GB2346891A

GB2346891A - Cleaning composition

Info

Publication number: GB2346891A
Application number: GB0002434A
Authority: GB
Inventors: Helen Elizabeth Herd; Robert Williams
Original assignee: Robert McBride Ltd
Current assignee: Robert McBride Ltd
Priority date: 1999-02-03
Filing date: 2000-02-03
Publication date: 2000-08-23
Also published as: GB9902337D0; GB0002434D0

Abstract

A method of producing a shear-thinning hard surface cleansing formulation comprises admixing water, a hydrophobically modified polymer which is a polycarboxylic or polycarboxylate polymer containing hydrophobic moieties providing associative groups, and other components of the formulation. The hydrophobically modified acrylic polymer is added to the water prior to any other component of the formulation which causes the ionic strength to increase above 200 microsiemens. By adopting the method, a composition of relatively low viscosity is obtained which thickens over time, e.g. 24 hours. This has advantages for pumping the composition around the manufacturing and packaging plant since the product may be packaged at low viscosity but has the desired high viscosity properties when used by the consumer. It is particularly preferred that composition does not include more than 0.5% by weight of fragrance. Glass cleaning formulations and bleaching formulations incorporating the above mentioned polyiners and low levels of fragrance are also disclosed.

Description

CLEANING COMPOSITION The present invention relates to shear-thinning, thickened, cleaning compositions and methods for producing such compositions.

There is a trend in the market place to thickened hard surface cleaners. In particular products with shear thinning characteristics are beneficial due to their easy dispensability (low viscosity at high shear) and slow drainage/low run off (high viscosity at low shear). Such products are produced by a mixing procedure in which a thickening polymer (for giving the shear thinning properties) is added at the end of the mixing procedure. The viscosity increases significantly on addition of the polymer.

Thus the viscosity only increases at the end of the mixing procedure and this ensures easiest stirring during the major part of the mixing.

Typically products are mixed in batches of several tonnes and then piped to a filling machine. Shear thinning only becomes significant at high shear (shear higher than 200 s'), i. e. when a product is squirted on use or on filling. If the product is piped from a holding tank to a filling machine via relatively large diameter pipes then it (i. e. the product) will be at low shear and hence high viscosity. If the product is piped by a relatively small diameter pipe then the shear is higher and viscosity is lower but resistance to flow is higher (Reynolds number change). In either case there is a significant pumping requirement.

It is an object of the present invention to obviate or mitigate the abovementioned disadvantages.

According to a first aspect of the present invention there is provided a method of producing a shear-thinning hard surface cleansing formulation comprising admixing water, a hydrophobically modified polymer which is a polycarboxylic or polycarboxylate polymer containing hydrophobic moieties providing associative groups, and other components of the formulation, wherein the hydrophobically modified acrylic polymer is added to the water prior to any other component of the formulation which causes the ionic strength to increase above 200 microsiemens.

Ionic strength may be measured using a JENWAY conductivity meter using a conductivity probe with 0. 5 square centimetre platinised platinum electrodes and calibrated using 0. 01 molar potassium chloride at 25 C. The measurement may be made by immersion of the electrode into a stirred sample at 25 C and waiting until a stable reading is recorded. Thus it is a relatively simple matter to test whether any particular component of the proposed formulation, when added to water, would increase the ionic strength to above 200 microsiemens.

We have found that before addition of any component which increases ionic strength to greater than 200 microsiemens inclusion of the hydrophobically modified polymer into the formulation produces a composition of relatively low viscosity which thickens over time, e. g. twenty four hours. Depending on its degree of hardness, the ionic strength of water is generally below 150 microsiemens. Examples of materials which might be included in the formulations of the invention and which would cause the ionic strength above 200 microsiemens are inorganic ionic substances (e. g. salts, sodium hydroxide etc.) and organic ionic materials such as anionic surface active agents. The"as-mixed"viscosity of the formulation may, for example, be 60 to 120cp. The viscosity increase may for example by from 20 to 150 (as measured by a Brookfield LVT viscometer with heliopath, spindle A, 12rpm (unless otherwise stated all viscosities referred to herein are measured by this method)) and may increase over 24 hours to a value in the range 90 to 160. Thus the formulation can be pumped around the manufacturing and packaging plant (and the product may easily be packaged at low viscosity) easily whilst also having the desired high viscosity properties when used by the consumer.

