hich are understood to have about 50% 2-methyl branching (Synperonic is a Trade ~ark o~ Imperial Chemical Industries Ltd~ or the primary alco~ols ha~ing more than 50% ~ranched chain structure sold under the Trade Mark Làal by Liquigas S.p.A. Specific examples of 3Q nonionic surfactants ~all~ g within the~scope of the invention in ~ude Dobano ~ 4, Dobanol 4~ 7, Dobanol 45-9, Doba~o r 91-3, Doba~ol~~1-6, Dobanol'~1-8, S~nperonic`~6, Synperonic'~14, the condensation products of coconut alcohol with an a~erage of between 5 and 12 mols of ethylene oxide per mol of alcohol, the coconut I :l781BO

alkyl portion having from 10 to 14 carbon atoms, and the condensation products o~ tallow alcohol with an average of between 7 and 12 mols of ethylene oxide per mol of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atoms. Secondary linear alkyl ethoxylates are also suitable in the present compositions, especially those ethoxylates of the Tergito ~ (T.M.Union Carbide Corp.~ sexies haYing from about 9 to 15 carbon atoms in the alkyl gxoup and up to about 11, especially from about 3 to 9, ethoxy residues per molecule; and (c~ bloc~ polymers formed b~ condensing ethylene oxide ~ith a hydxophobic base formed by the condensation of propylene oxide ~rith either propylene glycol or ethylene -diamine. Such synthetic nonionic detergents are ~
com~ercially available under the names "~luronic' and Tetronic", respectively ~T.M. BAS~ W~andotte Corp].

Of the above, preferred alkoxylated nonionic surfactants have an averaye HLB ~hydrophilic-lipophilic balance~ ln the range from about 9.5 to about 13.5, especially ~rom lQ to 12,5. ~ighly su~tabl~ nonionic sur~actants of this type are ethoxylated primary or secondary Cg 15 alcohols having an average degree of ethoxylation from about 3 to 9.

Expecially pre~erred non-soap surfactants are ClQ_18 alkyl diethanol amlde and the sodium sal~s of straight or ~ranched chain C~ 15 alkyl benzene sulfonate, C~ 8 alkyl sulfate, and Cl0-l8 alkyl polyethoxy sulfate containing from 1 to about 12 ethylene oxide moieties per fatty alcohol moiety.

3~ Soaps are speci~ically excluded from the surfactants disclosed hereinabove. Howe~er, soaps derived from fatty acids, natural or synthetic, saturated or unsaturated, havin~ alkyl ¢hains ranging from about I ~7~160 10 to about 18 carbon atoms in length, are also useful in the compositions of the present invention. Examples of preferred soaps are sodium and potassium laurate, myristate, palmitate, oleate and stearate; and sodium and potassium soaps dérived from coconut and tallow fatty acids.

Soaps are effective not only as supplemental cleaning agents, bu~ also aid in the solubilization of othex ingredients of the composition. In addition they control sudsing, which is hi~hly desirable ~or compo-~itions that are intended to not require rinsing.
~ccordingly, use of ~xom about 0.5~ to about 5% soap is preferred in khe compositions of t~is invention. T~is usage is, however, by no means essential to obtain superb cleaning performance characteristics and the requisite product homogeneity, and ~he broad limits of soap usage are there~ore ~rom zero to about 5~.

Builders. The builders o~ this invention are of two general types, each of which is charac~erized separately 2a hexein. Materials useful'as Sequestrants are hardness sequestering builders selected from the alkali metal salts of polyphosphates a~ p~lyphosphonates.

~

~ 178~0 Sequestrants are used in amounts rrom about 10.5~ to about 19% by weight of the composition, preferably from about 12~ to about 16~o It has been found that amounts up to about 10.5~ do not fully meet the multipurpose cleaning objectives of this invention while amounts over 19~ are unnecessary to meet these objectives, difficult to solubilize, and add to costs not only directly but also indirectly by increasing hydrotrope requirements.

Suitable polyphosphates include pyrophosphates such as tetrasodium pyrophosphate decahydrate and tetrapotassium pyrophosphate; tripolyphosphates such as pentapotassium tripolyphosphate; and higher poly-phosphates and metaphosphates such as sodium penta-polyphosphate and sodium hexametaphosphate.

Among preferred Sequestrants can be mentioned the al~ali metal salts, more particularly, the sodium and potassium salts, of pyrophosphoric acid and tri-polyphosphoric acid. Especially preferred is the potassium salt o~ pyrophosphoric acid.

.: ~

~ ~781~0 Alkalaine pH Buffers are a second type of builder. These materials include alkali metal carbon-ate, bicarbonate, orthophosphate, borate and silicate salts and ethanolamines. Buffers are not essential ingredients of the compositions of this invention.
However they are preferably used in amounts rom about 0.5% to about 6~ by weight of the composition to provide a source of reserve alkalinity. They are selected according to the conventional wisdom of the detergent arts to provide pH buffering from about 8.5 to about 11.0 for a 1% aqueous solution of the com-plete composition of this invention. The lower pH
boundary was selected in relation to cleaning effect-iveness and the upper boundary in relation to mildness and safety to surfaces.

