Cleaning agent for hard surfaces made of polymer containing material

The present invention relates to a liquid cleaning composition for general purposes, especially for hard surfaces, comprising surfactants and polymeric components.

In traditional cleaning of hard surfaces such as wood, glazed tiles, painted metal and the like, it is known to use a surfactant or solvent based composition for removing dirt, applying varnish, wax or polishing as a separate operation to cover the surface and reduce dirt re-deposition rate. Such two-stage cleaning and coating operations are time consuming and complex.

It is known to include in the surfactant-based compositions ingredients with the intention that the deposition of such ingredients on the surface will result in the formation of a protective layer in a single-step cleaning operation.

US 3 679 592 (1972) discloses alkaline, cleaning and soiling compositions that contain a surfactant and 1-10% by weight, particularly 4%, 4%, of a film-forming component with a specific structure having a molecular weight in the range of 500 to 100 000. In use, the compositions are intended to protect against palm buildup and to help remove dirt.

GB 1 528 592 (1978) discloses alkaline floor cleaning compositions that contain a copolymer of organic polycarboxylic acids having a molecular weight in the range of 100,000 - 2,500,000 that is soluble in aqueous solutions having a pH of 8.5 or greater. Such polymers are readily available in commercial quantities.

GB 1 534 722 (1978) discloses granular hard surface cleaning compositions which contain a surfactant and, as "a dirt-removing mixture", polyvinyl alcohol or pyrrolidone and biopolysaccharide. These polymers have molecular weights ranging from about 5000 to about 360,000 and are available in industrially useful amounts. The compositions form alkaline solutions.

US 4,252,665 (1979) discloses aqueous, alkaline hard surface cleaning compositions with a pH value of 9-12, which contain a "detergent enhancing" acrylic copolymer having a molecular weight well above 100,000 in combination with anionic surfactants.

US 07/297 807, as described in EP 0 467 472 A2 (Colgate Palmolive), shows that the incorporation of 2.3% 15-20% aqueous solution of a cationic polymer of poly [beta (methyl diethylammonium) ethyl methacrylate] into mixed non-ionic surfactant system for cleaning hard surfaces, significantly improves the use of previously soiled and cleaned ceramic tiles for the next cleaning. Such cationic polymers are rather more expensive than conventional acrylic and methacrylic polymers and have raised some doubts regarding the environmental acceptability of quaternary nitrogen containing agents.

It is known that surfactant-based compositions contain structuring agents that help achieve rheological properties to increase their spread and adhesion of the composition to the hard surface to be cleaned, in particular to provide adhesion to sloping surfaces.

Known structuring agents include polymers such as polysaccharides, for example sodium carboxymethyl cellulose and other chemically modified cellulosic materials, xanthan resins and other non-flocculating structuring materials such as Biopolymer PS87 cited in US Patent No. 4,329,448. Polymers of acrylic acid crosslinked with a polyfunctional agent such as CARbOPOLR are also used as structuring agents. The amount of such structuring agents can be as low as 0.001%, but more typically at least 0.01% by weight of the composition. A further task of such structuring agents is to suspend granular components such as abrasive.

It is also known to use at least partially esterified resins, such as at least partially esterified rosin and unsaturated dicarboxylic acid or anhydride adducts, or at least partially esterified derivatives of copolymerization products of mono-unsaturated aliphatic, cycloaliphatic or aromatic non-carboxylic acid unsaturated monomers dicarboxylic acids or their anhydrides. The purpose of such materials is to modify the wetting properties of the composition and to create a streak-free finish after drying.

Typical examples of suitable copolymers of this type include copolymers of ethylene, styrene and vinyl methyl ether with maleic acid, fumaric acid, itaconic acid, citraconic acid and the like and with their anhydrides, including styrene / maleic anhydride copolymers.

EP 0 467 472 A2 discloses polymers that facilitate soil removal such as, but not limited to, cationic poly [beta (methyl diethylammonium) ethyl methacrylate], also effective in combination with anionic and cationic surfactants. This published application states that "said adsorbed polymer forms a residual hydrophyte dirt layer on the surface in question, while

178 776 ne removal of subsequently deposited contaminants requires less work than without such a residual layer. " The molecular weight of the polymer is in the range of 4000-100,000, however, it should be considered when using polymers having a molecular weight above 50,000 due to solubilities (see EP 467 472, p. 3, paragraph 3).

EP 0 379 256 discloses compositions similar to those mentioned in the above document, having up to 2% by weight, optionally quaternized, antistatic polymers with a molecular weight in the range of 2000 - 500,000, which have an acidic pH of 2-4 and 2-4% by weight of a nonionic surface system active agent. Specific examples relate to compositions having a pH of 2.5 and containing 2.2% by weight of a mixed nonionic surfactant system and 0.07% of the specified cationic polymer.

And here it is believed that the modified polymer acts as a dirt removal agent.

In addition to the above, it is known from US 4,606,842 to use low molecular weight polyacrylic resins as a filler in spray type compositions and washable glass cleaners. Baker et al. in US 4 690 779 discloses the use of a combination of polyacrylic acid polymers having a molecular weight below 5000 with certain nonionic surfactants in hard surface cleaning compositions. The basic function of the polymer in such systems is to act as a filler.

