A cleaning paste with soluble abrasive

CLEANING PASTE WITH SOLUBLE ABRASIVE

The present invention relates to the formulation of a stable detergent composition for hard surfaces in the form of a non-reversible, substantially water-free viscous cleaning composition, i.e. ⁵ having a maximum water percentage of B% by weight, which comprises a gelled mixture of an organic liquid vehicle consisting essentially of organic solvents and nonionic surfactants including an ethoxylated fatty acid as an essential component in the in situ gelation of said vehicle liquid, after. addition of a small amount of about 0.7-1.5% by weight sodium hydroxide. The addition of gel insoluble ingredients, particularly a water soluble inorganic abrasive builder, to the gelled mixture forms a viscous paste containing a stable suspension of the relatively large particles of said abrasive.

The abrasive is insoluble in the gelled product, but soluble in water. Thus, after using this pasty product to clean a hard surface, the water used to rinse the detergent product dissolves both the gel and the abrasives, and does not leave an ashy residue on or around the cleaned surfaces.

The prior art abounds in hard surface cleaners containing abrasives both in the form of cleaning powders and in liquid form. Water insoluble abrasives as the major and primary detergent components in cleaning powders are well known, as described in US Pat. No. 3,850,833. However, it has been found that the use of said water insoluble abrasives in cleaning powders for hard surfaces leaves an unpleasant ashy residue on the cleaned surface. This problem has been addressed in the prior art by replacing all or part of the insoluble abrasive with a water-soluble abrasive, resulting in a composition where the water-soluble components are washed away with the rinse water, leaving virtually no residue on the surface. the cleaned surface, as described in the U.8 patent. 3,577,347. Another method of dealing with this abrasive residue problem is the use of a powdered or particulate water insoluble abrasive having maximum particle sizes of less than 0.15mm, and about 8% by weight of the particles. abrasives having a diameter of about 0.037 mm or more for effective cleaning, and a small amount of an organic hydrotropic agent (e.g. sodium cumenesulfonate) to improve grease removal, as disclosed in US patent 4,289,840.

Likewise, a liquid hard surface detergent composition containing water-insoluble abrasives suspended in an aqueous medium faces the problem of stability as well as the difficulty of completely removing insoluble abrasive particles from the surface. cleaned. These problems have been addressed in the prior art by preparing a high performance liquid detergent composition comprising a water soluble builder salt having particles of colloidal size (less than 1 micron and generally 0.1 micron), dispersed in a medium. aqueous containing an agent

fatty acid amide emulsifier as described in US Pat. No. 4,057,506. Another way to deal with the stability problem is disclosed in US Pat. No. 3,522,186 where a water insoluble abrasive dispersed in an aqueous medium is disclosed containing tetrapotassium pyrophosphate, sodium hydroxide soap, diethanolamide and the like. 0.25-1.5% methanol or ethanol to prevent separation of the aqueous liquid into two layers. Another way to tackle the stability problem is disclosed in US4,051,055 in which an aqueous hard surface detergent composition containing a water insoluble abrasive is suspended in an aqueous medium thickened with at least 1%. clay as a thickener, said thickened system preventing separation of the abrasive from the liquid medium. The presence of fluorides increases the ability of the clay thickened system to hold abrasive particles in suspension.

US Patent 4,657,692 also describes a thickened aqueous cleaning product, free of syneresis (separation of solids from liquid), which contains an abrasive insoluble in water in suspension in an aqueous medium containing as thickener a colloidal aluminum oxide. , inorganic salts of water soluble alkali metals such as phosphates, polyphosphates, carbonates, etc., and about 0.5-3% of a surfactant and a halogen bleach. European Patent Application No. 0193.375 relates to the use of a water soluble salt which functions as both an abrasive and a detergent builder, such as sodium bicarbonate, sodium tripolyphosphate, etc., in a homogeneous and pourable aqueous detergent composition containing an abrasive for cleaning hard surfaces, and also containing a mixture of anionic and nonionic surfactants in a weight ratio of 1: 1 to 9: 1 of anionic surfactant to nonionic surfactant.