So long as the composition has the proper pH
as defined herein, it is an effective cleaner without the presence of buffer for soils that do not contain an acidic component.
) Acco~dingly the broad limits for buffer are zero to about 6% by weight of the composition. There is a further limitation ~hat the total o Sequestering Builder plus pH Buffer be no* greater than about 21%
by weight o~ the composition; this limitation is in relation to solubilization requirements ~or the homogeneous liquids o~ this invention.

Solvents. The solvents of this invention are of two types that are characterized separately herein. The ~irst is a Principal Solvent that is required to meet the detergency ob~ectives. T~e second is an Auxiliary Solvent that under certain circumstances as described herein is utilized to solubilize the Princlpal Solvent in the composition in order to prepare a clear, homogeneous ~inished product.

The Principal Solvent o~ this inventlon is used in an amount ~rom about 6~ to about 15% by weight o~ the compos~tion, pre~er~ rom about 8~ to about 12%. ~t has the ~oll~wing physical properties at 20 25~C.:
Molar Volume: below about 200~cm3~g.mol) solubility parameters:
Polarit~ Parameter: zero to about 3.5 Ccal.~cm.3~1~2 H~drogen Bonding Parameter: zero to about 6 (cal.~cm.311~

The molar volume o~ a compound is the quotient o~ its molecular weig~t divided ~y its density. This has metric units of tgrams per g. mol~ divided ~y ~grams per cubic centimeterl which result~ in a unit of volume per ~ram mol Qf the compound in ~uestion.

1 1~81BO

The solubility parameters defined above are those of Hansen and Beerbower, "Solubility Parameters", Kirk-Othmer Encyclopedia of Chemical Technology, second ed., Supplementary Volume pp. 889-910, John Wiley & Sons, N.Y.
(1971). Hansen characterized the solubility behavior of liquids according to three modes of interaction between molecules: (1) dispersion (London) forces arising from fluctuating atomic dipoles caused by electrons rotating about a nucleus; (2) interaction between permanent or induced molecular dipoles; and (3) hydrogen bonds. These are frequently indentified as ~D~ ~p and ~H respectively, and are herein designated by the terms dispersion para-meter, polarity parameter, and hydrogen bonding parameter, respectively.

A listing of these four parameters at 25C. for over 200 solvents appears as Table L, of Hansen et al op. cit. The criteria for the Principal Solvents o~ the present invention have been selected as follows: Solvents having molar volumes above about 200 are so large that they do not penetrate and disperse soils rapidly and well.
A solvent's dispersion parameter has been ~ound incon-sequential to detergent efEectiveness. However, it has been determined that the Polarity and Hydrogen Bonding Parameters of a solvent must be lower than about 3.5 and 6.0, respecti~ely, to provide the superb detergency proper-ties across the great variety of detergency applications that this invention is intended to accomplish. Mixtures of Principal Solvents having molar volumes and solubility parameters within the range defined above are also suitable for use in the instant invention.

It has further been found that solvents having Polarity Parameters and/or Hydrogen Bonding ~ 178~60 ,~ .
_~g _ Para~etexs at or below about 2.0, while they perform superbly as cleaners in the compositions of the present invention, are often not sufficiently miscible with the other ingredients to form clear, stable, homogeneous S liquid composltions, even with the addition o~ hydro-txopes as hereinafter defined. Accordingly, Auxiliary Solvents having Polarity and/or Hydrogen Bonding Parameters highex than 3.51 and 6.01, respectively (i.e. higher than the limits defined hereinbefore for the Principal Solventl, can be added to compatibilize the ~rincipal Solvents in these compositions. As a guide to formulation, each parameter o~ a solvent rnixture can be estimated according to the weighted avexage of its components.

The ~uxiliary Solvents o~ this invention can be used in an amount up to about ~ o~ the composition b~ we~ght, i.e. ~rom zero to abou~ 10%. When used, pxefexred amounts are ~rom a~out 2% to about la%
~y weig~t o~ the comp~s~tion. Because o~ solubiliæation re~u~re~ents, the total o~ Princ~pal Solvent plus Auxiliar~ Solvent should not ~e greatex than about 22 o~ the composit~on by weight.

When the Polarity and Hydrogen Bonding Parametexs o~ the Principal Solvent are both above about 2.Q, an Auxiliar~ Solvent is in general not necessary fox solubilization and preferably is used in an in5ignlficant amount if at all; i.e. less t~an about 2% by weight o~ the composition.

