AU619545B2 - General-purpose cleaning compositions - Google Patents

General-purpose cleaning compositions Download PDF

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AU619545B2
AU619545B2 AU34807/89A AU3480789A AU619545B2 AU 619545 B2 AU619545 B2 AU 619545B2 AU 34807/89 A AU34807/89 A AU 34807/89A AU 3480789 A AU3480789 A AU 3480789A AU 619545 B2 AU619545 B2 AU 619545B2
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composition
weight
nonionic
cationic
surfactant
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AU3480789A (en
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Paolo Bernardi
George Kerr Rennie
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Unilever PLC
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Unilever PLC
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    • 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
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/835Mixtures of non-ionic with cationic compounds
    • 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
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

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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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

AUSTRALIA
PATENTS ACT 1952 Form COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: TO BE COMPLETED BY APPLICANT 6 0 Name of Applicant: UNILEVER PLC Address of Applicant: UNILEVER HOUSE
BLACKFRIARS
LONDON EC4
ENGLAND
e S Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.
Complete Specification for the invention entitled: GENERAL-PURPOSE CLEANING COMPOSITIONS The following statement is a full description of this invention including the best method of performing it known to me:- 1 C.7129 GENERAL-PURPOSE CLEANING COMPOSITIONS 00 The present invention relates to general-purpose cleaning compositions with improved properties. More SQ 5 particularly, it relates to general-purpose cleaning compositions which have a sanitizing effect and a streak-free cleaning benefit.
0 General-purpose cleaning compositions are 0o00 o 10 compositions which are intended for use in the cleaning of .o hard surfaces, such as tiles, walls, floors, kitchen furniture, glass, plastic-covered doors, etc. Such general-purpose cleaning compositions are well known in the art and have found substantial commercial use.
CC
c.'t These compositions are usually provided in the form of a particulate composition, from which the user prepares an aqueous solution, or in the form of a liquid composition which contains a suitable solvent, such as water, or a mixture of these. These liquids can be applied either neat for the removal of stubborn stains, or in the form of a more diluted solution for large surface area cleaning.
1 2 C.7129 However, despite the fact that many of such j general-purpose cleaning compositions often satisfactorily remove soil and dirt from hard surfaces, they often leave behind residues once the solvent medium has evaporated during the drying of the cleaned surface. The surface presents residues, visible as dull streaks, instead of the bright, shining surface that the consumer wants to see.
It is therefore an object of the present invention to provide general-purpose cleaning compositions with a "streak-free" cleaning benefit, i.e. after cleaning a hard surface with such a cleaning composition, the hard surface, when dry, does not show a residue in the form of °visible, dull streaks to any significant degree.
o o For brevity's sake, such a cleaning composition will 0 00 0:0. hereafter be called a streak-free, general-purpose o000 oo o. cleaning composition, "streak-free" being understood as described hereabove.
Frequently, an important aspect of general-purpose 0 0 .o .6 cleaners is that they should not only satisfactorily clean hard surfaces, but also sanitize the hard surfaces to render them hygienic. This has been recognized in the art, and many proposals concerning such cleaning compositions, often referred to as detergent sanitizers, i have been made (see e.g. "Surface Active Ethylene Oxide SCCAdducts" by N.Schnfeldt, Pergamon Press, 1969, pages t t 439-441). Such compositions are mainly based on a mixture of nonionic and cationic detergent surfactants although cationic alone can be used.
A disadvantage of such detergent sanitizers based on a mixture of nonionic and cationic detergent surfactants is that they frequently give rise to streak formation on
R
j i. 3 C.7129 the surfaces when dry, which, as explained above, is unattractive to the consumer.
It is therefore an object of the present invention to provide a general-purpose cleaner having a sanitizing effect, containing a mixture of a nonionic and a non-anionic detergent surfactant, which also provides a streak-free cleaning benefit.
In our European Patent 0 066 342, published on December 1986, we have described and claimed a streak-free, general-purpose cleaning composition comprising a nonionic detergent surfactant and an at least partially alcohol-esterified resin. However, the 0o[[ 15 inclusion of such partially esterified resins in a 0* composition which also contains a cationic detergent surfactant does not provide a streak-free benefit, but can rather give rise to worse streak formation.
We have now surprisingly found that the inclusion of a non-anionic polymer in general-purpose cleaners which Oo econtain a mixture of a nonionic and a cationic detergent surfactant significantly reduces streak formation and also provides an improved, streak-free cleaning benefit.
The invention will further be described below in its essential details.
The nonionic detergent surfactant used in the present invention can be any suitable type of nonionic detergent known. Basically, nonionic detergent surfactants consist of a hydrophobic moiety, such as a C 8
-C