US 4,678,596 relates to a rinse aid for manual and machine dishwashing at pH 7.5-10 which contains 5-60% non-ionic surfactant (in examples 15%) and preferably 2% by weight of anionic poly (meth) acid polymer ) with a molecular weight of 1000-50,000. Compositions having a pH value of 6.5 having a relatively high polymer content were considered to be unstable.

US 4,657,690 relates to a washing and foaming composition for hair and skin with an acid / neutral pH range (4.5-7.7) which contains a non-ionic surfactant (typically about 5%) and poly (meth) acrylic acid for improving the original cleansing effect of the surfactant in which the weight ratio of polymer to surfactant is no more than 0.2: 1.

It can be seen from the above that it is known to incorporate certain polymers into, generally alkaline, hard surface cleaning compositions so as to achieve either the first cleaning effect when the composition is applied to the surface for the first time, or to achieve a secondary effect by modifying the surface so that to inhibit dirt build-up or to facilitate re-cleaning. As the following examples show, known compositions are generally ineffective in both first and secondary cleaning.

We have found that the use of certain relatively long chain anionic, water-soluble polymers in acidic or neutral surfactant-based compositions brings an unexpected initial cleaning effect with an additional anti-deposition effect. We have surprisingly found that conventional acrylic, methacrylic and maleic anhydride polymers have the same effect in acidic solutions of nonionic surfactants in the same range as expensive cationic polymers.

Accordingly, the invention provides a liquid aqueous hard surface cleaning composition at pH 3-7 comprising:

a) 1-30% by weight of a non-ionic surfactant,

b) 0.005-3% by weight of a water-soluble anionic polymer with an average molecular weight of less than 1,000,000, which polymer is free of quaternary nitrogen groups, wherein the ratio of polymer to nonionic surfactant is 0.1: 1 or less.

Preferably the composition contains 0.2-2.0% by weight of anionic polymer.

A preferred composition of the invention comprises an anionic polymer selected from the group consisting of polymers of acrylic or methacrylic acid or maleic anhydride, copolymers of one or more of the above with each other or with other monomers, and mixtures thereof. It particularly preferably comprises a polymer selected from the group consisting of acid

178 776 polyacrylic, polymaleic anhydride and copolymers of the above with ethylene, styrene and methyl vinyl ether.

In a preferred embodiment, the composition comprises a polymer having an average molecular weight exceeding 100,000.

Preferably the composition contains no more than 33% by weight of anionic detergent based on total active detergents.

A particularly preferred composition according to the invention has a pH of 3-6 and contains:

a) 10-20% by weight of an alkoxylated alcohol as a non-ionic surfactant,

b) less than 3% by weight of anionic surfactants,

c) 0.2-2% by weight of a water-soluble anionic polymer with an average molecular weight of less than 1,000,000, which polymer is a homo- or heteropolymer of at least one of acrylic acid, methacrylic acid, maleic anhydride, ethylene, styrene and ether methyl vinyl, which polymer is essentially free of quaternary nitrogen groups.

Without wishing to be bound by any theory of action, it is believed that the cleaning benefit of the water-soluble polymer is due to the separation of the non-ionic surfactant phase, causing penetration into and / or deposition on the dirt, resulting in an increase in the effective surfactant concentration than is found in polymer-free compositions. An alternative explanation is that the deposition of a surfactant on a soiled surface can be increased by the formation and deposition of a polymeric surfactant complex.

polymers

The water-soluble polymer of the above-mentioned size range is the main component of the composition of the present invention.

Surprisingly, preferred polymers in embodiments of the present invention are those that are readily available on the market. These are polymers of acrylic acid, methacrylic acid or maleic anhydride, or copolymers of one or more of them or with each other or with other monomers.

Particularly suitable polymers include polyacrylic acid, polymaleic anhydride and copolymers of each of the abovementioned with ethylene, styrene and vinyl methyl ether.

The most preferred polymers are maleic anhydride copolymers, preferably formed with styrene, acrylic acid, methyl methyl ether and ethylene.

Preferably the molecular weight of the polymer is at least 5,000, more preferably at least 50,000 and most preferably more than 100,000.

In typical surfactant-based cleaning compositions, the polymer constitutes at least 0.01% of the product.

It has surprisingly been found that the positive effect of the presence of a polymer can be seen even in the presence of a very small amount of polymer and surfactant. This property of the low concentration persisting there is particularly useful in applications of the invention where significant dilution is envisaged.

The preferred polymer content is 0.05-5.0% by weight, at which the benefits of the anti-soiling effect become particularly significant. More preferably, the polymer is present in an amount of 0.2-2.0% by weight. We have found that higher polymer contents do not bring further significant benefits with conventional diluents, while increasing the cost of the composition. Presumably higher polymer contents increase the viscosity of the product and prevent wetting and penetration of dirt. In contrast, for concentrated products which are diluted before use, the starting polymer content may be up to 5% by weight.

