NO172592B - LIQUID CLEANING MIXTURE - Google Patents

Description

The background of the invention

1. The scope of the invention

The invention relates to liquid, aqueous, stable, effective, safe, non-abrasive cleaning agent mixtures for hard surfaces, of the type commonly referred to as scouring agent mixtures. The mixes are. physically stable and do not separate, and the user is thereby assured that optimal use results can be expected from the different components and their amounts and ratios with respect to each other, and the mixtures are safe and do not scratch the usual surfaces to be cleaned, such as glass , porcelain, ceramics, plastic, metal, wood, painted wood (enamelled and lacquered).

2. State of the art

The state of the art is, of course, very extensive when it comes to liquid scouring agent mixtures that are claimed to work in a safe and effective way, while others are stated to be physically and chemically stable, etc.

Some examples of previously known scouring mixtures include US patent 4005027 in which mixtures are described as including clay and insoluble abrasive. André inorganic abrasives are shown. The mixtures include surfactants which are bleach stable. Non-ionic surfactants are not used. It is claimed that the products are physically stable and also that they do not "significantly seep along vertical surfaces" (column 10, lines 45-47). Such stability is a sign of a false saturation fluid being formed when the smectite and attapulgite clays necessary in such mixtures are used. In US patent 4116849 compositions are described which are very similar to those described in US patent 4005027. Also in US patent 4116849 thickeners are described instead of the preferred smectite

and attapulgite clays, such as colloidal silicon dioxide, polystyrenes, sulphonated polystyrenes, polyethylene, oxidized polyethylenes, polypropylene, copolymers of styrene with methacrylic acid, methyl or ethyl acrylate or vinyl acetate to name a few. In the patent it is expressed that "... ethoxylated

non-ionic surfactants must be avoided." Furthermore, in neither of these two patents are soaps or fatty acids described as suitable materials. ' In US patent 4240919, mixtures of polyvalent stearate soap, water and water-insoluble abrasive are described. Various abrasives are indicated, and among the "organic" types are "melamine, urea formaldehyde resins, painted rigid polymeric materials, such as polyurethane foam"

(column 3, lines 10-12). Optionally, "substantially any surface-active materials compatible with the other components of the composition according to the present invention" may be present. These include "water-soluble anionic, nonionic, amphoteric, cationic and zwitterionic surfactants." (Column 3,

lines 57-62). In addition, reference is made to US patents 4051056 (expanded perlite as abrasive), 4457856 (poly-acrylate abrasive), West German patent 1956616 (polyvinyl chloride as abrasive), US patent 3645904 (skin cleanser containing a polymeric abrasive material) and US patent 4302347.

A composition that satisfies the optimal desire for a non-scratching, stable, effective and safe aqueous scouring agent is not included in the prior art. The ability to remove most stains from all hard surfaces that normally occur, and especially from plastic surfaces without damaging such delicate plastic materials that may occur as e.g. kitchen counter tops, anti-stick coatings on metal cages, polystyrene, polymethyl methacrylate, polyvinyl chloride, nylon, polyester (e.g. fiberglass) and similar items are the main object of the present invention. In addition to being able to remove stains, the mixtures according to the invention must also have good grease-removing properties. Physical stability is, as shown in the state of the art referred to above, a major problem and is a necessity to achieve good acceptance by consumers.

It is therefore an object of the present invention

to provide liquid, aqueous, stable, abrasive-containing cleaning compositions.

It is another object of the present invention

to provide a liquid, aqueous, abrasive cleaning composition which is safe and also substantially non-abrasive on most surfaces encountered, including plastic surfaces.

It is a further object of the present invention to provide stable, liquid, aqueous, polymer abrasive cleaning compositions which are safe, effective and non-abrasive.

Description of the invention

The objectives of this invention are met by means of the stable liquid, non-scratching, aqueous, scouring cleaning agent mixture as specified in the characterizing part of claim 1.

The fatty acid component can be any fatty acid with a carbon chain of Cg - De most

preferred is C1Q -.c^gf°9 typically it goes

excellent to use naturally occurring materials, such as coconut oil, palm kernel oil or animal tallow, as starting materials for the fatty acids. A particularly preferred range for the fatty acids is ^ i2~^ 18 of the type found in coconut oil. A typical coconut oil fatty acid mixture contains approx. 50% C12, 20% C14, 8.5% Clg and 10% C18, the rest being made up of other acids and perhaps even some neutral material, and is liquid at 40°C. Although the most convenient starting materials are natural oils or fats which naturally give mixed acids, the individual specified acids and also any mixture of any number of acids of any chain length within condition<n><c>g"C20 is used. The soaps used are the alkali metal and ammonium salts, the sodium and potassium salts being preferred. The fatty acid comprises from 0.5 to 15% by weight, preferably from 1 to 10% by weight, and more preferably from 1 to 7% by weight, of the mixture.