20 fatty acid amide, and a hydrophilic moiety which consists of alkylene oxide units. These nonionic detergent surfactants are, for instance, alkoxylation products of the above hydrophobic moieties containing from 2 to 30 moles of 4 C.7129 alkylene oxide. As alkylene oxides, ethylene, propylene and butylene oxides and mixtures thereof are used.
Typical examples of such nonionic detergents are
C
9
-C
11 primary, straight chain alcohols condensed with from 4-9 moles of ethylene oxide, C12-C 15 primary straight chain alcohols condensed with 6-12 moles of ethylene oxide, or with 7-9 moles of a mixture of ethylene oxide and propylene oxide, C 11
-C
15 secondary alcohols condensed with from 3-15 moles of ethylene oxide, and C 10
-C
18 fatty acid diethanolamides. Further examples of nonionic detergent surfactants may be found in M.Schick's textbook "Nonionic Surfactants", M.Dekker Inc., New York, 1967.
0o o. Mixtures of various nonionic surfactants may also be used.
.a 15 Tertiary amine oxides, such as higher alkyl di(lower o°a alkyl) amine oxides, e.g. lauryl dihyroxyethyl amine 0°00 oxide, may also be used as a suitable nonionic surfactant.
0 0 0 0 0 Nonionic detergent surfactants known in the art as "topped" or "peaked" nonionic detergent surfactants are o also useful in the present invention. Topped nonionic O detergent surfactants can be made by subjecting the usual nonionic detergent surfactant to a steam distillation treatment, by which the free and low alkoxylated alcohol can be removed, and peaked nonionic detergent surfactants can be made by carrying out the alkoxylation with special catalysts, which results in products with a much sharper peak in the alkoxylate distribution. Topped nonionic t detergent surfactants are e.g. described in US Patent Specification 3 682 849.
Topped or peaked nonionic detergent surfactants suitable for the present invention contain an average number of alkylene oxide units of between 3 and preferably between 4 and 12, per molecule of the hydrophobic moiety, i.e. a C 6
-C
18 primary or secondary, C.7129 straight or branched chain alcohol, and preferably contain less than 2% by weight of non-alkoxylated alcohol, and less than 4% by weight of mono-alkoxylated alcohol.
Particularly suitable are nonionic detergent surfactants with these specifications and prepared from C 11
-C
15 linear primary alcohols condensed with 7-11 moles of ethylene oxide, C 9
-C
11 oxo-alcohols condensed with 5 moles of ethylene oxide, and C 6
-C
10 linear primary alcohols condensed with 4-5 moles of ethylene oxide.
For optimum detergency, the shorter alkyl chain length nonionic surfactants are preferred, particularly when the degree of alkoxylation is relatively low. Thus, the alkoxylated C 9
-C
1 1 alcohols are preferred to the °000 15 correspondingly alkoxylated C 1 2
-C
15 alcohols, and the C -C 11 alcohols condensed with 5 moles of ethylene oxide O are preferred to the same alcohols but condensed with 8 .oo moles of ethylene oxide.
0 In general, when dissolved in water, the HLB-value of the nonionic surfactant or mixture of nonionic surfactants OOo should lie between 10 and 15. Nonionic surfactants with an HLB-value of below 11 are generally not soluble in water to any appreciable extent without another active detergent present, but it is possible to dissolve higher levels of such low HLB-nonionic surfactants in mixtures of water and an organic solvent.
t t For optimum streak-free results, the nonionic surfactant should preferably provide a cloud point of the aqueous solution of the final composition above the temperature of normal use of the diluted solution.
This can be achieved by a proper choice of the type of nonionic surfactant or mixtures of various nonionic .8 r i C.7129 surfactants or by the co-use of another detergent surfactant, such as an anionic or amphoteric surfactant.
From 0.1 to 30% by weight with respect to the final composition of one or more nonionic surfactants will be present in the final composition. It has been found that at least 1% should be present to obtain both a reduced streaking and an improved cleaning effect. Preferably therefore, the amount of nonionic detergent surfactant will range from 1% to 30%, and especially preferably from 1% to 10% by weight of the final composition.
o o00 oo The cationic detergent surfactant to be used in the o°"o 15 present invention can be any cationic detergent surfactant ooO, with a sanitizing action well known in the art. Examples 0 o0 o oo of such cationic detergent surfactants are the quaternary 0000 ammonium compounds, such as the mono- or di(long chain 00 0 0 0 alkyl) tri- or di(short chain) alkyl quaternary ammonium salts; mono- or di(long chain alkyl) imidazolinium compounds; substituted long chain alkyl polyamine salts; alkyl pyridinium salts and so on. Further suitable OO° examples can be found in Schwartz, Perry and Berch, Vol.II oo' (1958), "Surface-active Agents and Detergents" under the heading "Cationic Surface Active Agents".
0 000000 0 Specific examples of suitable cationic detergent 0 o surfactants are the long chain (C 8 and higher) S" 30 alkyldimethylbenzylammonium chlorides the commercial product Dodigen ex American Hoechst Corp.), the alkyl (C 12 and higher) trimethylammonium chloride, tetradecyl pyridinium chloride, alkyl (C 12
-C
16 trimethylammonium bromide, di-isobutyl-phenoxy- ethoxyethyl dimethylbenzylammonium chloride. Quaternary phospbonium and sulphonium compounds can also be used. These examples 4.I 7 C.7129 are, however, not limiting the scope of the invention; other detergent surfactants with a sanitizing action can be suitably used.
In general, the amount of cationic detergent surfactant used in the present invention ranges from 0.005, usually from 0.1, and preferably from 0.25, up to by weight.