The hydrophobically modified polymer may for example be polymer with a molecular weight greater than 10, 000 (more preferably greater than 20, 000) and less than 2, 000, 000 (more preferably less than 1, 000, 000) with from 1% to 50% (preferably 1% to 15%) by weight of partially hydrophobic monomers that can act as associative groups. The polymer may be cross-linked but preferably by no more than 2% of monomer residues (more preferably 0 to 0. 5%) providing the cross-links.

The hydrophobically modified polymer may for example be a copolymer of an ethylenically unsaturated carboxylic acid monomer and an ethylenically unsaturated monomer having a hydrophobic group. Suitable polymers may comprise 10-97% by weight of the residues derived from the ethylenically unsaturated carboxylic acid, 1 % to 80% of monomer residues having the hydrophobic grouping, and optionally other co-monomers.

Examples of unsaturated carboxylic acid monomers include acrylic, methacrylic, itaconic, maleic, sorbic, crotonic, oleic and linoleic acid.

Examples of co-monomers with hydrophobic groups include compounds of formula : A-O-(CH2-CHR2-O) X-(CH2) y-Ri wherein : A is the acylic residue of an ethylenically unsaturated carboxylic acid, selected from acrylic, methacrylic, itaconic, maleic, sorbic, crotonic, oleic or linoleic acid, Rl is an alkyl, alkylphenyl or aralkyl residue having from 1-30 carbon atoms.

R2 is hydrogen methyl or ethyl x is 0 to 50 and y is 0 to 30 with the sum of x and y being between 0 and 80 More preferred co-monomers with hydrophobic groups are the esters of cetylstearyl alcohol ethoxylated with 25 moles of ethylene oxide, particularly the acrylate esters thereof.

The polymer may have a degree of cross-linking. Cross-linking may be achieved by the presence, in the polymerisation reaction, of a di-or higher ester of an ethylenically unsaturated carboxylic acid and a diol or higher functionality polyol.

Suitable examples of polymers disclosed in EP-A-0 870 785, the disclosure of which is incorporated herein by reference.

Examples of suitable polymers are available under the names POLYGEL W30 (ex 3V UK Ltd), Rheovis CRX and Rheovis CR (ex Allied Colloids).

It is preferred that the hydrophobically modified polymer constitutes from 0. 05-4% by weight of the hard surface cleaning composition. More preferably the polymeric material constitutes from 0. 1-1. 5% and even more preferably from 0. 20. 75% of the composition.

Compositions in accordance with the invention may be produced by batch or continuous mixing.

Various types of hard surface cleansing compositions may be produced using the method of the present invention, e. g. glass, toilet, kitchen and bathroom and cleaners and thickened bleach compositions.

Depending on the type of composition, any or all of the following components may be included.

(i) Surface active agent (anionic, cationic, non-ionic, zwitterionic) (ii) Bleaching agents, e. g. hypochlorite, peroxy compounds.

(iii) Solvent, e. g. isopropyl alcohol, DPM (Dipropropylene glycol mono methyl ether).

(iv) pH modifying agent, e. g. caustic soda.

(v) Fragrance.

(vi) dye, e. g. brilliant blue.

(vii) Preservative, e. g. formalin.

(viii) Thickener, e. g. amine oxide.

(ix) Crystal growth inhibitor.

(x) Builders (e. g. carbonate/bicarbonate/citrate/phosphate) (xi) Sequestrants (e. g. EDTA, phosphonates) It is preferred that the composition does not include more than 0. 5%, preferably not more than 0. 2%, by weight of the fragrance. Higher amounts may affect the viscosity increase.