A water-based hard surface cleaning agent in paste form comprising 50-65½ sodium bicarbonate and 50-35% by weight water containing sodium chloride and a diethanol fatty acid amide (Ci₂-VS_{i &}) is described in US Pat. No. 4,179,414.

A water based gel containing at least 40% anionic surfactant and 2-10% water soluble builder salts is disclosed in US Patent 4,107,067 as a laundry detergent composition in the form of a pourable gel.

US Patent 4,257,908 also describes a laundry detergent composition in stable pourable form, containing 25-55% of a builder salt of the phosphate type, 5-40% of an anionic surfactant in 30-50% of a medium. aqueous alcohol containing a water: alcohol weight ratio of 5: 1 to 20: 1.

US patent 3.981.826 also discloses pasty or gelatinous non-aqueous liquid detergent compositions having cleaning properties and comprising a dispersion of a water-soluble, normally solid anionic surfactant of a solid particulate water-soluble inorganic salt (builder salt) and an agent. suspending such as very large oxides (silica, magnesia, alumina or clay) in about 19-79% of a water-miscible organic liquid solvent such as a polyol (glycerol, ethylene glycol, etc.), and optionally a lower mono-alcohol (ethanol, methanol, etc.). Another pourable and pourable organic solvent-based hard surface detergent composition is disclosed in US Pat. 3,865,756 and comprises a gelling agent which acts as an abrasive such as colloidal silica, an alkaline builder salt such as water soluble phosphates and silicates, a surfactant, a water insoluble abrasive, eg 5 silicate. calcium, and about 55-90% of an organic cleaning solvent such as a substantial amount of mineral spirits based on aliphatic hydrocarbons mixed with 4-7% of ethylene glycol monobutyl ether. US patent 2,864,770 also discloses a pourable organic solvent-based water-soluble aqueous thixotropic liquid detergent composition which contains glycols and glycerol as an organic solvent, an anionic surfactant, and a suspended phosphate builder. 15 However, none of the above-mentioned patents disclose a non-reversible, substantially water-free, viscous detergent composition comprising a gelled mixture of an organic liquid vehicle consisting essentially of water-soluble organic solvents and non-ionic surfactants. containing an ethoxylated fatty acid as one of the surfactants, and a small amount of sodium hydroxide which reacts in situ with the ethoxylated fatty acid to form a clear, non-pourable organic gel, and about 10-25% of a water soluble abrasive builder suspended in said gelled vehicle.

It has now been found that the formulation of the novel detergent composition of the present invention is based on the ability of ethoxylated fatty acid, especially ethoxylated lauric acid, to react with sodium hydroxide in organic media and form. a gel with these media. Another feature of the present novel formulation is the incorporation of a water-soluble abrasive material into³⁵ the organic gelling mixture. This allows the preparation of viscous products containing inorganic solids suspended in a gelled organic vehicle. While this abrasive is insoluble in the gelled vehicle, it becomes soluble on dilution of the product with water. Cleaning with the undiluted product is aided by the low abrasive action of the abrasive, especially sodium pyrophosphate. The overall product dissolves in water leaving no ashy residue on or around the cleaned surfaces. In addition, this abrasive becomes a surfactant builder when the product is used diluted. Household surfaces such as ceramic and Formica surfaces can be cleaned with the new products of this invention in the absence or presence of water without scratching the surface. This product, whether undiluted or diluted, has significantly improved cleaning power due to the triple action of organic solvent, non-ionic detergent and abrasive. In the diluted product, the abrasive dissolves in water and becomes a detergency builder. The organic viscous product for hard surfaces according to the present invention can function as a spray detergent, degreasing cream and multi-purpose maintenance product for floors and walls. Simulated floor cleaning tests show that at d 3 g / l of the present cleaning product the result is better than with Mr. Clean at 15 g / l. This results in the fact that 5 bottles of Mr. Clean is equivalent to 1 bottle of the present cleaning product.

Accordingly, the first object of the present invention is to provide a novel viscous organic hard surface cleaner which comprises an ethoxylated fatty acid and sodium hydroxide dissolved in an organic vehicle which reacts in situ to form a gelled vehicle. .