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In the context of the present invention, anionic polymers are those that carry a negative charge, or similar polymers in protonated form. Mixtures of polymers may be used.

As mentioned above, the molecular weight of the polymer is less than 1,000,000 Daltons. As the molecular weight increased, the advantages of the polymer were reduced.

Surfactants

It is essential that the compositions of the present invention contain at least one nonionic surfactant.

The composition of the invention contains active detergents, which can be selected from nonionic active detergents. We have found that harmful effects occur if anionic polymers are used only with anionic surfactants, or with mixtures of anionic and nonionic surfactants that contain most of the anionic surfactant.

Suitable active nonionic detergents can be widely described as compounds formed by condensation of alkylene oxide groups that are hydrophilic in nature, with organic hydrophobic compounds that can be aliphatic or alkyl aromatic in nature.

The length of the hydrophilic or polyoxyalkylene radical that condenses with any particular hydrophobic group can easily be adjusted to form a water-soluble compound having the desired balance between hydrophobic and hydrophobic elements.

Specific examples include the condensation products of aliphatic alcohols having 8 to 22 carbon atoms with both straight and branched chain configuration, with ethylene oxide, as well as condensate of coconut oil and ethylene oxide having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; alkylphenol condensates, the alkyl group of which contains 6 to 12 carbon atoms, with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide; condensates containing 40 to 80% by weight of polyoxyethylene radicals and having a molecular weight of from 5000 to 11,000; tertiary amine oxides with R structure₃NO, where one of the R groups is an alkyl group with 8 to 18 carbon atoms and each of the others is a methyl, ethyl or hydroxyethyl group, for example dimethyldodecylamine oxide; tertiary phosphine oxides with the structure R3PO, where the R group is an alkyl group with 10 to 18 carbon atoms and each of the other groups is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms, for example dimethyldodecylphosphine oxide; and dialkyl sulfoxides with the structure R₂SO, where the R group is an alkyl group with 10 to 18 carbon atoms and the remainder is a methyl or ethyl group, for example methyl tetradecyl sulfoxide; fatty acid alkylamides; alkylene oxide condensates of fatty acid alkylamides and alkyl mercaptans.

The amount of it active detergent to be used in the composition and according to the invention will usually be from 1 to 30% by weight, preferably from 10 to 20% by weight, and most preferably from 12 to 20% by weight. Contents of about 15% active (detergent) are particularly advantageous as there is a slight increase in the cleaning effect at higher contents, although such higher contents can be used in products intended to be significantly diluted before use.

The anionic surfactant, optionally, may be present in relatively small amounts.

Suitable anionic detergent compounds include the water-soluble salts of organic sulfate reaction products having in the molecule structure an alkyl radical having from 8 to 22 carbon atoms and a radical selected from sulfonic acid radicals or sulfuric acid esters and mixtures thereof.

Examples of anionic detergents are the salts of sodium and potassium alcohol sulfates, especially those obtained by sulfating higher alcohols, produced by reducing tallow glycerides and coconut oil; sodium and potassium alkyl benzene sulfonates, in which the alkyl group has from 9 to 15 carbon atoms; secondary sodium and potassium alkanesulphonates; sodium salts of alkyl glyceryl ether sulfates, especially ethers of higher alcohols derived from tallow and coconut oil; coconut oil monoglyceride sulfate sodium salts; sodium and potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol and from 1 to 6 moles of ethylene oxide; sodium and potassium salts of alkylphenol ether and ethylene oxide sulfate with 1 to 8 units of ethylene oxide molecules and in which the alkyl radicals contain from 4 to 14 carbon atoms; reaction products of fatty acids esterified with isethionate, neutralized with sodium hydroxide, where, for example, the fatty acids are derived from coconut oil and mixtures thereof.

Preferred water-soluble synthetic, anionic, active detergent compounds include ammonium and substituted ammonium salts (such as mono-, di- and tri-ethanolammonium), alkali metals (such as sodium and potassium) and alkaline earth metals (such as calcium and magnesium) higher alkyl benzene sulfonates and mixtures with higher alkyl olefin sulfonates and sulfates, and monoglyceride sulfates of higher fatty acids.

The most preferred anionic, active detergent compounds are higher alkyl aromatic sulfonates such as higher alkyl benzene sulfonates, having from 6 to 20 carbon atoms in the straight or branched chain alkyl group, particular examples of which are the sodium salts of higher alkyl benzene sulfonates or higher alkyl toluene sulfonates, xylenes or phenols, alkyl naphthalene sulfonates, ammonium diamyl naphthalene sulfonate and sodium dinonyl naphthalene sulfonate.

The amount of synthetic active anionic detergent to be used in the detergent composition of the invention will generally be from 0.5 to 50% by weight (based on total active), preferably less than 33% by weight (based on total active). For products containing about 15% by weight of surfactants, the level of anionic surfactant should not be more than 5% by weight of the product.

It is also possible to include amphoteric, cationic or zwitterionic active detergents in the compositions of the invention.