A preferred embodiment of the method of the invention is in the production of glass cleaning compositions, particularly a window cleaning composition. Such compositions as produced in accordance with the method of the present invention may comprise : Hydrophobically modified polymer 0. 10-2. 0 wt% Water Miscible Solvent 2. 0-18. 0 wt% Fragrance 0. 0 to 0. 06% Formaldehyde 0-0. 10wt% Dyes As Required Water To 100wt% The glass cleaning composition is an important aspect of the invention in its own right and therefore according to a second aspect of the present invention there is provided a glass cleaning composition comprising water, a hydrophobically modified polymer which is a polycarboxylic or polycarboxylate polymer containing hydrophobic moieties providing associative groups, and at least one water miscible organic solvent, said formulation containing less than 0. 2% by weight of fragrance and preferably not containing surface active agent. The glass cleaning formulation of the second aspect of the invention may be as identified in the previous paragraph and may be produced by the method of the first aspect.

The water miscible solvent may for example be at least one of isopropyl alcohol and dipropylene glycol mono methyl ether (DPM). Preferably the composition contains 2. 0 to 8. 0% by weight of isopropyl alcohol and 2. 0 to 10. 0% by weight of DPM.

Preferably the glass cleaning formulation has a pH of at least 9, more preferably 10 or more, (e. g. provided by inclusion of sodium hydroxide).

The above glass cleaning compositions are particularly effective at cleaning glass even though they do not contain a surface active agent. Furthermore we have observed that the compositions are not only able to clean glass without the addition of a surfactant but do so without leaving any residual smears on the glass. We believe that the properties are due to the hydrophobically modified poly-acrylic polymer having a degree of surface active character.

A further preferred embodiment of the method of the invention is in the production of thickened bleach compositions. The bleach composition may comprise, in addition to the hydrophobically modified polymer and water, a hypochlorite bleach and a bleach stable surfactant system. We have found that such formulations (which provide a further third aspect of the invention in their own right), in addition to their ease of manufacture, also have excellent"clingability"characteristics. As such, the thickened bleach (e. g. in the form of a gel) allows for greater residence time on vertical surfaces for improved bacterial kill. This film forming property can also inhibit limescale deposits on surfaces due to its gel like nature. This allows for significantly greater contact time on vertical surfaces for improved bacterial kill.

The composition of the third aspect of the invention may be produced by the method of the first aspect.

The bleach composition may comprise : Hydrophobically modified polymer 0. 10-5. 0 wt% (preferably 0. 1-3%) Hypochlorite bleach 3. 0-5. 0 wt% (preferably 4. 0-5. 0%) (expressed as available chlorine) Sodium or Potassium Hydroxide 0. 1-5. 0 wt% Bleach Stable Surfactant System 1. 0-l0. 0wt% Fragrance 0. 01 to 0. 5% (preferably 0. 01 to 0. 1%) Water Balance The above composition is particularly effective for use as a toilet cleaner.

It is preferred that the bleach formulation does not contain more than 0. 2% by weight of the fragrance as higher amounts may affect the viscosity increase.

The pH of the composition is preferably greater than 12, e. g. a pH of 13 is suitable.

The bleach stable surfactant system may comprise an amine oxide of the formula :

where Rl and R2 are the same or different C)-4 alky ! groups (preferably methyl) and R3 is a C822 alkyl group.

A further bleach stable surface active agent which may be used is an alkyl ether sulphate having an alkyl group of 8 to 22 carbon atoms and an average of 3-5 moles EO. A preferred surface active agent in this category is sodium lauryl ether sulphate with an average of 2 moles EO.

The surface active agent system preferably comprises, by weight of the thickened composition, 1-5% (more preferably 1. 54%) amine oxide and 1-5% (more preferably 1. 5-4%) of alkyl ether sulphate. This mixture of anionic and non-ionic surfactants helps to boost and maintain the viscosity of the formulation.