Another object of this invention is to provide a novel viscous organic cleaning composition containing an inorganic water-soluble particulate abrasive suspended in the gelled organic vehicle.

Yet another object of the present invention is to provide an organic gel comprising an abrasive which dissolves in water leaving no ashy residue on or around the cleaned surfaces.

Yet another object of this invention is to provide a multipurpose maintenance product having a triple cleaning action.

Other objects, advantages and new features of the invention will become apparent in part from the description which follows, and in part upon examination of the following description or may be taught by the practice of the present invention;

In order to achieve the foregoing and other objects according to the present invention, the non-spillable organic gelled hard surface detergent composition of the invention contains from about 65 to 80% by weight of an organic liquid carrier consisting essentially of about 15%. 35% by weight of a water-miscible organic solvent, about 35-70% of a mixture of ro-icraqje surfactant had an ethoxylated fatty acid as one of the surfactants, and a small amount of about 0.7 to 1.5% by weight sodium hydroxide, which reacts in situ with the ethoxylated fatty acid. ⁸⁸ to form a clear, non-pourable, gelled vehicle substantially free of water and capable of suspending a water-soluble inorganic particulate abrasive.

More specifically, the gelled organic composition of the present invention comprises about 65%

80% by weight of a substantially anhydrous organic vehicle consisting essentially of about 15 to 35% by weight of a water soluble organic solvent and about 35 to 70% by weight of a nonionic surfactant mixture ⁵ containing an ethoxylated fatty acid as one of the surfactants, about 0.7 to 1.5% by weight sodium hydroxide, gelled by in situ reaction of the ethoxylated fatty acid with sodium hydroxide; and about 10 to 25% by weight of an inorganic water soluble particulate abrasive (builder salt) uniformly suspended in the gelled vehicle.

The water-miscible organic solvent is selected from glycol ethers alkylated with lower alkyl groups, monoalcohols alkylated with lower alkyl groups, diols alkylated with lower alkyl groups, and mixtures thereof.

The hard surface detergent products of the present invention described are thick (viscous), clear, non-pourable and stable pastes having a minimum viscosity of about 14,000-15,000 cps (14 - 15 Pa.s) measured with a viscometer. Brookfield HATD. The viscosity of the gelled product results in a stable suspension of relatively large particles of water soluble abrasives, i.e. larger than the particles of collofal size. The product of the present invention has many applications as a multipurpose detergent. Undiluted with water, the product can be used as a cleaner for sinks and tubs, and as a stain remover for soiled hard surfaces, producing a triple cleaning action due to the combined action of the organic solvent, non-detergent. ionic and abrasive, without leaving the usual ashy residue with abrasive detergents. The novel organic pastes of the present invention diluted with water can be used as a maintenance product for floors and walls. The novel organic detergents of the present invention can also be used as anhydrous hand detergents, in particular for mechanics and gardeners; for cleaning cooking vessels, pots etc. industries and communities.

The major essential component of the present viscous non-pourable detergent composition is the nonionic surfactant system which constitutes from about 35 to 70% by weight of a mixture of nonionic surfactants containing about 3% of an ethoxylated fatty acid, and about 10-64% of the other ethoxylated nonionic surfactants which may be a fatty alcohol, an alkylphenol, a propylene oxide-propylene glycol condensation product, or a mixture thereof. More specifically, the additional ethoxylated nonionic surfactant may be selected from a polyethylene oxide condensate of an alkylphenol having an alkyl group having 6 to 12 carbon atoms, a polyethylene oxide condensate of an alcohol. aliphatic containing about 8 to 22 carbon atoms, a polyethylene oxide condensate of the condensation product of propylene oxide with propylene glycol having a molecular weight of about 1500 to 1800, and mixtures thereof. Typical examples of polyethylene alkylphenol oxide condensate are nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol, dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol. Typical examples of alcohols. Ethoxylates include: about 6 moles of ethylene oxide condensed with one mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide, C10-Cia fatty alcohol condensed with about 8 moles of oxide of ethylene, a C10Ci ^ alcohol condensed with 5 moles of ethylene oxide per mole of alcohol (Alfonic 1012-60). Examples of polyethylene oxide condensate with the condensation product of propylene oxide with propylene glycol are commercially available as Pluronic surfactants marketed by the Wyandotte Chemicals Corporation. The liquid character of this product is maintained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product. Examples of ethoxylated fatty acids include lauric, palmitic, stearic, etc., ethoxylated with about 5 to 10 ethylene oxides per mole of fatty acid. A preferred fatty acid ethoxylate is lauric acid having 9 ethylene oxides (Alkasurf-L-9). The presence of the ethoxylated fatty acid in the organic vehicle is essential for gel formation, for the in situ reaction in the organic solvent with sodium hydroxide to form a small amount of a soap which thickens and gels the gel. organic liquid media. A small amount of sodium hydroxide induces delayed hydrolysis followed by gelation of the vehicle leaving the ethoxylated acid.