Suitable amphoteric, detergent active compounds that can optionally be used include derivatives of aliphatic secondary and tertiary amines, containing an alkyl group with 8 to 18 carbon atoms and an aliphatic radical substituted with an anionic, water solubilizing group, e.g. sodium 3-dodecylamino propionate. Sodium 3-dodecylamino propane sulfonate and sodium N-2-hydroxydodecyl-N-methyl taurate.

Suitable cationic detergent active compounds include quaternary ammonium salts having an aliphatic radical of 8 to 18 carbon atoms, for example cetyl trimethylammonium bromide.

Suitable zwitterionic, detergent active compounds which may optionally be used include derivatives of quaternary ammonium, sulfonium and phosphonium compounds having an aliphatic radical of 8 to 18 carbon atoms and an aliphatic radical substituted with a water solubilizing group, e.g. propane-1-sulfonate-3- (N , N-dimethic-N-hexadecyl ammonium) betaines, propane-1-sulfonate-3- (dodecylmethylsulfonium) beaine, and ethane-sulfonate-3- (cetylmethyl phosphinium ') betaine.

Further examples of suitable detergent active compounds include those commonly used as surfactants given in the well-known Schwartz and Perry textbook: "Surface Active Agents", Tom I and Schwartz, Perry and Berch: "Surface Active Agents and Detergents ", Volume II.

The total amount of detergent active compounds to be used in the composition of the invention will generally be from 1.5 to 30%, preferably from 2 to 20% by weight, and most preferably 10-20% by weight.

The composition of the invention may contain other ingredients to aid in its cleaning effect.

178 776

For example, the composition may contain detergent builders, other than those defined above, special water-soluble salts such as nitrile triacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates, especially polyphosphates, mixtures of ortho- and pyrophosphate, zeolites and mixtures thereof. Such fillers can act as abrasives if present in amounts above their water solubility, as explained below. In general, fillers, other than special, water-soluble salts, when used, preferably constitute from 0.1 to 25% by weight of the composition.

Alternatively, metal ion sequestrants such as ethylenediamine tetraacetates, aminopolyphosphonates (DEQUEST) can also be used^R) and phosphates and many other polyfunctional organic acids and salts.

A further optional component of the compositions of the invention is the foam control material that can be used in the compositions of the invention, which in use tends to produce rich foam. One example of a foam regulating material is soap. Soaps are salts of fatty acids and include alkali metal soaps such as sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 10 to 20 carbon atoms. Sodium, potassium, mono-, di- and triethanolammonium mixtures of fatty acids derived from coconut oil and ground nuts are particularly useful. If used, the amount of soap may be at least 0.005%, preferably 0.5% to 2% by weight of the composition. A further example of a foam control material is an organic solvent, hydrophobic silica, silicone oil and carbohydrates.

The compositions of the invention, in addition to the ingredients already mentioned, may also contain other optional ingredients such as pH regulators, colorants, optical brighteners, dirt suspending agents, cleansing enzymes, compatible bleaching agents, gelation suppressants, melting freeze stabilizers, bactericides, preservatives, solvents , fungicides, insect repellents, compounds that increase the solubility of detergents in water, fragrances and opacifiers.

It is desirable that the compositions of the present invention contain essentially no abrasive particles. Experiments have shown that the presence of abrasive particles reduces the cleaning benefits of the presence of polymer, as the abrasive substance itself provides separate cleaning benefits. Presumably, the abrasive, surfactant and polymer form a complex that reduces the effective concentration of surfactant on the surface being cleaned.

As mentioned above, the compositions of the present invention have an acidic or neutral pH value. We have found that these pH values ​​provide better cleaning and / or protection against re-contamination benefits. The preferred product pH is 3-6. A particularly preferred value is pH 4-6 to provide a balance between the dangers of acid compositions and the benefits of acids to remove limescale.

Particularly preferred compositions of the present invention are mobile aqueous liquids, pH 3-6, which contain:

a) 10-20% by weight of an alkoxylated alcohol, non-ionic surfactant,

b) less than 3% by weight of anionic surfactants,

c) 0.2-2% by weight of a water-soluble anionic polymer with an average molecular weight of less than 1,000,000, which polymer is a homo- or heteropolymer of at least one of acrylic or methacrylic acids or maleic anhydride with at least one such as acrylic acid , methacrylic acid, maleic anhydride, ethylene, styrene and methyl vinyl ether, the polymer being essentially free of quaternary nitrogen groups.

178 776

To make the present invention clearer, it will be described below by way of examples and with reference to the accompanying drawings, in which:

Figure 1 is a graph showing the effect of polymer concentration on the results of cleaning and preventing soiling, and Figure 2 is a graph of the relationship of primary and secondary cleaning benefits for a number of polymer types.

Examples

In examples I-VIII the following materials are used:

Sokolan series (TM) Gantrez series (TM)

Scripset 520 (Tm)

EMA 31

SCMC (Courlose A600) 6047 polyacrylamides FRS 3966 Jaguar C162

Ethylene oxide (WSRN 80) Polyvinyl pyrrolidone from BASF from GAF from Mons anto from Mons non from CourCiulds from Allied Colloids from Allied Colłoids from Meyhzll from Union Carbide from PolySciences

Polyvinylnnirnlidone had a molecular weight of about 386,000 Dalton.