The non-soap anionic agent may be selected from any of the usual anionic agents, such as the alkyl benzene sulfonates, alkyl sulfates, alcohol sulfates, alcohol ether sulfates, olefin sulfonates, paraffin sulfonates,

from 1 to 7% by weight, of the mixture.

The non-soap anionic surfactant may be selected from any of the usual anionic sulfate or sulfonate surfactants, such as the alkylbenzene sulfonates, alkyl sulfates, alcohol sulfates, alcohol ether sulfates, olefin sulfonates, paraffin sulfonates, fatty acid monoglyceride sulfates, sarcosides, taurides or the like or their salts, such as alkali, alkaline earth or ammonium salts. Among these, the sulfates and sulfonates are preferred. It is a prerequisite that these surfactants have a linear ciq~C20 aliphatic hydrocarbon chain in their structure.

The preferred non-soap anionic surfactants are the paraffin sulfonates, the linear alkylbenzene sulfonates, the alcohol and alcohol ether sulfates.

The most preferred anionic surfactants (not soap) are the C12~C18 paraffin sulfonates in the form of their alkali metal or ammonium salts, C10~C20 alkylbenzene sulfonates with C±2~C16 being most preferred, alkyl (i.e. alcohol) sulfates of < C>12~C18 and the corresponding ether sulfates with from 3 to 50 (e.g. 3, 5, 10, 20, 30 or 50) moles of condensed ethylene oxide. The most preferred salt-forming cation is sodium. The amount of the non-soap anionic surfactant ranges from 1 to 15% by weight, preferably from 1 to 10% by weight, and more preferably from 1 to 5% by weight.

Some specific examples of suitable anionic surfactants are sodium lauryl sulfate, sodium paraffin (C14~<C>17)<-s>sulfonate, sodium decyl sulfate, sodium tridecyl sulfonate, sodium tallow r,alkyl sulfate, sodium coconut alkyl sulfate, sodium oxotridecyl (triethoxyl) sulfate (sulfated - 3 EO condensate with oxotridecyl alcohol), sodium dodecylbenzenesulfonate, sodium tridecylbenzenesulfonate, sodium tetradecylbenzenesulfonate and sodium (C15)-olefinsulfonate.

The non-ionic surfactants that can be used here are generally characterized by a long-chain hydrophobic chain and a hydrophilic poly(ethylene oxide) chain. The hydrophobic chain can be and is preferably from an alcohol

(<C>10 - C2Q, preferably C1Q - C^6, typically a C13 alcohol, such as linear tridecyl alcohol) or

a polypropylene backbone. Other hydrophobic compounds, viz

thioalcohols, acids, amines or the like can also be used. The preferred alcohol is a C₁₂-C₁₀ alcohol with from 1 to less than 5 mol of ethylene oxide and most preferably with from 2 to 4 mol of ethylene oxide, typically 3 mol of ethylene oxide. the concentration of non-ionic compound in the recipe can vary from 0.5 to 15 by weight, with preferred concentrations being from 1 to 10, most preferably from 3.5 to 6.5,

and typically and most preferably 5% by weight.

The electrolyte used here is a water-soluble, alkaline, inorganic or organic building salt. The usual salts include the alkali metal bicarbonates, borates, carbonates, phosphates, polyphosphates or silicates among the inorganic salts and polycarboxylates, such as polyacetates, tartrates, citrates, maleates, oxydiacetates, alkenyl succinates, carboxymethyloxysuccinates, -oxydi-succinates or the like among the organic salts. Polymeric building salts, such as the water-soluble salts of polymers of maleic acid, itaconic acid or a similar acid, can be used as well as copolymers and interpolymers of these with polymerizable α, :3-ethylenically unsaturated compounds, such as vinyl ethers, esters, alkyl alcohol, acrylic or metha- acrylic acid or esters thereof etc.

