A cleaning paste with soluble abrasive

(42) Date of commencement of the patent: 15. 5. 1994 (45) Date of issue: 27.12.1994 (30) Priority:

(73)

Patentee:

14.12.1987 US 132527 claims.

COLGATE-PALMOLIVE COMPANY 10022 NEW YORK (US).

CQ (54) HIGH VIS COSIC HARD SURFACE CLEANING AGENT (57) High viscosity hard surface cleaner, consisting essentially of

a) 65 to 85% by weight of an organic carrier liquid, based on the total composition, consisting essentially of a 1) 15 to 35% by weight of a water-miscible organic solvent and a 2) to 70% by weight of an ethoxylated fatty acid as one the surfactant-containing mixture of non-ionic surfactants is formed,

b) 0.7 to 1.5% by weight of sodium hydroxide which reacts with the ethoxylated fatty acid in situ to form a clear, non-flowing, substantially anhydrous, gelled carrier, and

c) 10 to 25% by weight of an inorganic water-soluble particulate scouring agent incorporated in the gelled carrier liquid.

AT 398 577

UffieoTSäis

AT 398 577 Β

The invention relates to a high viscosity hard surface cleaner which is stable, non-pourable and substantially free of water.

Scouring agent-containing hard surface cleaners are known both in the form of scouring powders and in liquid form. According to US Pat. No. 3,850,833, water-insoluble abrasives are known as the main cleaning component of scouring powder cleaners. However, with the use of water-insoluble abrasives, an undesirable, granular residue remains on the cleaned surface. This problem is overcome, according to US Pat. No. 3,577,347, by replacing some or all of the insoluble scouring agent with a water-soluble scrubbing agent which is rinsed with the wash water and therefore forms substantially no residue on the cleaned surface. Another way to avoid scouring residues is, according to US Pat. No. 4,289,640, the use of a powdered or particulate water-insoluble abrasive having a maximum particle size of less than 0.15 mm, with about 8 wt% of the abrasive particles having a diameter for effective cleaning of about 0.037 mm or more, and in addition a small amount of a hydrotrope organic compound is present so that grease can be better removed.

In addition, liquid detergents containing water-insoluble abrasives suspended in an aqueous medium have problems with stability and difficulty in completely removing insoluble abrasive particles from the cleaned surface. To overcome these difficulties, US Pat. No. 4,057,506 discloses a liquid coarse cleaning composition containing a water-soluble builder salt having particles of colloid size less than 1 .mu.m, and usually less than 0.1 .mu.m, which disperses in an aqueous medium containing a fatty acid amide emulsifier are. U.S. Patent No. 3,522,186 discloses a water-insoluble abrasive dispersed in an aqueous medium containing tetrapotassium pyrophosphate, sodium soap, diethanolamide and about 0.25 to 1.5% methanol or ethanol to facilitate separation of the aqueous liquid into water to prevent two layers. U.S. Patent No. 4,051,055 discloses an aqueous hard surface cleaner which contains water insoluble abrasive which is suspended in a thickened aqueous medium having at least 1% clay as the thickening agent to prevent separation of the scrubbing agent from the liquid. The presence of fluoride salts enhances the ability of the clay thickened detergent to hold the abrasive particles in suspension.

U.S. Patent No. 4,657,692 also discloses a thickened, aqueous scrubbing detergent having no syneresis properties with a water-insoluble abrasive dispersed in an aqueous medium, the aqueous medium comprising a colloidal alumina thickener, water-soluble inorganic alkali metal salts, such as Phosphates, polyphosphates and carbonates, about 0.5 to 3% of a surfactant and a Haogen bleach contains. EP-A 193 375 describes a pourable, homogeneous, abrasive-containing, aqueous, hard-surface cleaner which comprises a water-soluble salt serving as a scouring agent as well as a detergency builder such as, for example Sodium bicarbonate and tripolyphosphate, and, a mixture of anionic and nonionic surfactants in the weight ratio of 1: 1 to 9: 1.

No. 4,179,414 discloses a pasty water-based cleaner for hard surfaces which contains 50 to 65% by weight of sodium bicarbonate and 50 to 35% by weight of water mixed with sodium chloride and a fatty acid (C12 to Cis) diethanolamide.

Water-based gels containing at least 40% non-ionic surfactant and 2 to 10% water-soluble builder salts are known as flowable gel detergent according to US Pat. No. 4,107,067.