Another essential component of the present cleaning composition is the water-miscible organic solvent in an amount of about 15 to 35% by weight of the total formulation. The organic solvent provides an organic medium for the in situ reaction between the ethoxylated fatty acid and sodium hydroxide for gelation of the organic medium. Suitable water-miscible organic solvents include monoalcohols alkylated with lower alkyl groups, diols alkylated with lower alkyl groups (glycols), ethers of glycols alkylated with lower alkyl groups, and mixtures thereof.

Examples of water soluble lower monoalcohols are ethanol, isopropanol and butanol. Examples of suitable glycols are ethylene glycol, diethylene glycol (Carbitol), and propylene glycol. Examples of lower alkyl glycol ethers are diethylene glycol monobutyl ether of formula: C ^ H ^ OCHzCHzOCHzCHzOH also known as Butyl Carbitol (Union Carbide), ethylene glycol monobutyl ether of formula: C ^ H ^ OCH ^ CH ^ OH etc. It is preferred to use a mixture of monoalcohols and diols, and even better still a mixture of a monoalcohol, a diol and a glycol ether as solvent for the nonionic surfactant mixture. Another essential ingredient in the present viscous cleaning composition is a water soluble inorganic particulate abrasive suspended in the gelled vehicle in an amount of about 10-25% by weight of the total composition. The abrasive is insoluble in the gel but soluble in water. The water soluble abrasive particles are relatively large particles about 1/2 mm in diameter. The viscosity of the gelled vehicle, which is πύninunde 14,000 to 15,000 cps (14 to 15 Pa.s), is capable of mainbaür 'large particles in suspension. Suitable water soluble abrasives are selected from alkali metal phosphates, polyphosphates and carbonates. Examples of suitable water soluble abrasives include pyrophosphates such as tetrasodium and tetrapotassium pyrophosphates, tripolyphosphates, tetrapolyphosphates, carbonates, etc. This abrasive becomes a surfactant builder when the product is used diluted and is easily removed from the cleaned surface leaving no ashy residue. Preferred abrasives include tetrasodium pyrophosphate and sodium carbonate.

The hard surface cleaning composition of the present invention may also contain minor amounts of additional conventional components to introduce any desirable characteristics which components are compatible with the gel and do not adversely affect the structure of the gel. Suitable additives are dyes, perfumes, preservatives, antiseptics etc. These additives represent a maximum of 15% by weight of the composition.

The cleaning compositions of the present invention are generally prepared by mixing water-miscible organic solvent components with an ethoxylated fatty acid and at least one nonionic surfactant component to form a transparent, low viscosity liquid vehicle; adding sodium hydroxide solution to the clear liquid vehicle and mixing until the liquid gels, which can take anywhere from a few minutes to several hours, depending on the amounts of components; and finally adding to the gelled vehicle the water soluble abrasive, a colorant, even as a customary additional ingredient, until the abrasive is uniformly dispersed within the gelled vehicle and a paste is formed. The detergent composition is packaged in any suitable container, whether rigid or flexible. The dough can be extruded from a compressible container.