Auxiliary solvents used in this manner have 3Q sometimes been described in the priox art as "coupling agents". This texm is avoided herein, as the solubilizing ~unction can often be accomplished not only ~y Auxilia~y Solvents as defined herein, ~ut also by Principal l~

Solvents of relatively high Polarity and Hydrogen Bonding Parameters. So doing not only accomplishes the solubilizing function but also contributes effectively to cleaning. According to these principles, it may be preferred, for example, to solubilize xylene with diethylene glycol mono-n-butyl ether than with isopropyl~
alcohol. l Examples of ho~ solvents meet these definitions are as ~ollows;
~ydrogen Molar Polarlty Bonding Volume Parameter Parameter cm.'3 ' cal, 1/2 ' cal 1/2 Code Sol~ent ' '' ~ mol '' cm.3 ~.
A Dodecane 228 ~ a- ~
B Toluene 106 0.7 1.0 C Naphthalene 112 1.0 2.~
D ~sopropyl ~lcohol77 3.0 8.0 E Glycerol 73 S.9 14.3 ~exylene Glycol 123 4.1 8.7 G Propylene Carbonate 85 8.8 2.0 H ~thylene glycol monoethyl ether ~8 4.5 7.0 ~iethylene ~lycol mono-n-butyl ether 170 3.4 5.2 J But~l acetate 133 1.8 3.1 K Pine Oil ~ 126 ~ 2.0 ~ 5.6 L Orange te~pene ~ ~4 ~ 0 ~ a.3 Di~cussin~ ~ese solYents individually:
A. T~e molar ~olume o dodecane is too high to s~tisfy the requirements of this invention as to Rrincipal SolYe~t.
~,C. Toluene o~ n~phthalene can ~e used as Principal ~olyent, ~ut ~e~u~re t~e addition o~ an ~uxil~ SolYent to satis~y the solu~ility xequixements of t~is invent~on.

.

î ~7818~

, ~,o ~"~,.
D,~,~,G,H. Isopropyl alcohol, hexylene glycol-, glycerol, propylene carbonate and ethylene glycol monoethyl ether are too high in Polarity Parameter and/or-Hydrogen Bonding Parameter to satisfy the re~uirements of Principal Solvent. However the~ are acceptable as Auxiliary Solvents.
I,J,K,L. Diethylene glycol mono-n-butyl ethex can ~e used as Principal Solvent of this invention.

In the foregoiny table, parameters ~ox solvents ~-J a~e those appearing in Hansen et al, op. cit.
Parameters ~or solvents K and L wexe estimated, as ~ollows:

Pin~ oil, according to the Pine Oil Foxmular~, Hercules Powder Compan~ ca. 1963, is derived from extracts of p~ne wood and is compx~sed predominantl~ of cyclic texpene alcoh~ls. Its chief con~tituent is alpha terpineol, a tertlary alcohol having the structure ~c(cH3l2oH~ Wh~ch is present at levels ran~ing ~rom below 70~ to as high as 85~, depending upon the commercial grade, with`the remaindex being a mixture of terpene hydrocarbons, ethers and ketones. Values for the molar volume, Polarity Parameter and Hydrogen B~nding Parametex of alpha terpineol and pine oil are not available in the literature. However, based on literatuxe value~ ~or chemicals of closely related structure and upon ~leanin~ data, these three values axe estimated ox ~oth su~stances to ~e approximately those appeaxin~ in the foregoing ~able for solvent K.

Orange terpenes and limonenes, also, are mixtures of chemicals derived from naturally occurring materials that Vary somewhat accord~ng to source.
These three values ~Qr both substances are estimated to ~e approximately t~ose appearing in the foregoing table for solvent L.

11 17816~ -~ t ~ill be understood that selection of Principal Solvents ànd Auxiliary Solvents for particular applications of this inve~ntion will take into consideration not only the parameters discussed hereinabove but also such usual criteria as cost, availability, odor, ~lammability, safety, etc.

Solvents meetin~ the criteria herein expressed ~or Principal Solvents o~ this invent~on, that ordinarily :
do not require the use of Auxiliary Solvents, include ethylene glycol mono-n-butyl ether, ethylene glycol ..
mono-n-hexyl ether, diethylene gl~col mono-n-butvl eth.er, diethylene glycol mono-n-hexyl ether, isopropylene glycol mono ethyl ether, isopropylene glycol mono propyl ether, lsopropylene glycol mono butyl ether, methyl cycloh.exane, butyl acetate, amyl acet~te, butyl ~utyrate, ~ut~l lactate, diethyl ca~bonate, dlet~lyl sucainate, m~th~l ~-amyl ketone, morpholine, and anisole.

$olvents meeting the criteria herein expressed for Principal Solvents of this invention, for which ~uxiliary Solvents are ordinarily required, include n-hexane, n-decane, cyclohexane, toluene, xylene, naphtha-lene, diethyl ~enzene, chlorobenzene, trichloroethylene, pine oil, alpha texpineol, d~limonene, and orange terpene.