The electrolyte can vary within a considerable concentration range from as little as 1% to 25%-

A preferred range is from 2 to 15%. A mixture of carbonate and phosphate can typically amount to 5 to 10% in total. Other convenient and preferred mixtures may likewise comprise carbonate, polyphosphate and possibly end silicate in amounts of from 5 to 10%.

Specific electrolytes include sodium and potassium carbonate, sodium and potassium bicarbonate, sodium and potassium sesquicarbonate, sodium and potassium orthophosphates,

-pyrophosphates, -tripolyphosphate or -hexametaphosphates, sodium and potassium tetraborate in anhydrous form or as pentahydrate or decahydrate, sodium silicate (e.g. sodium metasilicate or other silicates with a Na2O:SiC^ ratio in the range of from 3.5 to 1 to 1:1), as illustrative of the inorganic electrolytes, and tetrasodium or tetrapotassium

ethylenediaminetetraacetic acid salt, trisodium nitrile triacetate or disodium polymaleate etc. only as illustrative examples of the organic electrolytes.

"The abrasive consists of poly-

ethylene, polypropylene, polystyrene, polyesters, polyvinyl chloride, polyvinyl acetate, polymethyl methacrylate or various copolymers and copolymers of the above. The criterion for suitability is that the material does not scratch polymethyl methacrylate and that the average particle size lies within the range from 10 to 150 µm, preferably from 25 to 100 µm, and most preferably from 30 to 75 µm, e.g. 60 µm. For optimal use results, it is most desirable to use a polyvinyl chloride sanding powder whose average particle size is approx. 60 µm, with a main amount lying within the range from 30 to 75 µm. The molecular weight ranges for the polymeric: abrasives can vary greatly as long as the above . physical properties are satisfied. In general, molecular weights will range from several thousand (e.g. 2000, 5000, 20000) to several hundred thousand (e.g. 125000, 250000, 400000) and upwards to several million (e.g. 1000000, 2000000, 4000000 , 6000000). The amount of abrasive can vary from 2

to 30%. A preferred area for

the preferred recipes are from 5 to 25% and more preferably from 5 to 15%, e.g. 7%, 10% or 12%.

A number of different optional components can be incorporated into the mixtures according to the invention. Some are even preferred, such as inorganic viscosity-influencing agents (e.g. montmorillonite clays, such as bentonite or attapulgite etc), organic ones, such as methylcellulose, carboxymethylcellulose or hydroxypropylmethylcellulose. Such materials are particularly advantageous for obtaining a "creamy" scouring agent where a "thickened" type of material is desired by the consumer. For such products, it may be desirable to have viscosities in the range from several hundred (250, 400 or 500 cPs) to several thousand (e.g. 1100, 1500 or 2000 cP s etc.)

It is of the greatest importance that the compositions according to the invention exhibit unusual stability (ie absence of or minimal phase separation) in the absence of the viscosity "increasers" whose main function, as mentioned above, is simply to thicken. The amount of the viscosity influencing agent can be in the range from 0.1 to 5 to 10%, usually from 0.5 to 3%. Other optional, but again preferred, additives include a hydrocarbon material, especially a terpene, such as d-limonene. Such terpenes are readily available in several perfume materials which are generally added to most cleaning products for sale to consumers. The amount of the hydrocarbon may vary from 0.05 to 5%, preferably from 0.1 to 2 to 3%. Other additives that may be used include bleaching agents (liquid and solid hypochlorites available e.g. as NaOCl solution or calcium hypochlorite powder, chloramines, chlorinated di- or trisodium phosphates, sodium or potassium dichloroisocyanurate or trichloric cyanuric acid, etc.) , buffers, sodium hydroxide, potassium hydroxide, foaming agents, enzymes, preservatives, disinfectants, coloring agents, odorants and the like can be used if desired and if they are compatible. Generally, smaller quantities of such auxiliary materials are used, e.g. from 0.01 to 10% and often from

0.1 to 5%.

The mixtures according to the present invention are alkaline and have a pH of from 10 to 12.

is generally drawn to the mixtures to add the fatty acid in free acid form and to neutralize in situ with sodium hydroxide or potassium hydroxide while the pH is regulated to the desired level. A typically preferred pH is 11 × 0.5.