The non-anionic polymer to be used in the present invention should have an adsorptive affinity to the hard surface and should be hydrophilic. Preferably, it should bear a positive charge on its molecular structure (either oon° as such or under the conditions of use), and consequently cationic polymers are clearly preferred to nonionic polymers.
040 oeoQ 0 000 S° Suitable cationic polymers for use in the present invention are those which adsorb on to the hard surface at least as quickly as, and preferably, more quickly than, the cationic detergent surfactant.
0ooo .0O Typical examples of such cationic polymers are Busan 77 (ex Buckman) which is a poly[oxyethylene 25 (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] with a polymerization degree of about Busan 79 (ex Buckman) which is a poly[hydroxy-ethylene 40 (dimethyliminio) ethylene (dimethyliminio) methylene dichloride], Busan 1055 (ex Buckman) which is a poly[2hydroxyethylenedimethyliminio-2hydroxypropylenedimethyliminio methylene) dichloride and structurally related cationic polymers such as 4/polyethylene glycol lonene bromides where the molecular weights of the PEG portion are 6000 and 1500 respectively, Zetag 57 and Zetag 87 which are high molecular weight cationic acylamides ex Allied Colloids, Merquat 100 which H 9 rrv ~mnrr^l^iPs~-r I~ IFlr~ l~upr 8 C.7129 is a polydimethyldiallylammonium chloride ex Merck, Mirapol A15 which is a poly[N-(3-dimethylammonio) propyl[-N [3-(ethyl-eneoxyethylene dimethylammonio) propyl] urea dichloride with a polymerisation degree of about 6 and homopolymer 78-4396 ex National Starch which is poly(dimethyldiallyl ammonium chloride).
Particularly preferred cationic polymers for use in the present invention are Busan 77 (ex Buckman) Merquat 100 (ex Merck) and Mirapol A15 (ex Miranol).
Examples of suitable nonionic polymers are Jaguar HP 8 and HP60 (ex Meyhall), which are nonionic substituted hydroxypropyl guar gums, and 0000 Sooo0 15 polyvinylpyrrolidones and poly(2-vinylpvridines) which are o P especially suitable for very low pH compositions.
00.. However, as said above, the cationic polymers are clearly 0 ooo00 preferred to the nonionic polymers.
o 0 It has been found that contact angle measurements may o °0o provide a guide as to the suitability of non-anionic 0O polymers for use in the composition. In particular low contact angles are an indication of suitability. The I contact angle is measured as the receding angle of a drop of water (approximately 0.4cm forced to spread by tilting movements on a horizontal black ceramic tile which has r been previously treated with a formulation comprising
C
8
-C
18 alkyldimethylbenzylammonium chloride, 1.2% C 11 alkyl polyoxyethylene (3EO), 0.6% C 9
-C
11 linear alcohol condensed with 5 moles of ethylene oxide and 0.8% by weight of the non-anionic polymer, and then allowed to dry. Preferably the non-anionic polymers have contact angles of less than 150 and more preferably less than However, such measurements can only be used as a guide.
Some polymers moreover are not soluble at the levels of the above test and yet still give a streak free benefit.
3- pi l~ -i IP -il Y i- ii 9 C.7129 A more reliable guide to suitable non-anionic polymers is provided by an adsorption test which, by way of surface tension measurements, determines the adsorptive affinity of the non-anionic polymer compared to that of a typical cationic surfactant when the components are in competition for an "ideal" surface such as colloidal silica. The adsorption test comprises the following steps: 10g of a 0.015% solution of the cationic surfactant cetyltrimethyl ammonium bromide (CTAB) is placed in a tensiometer vessel and equilibrated to 25 0 C. The surface tension is measured.
00.
o 0oo "coo 15 (ii) 100 microlitres of a 1% solution in distilled water o of the non-anionic polymer is pipetted into the CTAB 0 00 00.0 solution and mixed thoroughly. The surface tension 0 0000 0, 0 is measured again.
0 (iii)30 microlitres of an aqueous colloidal silica .0 solution (Ludox HS-40) is pipetted into the solution oo0 oo o and mixed thoroughly. The surface tension is then measured at timed intervals.
The quantity of silica added is chosen so that the non-anionic polymer and the surfactant must compete for adsorption sites. It has been found that the preferred t cationic polymers according to the invention cause a less than 15 dyne change in surface tension when tested according to the adsorption test defined above, particularly preferred cationic polymers cause a less than dyne change in surface tension according to the adsorption test.
10 The amount of non-anionic polymer in the compositions of the invention may range from 0.003 to usually from 0.01 to 15%, and preferably from 0.1 to 5% by weight.
The compositions may furthermore contain optional ingredients, such as preservatives, bactericides, bleaching agents, enzymes, thickening agents, colouring agents, perfumes, alkaline materials, sequestering agents, solvents and the like. They may also contain particulate abrasive, such as particulate calcite, to form an abrasive cleaning composition. They may be made in any physical form, such as powders, blocks, aqueous and non-aqueous liquids etc.
Preferably, they are in liquid form, the balance of the 0.oo formulation being an aqueous or non-aqueous medium. They may be applied as such, i.e. neat, or they may be made up into a solution before use to a concentration of generally o00.
0.1 to a. 0& @4 I In general the streak-free benefit is independent of the pH of the composition. One exception is poly(2vinylpyridine) in which case a composition of very low pH is necessary for optimum streak-free results to be j obtained.
SThe invention will further be illustrated by way of Example.
S 25 EXAMPLE 1 The streak-free benefits of cationic polymers were tested as follows: rr
J
11 C.7129 1. A solution of 0.5-1% of polymer in an aqueous liquid containing 1.5% (C 12
-C
16 alkylbenzyldimethyl ammonium chloride, 4% nonylphenol condensed with moles of ethylene oxide, 0.3% perfume, balance water is prepared.