Solvents wh~ch can be used as Auxiliary Solvents in thls invention, that do not meet the criteria ~or Principal Solvents, include propylene car~onate, meth~1 eth~1 ~etone, acetone, et~ylene glycol mono meth~l ether, ethylene glycol mono ethyl 3Q ether, diethylene glycol mono methyl ether, diethylene glycol mono ethyl ether, benzyl alcohol, diethylene ~lycol, glycexol, hexylene glycol, propylene glycol, ethylene glycol, l-butanol, l-propa~ol, and ethanol.
~:, , ~ ~781~ `

_22-The ~oregoing lists are not intended to be exhaustive but rather to exemplify the varied kinds of solvents that meet the parameters of this invention as defined hereinbefore. Provided solvents meet the molar volume, polarit~ parameter and hydrogen bonding parameter limits as hereinbefore defined, the Principal Solvents of this invention can be selected from among aliphatic, aromatic and chlorinated hydrocarbons; alcohols;
esters; ethers; glycol ethers; ketones; and amines.

Preferred Principal Solvents are ethylene glycol mono-n-~ut~l ether, ethylene glycol mono-n-hexyl ether, diethylene gl~col mono-n-butyl ether, diethylene ~lycol mono-n-he~yl ether, isopropylene glycol mono ethyl ether, mixed isopropylene glycol mono-butyl, et~l and propyl ethers, pine oil, alpha terpineol, orange ter~ene, met~yl cyclohe~ane, toluene, xylene, but~l acetate and amyl acetate. Especially preferred is diethylene glycol mono-n-butyl ether, used in the essential absence of an ~ux~liary Solvent.

2a Hydrotrope. Solubilization of ingredients of dissimilar characteristics such as solvents and electrolytes is achieved by the use o~ hydrotropes. ~ater soluble salts o low molecular weight organic acids are suitable hydrotropes. Among such materials are sodium and potassium salts of toluene, benzene and cumene sulfonic acids, and sodium and potassium sulfosuccinate. Urea is also a suitable hydrotrope. Hydrotropes are used in amounts from about 3~ to about 25~ by weight of the composition, pr~ferably ~rom about 6~ to about 14%.

Optional Ingredients. T~e compositions of the present invention can optionally contain minor amounts of colorants; perfumes;

... .. .
. . .

1 ~781~0 soil suspending agents such as carboxymethyl cellulose, sodium polyacrylate, and polyethylene glycols having a molecular weight from about 400 to about 10,000;
fluorescers; suds boosters; suds regulants; opacifiers;
enzymes and enzyme stabilizers; germicides; and other materials known to the liquid detergent arts.

INDUSTRIAL APPLICATION

The following examples describe the ~ormulation of compositionS o this invention and the benefits derived therefrom. The~ axe illustrative of the ~nvention and ~re not ko be construed as limiting t~ereof.

Example_l.
Composition ~ wa~ prepared by mixing the followin~ components together in the order listed:
wt.~ of active Component ~rams ~ngredient_ ~ater 67.5 S9.1 KTS (51.5~ 38.8 10.0 Na2C3 3.1 1.55 NaHCO3 2.5 1.25 Coconut ~atty Acid 3.6 1.8 NaAE3S ~27~ active pastel 18.5 2.5 TKPP (60~ solution)46.0 13.8 diethylene glycol mono n-butyl ether- 20.0 10.Q
20Q.0 100.Q

In the table above, NaAE3S designates the sodium salt o~ the condensation product of 3 mols of ethylene oxide ~ith coconut fatty alcohol. TKPP
designates tetrapotassium pyrophosphate. ~TS designates potassium toluene sulfonate. The coconut fatty acid , ~
was neutralized during the mixing process to form coconut soap. The pH of the composition was measured to be 9.5 when measured full strength and 9.3 when measured as a 1~ aqueous solution.

This composition was tested for cleaning performance against 5 kinds of artificial soil designed to simulate in a reproducible manner a liXe number of natural soils ~ound around a house:
1~ Greasy~waxy soil found on kitchen floors: a mixture of cooking oil and floor-wax applied to vinyl-as~estos tiles; and aged.
21 Greas~ soil ~ound on kitchen walls: a mixture of cooking oil and humus applied to vinyl-asbestos tiles; baked; ancl aged.
lS 3~ Bathroom soil found in bat:htubs: a mixture o~ skin o~1, soap and humus applied to etched porcelain plates; three coats applied and ~aked; aged.
41 Bathroom soil found on walls above the tub or in shower stalls or in toilet bowls:
calcium stearate applied to smooth porcelain plates; baked.
All soils were pigmented with small amounts of carbon black to aid in the evaluation of cleaning per~ormance.
Cleaning tests were performed on a modi~ied Gardner straight line tester (Gardner Lab Inc., Bethesda, Maryland, U.S.A~). In this machine, a rectangular sponge is moved back and forth across the test surface with constant, uniform pressure applied. The cleaning product was applied to the sponge, and a ~ixed number of strokes was made across the sur~aces. The total number of strokes for each test was fixed at the point where the cleaning level of approximately 7Q to qO%
was visually estimated for the ~est composition in that particular test. Each product was replicated four times on different tiles.