Example I ac

Comparison with cationic polymers

0.25 mg / cm 0.25 mg / cm was deposited on the test surface with "Decamel" (RTM from Formica) with the dimensions "A.4" by spraying² dirt (without volatile substances). The dirt consisted of 1% glycerol tripalmitate, 0.5% glycerol tbioleieia, 0.5% kaolin, 0.2% liquid paraffin, 0.1% palmitic acid, 0.02% carbon black in labeled spirit. The dirt was allowed to age for 24 hours at room temperature before cleaning.

The effort used to remove dirt from the test surface was measured using cellulose sponge fabric. The formulations contained a nonionic surfactant and water, and were with or without polymer. The surfactant used was Imbentin 91-35 OFA (TM) (C₉-C_n alkyl, 3-5 EO alkyl ethoxylate from KOLB). The illustrative polymer of the present invention was agricultural acid (from BDH), which had an average molecular weight of 230,000 Daltons. The cationic polymer used in the comparative examples was Polymer JR-400 (TM: from Union Carbide), which had an average molecular weight of 400,000 Dalton. The formulations are listed in Table 1 below, along with the effort required for the cleaning operation.

The results given are geometric means from eight repeated experiments. In order to remove overnight changes resulting from differences in soil levels, the data was normalized in such a way that the effort needed to clean the DECAMEL plate with the same polymer-free composition was constant.

From the results given under "initial" it can be seen that the compositions of the present invention show better cleaning performance compared to example Ia, where there was no polymer. This improvement is statistically significant at a 95% confidence level

In order to test the operation when re-soiled, DECAMEL tiles were again soiled and cleaned again using the same dirt and according to the same cleaning recipe. The cleaning results for the first and second cleaning cycles are given under "same (2)" and "same (3)".

These results show significant benefits due to the presence of the polymer. For compositions that did not contain a polymer (see example Ia), the effort required in subsequent cycles of cleansing remains essentially constant. It is apparent that much less effort is needed where the surfaces are cleaned using a composition containing the polymer and which are cleaned again using the same of the composition.

The results given under "normal (4)" are the next cleaning of the test surfaces used in Examples Ia-e with the composition used in Example Ia (i.e. the surfactant itself). This confirms that the benefit of the present invention is 10

178 776 remains when the surfaces have been cleaned with a conventional composition only with the surfactant.

It should be noted that the initial cleaning benefits of the polymers of the invention (Examples Ic and Ie) are comparable, if not simply slightly better than those obtained with the quaternized polymer (as used in comparative examples Ib and Id).

Table 1

<td></td><td>ia</td><td>b</td><td>ic</td><td>Id</td><td>Ie</td>

<td>Imbentin</td><td> 10%</td><td> 10%</td><td> 10%</td><td> 10%</td><td> 10%</td>

<td>Polymer JR</td><td> -</td><td> 0,25%</td><td> -</td><td> 1%</td><td></td>

<td>Polyacrylic acid heavy part. 230 kD</td><td> -</td><td> -</td><td> 0,25%</td><td> -</td><td> 1%</td>

<td>Water up to 100%</td><td></td><td></td><td></td><td></td><td></td>

<td>PH</td><td> 4,2</td><td> 4,4</td><td> 3,7</td><td> 4,6</td><td> 3,3</td>

<td colspan="6"></td>

<td>Initial</td><td> 1</td><td> 0,29</td><td> 0,24</td><td> 0,36</td><td> 0,25</td>

<td>Same (2)</td><td> 1</td><td> 0,11</td><td> 0,15</td><td> 0,12</td><td> 0,14</td>

<td>Same (3)</td><td> 1</td><td> 0,05</td><td> 0,06</td><td> 0,06</td><td> 0,06</td>

<td>Normal</td><td> 1</td><td> 0,18</td><td> 0,18</td><td> 0,17</td><td> 0,21</td>

Example dg

Impact of polymer content

Example 1 was repeated using the formulations given in Table 2 below, except that the polyacrylic acid used was VER.SiCOL E11 (RTM) (from Allied Colloids - 250 kD). The DECAMEL tile cleaning effort (RTM) is expressed as the logarithm (base 10) of the effort required. The examples were repeated both with and without polymer and at varying concentrations of surfactant. The values ​​given are averages of four replicates.

"Initial" results were obtained using the specified polymer compositions. "Normal (1)" results were obtained when cleaning using the specified compositions but without the polymer.

The "Same (2)" values ​​were obtained by re-cleaning tiles originally cleaned with the composition containing the polymer to obtain the results given as "Initial (1)" using the same composition in the same way as the tiles were originally cleaned. "Normal (2)" values ​​were obtained when cleaning re-soiled "Normal (1)" tiles with a polymer-free composition at the same level of surfactant.