U.S. Patent 4,257,908 also discloses a stable, pourable detergent containing from 25 to 55% of a phosphate builder salt, from 5 to 40% of an anionic surfactant in from 30 to 50% of an aqueous medium comprising water and alcohol in a weight ratio from 5: 1 to 20: 1.

Also, US Pat. No. 3,981,826 discloses non-aqueous liquid pasty or gel scrubbing detergents composed of a dispersion of a normally solid water-soluble anionic surfactant, a solid particulate water-soluble inorganic builder salt, and a suspending agent such as Large volume oxides, such as silica, magnesia, alumina or clay, in about 19 to 79% of a water-miscible organic solvent, such as a polyhydric alcohol such as glycerol and ethylene glycol, and optionally a lower monoalcohol such as ethanol and methanol. US Pat. No. 3,865,756 discloses an organic solvent-containing, gelled or thickened hard surface cleaner which is pourable and pourable, and a gelling agent, such as a gelling agent, which serves as a scouring agent colloidal silica, an alkaline builder salt such as water-soluble phosphates and silicates, a surfactant, a water-insoluble abrasive, namely calcium silicate, and about 55 to 90% of an organic cleaning solvent, such as a mixed with 4 to 7% ethylene glycol monobutyl ether aliphatic hydrocarbon

AT 398 577 B contains. U.S. Patent 2,864,770 discloses a pourable, non-aqueous, water-soluble, thixotropic liquid organic solvent-based cleaner which contains glycols and glycerin as the organic solvent, an anionic surfactant and a phosphate builder suspended in suspension.

The invention has for its object to provide a highly viscous organic hard surface cleaning agent that is stable, is soluble in water without the formation of a granular residue, shows improved cleaning performance and in particular as

All-purpose cleaner, scrubber and spray cleaner is usable.

This object is achieved by a highly viscous organic hard surface cleaning agent which is essentially made according to the invention

a) 65 to 85% by weight of an organic carrier liquid which, based on the total composition, consists essentially of a 1) 15 to 35% by weight of a water-miscible organic solvent and a 2) 35 to 70% by weight of an ethoxylated fatty acid one of the surfactants-containing mixture of nonionic surfactants is formed

b) 0.7 to 1.5% by weight of sodium hydroxide which reacts in situ with the ethoxylated fatty acid to form a gelled carrier liquid, and

c) 10 to 25 wt.% Of an inorganic, water-insoluble, particulate abrasive agent, which is incorporated in the gelled carrier liquid consists.

A particular feature of the cleaning agent according to the invention is based on the ability of the ethoxylated fatty acid, eg ethoxylated lauric acid, in the organic medium with sodium hydroxide to react and form a gel with the medium. The incorporation of a water soluble scouring agent into the organic gelling mixture permits the preparation of viscous products containing inorganic solids suspended in a gelled organic carrier liquid. While the scouring agent is insoluble in the gelled carrier liquid, it is dissolved in dilution of the detergent with water. The cleaning with the undiluted detergent is characterized by the mild scouring action of the scrubbing agent, z. B. Sodium pyrophosphate, supported. The entire cleaning agent dissolves in water, leaving no granular residue on the cleaned surfaces. In addition, the scouring agent becomes a builder when the detergent is used in a dilute form. Household areas, such as Ceramic and plastic surfaces, can be cleaned with the undiluted or diluted with water detergent, without the surface being scratched. Both the undiluted and the diluted detergent show a significantly improved cleaning performance by the interaction of the organic solvent, the nonionic surfactant and the scouring agent. The hard surface cleaner of the present invention can serve as a spray cleaner, scouring paste, and general purpose cleaner for floors and walls. Investigations show that the detergent according to the invention at a concentration of 3 g / t of soil cleans better than a commercial product at a concentration of 15 g / t.

The cleaning agent is a stable, non-pourable, clear, viscous paste which has a minimum viscosity of about 14,000 to 15,000 mPa.s as measured by a Brookfield HATD viscometer. The high viscosity of the gel mass results in a stable suspension of relatively large particles of water soluble scouring agent. By the term relatively large particles is meant particles which are larger than colloidal particles. As a general purpose cleaner, the detergent according to the invention can be used in many ways. Undiluted, the detergent can serve as a scouring cleaner for sinks and baths and as a stain remover for soiled hard surfaces, wherein due to the interaction of the organic solvent, the nonionic surfactant and the scouring agent, a triple cleaning effect is exerted without a granular residue as in conventional scouring cleaners remains. In its water-diluted form, the cleaning agent according to the invention can be used as a cleaner for floors and walls. In addition, the organic cleaning pastes according to the invention can be used as water-free hand cleaners, in particular for mechanics and gardeners, as well as for the cleaning of industrially used cooking kettles.