The formulation may also incorporate a water soluble acrylic acid homopolymer, e. g. in an amount 0. 1 to 5% by weight, preferably 0. 1 to 2% by weight.

The polymer serves to prevent/remove limescale. Suitable acrylic polymers are those having a pH in the range 6-10 and are available under the trade name Sokolan (ex BASF), e. g. Sokolan PA30 CL.

The bleach composition may incorporate minor components, e. g. fragrances and dyes. It is however preferred that the amount of fragrance does not exceed 0. 2% by weight (preferably does not exceed 0. 1% by weight) since greater amounts may adversely affect the viscosity increase of the formulation. We prefer that the amount of fragrance be in the range 0. 01% to 0. 1% by weight.

In producing the bleach composition it is preferred that the surfactant is added after the polymer. It is also preferred that the sodium (or potassium) hydroxide is added to provide a pH greater than 7 after the hydrophobically modified acrylic polymer, but before surface active agent system since the surfactant may interfere with neutralisation of the bleach giving anomalous results. The bleach may be added after the surface active agent system).

The invention will be further illustrated by the following, non-limiting Examples.

Example 1 Using the procedures described below, a thickened glass cleaning composition was produced using Polygel W30 as a hydrophobically modified acrylic polymer. Comparative compositions were also prepared using various grades of Carbopol as thickening polymer.

Method The compositions produced (Invention and Comparative) are as shown in Table 1.

TABLE 1

Invention Comparative Comparative WN Wt% wi% Water To 100 To 100 To 100 Polygel W30 0. 75 - Carbopol 672-0. 20- (ex B. F. Goodrich) Carbopol 2623--0. 4% (ex B. F Goodrich) Isopropyl alcohol 20. 0 20. 0 20. 0 (20% v/v) (ex Hays Chemicals) Sodium Hydroxide QS QS QS (50%) Dowanol DPM * 6. 0 6. 0 6. 0 (ex Dow) GCW 0123B * 0. 03 0. 03 0. 03 (Perfume) 1% Neolan Flavine 0. 15 0. 15 0. 15 (Yellow Dye) (ex Townend Chemicals) 0. 1% Brilliant Blue 0. 60 0. 60 0. 60 (ex Ellis & Everard) Formalin 0. 10 0. 10 0. 10 (ex Synthite) Reference 355 353 354 *= The Dowanol DPM and the perfume were pre-mixed before adding to the main mix.

The compositions were produced by the following procedure : 1) The water was measured into the mixing vessel and stirred.

2) The polymer thickener was added to the water and stirred.

3) The isopropyl alcohol was added.

4) The pH of the admixture was adjusted to just above pH 10, by addition of sodium hydroxide.

5) The stirring speed was reduced so that the thickening polymer was stirred slowly and efficiently.

6) Dowanol DPM and the perfume, which had been pre-mixed in a separate vessel, were added to the main admixture, adjusting their quantities to allow for losses in the pre-mixing vessel.

7) The dye was added.

8) The formalin was added and the admixture was stirred for a minimum of a further ten minutes.

Properties The compositions designated 354 (Comparative) and 355 (Invention) were clear compositions whereas 353 (Comparative) was hazy. This is a standard characteristic of Carbopol 672.

The viscosities of the formulations were measured"as prepared"and also after standing for 18 hours. (Viscosities were measured using a Brookfield LVT Viscometer with Heliopath, Spindle A, speed 12 rpm). The results are shown in Table 2.

TABLE 2

Invention Comparative Comparative 355 354 353 Viscosity on Preparation 95 1100 295 (cp) Viscosity on Overnight 125 1100 280 Standing (cp) The results in Table 2, clearly demonstrate that"as-manufactured"the composition in accordance with the invention is of low viscosity but that this viscosity increases on standing. In contrast the"as-manufactured"comparative composition are of high viscosity.

Example 2 Using the procedure of Example 1, the following glass cleaning formulations (Invention and Comparative) were prepared. For compositions containing lauryl ether sulphate this was added as the final component.