The final gel cleaning product is a stable hard surface detergent with a thick (viscous) creamy appearance, substantially anhydrous and having an alkaline pH in the range of about 8 to 11. It can be applied to the surface. to be cleaned in any suitable manner, ie with a sponge or cloth, then rinsing the surface with water, without leaving an ashy residue.

The following non-limiting examples illustrate the invention. All amounts of the various ingredients in the examples and elsewhere in the description are by weight unless otherwise indicated.

Example 1

<td>Ingredients</td><td> %</td>

<td>Lauric acid ethoxylate (90E)</td><td> 23,30</td>

<td>Tetrasodium pyrophosphate</td><td> 20,00</td>

<td>Diethylene glycol monobutyl ether</td><td> 14,00</td>

<td>Ethanol</td><td> 14,00</td>

<td>Alcohol C_lo-VS₁₄ OE 5: 1</td><td> 10,00</td>

<td>Propylene glycol</td><td> 6,00</td>

<td>Deionized water</td><td> 4,00</td>

<td>Caustic soda (50%)</td><td> 3,00</td>

<td>Graphtol Blue 1%</td><td> 0,40</td>

<td>By smoke</td><td> 0,30</td>

<td>pH (1%) = 10.9</td><td></td>

The ingredients of the vehicle, namely ethoxylated lauric acid, ethoxylated alcohol, butylcarbitol, ethanol and propylene glycol and the perfume are mixed to form a clear mobile liquid. NaOH is added to this liquid until the vehicle gels and forms a solid gel. After 5 minutes of gel ripening, the tetrasodium pyrophosphate is mixed with the ripe gel to form a cream (paste). The blue pigment is then dispersed within the cream.

This formulation provides a blue cleaner with superior cleaning properties and does not leave an ashy residue on the cleaned surface.

Example 2

Ingredients - X

Lauric acid ethoxylate C90E) 28.00

Sodium carbonate 23.00

Alcohol Cio^-Ci ^ DE 5s1 21.00

Ethanol12.5

Diethyleneglycol monobutyl ether7.00

Propylene glycol 5.00

Caustic soda 38X3.00

Perfume0.30

Lemon colored solution0.20

This product is prepared according to the process of Example 1.

This product is a viscous colored paste.

possessing superior cleaning properties.

Examples 3-5

<td colspan="2"> 20</td><td colspan="3"> 3 4 5</td>

<td></td><td>Alfonic 1012-60¹</td><td> 48,0</td><td> 10,0</td><td> 14,0</td>

<td></td><td>Alkasurf L-9²</td><td> 6,0</td><td> 28,3</td><td> 21,0</td>

<td></td><td>Plurafac RA40^To</td><td> —</td><td> —</td><td> 7,0</td>

<td></td><td>Pluronic L-64 *</td><td> 15,5</td><td> —</td><td> —</td>

<td> 25</td><td>Butyl Carbitoi</td><td> 8,0</td><td> 14,0</td><td> 7,0</td>

<td></td><td>Propylene glycol</td><td> —</td><td> 6,0</td><td> 6,0</td>

<td></td><td>Ethanol</td><td> 8,0</td><td> 14,0</td><td> 14,0</td>

<td></td><td>Water and dye</td><td> 0,9</td><td> 5,9</td><td> 5,9</td>

<td></td><td>NaOH</td><td> 0.7</td><td> 1,5</td><td> 1,5</td>

<td> 30</td><td>Tetrasodium pyrophosphate</td><td> 12,0</td><td> 20,0</td><td> 23,0</td>

<td></td><td>By smoke</td><td> 0,5</td><td> 0,3</td><td> 0,3</td>

1.Alcohol CioCi ^ DE 5: 1

2. Lauric acid DE 9: 1 '

3.Low foaming polyol:

polycondensates of propylene oxide and ethylene oxide and propylene glycol.

4.High foaming polyol:

These compositions are prepared according to the process of example i.

The end products are viscous cleaning compositions for hard surfaces, easily removed by rinsing with water without leaving an ashy residue.

All of the undiluted cleaning pastes mentioned above can be diluted with water for equally effective cleaning of hard surfaces. The pasty product dissolves completely in water without leaving an ashy residue, i.e. abrasive particles, on or around the cleaned surfaces.