Normal (3-5) values ​​were obtained when cleaning the tiles, which were originally cleaned with the composition containing the polymer [to obtain the results 'Same (2)'], the composition containing the polymer. The same surfactant content (7% by weight, IMBENTIN) was used in all re-cleanings of the Normal (3-5) series.

Table 2

<td></td><td>ild</td><td>How much</td><td>Ilf</td><td>IIg</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>

<td>Imbentin</td><td> 16%</td><td> 8%</td><td> 4%</td><td> 2%</td>

<td>Polyacrylic acid (250 kD low frequency)</td><td> 1%</td><td> 0,5%</td><td> 0,25%</td><td> 0,15%</td>

<td>Water up to 100%</td><td></td><td></td><td></td><td></td>

178 776 table 2 continued

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>

<td colspan="5"></td>

<td>Log the initial effort needed</td><td></td><td></td><td></td><td></td>

<td>Initial (1)</td><td> 2,36</td><td> 2,38</td><td> 2,69</td><td> 3,35</td>

<td>Normal (1)</td><td> 2,37</td><td> 3,04</td><td> 3,43</td><td> ****</td>

<td colspan="5"></td>

<td>Same (2)</td><td> 2,18</td><td> 2,14</td><td> 2,18</td><td> 2,80</td>

<td>Normal (2)</td><td colspan="4">without significant reduction versus Normal (1)</td>

<td colspan="5"></td>

<td colspan="5">Re-cleaning "Same" (2) without polymer</td>

<td>Normal (3)</td><td> 2,17</td><td> 1,98</td><td> 1,99</td><td> 2,02</td>

<td>Normal (4)</td><td> 2,86</td><td> 2,96</td><td> 2,90</td><td> 2,83</td>

<td>Normal (5)</td><td> 3,02</td><td> 3,04</td><td> 2,99</td><td> 3,03</td>

The results show that the presence of a polymer gives the benefit of first cleaning, namely that less effort is needed in the presence of the polymer than in the absence of it [cf. results "Normal (1)" with results "Initial (1)"]. The magnitude of this effect increases clearly less than the concentration of surfactants. Presumably this is due to the expectation of perfect cleaning at high concentrations of surfactant, masking the effects of the polymer. In Example IIg it was shown that the plate could not be cleaned using considerable effort when using a low surfactant content in the absence of polymer.

It can also be seen that the effect of the polymer remains in subsequent cleaning cycles, but this effect decreases as the number of cycles increases.

Importantly, the low levels of polymer and surfactant show a slight improvement on repeated cleaning performance compared to higher levels. So compositions containing low levels of surfactant and polymer clean at least as well as compositions with higher levels of these ingredients: compare IId with IIf, where the levels of surfactant and polymer are four times higher and the same effort is needed for cleaning shallow. Compositions which do not contain polymer do not clean if small amounts of surfactant are present in nichedin. The compositions have also been found to,. which do not contain polymer, do not show a reduction in the effort required for repeated use.

Examples IIh-1

Comparison with commercial hard surface cleaners

Examples IIh-IIl compare the effort required when using the very dilute product solutions listed in Table 2c. The compositions are diluted to typical floor cleaning dilutions according to the recommendations and manufacturers (approximately 3 g / l).

Preparation constituting a variant of the invention: 28% IMBENTIN, 2% polyacrylic acid [250 kD: VERSICOL E11 (RTM) from Allied Colloids]. In the example. comparator, non-ionic (surfactant) alone is used without the polymer.

The results of the percentage dirt removal on a hydrophobic surface determined by a standard colorimetric method after 40 cleaning strokes were obtained using a SHEEN linear wiper (RTM) at a pressure of 80 g / cm². The surface was

178 776

DECAMEL (RTM) pre-soiled 0.061 mg / cm² (counting without volatile substances) dirt. Cleaning was carried out with a cellulose sponge pre-saturated with a suitable cleaning solution.

The results for the percentage dirt removal on a hydrophilic surface were determined using the same dirt applied to ceramic floor tiles, under the same conditions, but with a single cleaning stroke.

Both sets of experiments were carried out in three series with dirt type:

a) 1% glycerol tripalmitate, 0.5% glycerine trioleate, 0.5% kaolin, 0.2% liquid paraffin, 0.1% palmitic acid, 0.02% carbon black in methylated spirit (i.e. 80:20 fat: particles)

b) as (a) 50:50 fat particles, and

c) as (a) with 20:80 fat particles.

The use of these three different models of dirt types and two surfaces illustrates how the composition works in practice. Three replications were carried out with each of the three types of dirt, and the average values ​​of all nine measurements summarized in the table were taken as indicators of the composition's work in practice on the marked surface.

Table 3

<td>Example</td><td>Solution</td><td>Decamel</td><td>Ceramics</td>

<td>IIh</td><td>according to</td><td> 65%</td><td> 47%</td>

<td>II and</td><td>Non-ionic alone</td><td> 58%</td><td> 35%</td>

<td>uh</td><td>Ajax Compact (RTM)</td><td> 45%</td><td> 30%</td>

<td>II k</td><td>Flash Ultra (RTM)</td><td> 40%</td><td> 12%</td>

<td>Ill</td><td>Flash Liquid (RTM)</td><td> 28%</td><td> 8%</td>

From these results it can be seen that the solution according to the invention far exceeds the comparative examples under the same conditions mentioned above.