FORMULATION SWC SWC SWC SWC SWC SWC 358 359 361 362 364 365 % W % W % W % W % W % W Water To 100 To 100 To 100 To 100 To 100 To 100 Polygel W30 0. 75 0. 75 N/A N/A N/A N/A Carbopol 672 N/A N/A 0. 2 0. 2 N/A N/A Carbopol 2623 NIA N/A N/A N/A 0. 1 0. 1 Sodium Hydroxide QS QS QS QS QS QS (50%) IPA 20% 20. 0 20. 0 20. 0 20. 00 20. 00 20. 00 Downanol DPM 6. 0 6. 0 6. 0 6. 0 6. 00 6. 00 Dye Neolan Flavine 0. 0015 0. 0015 0. 0015 0. 0015 0. 0015 0. 0015 Dye Brilliant Blue 0. 0006 0. 0006 0. 0006 0. 0006 0. 0006 0. 0006 Perfume LU67064 0. 03 0. 03 0. 03 0. 03 0. 03 0. 03 (ex BBA) Formalin 0.1 0.1 0.1 0.1 0.1 0.1 Lauryl Ether Sulphate N/A 0. 05 N/A 0. 05 N/A 0. 05 (28%) (ex Albright & Wilson)

SWC 366 SWC 367 % W % W Water To 100 To 100 Norasol 460N (25%) 2. 18 N/A (sodium acrylate, ex Rohn & Haas) Acusol 820 (25%) 0. 8 0. 8 (hydrophobic polymer, ex Rohn & Haas) Variquat 66 3. 00 N/A (ex Witco) Triton DF-12 3. 00 N/A (ex Surfachem Ltd) Empilan CDE 3. 00 N/A (ex Albright & Wilson) SXS 30 8. 00 N/A (ex Manro) Sodium Gluconate 7. 65 7. 65 (ex Ellis & Everard) 1% Sodium Silicate (Crystal 0120) 0.34 0.34 (ex Crosfield Ltd) Monoethanolamine 80% 0. 5 N/A Of the above formulations, SWC 358 and SWC 359 are in accordance with the invention and differ in that the former does not include surface active agent whereas the latter does. All of the other formulations on are comparative. Formulation SWC 366 was prepared as described in WO-A-9743372, SWC 367 is based on SWC 366 but excludes surface active agents.

The above formulations together with Windowlene spray cleaner (original variant) designated as 368 were tested for their efficiency in cleaning glass.

(Windowlene is a Registered Trade Mark.) For the purposes of the test, the products were packaged and labelled only with the three figure identifying codes given above. Each formulation was used to clean one of a number of adjacent sections of window glass with the boundary of each section being clearly marked on the glass by marker pen. (The reverse side of the glass were cleaned prior to the test with a UK Brand Glass Cleaner).

10 panellists were asked separately visually to evaluate each section of the glass and to score the degree of cleaning and degree of smearing in scales of 0-10 as follows : Cleaning 0 = No cleaning 10 = Total cleaning Smearing 10 = No smearing 0 = Total smearing The results were as follows : SAMPLE REFERENCE

SWC SWC SWC SWC SWC SWC SWC SWC SWC SWC 358 361 364 367 368 358 362 365 366 3S9 Cleaning 8.9 6.0 6.5 4.0 7.5 8.8 7.2 6.8 6.0 9.0 Smearing 9.1 7.0 6.5 6.5 7.3 9.0 6.0 6.4 5.5 7.1 Cleaning It will be seen from the above table that the thickened formulation with W30 polymer and no surfactant (i. e. SWC 358) gave improved cleaning vs formulations incorporating both Carbopol (with and without surfactant), the formulation based on WO-A-97143372 (with and without surfactant) and the brand formulation.

Formulation with W30 polymer and no surfactant (i. e. SWC 358) gave comparable cleaning to the same formulation incorporating surfactant (i. e. SWC 359).

Smearing The thickened formulation with W30 (and no surfactant) (i. e. SWC 358) gave improved"none smearing"performance vs all other formulations testedincluding those prepared without surfactant.