The main essential component of the non-pourable, viscous cleaning agent is the mixture of nonionic surfactants, which constitutes 35 to 70% by weight of the total mass and contains 6 to 38% by weight of ethoxylated fatty acid and 10 to 64% by weight of other ethoxylated nonionic surfactants which may be a fatty alcohol, an alkylphenol, a propylene oxide-propylene glycol condensation product or mixtures thereof. In particular, the additionally used ethoxylated nonionic surfactant may be a polyethylene oxide condensate of an alkylphenol having a C 12 to C 12 alkyl group, a polyethylene oxide condensate of an aliphatic C 12 to C 22 alcohol, a polyether oxide condensate of the condensation product of propylene oxide with propylene glycol with a Molecular weight of about 1,500 to 1,800 or

AT 398 577 Β be their mixture. Typical examples of polyethylene oxide condensates of alkylphenol are nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol and dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol. Examples of Ethoxylated Alcohols Tridecanol condensed with about 6 moles of ethylene oxide per mole of alcohol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol, Cio to C15 fatty alcohol condensed with about 6 moles of ethylene oxide, and C4 to C4 condensed with 5 moles of ethylene oxide per mole of alcohol Alcohol, which is traded under the name Alfonic 1012-60®. Examples of the polyether oxide condensates of the condensation product of propylene oxide with propylene glycol are the substances commercially available as Pluronic surfactants from Wyandotte Chemicals Corporation. The liquid character of these products is ensured to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product. Examples of ethoxylated fatty acids are ethoxylated lauric, palmitic, and stearic acid with about 5 to 10 moles of ethylene oxide per mole of fatty acid. A preferred fatty acid ethoxylate is lauric acid ethoxylated with 9 moles of ethylene oxide, which is traded under the name Alkasurf L-9R. The presence of ethoxylated fatty acid in the organic carrier fluid is essential to the formation of the gel. The gelation is carried out by in situ reaction of sodium hydroxide with the ethoxylated fatty acid in the organic solvent to form a small amount of soap which thickens and gels the liquid organic medium. A small amount of sodium hydroxide causes a time-delayed hydrolysis, followed by gelation of the carrier fluid containing ethoxylated fatty acid.

Another essential component of the cleaning agents according to the invention is the water-miscible organic solvent in an amount of 15 to 35 wt.% Based on the weight of the total mass. The organic solvent provides an organic medium for the in-situ reaction between ethoxylated fatty acid and sodium hydroxide which takes place during gelation of the carrier liquid. Suitable water-miscible organic solvents are alkyl monoalcohols, glycols, lower alkyl glycol ethers and mixtures thereof. Examples of water-soluble lower monoalcohols are ethanol, isopropanol and butanol. Examples of suitable glycols are ethylene glycol, diethylene glycol and propylene glycol. Examples of lower alkyl glycol ethers are diethylene glycol monobutyl ether of the formula C 4 H 9 OCH 2 CH 2 OCH 2 CH 2 OH, also known as butylcarbitol from Union Carbide, and ethylene glycol monobutyl ether of the formula C 4 H 9 OCH₂CH 2 OH. The use of a mixture of mono- and dialcohols, in particular a mixture of a monoalcohol, a dialcohol and a glycol ether as solvent for the mixture of nonionic surfactants is preferred.

Another essential component of the viscous cleaning agents is a water-soluble, inorganic, particulate abrasive, which is suspended in the gelled carrier liquid in an amount of 10 to 25 wt.%, Based on the total composition. The scouring agent is insoluble in the gel but soluble in water and has relatively large particles about 0.5 mm in diameter. Due to the minimum viscosity of the gelled carrier fluid of 14,000 to 15,000 mPa · s, it is able to keep the large particles in suspension. Suitable water-soluble abrasives are selected from alkali metal phosphates, polyphosphates and carbonates. Examples of suitable water-soluble penetrants are tetrasodium or tetrapotassium pyrophosphates, tripolyphosphates, tetrapolyphosphates and carbonates. When the detergent is used in a dilute form, the scouring agent becomes a builder, which can be easily removed from the cleaned surface without leaving a granular residue. The preferred abrasives are tetrasodium pyrophosphate and sodium carbonate.