1 1 7 ~

---~6~
Cleaning results were quantitively evaluated by using the L (lightness~ values of a Hunter colorimeter (Hunter Associates Laboratory, Fairfax, Virginia, U.S.A.). Performance was measured as the percentage of soil removed. Quantitatively, where Lb ~ the L --value of the substrate before soil was applied; Ls =
the L value after soil was applied; and Lc = the L
value after cleaning; the cleaning performance in %
was calculated to be (lOO~Lc-Lb~/~Ls-L~l.

In the performance tests described infra, li~uid cleaning compositions were used full strength on both bathroom soils ~nd on the greasy kitchen wall soil; while the liquid compositions were used in dilute foxm on both k~tchen soils; making 5 teSts in 15 all. These practices simulated consumer practices in cleaning these surfaces, either full strength from the ~ottle or diluted in a scrub bucket. For tesk purposes, 2 grams of the liquid compositions were applied to each Gardner test sponge and used for full strength cleaning; while a mixture o~ 0.15 ~rams ol the li~uid composition with 9.85 ~rams of water was used for dilute cleaning. To simulate consumer use of dr~
abrasive cleanser, 2 grams of the composition plus 2 grams of water was applied to the sponge.

Cleaning ~erformance was as follows:
Percentage of Soil Removed Simulated Product Ccmp. Commercial Products Soil Collc. A Mr.Clean Pine Sol Ca~et Kitchen floor dilute 6~% 71% 7% -" wall " 83 74 57 " " full str. ~Q 38 81 Bathroom tub " " 85 57 52 85 Shower wall " " 77 25 1~ 4a 1 17~160 ~6 .. ., ~
In the above comparison, Mr. Clean ~TM Procter &
Gamble Inc.~ is a built liquid composition sold commercially for hard sur~ace cleaning, containing sodium nitrilotriacetate and mixed diethanol amide/
ethoxylated nonionic surfactant as principal cleaning ingredients; Pine Sol (TM American Cyanamid Co.~ is a liquid composition sold commercially for hard surface cleaning, containins pine oil, isopropanol and soap;
and Comet (TM Procter & Gamble Inc.~ is an abrasive cleanser sold for Scouring tu~s and sinks, containing finel~ divided s~lica as the scouring agent, and lesser a~ounts o~ anionic surfactant, chlorine bleach, and builder.

In the fore~oin~ table, cleaning differences between products greater than about 3~ are significant.
Acco~dlngly, Composition A, fo~mulat~d according to this invention, was approximately e~ual to or was superior to each o~ these commercial products in evexy application. This same conclusion was also reached by a panel of ~rade~s w~o ~lsuall~ examined t~e tile surfaces after cleaning.

N~te that it is appropriate to compare cleaning results or each type of soil as obtained fox the 4 products tested ~i.e. numbers within each single row of the table ~ove~. ~t is not appropriate to compare numbers ~ithin columns of the table, because the number of strokes on the test machine were different for each type of soil.

~ second composition of this invention, B, ~as prepaxed that differed from A only in that 2 diethanolamine was used as ~uffer, replacing the mixture of 1.55~ Na2CO3 plus 1.25~ NaHC03, ~ith a I ~ 781~

minor adjustment in the water content. The cleaning tests were repeated with approximately the same results.

Composition C of this invention was like that of Composition A except that it contained 6~ instead of 10% of diethylene glycol mono-n-butyl ether, with the difference made up by water.

Composition C was tested on the two bathroom soils in the manner hereinbefore described, and in the same series of tests, with the following results: 75 removal of simulated bathtub soil and 46% removal of simulated shower wall soil. It is apparent that the 6% solvent level, which is at the lower end of the formulation range of the compositions of this invention, while it reduces performance against both types of soil, is still well within the range of commercial products against bathtub soil and remains superior to all commercial products against shower wall soil.

Compositions ~, B, and C were homogeneous and were stable indefinitely at room temperature.

Example 2 The following homogenous liquid compositions were similarly prepared, with all figures being percent _2~
by weight, ~nd the balance being water:
D E F G
NaAE3S 2.5 0 2.5 2.5 wt.%
TKPP 13.8 13.8 10.0 13.8 5 dieth~lene glycol mono n-but~l ether 10.0 10.0 10.0 5.0 coconut fatty acid 1.8 1.8 1.8 1.8 Na2C~3 1.55 1.55 1.55 1.55 NaHCO3 1.25 1.25 1.25 1.25 10 KTS 12.0 12.0 12.0 12.0 The a~oVe compositlons were tested in the m~nner described in Example 1, With the following results:
.
Product ~excenta~ie o~ Soil Removed Soil Conc D ~ F G
~ .. ... . . . . ~
Kltchen Floor dilute 72 53 ~7 75 " ~all " 56 41 49 55 " " full str. 78 76 79 70 Bathroom Tub " "89 8~ 87 79 20 ~hower Wall" " 72 79 51 69 Composition D is the onl~ one of the foregoing that is according to t~s invent~on. It is clearly apparent from the above results that removal of surfactant or reduction of builder to a level outside the scope of this invention caused a significant reduction in cleaning when the compositions were used in dilute form on either simulated floor soil or wall soil; builder reduction diminished effectiveness against simulated shower wall soil as well. It is also clear that reduction of a solvent to a level outside tha scope of this invention caused a signi-ficant reduction in cleaning when the compositions wereused full strength on all three soils: simulated kitchen wall, bathroom tub and shower wall soils. These data ~' ~

.. . .. . . ....... . ..