Example 3 Bleaching formulations of the compositions shown in the following table were produced as described below. The percentages in the table are by weight

Formulations 1 2 Amine Oxide (30%) 2. 0 5. 0 Lauryl Ether Sulphate (26%) 4. 0 4. 0 Fragrance 0. 03 0. 2 Caustic Soda (47%) 1. 5 1.. 5 Hypochlorite 30. 7 30. 7 Polygel W30 0. 5 0. 5 Water to 100 to 100 As shown in the table, the formulations differ in the amount of fragrance.

Two methods (I and II) were used to produce the formulation 2 using the order of addition specified below. Formulation 1 was prepared using method I.

Method I Method II 1) Water Water 2) Polygel Polygel 3) Caustic Amine Oxide 4) Fragrance Ether Sulphate 5) Amine oxide Fragrance 6) Ether Sulphate Caustic 7) Hypochlorite Hypochlorite Each of methods I and II was carried out to produce a 500ml sample in a 500ml glass beaker using a heidolph RZR1 strirrer on shaft one speed 0 which equates to 250-300 rpm. The strirrer blade was plastic and of U-shaped design.

In each method, the Polygel 30 W was added with mixing to the water and mixing was continued for 15 minutes prior to addition of the next component. After addition of caustic soda, mixing was continued for 15 minutes before addition of the next component.

For the purposes of nomenclature, formulation 1 as produced by, method I is designated as formulation 1 (I). On the same basis, the other formulations are designated 1 (II) and 2 (11).

The thickness of each formulation was measured 30 minutes after mixing and also after 18 hours using a flow cup method. The flow cup had an outlet orifice which was 3mm in diameter and 5mm deep. The time taken (in seconds) for a 100ml sample of the product to pass through the orifice was used as the measure of thickness.

The"clingability"of the formulations was also measured at the same time points by a method involving use of a white porcelain tile inclined at 45 C to the horizontal and having two marks spaced apart along the tile by 12cm. The time taken (in seconds) for 0. 1 g of the liquid applied to the upper line (by pipette) to travel to the lower line was taken to be a measure of"clingability".

The results are shown in the following table

Formulation Thickness Thickness Thickness Cling Cling Cling No. (30mins) (18 hrs) Increase (30 (18 hrs) Increase (secs) (secs) (secs) mins) (secs) (secs) (secs) 1 (I) 126 144 18 155 222 67 1 (In 180 286 106 105 320 215 2 (In 80 156 76 101 213 112 All formulations provided an increase in thickness and"clingability"after 18 hours. The increases were greater for the formulations produced by method II (as compared method I). For the two formulations produced by method II, the increases were less at the highest fragrance levels.

This emphasised the requirement for a consistent method of manufacture with an appropriate order of material addition.

This is vital to the stability of the formulation.

Claims

CLAIMS 1. A method of producing a shear-thinning hard surface cleansing formulation comprising admixing water, a hydrophobically modified polymer which is a polycarboxylic or polycarboxylate polymer containing hydrophobic moieties providing associative groups, and other components of the formulation, wherein the hydrophobically modified acrylic polymer is added to the water prior to any other component of the formulation which causes the ionic strength to increase above 200 microsiemens.
2. A method as claimed in claim 1 wherein the viscosity of the"as-mixed" formulation is 60 to 120 cp.
3. A method as claimed in claim 2 wherein the viscosity of the formulation after 24 hours is in the range increases by 20 to 150 cp as compared to the"as-mixed" viscosity.
4. A method as claimed in any one of claims 1 to 3 wherein the hydrophobically modified polymer is a copolymer of an ethylenically unsaturated carboxylic acid monomer and an ethylenically unsaturated monomer having a hydrophobic group.
5. A method as claimed in claim 4 wherein the hydrophobically modified polymer comprises 10 to 97% by weight of residues derived from the ethylenically unsaturated carboxylic acid, 0. 5 to 8. 0% by weight of monomer residues having the hydrophobic group and optionally other comonomers.
6. A method as claimed in claims 4 or 5 wherein the ethylenically unsaturated carboxylic acid is selected from acrylic, methacrylic, itaconic, maleic, sorbic, crotonic, oleic or linoleic acid.
7. A method as claimed in any one of claims 4 to 6 wherein the monomer with the hydrophobic group is a compound of the formula A-O-(CH2-CHR2-O) X-(CH2) y~Rl wherein A is the acylic residue of an ethylenically unsaturated carboxylic acid, selected from acrylic, methacrylic, itaconic, maleic, sorbic, crotonic, oleic or linoleic acid, Rl is an alkyl, alkylphenyl or aralkyl residue having from 1-30 carbon atoms.