2. A quarter of a sponge cloth is cut; it is rinsed with plenty of tap water of average hardness (ca. 12 degrees French Hard) and then gently squeezed.
3. Ten drops of the solution are dropped on the sponge cloth.
4. A single black ceramic tile is washed with this sponge and, after rinsing the sponge cloth, wiped again.
5. Then the tile is left to dry naturally.
The streak-free benefit is then assessed visually.
The following results were obtained: 00 0000 o o0 o0 o 0 ao 0 00 0 0000 00 09 0o0 m o a 0 00 0 00 o 0 b 0 0 Polymer used: Streak-free benefit Nonionic polymers Polyvinyl pyrrolidone (K 90 ex GAF) Hydroxypropyl guar (Jaguar HP 8) Slightly streaky Slightly streaky Cationic polymers Jaguar C13 (ex Meyhall) No benefit
_I
1 to 10% by weight of a nonionic surfactant; 0.25 to 5% by weight of a cationic detergent /2 44 p I
'I
C.7129 Jaguar C15 (Ex Meyhall) Merquat 550 (ex Merck) Polymer JR 400 (ex Union Carbide) Mirapol A15 Celquat L 233 Homopolymer DMDAAC Merquat 100 Busan 77 No benefit No benefit No benefit Very slightly streaky Very slightly streaky Very slightly streaky No streaks No streaks 4 $44 4 I *64 .4(
Q
EXAMPLE 2 The following formulation containing: C12-C16 alkyldimethyl benzyl ammonium chloride 1.2% C 1-C13 oxo-alcohol condensed with 3 moles of ethylene oxide 0.6% C 9
-C
1 1 linear alcohol condensed with 5 moles of ethylene oxide 0 4 6 20 9 a 4 4 4 4 44 q.s.
also water containing
(A)
(B)
(C)
(D)
0.6% Busan 77, or 0.9% Busan 77, or 0.6% Merquat 100, or 0.8% Merquat 100 i" UJn Ad d.4 13 C.7129 was tested and compared with the formulation of Example 1 (without polymer) as control.
The following results were obtained.
a. Soil removal (triolein carbon black) Control
A
B
C
D
52.5% 52% 46.9% 52.6% S0 o 0 So 0 000 0 0* 0 00 0040 0 o0 0 0000 0 00 0 0 a 0 00 6 0 0 00 0 00, D I E~r b. Streaking test Control
A
B
C
D
diluted in hard water (40 0 FH) 45 0
C
Streaky Slightly streaky Not streaky Not streaky Not streaky neat Very streaky Not streaky Not streaky Not streaky Not streaky c. Logarithm of bacteria survivors in solutions (1:20 dil.) (solution containing 10 bacteria/cm 3 after 10' after 30' after 2 hrs Control
A
B
C
D
4.0 5.5 3.9 3.9 5.4 3.7 4.6 3.8 3.7 5.0 3.3 3.6 3.4 4.1 3i B
L-'
_i i _b i 11.._1.L P L~L Li~_ i- CI
I
~I L l c- 14 C.7129 d. Logarithm of bacteria survivors on cloth (1:10 dil.) (dish cloths contaminated, contacted for 30 seconds with the solution) Control
A
B
C
D
after 2 hrs 5.7 4.2 2.2 3.4 5.9 after 24 hrs 5.6 5.4 5.8 5.9 01 0 0 o o* Q0 0 000 o 0 00 00 0 0 0 0060 00 0 oa 0 0 0 1 00 0 0 00 00 9 Co 0 0 C C C C T EXAMPLE 3 The following formulation is a liquid abrasive cleaning composition with an improved streak-free benefit.
Topped C 9 -C11 alcohol condensed with 5 moles of ethylene oxide C12-C16 alkyldimethylbenzyl ammonium chloride Particulate calcite Nonionic polymer (Jaguar HP-8) 4.8 45.0 0.4 0.2 Perfume Water balance -d 15 C.7129 EXAMPLE 4 The adsorptive affinity of a range of non-anion'ic polymers was determined by the following adsorption test.
Adsorption test method The adsorption test comprises the following steps: 10g of a 0.015% solution of the cationic surfactant CTAB is placed in a tensiometer vessel and equilibrated to 25 0 C. The surface tension is measured as approximately 51 dynes.
o 000 S° 15 (ii) 100 microlitres of a 1% solution in distilled water Sof the non-anionic polymer is pipetted into the CTAB 4ao, solution and mixed thoroughly. The surface tension is again measured. A value close to 51 dynes osuggests that any interaction between the polymer and the surfactant is negligible.
0 (iii)30 microlitres of an aqueous colloidal silica 0° solution (Ludox HS-40) are pipetted into the solution So. and mixed thoroughly. The surface tension is then measured at timed intervals.
The non-anionic polymer from (ii) above was then S incorporated in the following composition.
1.5% Alkyl (C 8
-C
18 benzyldimethylammonium chloride 1.2% Alkyl (C 11 polyoxyethylene (3EO) 0.6% Alkyl (C 9
-C
11 polyoxyethylene 0.8% Non-anionic polymer balance water to 100% i f i; i..
i i i I J 16 C.7129 The formulation was tested both neat and dilute as follows: Neat: 2g of the formulation were placed on a clean folded sponge cloth and wiped over a clean, dry, vertical, black ceramic tile board. The cloth was then rinsed in demineralised water and the board wiped again before being left to dry naturally.
Dilute: 4g of the formulation were diluted to 400g using 40 0 FH water at 45 0 C. A clean folded sponge cloth was immersed in the liquid, squeezed gently and wiped over the tile board. The cloth was then re-immersed, squeezed until damp and wiped over the 15 tile board. The board was left to dry naturally.
'0 o64 The following results were obtained: 0 00 00 S Polymer Surface tension (dynes) Effect Time (Minutes) Neat Dilute 1 2 5 (b) 0 '0 2 Busan 77 49.5 49.3 49.0 Streak Free Busan 79 55.4 55.3 54.9 Streak Free Busan 1055 52.8 52.7 52.2 Streak Free Merquat 100 58.6 58.1 57.4 Streak Free S Mirapol A15 50.3 49.9 49.7 Streak Free Merquat 550 66.5 65.8 65.5 Very Streaky JR 125 67.3 66.5 65.2 Very Streaky PVP K90 67.9 67.2 66.8 Very Streaky JR 125 is a cationic substituted hydroxyethylcellulose ex Union Carbide. PVP K90 is a polyvinylpyrrolidone ex GAF.
17 C.7129 None of the above polymers showed surface activity when added to distilled water. Little or no change in surface activity resulted from the addition of polymer to surfactant little or no change in surface tension from step to step The results of the adsorption test correlate well with the streak free benefit for cationic polymers having a change in surface tension (when silica is added to a solution comprising surfactant and polymer according to the adsorption test as define above) of less than about 15 dynes and preferably less than about 8 dynes.
4 0 0 o t a* 40 4 0 a '4 O 0 -C4 4 4 i F I L_