. -29.-demonstrate both the need and the effectiveness of concurrent high levels of both builder and solvent, in liquid compositions containing surfactant and other ingredients, to obtain the multiple cleaning objectives of this invention: a standard of accomplishment that has not been achieved heretofore.

Other composi~ions are prepared like Composition D except for the followlng differences:

Coconut fatty acid:
i~. omitted ~il lncreased to 4%
iiil oleic acid su~st~tutecl ~or coconut atty acid Su~stituted for NaAE3S:
vi~ C16 diethanolamide viil coconut monoethanolam~de viil~ sodium coconut alkyl sulfate ixl C14 sodium paraffin sulfonate x) C12 magnesium AE6S
xi~ coconut d~meth~l amine oxide xii~ sodium salt of N-lauryl-N,N-dimethyl - ammonio-hydroxy-propane-sulf~onic acid xiii~ 1.8% NaAE3S plus 0.7% C14AE6 ~linear alkyl ethoxylate containing 6 moieties of ethylene oxide per moiety of myristyl alcoholl Substituted for car~onate~bicarbonate:
xi~l sodium orthophosphate xvl sodium metasilicate x~il sodium tetraborate .

1 178~60 The cleaning performance of the foregoing compositions is comparable to that of Composition D.

Example 3.

Compositions H and I were prepared according to this invention as follows:
H
Na-Cll 8 linear al~yl benzene sulfonate CLASl 10.0 - wt.
Na-~E3~ - 2.3 10 TKPP 13.8 13.8 diethylene glycol mono-n-butyl ether lO.Q
diethyl succinate - 10.0 coconut atty acid 1.8 ~.6 15 Na2C3 1.6 1.6 Na~lCO3 1.2 1.2 KTS 12.0 Na cumene sulfonate - 7.Q
Na2SO3~ammonta~opacifier~color - 3.3 20 water bal. bal~

Each of t~e a~ove compositions ~as homogeneous and stable indefinitely at room temperature. A number of other compositions were pre~ared t~at ~ere identical to Composition H except ox differences in sol~ent.
2~ They too were homogeneous and sta~le indefinitely at room temperature. These solvents were: a mixture of 3% n-decane and 7% diethylene glycol mono-n-butyl ether Chereinafter ~eferred to as DGBEI; a mixture of 3% cyclohexane and 7% DGBE; a mixture of 3% xylene and 7% DGBE; a mixture of 5% xylene and 5% DGBE; a mixture o 2.2% diethyl benzene and 7.8~ DGBE; 10% but~l acetate; 10~ amyl acetate; 10% diethyl carbonate; 8%

. . . . . . . .. .

Ba diethyl succinate; 7.5% methyl i-amyl ketone; lQ%
methyl i-amyl ketone; 10% ethylene glycol mono-n-butyl ether; 10~ ethylene glycol mono-n-hexyl ether; 10~
diethylene glycol mono-n-hexyl ether; 10% isopropylene glycoL mono propyl ether; 10~ of a mixture of isopropylene glycol mono-butyl, ethyl and propyl ethers tpropa BEP, TM Union Carbide Corp.~; 6~ pine oil and 4 isopropyl alcohol; 2% pine oil and 8~ DGBE.

~11 of the compos~tions descri~ed in Example 3 hexein ~exe tested for cleaning performance on both bathx~om soils ~n the manner described ~erein~efore.
Results were comparable to thase of compositions A and D.

Example 4.
.

The following composition was prepared, was homogeneous and stable at room tempexature;
and cleans well accoxding to the tests described herein-before, J
NaLAS 8.~
20 Coconut fatt~ acid 1.4 TKPP 16.Q

KTS 1~.3 diethanola~ine 1.6 diethylene glycol mono-n-butyl ether 12.Q
isopropyl alco~ol -w~ter bal.

Example 5.

- Certain pure solvents were screened for cleaning as de~cri~ed belo~. T~e Gardner test mac~ine _.___ .... .. . .. .. ...... . .. . ... .. . .. .

!L 1~781GO

was used with simulated bathtub soil tiles and 2 grams of solvent per sponge. The data are consistent with the selection of solvent parameters that define the invention herein. The numbers which follow are the number of strokes required, as judged visually, to completely clean the tiles. Solvents meeting the criteria herein for principal solvent: trichloro-eth~lene - 4; xylene - 5; hexane - 5; chloroform - 5;
carbon tetrachlor~de - 6. Solvents not meeting the criteria herein for principal solvent: meth~l ethyl ketone - 18; l-hutanol - 2Q; dieth~lene glycol mono ~-ethyl ether - 35; et~anol - 40; acetone - more than
4$; methanol - more than 45; dimethylfoxmamide -more than 45, Example 6.