In further experiments, it was found that the variety of Example IIh gave less residue and better gloss on black ceramic tiles (determined by gloss assessment) than the comparative formulations of Examples II-IIl.

Example III

Anionic surfactant / Anionic polymer (Comparative example)

Example 1 was repeated using simplified formulations consisting only of anionic surfactant in water with and without anionic or cationic polymer. The surfactant used was PAS magnesium salt. The anionic polymer was polyacrylic acid as used in Example 1. The cationic polymer was Polymer JR as used in Example 1. The compositions are given in Table 4 below, along with the effort required for the cleaning operation as given in Example I. The numbers provided are geometric means of eight replicate experiments, adjusted as data for a polymer-free composition and always requiring the same cleaning effort.

The initial cleaning action is represented by the data "Initalia (ł)". As can be seen the polymer-containing compositions do not have significant benefits in first cleaning, and rather that it is generally more difficult to clean the surface with anionic surfactant containing anionic or cationic polymer compositions than similar compositions without polymer: for example, in Example IIIc, it can be seen that for compositions containing a polymer for initial cleaning, about two and a half times more effort is needed compared to compositions containing no polymer.

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To test the effect of re-cleaning, the DECAMEL sheets were again soiled and cleaned again according to the same procedure. The cleaning results for the first and second re-cleaning cycles are given as "Same (2)" and "Same (3)". These results show generally negative effects that are presumably due to the presence of anionic polymer and surfactant of the same type of charge.

The results given as "Narmal (4)" are the results obtained at the next cleaning of the test surfaces used in Examples IIIa-e with the composition used in Example IIIa, i.e. when cleaning with a composition containing only a surfactant (basic conventional composition) without a polymer. This shows that the negative effect of the anionic polymer remains if the test surfaces are cleaned with a conventional composition containing only a surfactant. These results also show that cationic polymers have re-cleaning benefits that are not seen with anionic polymers in the presence of anionic surfactant.

Table 4

<td></td><td>IIIa</td><td>mb</td><td>IIIc</td><td>IIId</td><td>IIIe</td>

<td colspan="6"></td>

<td>Magnesium salt PAS</td><td> 5%</td><td> 5%</td><td> 5%</td><td> 5%</td><td> 5%</td>

<td>Polymer JR</td><td> -</td><td> 0,25%</td><td> -</td><td> 1%</td><td> -</td>

<td>Polyacrylic acid</td><td> -</td><td> -</td><td> 0,25%</td><td> -</td><td> 1%</td>

<td>Water up to 100%</td><td></td><td></td><td></td><td></td><td></td>

<td>pH</td><td> 6,5</td><td> 5,5</td><td> 3,4</td><td> 5,3</td><td> 3,0</td>

<td colspan="6"></td>

<td>Initial (1)</td><td> 1</td><td> 1,18</td><td> 2,42</td><td> 1</td><td> 1,18</td>

<td>Same (2)</td><td> 1</td><td> 0,20</td><td> 2,10</td><td> 0,18</td><td> 1,10</td>

<td>Same (3)</td><td> 1</td><td> 0,15</td><td> 2,01</td><td> 0,16</td><td> 0,90,</td>

<td>Normal (4)</td><td> 1</td><td> 0,22</td><td> 1,47</td><td> 0,22</td><td> 1,26</td>

Similar experiments were carried out with a cationic polymer (Polymer JR) and a cationic surfactant (tetradecylb-trimethylammonium hydrogen sulfate). No benefits found. Presumably, the lack of benefit is due to the surfactant and polymer having the same charge and, consequently, the inability of the surfactant and polymer to form a complex.

Example IV

Comparison with other polymers

A series of further experiments was carried out using the materials listed in Table 5 below. The simplified preparations consisted of a non-ionic surfactant (10%) and water with or without polymer. Imbentin91-35 OFA (C₉-C_n alkyl, 3-5 EO alkyl ethoxylate). The polymers listed in the table were present in an amount of 0.5% by weight.

The results were normalized so that the initial effort required for cleaning with the surfactant alone was 100%. The benefit of re-cleaning was assessed by cleaning the surface with a 7.5% aqueous solution of non-ionic surfactant alone and measuring the effort required: results here normalized, assuming 100% effort for the surfactant alone.