Claims (8)

1. A general purpose cleaning composition comprising: e o o9a se0o 10 o 0oo e000 0000 0e o e D 0.1 to 30% by weight of a nonionic surfactant; 0.005 to 5% by weight of a cationic detergent surfactant which has a sanitising action; 0.003 to 20% by weight of a hydrophilic non- anionic polymer which has an adsorptive affinity to hard surfaces.
2. A composition as claimed in claim 1 wherein the non- anionic polymer is a cationic polymer.
3. A composition as claimed in claim 1 or claim 2 wherein the nonionic surfactant is a topped nonionic.
4. A composition as claimed in any preceding claim wherein the composition comprises from 1 to 10% by weight of ot 0 0 ooo00 o 0 a 0 e e 4 t 20 A composition as claimed in any preceding claim wherein the composition comprises from 0.1 to 5% by weight of
6. A composition as claimed in any preceding claim wherein the composition comprises from 0.01 to 15% by weight of
7. A composition as claimed in claim 2 wherein the V i L J v tYS 19 cationic polymer has a change in surface tension of less than 15 dynes when measured according to an adsorption test as hereinbefore defined.
8. A composition as claimed in claim 7 wherein the cationic polymer has a change in surface tension of less than 8 dynes when measured according to the adsorption test. 00 o .0 9. A composition as claimed in any preceding claim wherein 0o0 10 the contact angle of a drop of water on a surface previously °0R° treated with the formulation of Example 2 comprising 0.8% by weight of is less than 100. A general purpose cleaning composition comprising: 1 to 10% by weight of a nonionic surfactant; 0.25 to 5% by weight of a cationic detergent Sc surfactant which has a sanitising action; 0.1 to 5% by weight of a hydrophilic non-anionic polymer which has an adsorptive affinity to hard surfaces.
11. A composition according to any one of the preceding claims wherein the cationic detergent surfactant contains not more than one alkyl group with eight or more carbon atoms therein. DATED THIS 8TH DAY OF NOVEMBER 1991 UNILEVER PLC By its Patent Attorneys: GRIFFITH HACK CO. Fellows Institute of Patent .4"Y Attorneys of Australia. o e a
AU34807/89A 1988-05-20 1989-05-16 General-purpose cleaning compositions Ceased AU619545B2 (en)