The ~ollowing compositions o~ this invention were prepared in greater quantlty ~or the purpose of stabilit~ testing:
-K L M
NaLAS 10.0 4.0 ~ wt.%
NaAE3S 2.5 Coconut fatty acàd 1.8 1.8 1.2 TKPP 13.8 13.3 13.3 KTS 12.0 7.0 12.0 Na2C3 1.6 NaHC~3 1.2 diethanolamine - 2.0 2.0 diethylene ~lycol ~ono-n-butyl et~er lQ.0 8.5 8.5 30 pexfume - - Q.75 water bal. ~al. ~al.

Composition N was prepared identical to that of Compos~tion Kexcept that its sol~ent ~as 10~
ethylene ~l~col mono-n-butyl ether. Compositions ~ and ", . '-1 6 ~

N were clear, homogeneous liquids and remained so after storaye for 3 months at 4, 21 and 49C. ~oth fully recovered to their original homogeneoùs appearance after 3 cycles alternating between 24 hours at -18C.
and 72 hours at +10C.

Composition O ~as prepared identical to that of Composition L except that the KTS level was 12~.
Compositions L, ~ and O were tested using procedures and obtainin~ results the same as for Compositions R
and N except that the storage tests at 4, 21 and 49C. we~e d~scontinued after 2 weeks, wit~ no visi~le changes having occurred during that time.

Co~positions containing ~igher or lower amounts of ~uilder and~or solvent ~ithin tAe scope of this invention can be stabiliæed ~ adjusting levels of ICTS and fatt~ acid within the ranges specified herein, accordlny to principles known in the art. Diethanolamine is pre~e~red to inorganic ~u~fers rom the standpoint of inc~easing st~bilit~ under severe storage conditions.

i~
.. . , ,' ~ '

Claims (8)