R2 is hydrogen methyl or ethyl x is 0 to 50 and y is 0 to 30 with the sum of x and y being between 0 and 80
8. A method as claimed in claim 7 wherein the comonomer with hydrophobic groups is ester of cetyl-stearyl alcohol ethoxylated with 25 moles of ethylene oxide.
9. A method as claimed in any one of claims 5 to 8 wherein the hydrophobically modified acrylic polymer is partially cross-linked.
10. A method as claimed in any one of claims 1 to 9 wherein the composition comprises 0. 05 to 4. 0% by weight of the hydrophobically modified acrylic polymer.
11. A method as claimed in claim 10 wherein the composition comprises 0. 1 to 1. 5% by weight of the hydrophobically modified acrylic polymer.
12. A method as claimed in claim 11 wherein the composition comprises 0. 2 to 0. 75% by weight of the hydrophobically modified acrylic polymer.
13. A method as claimed in any one of claims 1 to 12 wherein the composition is a glass cleaning composition.
14. A method as claimed in claim 13 wherein the glass cleaning composition comprises : Hydrophobically modified polymer 0. 10-0. 50 wt% Water Miscible Solvent 2. 0-18. 0 wt% Fragrance 0-0. 06 wt% Formaldehyde 0-0. 10wt% Dyes As Required Water To 100wt%
15. A method as claimed in claim 14 wherein the water miscible solvent is isopropyl alcohol and/or dipropylene glycol mono methyl ether.
16. A method as claimed in claim 15 wherein the water miscible solvent comprises 2. 0 to 8. 0% by weight of isopropyl alcohol and 2. 0 to 10. 0% by weight dipropylene glycol mono methyl ether.
17. A method as claimed in any one of claims 13 to 16 wherein the glass cleaning composition has a pH of at least 9.
18. A method as claimed in any one of claims 1 to 12 wherein the composition is a thickened bleach composition.
19. A method as claimed in claim 18 wherein the thickened bleach composition incorporates a bleach stable surfactant system.
20. A method as claimed in claim 19 wherein the bleach composition comprises : Hydrophobically modified polymer 0. 10-5. 0 wt% (preferably 0. 1-3%) Hypochlorite bleach 3. 0-5. 0 wt% (preferably 4. 0-5. 0%) (expressed as available chlorine) Sodium or Potassium Hydroxide 0. 1-5. 0 wt% Bleach Stable Surfactant System 1. 0-10. 0wt% Water Balance
21. A method as claimed in claim 19 or 20 wherein the bleach stable surfactant system comprises an amine oxide of the formula :