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GB888811953A GB8811953D0 (en) 1988-05-20 1988-05-20 General-purpose cleaning compositions
GB8811953 1988-05-20

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AU619545B2 true AU619545B2 (en) 1992-01-30

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KR (1) KR960000201B1 (en)
AU (1) AU619545B2 (en)
BR (1) BR8902331A (en)
DE (1) DE68917371T2 (en)
ES (1) ES2058522T5 (en)
GB (1) GB8811953D0 (en)
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ZA (1) ZA893779B (en)

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EP0342997B2 (en) 1997-10-01
GB8811953D0 (en) 1988-06-22
EP0342997B1 (en) 1994-08-10
JP2857168B2 (en) 1999-02-10
ES2058522T5 (en) 1997-12-16
EP0342997A3 (en) 1990-05-02
DE68917371D1 (en) 1994-09-15
AU3480789A (en) 1989-11-23
TR25242A (en) 1992-12-01
BR8902331A (en) 1990-01-09
ES2058522T3 (en) 1994-11-01
DE68917371T2 (en) 1994-12-01
JPH0218499A (en) 1990-01-22
ZA893779B (en) 1991-01-30
EP0342997A2 (en) 1989-11-23
KR890017350A (en) 1989-12-15
KR960000201B1 (en) 1996-01-03

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