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Table 5

<td></td><td>initial</td><td>Again</td>

<td>Copolymers of maleic anhydride and acrylic acid.</td><td></td><td></td>

<td>IVa Sokolan CP12 (TM)</td><td> 24</td><td> 10</td>

<td>IVb Sokolan CP13 (TM)</td><td> 32</td><td> 17</td>

<td>Methyl vinyl ether</td><td></td><td></td>

<td>IVc Gantrez AN119 (TM)</td><td> 25</td><td> 8</td>

<td>IVd Gantrez AN169 (TM)</td><td> 34</td><td> 12</td>

<td>styrene</td><td></td><td></td>

<td>IVe Scripset 520 (TM)</td><td> 29</td><td> 9</td>

<td>Ethylene</td><td></td><td></td>

<td>IVf EMA 31</td><td> 22</td><td> 11</td>

<td>Carboxylate polymer</td><td></td><td></td>

<td>IVg SCMC</td><td> 48</td><td> 22</td>

<td>Cationic polymers</td><td></td><td></td>

<td>Pnliakrcloamiey</td><td></td><td></td>

<td>IVh 6047 A.</td><td> 34</td><td> 21</td>

<td>IVi 6047 B</td><td> 42</td><td> 26</td>

<td>IVj6047 C.</td><td> 47</td><td> 23</td>

<td>IVk 6047 D</td><td> 82</td><td> 16</td>

<td>IV1 FRS 3966</td><td> 80</td><td> 24</td>

<td>Modified Guar</td><td></td><td></td>

<td>Jaguar C162</td><td> 54</td><td> 22</td>

<td>Nonionic polymers</td><td></td><td></td>

<td>IVn Polyethylene oxide</td><td> 29</td><td> 49</td>

<td>IVo Pnieniemyln-pyrroliene</td><td> 37</td><td> 43</td>

These results are shown graphically in Figure 2. In this figure, the first (initial) and second (re) operations are plotted on separate axes. References to data from Figure 2 are given using coordinates.

Examples of nonionic polymers listed in GB 1 534 722 as PO (polyethylene oxide) coating agents (at 49.29) and PWP (at 43.37) show particularly poor benefits in re-cleaning, although the first cleaning effect is good.

Cationic polymers have some benefits in both first and re-cleaning, although the trend shows that both factors have opposite references, i.e. better cleaning in one situation is associated with poorer performance in another: compare polyacrylamide at (82,16) and Pnliacrclamide at (42.26).

It is clear from Figure 2 that more significant benefits are obtained with the anionic polymers of the present invention, in particular with maleic anhydride copolymers, preferably formed with styrene, acrylic acid, methyl vincl ether and ethylene. The results show that, except for kαrbokscmetclncelulozc (22.48) and Sokolan CP13 (TM) (17.32), anionic polymers generally show better performance than comparative examples for first and second cleaning.

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Example V

Impact of polymer concentration

Returning to Figure 1, it shows a graph of the effect of polymer concentration (230 kD, with BDH) on the cleaning effort and the benefits of counteracting soiling. All compositions had a natural pH value and contained a surfactant (Imbentin 91-35 OFA: C₉-C_n alkyl, 3-5 EO alkyl ethoxylate) at 10% by weight. The cleaning and the benefit of preventing soiling were evaluated as in Example IV.

The drawing shows that with the compositions of the present invention the benefit of initial (first) cleaning becomes significant even at very low polymer levels and remains when the polymer level increases. The benefits of preventing soiling become visible at levels of about 0.2% of the polymer and also remain. This is in line with the results obtained in Example II dg.

Example VI- Impact of pH

Table 6 shows the effect of pH on compositions of the present invention containing 0.5% polyacrylic acid polymer (230 kD, from BDH) and comparative compositions that do not contain polymer. All compositions contained a surfactant (Imbentin 91-35 OFA: C₉-C_at alkyl, 3-5 EO alkyl ethoxylate) at 10% by weight. The pH value was modified by the presence of NaOH. The benefits of cleaning and preventing soiling were evaluated as in Example IV. The cleaning effort was expressed as the logarithm (base 10) of the effort required.

This column 6

<td></td><td></td><td colspan="2">First effort</td><td colspan="2">Second effort</td>

<td></td><td>pH</td><td>with polymer</td><td>no polymer</td><td>with polymer</td><td>no polymer</td>

<td>VIa</td><td> 3,5</td><td> 2,25</td><td> 2,45</td><td> 2,25</td><td> 2,72</td>

<td>VIb</td><td> 5,0</td><td> 2,30</td><td> 2,45</td><td> 2,30</td><td> 2,72</td>

<td>VIc</td><td> 7,0</td><td> 2,50</td><td> 2,45</td><td> 2,85</td><td> 2,72</td>

<td>VIc</td><td> 9,0</td><td> 2,70</td><td> 2,45</td><td> 2,72</td><td> 2,72</td>

As can be seen at low pH values, especially below pH 7.0, there is a significant reduction in the requirements for both first and second cleaning for polymer-containing systems compared to compositions containing only non-ionic (surfactant).

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Nonionic surfactant with polymer added, cleaning relative to (100%) surfactant alone surfactant% relative initial effort

100 η

8060h anionic ⁺ cationic.

her +

H +

402010 Relative effort

40 45 50 cleaning again

Fig. 2 Graph of the relationship of primary and secondary cleaning benefits for different types of polymers

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<img file="PL178776B1_D0001.tif" />

POLYMER CONCENTRATION [%] ί EFFORT RELATED TO NON-Ionic - 1

Fig. 1 Effect of polymer concentration on cleaning results and prevention of re-contamination

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