where Rl and R2 are the same or different Cl. alkyl groups (preferably methyl) and R3 is a Cg-22 alkyl group.
22. A method as claimed in claim 19 or 20 wherein the bleach stable surface active agent system comprises an alkyl ether sulphate having an alkyl group of 8 to 22 carbon atoms and an average of 3-5 moles EO.
23. A method as claimed in claim 22 wherein the surface active agent system comprises 1 to 5% (preferably 1. 5-4. 0%) amine oxide and 1-5% (preferably 1. 5-4. 0%) of alkyl ether sulphate.
24. A method as claimed in any one of claims 18 to 23 wherein the thickened bleach incorporates a water soluble acrylic acid polymer.
25. A method as claimed in claim 24 wherein the composition comprises 0. 1 to 5. 0% by weight of the acrylic acid polymer.
26. A method as claimed in any one of claims 1 to 25 wherein the composition does not contain more than 0. 5% by weight of fragrance.
27. A method as claimed in any one of claims 1 to 26 which comprises the steps of mixing the hydrophobically modified polymer with water prior to addition of other components.
28. A method as claimed in any one of claims 1 to 27 wherein the composition contains sodium hydroxide or potassium hydroxide and a surface active agent, and the method comprises adding the sodium or potassium hydroxide after addition of the hydrophobically modified acrylic polymer but prior to addition of the surface active agent.
29. A glass cleaning composition comprising water, a hydrophobically modified polymer which is a polycarboxylic or carboxylate polymer containing hydrophobic moieties providing associative groups, and at least one water miscible organic solvent, said formulation containing less than 0. 2% by weight of fragrance and preferably not containing surface active agent.
30. A composition as claimed in claim 29 which comprises : Hydrophobically modified polymer 0. 10-0. 50 wt% Water Miscible Solvent 2. 0-18. 0 wt% Fragrance 0-0. 06 wt% Formaldehyde 0-0. 1 Owt% Dyes As Required Water To 100wt%
31. A composition as claimed in claim 30 wherein the water miscible solvent is isopropyl alcohol and/or dipropylene glycol mono methyl ether.
32. A composition as claimed in claim 31 wherein the water miscible solvent comprises 2. 0 to 8. 0% by weight of isopropyl alcohol and 2. 0 to 10. 0% by weight dipropylene glycol mono methyl ether.
33. A composition as claimed in any one of claims 29 to 32 having a pH of at least 9.
34. A thickened bleach composition which comprises a hydrophobically modified polymer which is a polycarboxylic or polycarboxylate polymer containing hydrophobic moieties providing associative groups, a hypochlorite bleach and a bleach stable surfactant system.
35. A composition as claimed in claim 34 comprising : Hydrophobically modified polymer 0. 10-5. 0 wt% (preferably 0. 1-3%) Hypochlorite bleach 3. 0-5. 0 wt% (preferably 4. 0-5. 0%) (expressed as available chlorine) Sodium or Potassium Hydroxide 0. 1-5. 0 wt% Bleach Stable Surfactant System 1. 0-10. 0wt% Fragrance 0. 01 to 0. 5% (preferably 0. 01 to 0. 1%) Water Balance
36. A composition as claimed in claims 34 or 35 wherein the bleach stable surfactant system comprises an amine oxide of the formula :

where Rl and R2 are the same or different Cl alkyl groups (preferably methyl) and R3 is a Cg-22 alkyl group.
37. A composition as claimed in any of claims 34 to 36 wherein the bleach stable surface active agent system comprises an alkyl ether sulphate having an alkyl group of 8 to 22 carbon atoms and an average of 3-5 moles EO.
38. A composition as claimed in claim 37 wherein the surface active agent system comprises 1 to 5% (preferably 1. 5-4. 0%) amine oxide and 1-5% (preferably 1. 5-4. 0%) of alkyl ether sulphate.
39. A composition as claimed in any one of claims 34 to 38 wherein the thickened bleach incorporates a water soluble acrylic acid polymer.
40. A composition as claimed in claim 39 wherein the composition comprises 0. 1 to 5. 0% by weight of the acrylic acid polymer.
41. A composition as claimed in any one of claims 34 to 40 wherein the composition does not contain more than 0. 2% by weight of fragrance.
42. A method of producing a shear thinning hard surface cleansing formulation as claimed in claim 1 substantially as herein described in any one of the foregoing Examples.
43. A glass cleaning formulation as claimed in claim 29 substantially as hereinbefore described in any one of Examples 1 or 2.
44. A thickened bleach formulation as claimed in claim 34 substantially as hereinbefore described as in Example 3.