The mixtures according to the invention are generally prepared by adding to the recipe weight of hot water while stirring in a suitable mixer and homogenizer (at a temperature of from 50 to 80°C, e.g. 60°C) the following mixture in the indicated order: fatty acid, non-ionic, viscosity modifier (if used), abrasive polymer particles and alkali for neutralization of fatty acid. At this stage the temperature of the mixture is lowered to approximately room temperature and the electrolyte (e.g. building salts) is then added followed by the non-soap anionic agent and finally the perfume (also as a starting material for the hydrocarbon should this be desired). If no hydrocarbon is to be used, an odorant that does not contain hydrocarbons can of course be used, but a hydrocarbon material has proven to be desirable in order to achieve increased grease removal properties.

The examples below serve to illustrate

the present invention without limiting it. Parts and percentages are based on weight unless otherwise stated.

Example 1

A mixture of the following components is prepared:

The mixture is prepared in the manner previously described as preferred. To the recipe weight of water at 60°C, the fatty acid, the non-ionic agent, the clay, the abrasive and the potassium hydroxide are added with vigorous stirring. After a smooth mixture has been obtained, it is cooled to room temperature (20°C) and the remaining ingredients (in the order indicated) are added with stirring. A cream-like, stable product is obtained. Its pH is approx. 11 and its viscosity approx. 1100 cP<s.

Example 2

Example 1 is repeated, except that the following fatty acids are used instead of 2% distilled coconut fatty acid:

Example 3

Example 1 is repeated using 5% sodium lauryl sulfate instead of the sodium paraffin sulfonate.

Example 4'

Examples 1 and 3 are repeated with separate replacement of the used TKPP and I^CO^ with 4% anhydrous sodium carbonate (Na2C03).

Example 5

Each of the above examples is separately repeated, but instead 5% non-ionic agent is used

(a) 3% nonionic agent

(b) 6% nonionic agent.

The product according to example 1 is used for a standardized test method to determine the degree of scratching against a plastic surface. This product is compared to two commercial products. The method involves the use of a reciprocating sponge ("spontex") containing 1 g of the test product which is applied to a plastic tile, and after 200 strokes the plastic tile is washed and the gloss is compared to the gloss of the original plastic tile. The used tile has an original gloss reading of 79, and this remains unchanged after the test with the product according to example 1. The two commercial products gave readings of 72 and 73, and this shows partial damage to the tile by the commercial materials and no damage when using the cleaning agent mixture according to the present invention.

Claims (1)

1. Stable, liquid, aqueous, non-scratching, scouring detergent mixture, characterized in that it comprises 0.5-15% by weight of a water-soluble C8-C20 fatty acid soap, 1-15% by weight of a water-soluble anionic sulfate or sulfonate surfactant which is not a soap and which has a linear C10-C20 aliphatic hydrocarbon chain in its molecular structure, 0.5-15% by weight of a water-soluble non-ionic surfactant which is a condensate of a hydrophobic compound containing a linear C10-C20 aliphatic hydrocarbon chain and ethylene oxide, 1-25% by weight of a water-soluble, inorganic or organic alkaline building salt, 2-30% by weight of a polymeric abrasive which has a particle size within the range of 10-150 µm and which is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyesters, polyvinyl chloride, polyvinyl acetate, polymethyl methacrylate and copolymers or interpolymers of the above as the only abrasive, water and possibly a hydrocarbon, the cleaning agent mixture having a pH of 10-12. 2. Detergent mixture according to claim 1, characterized in that the anionic surfactant that is not soap contains a linear C12-C18 aliphatic hydrocarbon group and that the non-ionic surfactant contains a linear C10-C16 aliphatic hydrocarbon group. 3. Cleaning agent mixture according to claim 2, characterized in that a hydrocarbon is present and that this is a terpene hydrocarbon in an amount of 0.05-5% by weight. •<4.> "Detergent mixture according to claim 2, characterized in that the fatty acid soap is made from coconut oil, that the anionic surfactant that is not soap is a paraffin sulphonate, that the non-ionic surfactant is a C10-C16 alcohol ethoxylate and that the building salt comprises a polyphosphate. 5. Cleaning agent mixture according to claim 3 or 4, characterized in that the abrasive is polyvinyl chloride. 6. Cleaning agent mixture according to claim 5, characterized in that it contains d-limonene as a terpene hydrocarbon. 7. Detergent mixture according to claim 1, characterized in that the amount of fatty acid soap is 1-5% by weight, the amount of anionic surfactant that is not soap is 1-5% by weight, the amount of non-ionic surfactant is 1-10% by weight, the amount of building salt is 5-10% by weight, and the amount of polymeric abrasive is 5-15% by weight.