What is claimed is:
1. A homogeneous aqueous liquid hard-surface-cleaning detergent composition comprising the following components:
a) from about 0.9% to about 10% of a non-soap anionic, amphoteric, zwitterionic or nonionic surfactant;
b) from zero to about 5% soap;
c) from about 10.5% to about 19% of a polyphos-phate or polyphosphonate sequestrant;
d) from zero to about 6% of an alkaline pH
buffer, with the proviso that the sum of components (c) and (d) is not greater than about 21% of the composition;
e) from about 6% to about 15% of a Principal Solvent having a molar volume below about 200 (cm.3/gm.mol) and solubility parameters at 25°C. as follows: Polarity Parameter from zero to about 3.5(cal./cm3)1/2 and Hydrogen Bond-ing Parameter from zero to about 6(cal./cm.3)1/2;
f) from zero to about 10% of an Auxiliary Solvent having a Polarity Parameter of about 3.51 or above and/or a Hydrogen Bonding Parameter of about 6.01 or above, with the proviso that the sum of components (e) and (f) is not greater than about 22% of the composition;
g) from about 3% to about 25% of a hydrotrope;
and h) the balance water;
wherein all percentages are by weight of the composition; and wherein the pH of a 1% aqueous solution of the detergent composition is from about 8.5 to about 11.
2. The composition of claim 1 wherein element (a) the non-soap surfactant, is an anionic surfactant or is an alkyl ethanol amide; element (c), the sequestrant, is an alkali metal polyphosphate salt;
element (d), the alkaline pH buffer, is from about 0.5% to about 6% by weight of the composition and is an alkali metal carbonate, bicarbonate, orthophosphate, borate, or silicate salt or is an ethanolamine; and element (c) the Principal Solvent, is from about 8% to about 12% by weight of the composition.
3. The composition of claim 2 wherein element (a), the non-soap surfactant, is from about 2% to about 7% by weight of the composition and is selected from the group consisting of C10-18 alkyl diethanol amide and the sodium salts of straight or branched chain C9-15 alkyl benzene sulfonate, C10-18 alkyl sulfate, and C10-18 alkyl polyethoxy sulfate containing from 1 to about 12 ethylene oxide moieties per fatty alcohol moiety; element (b) soap, is from about 0.5% to about 5% by weight of the composition; element (c), the sequestrant, is from about 12% to about 16% by weight of the composition and is selected from the group consisting of alkali metal salts of tripolyphosphoric acid and pyrophosphoric acid;
element (d), the alkaline pH buffer, is from 0.5% to about 6% by weight of the composition and is diethan-olamine; and element (g), the hydrotrope, is selected from the group consisting of the alkali metal salts of toluene sulfonate, xylene sulfonate and cumene sulfonate.
4. The composition of any of claims 1-3 wherein element (e), the Principal Solvent, is selected from the group consisting of n-hexane, n-decane, cyclohexane, toluene, xylene, naphthalene, diethyl benzene, chlorobenzene, trichloroethylene, pine oil, alpha terpineol, d-limonene, orange terpene, ethylene qlycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, isopropylene glycol mono ethyl ether, isopropylene glycol mono propyl ether, isopropylene glycol mono butyl ether, methyl cyclohexane, butyl acetate, amyl acetate, butyl butyrate, butyl lactate, diethyl carbonate, diethyl succinate and methyl i-amyl ketone, morpholine and anisole.
5. The composition of any of claims 1-3 wherein element (e), the Principal Solvent, is selected from the group consisting of ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, isopropylene glycol mono ethyl ether, isopropylene glycol mono propyl ether, isopropylene glycol mono propyl ether, isopropylene glycol mono butyl ether, methyl cyclohexane, butyl acetate, amyl acetate, butyl butyrate, butyl lactate, diethyl carbonate, diethyl succinate, methyl i-amyl ketone, morpholine, and anisole; and wherein the Auxiliary Solvent is less than about 2% by weight of the composition.
6. The composition of any of claims 1-3 wherein element (e), the Principal Solvent, is selected from the group consisting of n-hexane, n-decane, chlorobenzene, trichloroethylene, pine oil, alpha terpineol, d-limonene, and orange terpene and wherein the Auxiliary Solvent is from about 2% to about 10% by weight of the composition and is selected from the group consisting of propylene carbonate, methyl ethyl ketone, acetone, ethylene glycol mono methyl ether, ethylene glycol mono ethyl ether, diethylene glycol mono methyl ether, diethylene glycol mono ethyl ether, benzyl alcohol, diethylene glycol, glycerol, hexylene glycol, propylene glycol, ethylene glycol, 1-butanol, 1-propanol, and ethanol.
7. The composition of any of claims 1-3 wherein element (e), the Principal Solvent, is selected from the group consisting of ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, isopropylene glycol mono ethyl ether, mixed isopropylene glycol mono-butyl, ethyl and propyl ethers, pine oil, alpha terpineol, orange terpene, methyl cyclohexane, toluene xylene, butyl acetate and amyl acetate.
8. The composition of claim 3 wherein element (e), the Principal Solvent, is diethylene glycol mono-n-butyl ether.
CA000385586A 1981-09-10 1981-09-10 Liquid hard-surface cleaner Expired CA1178160A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CA000385586A CA1178160A (en) 1981-09-10 1981-09-10 Liquid hard-surface cleaner
GR69130A GR78090B (en) 1981-09-10 1982-08-26
AU88168/82A AU555988B2 (en) 1981-09-10 1982-09-09 Liquid hard-surface cleaner
IE2215/82A IE53499B1 (en) 1981-09-10 1982-09-09 Liquid hard-surface cleaner
MX194348A MX158027A (en) 1981-09-10 1982-09-10 LIQUID DETERGENT COMPOSITION TO CLEAN HARD SURFACES
SE8205171A SE8205171L (en) 1981-09-10 1982-09-10 LIQUID CLEANER FOR HARDA SURFACE
EP82305211A EP0105063B1 (en) 1981-09-10 1982-09-30 Liquid hard-surface cleaner

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CA000385586A CA1178160A (en) 1981-09-10 1981-09-10 Liquid hard-surface cleaner
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* Cited by examiner, † Cited by third party
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US4921629A (en) * 1988-04-13 1990-05-01 Colgate-Palmolive Company Heavy duty hard surface liquid detergent
US5102573A (en) * 1987-04-10 1992-04-07 Colgate Palmolive Co. Detergent composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0137616B1 (en) * 1983-08-11 1988-01-27 The Procter & Gamble Company Liquid detergents with solvent
GB8409054D0 (en) * 1984-04-07 1984-05-16 Procter & Gamble Stabilized oil-in-water cleaning microemulsions
US4749509A (en) * 1986-11-24 1988-06-07 The Proctor & Gamble Company Aqueous detergent compositions containing diethyleneglycol monohexyl ether solvent
US5202050A (en) * 1987-04-06 1993-04-13 The Procter & Gamble Company Method for cleaning hard-surfaces using a composition containing organic solvent and polycarboxylated chelating agent
NZ224148A (en) * 1987-04-10 1991-02-26 Colgate Palmolive Co Pre-spotting composition for food residue removal
GB8802106D0 (en) * 1988-01-30 1988-02-24 Procter & Gamble Hard-surface cleaning compositions
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US4921629A (en) * 1988-04-13 1990-05-01 Colgate-Palmolive Company Heavy duty hard surface liquid detergent

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EP0105063B1 (en) 1986-12-30
GR78090B (en) 1984-09-26
SE8205171L (en) 1983-03-11
IE53499B1 (en) 1988-11-23
EP0105063A1 (en) 1984-04-11
IE822215L (en) 1983-03-10
SE8205171D0 (en) 1982-09-10

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