In addition, the hard surface cleaner of the present invention may also contain small amounts of conventional components which impart a desired property thereto while not adversely affecting the gel structure. Suitable additives are colorants, perfumes, preservatives and antiseptics. These additives make up a maximum of 15% by weight of the cleaning agent. In the generally used process for preparing the detergent of the invention, the organic water-miscible solvent is reacted with an ethoxylated fatty acid and at least one additional nonionic surfactant to form a clear, low viscous carrier liquid mixed, add a sodium hydroxide solution to the clear carrier liquid and mix until the liquid is gelled, depending on the quantities of components used, a few minutes to several hours are required. Finally, the water-soluble abrasive, dye, perfume and other conventional additives are added to the gelled carrier liquid until the abrasive is uniformly dispersed throughout the gelled carrier liquid and a paste is formed. The cleaning agent can be filled into any container. It can also be expressed in terms of a collapsible container.

AT 398 577 Β

The finished gel cleaner is a stable, viscous, creamy hard surface cleaner that is substantially anhydrous and has a pH in the alkaline range of 8 to 11. The cleaner can be applied to the surface to be cleaned in any manner, eg by means of a sponge or a cloth. Then the surface is rinsed with water: leaving behind no granular residue.

In the following the invention will be explained in more detail with reference to the examples.

The percentages given in the description, the examples and the claims are, unless stated otherwise, data in% by weight based on the total weight of the mixture.

example 1

<td>ingredients:</td><td>Wt.%</td>

<td>Lauric Acid Ethoxylate (9EO)</td><td>28.3</td>

<td>tetrasodium pyrophosphate</td><td>20.0</td>

<td>Diethylenglykolmonobutyiether</td><td>14.0</td>

<td>ethanol</td><td>14.0</td>

<td>Ci6- to Ci 4-alcohol condensed with 5 moles of ethylene oxide per mole of alcohol</td><td>10.0</td>

<td>propylene glycol</td><td>6.0</td>

<td>deionized water</td><td>4.0</td>

<td>Sodium hydroxide 50%</td><td>3.0</td>

<td>Graphite blue 1%</td><td>0.4</td>

<td>Parfums</td><td>0.3</td>

<td colspan="2">pH (1%) = 10.9</td>

The components of the carrier liquid, namely ethoxylated lauric acid, ethoxylated alcohol, butyl carbitol, ethanol and propylene glycol and the perfume were mixed to form a clear mobile liquid. The sodium hydroxide was added to the clear liquid and mixed with it until the carrier liquid formed a solid gel. After 5 minutes of gelation, tetrasodium pyrophosphate was mixed with the gel formed to form a paste. Subsequently, the color pigment was added to the paste.

The resulting creamy blue detergent had excellent detergency and did not leave any granular residue on the cleaned surface.

Example 2

<td>ingredients:</td><td>Wt%.:</td>

<td>Lauric Acid Ethoxylate (9EO)</td><td>28.0</td>

<td>sodium</td><td>23.0</td>

<td>C10 to Cu alcohol condenses with 5 moles of ethylene oxide per mole of alcohol</td><td>21.0</td>

<td>ethanol</td><td>12.5</td>

<td>Diethylenglykolmonobutyiether</td><td>7.0</td>

<td>propylene glycol</td><td>5.0</td>

<td>Sodium hydroxide 38%</td><td>3.0</td>

<td>Perfume</td><td>0.3</td>

<td>Lemon / lime color solution</td><td>0.2</td>

The product was prepared according to the method of Example 1 and was in the form of a viscous colored paste which showed excellent cleaning performance.

AT 398 577 B

Examples 3 - 5

<td></td><td>3</td><td>4</td><td>5</td>

<td>Alfonic 1012-60¹</td><td>48.0</td><td>10.0</td><td>14.0</td>

<td>Aikasurf L-92²</td><td>6.0</td><td>28.3</td><td>21.0</td>

<td>Plurafac RA40³</td><td>-</td><td>-</td><td>7.0</td>

<td>Pluronic L-64⁴</td><td>15.5</td><td>-</td><td>-</td>

<td>carbitol</td><td>8.0</td><td>14.0</td><td>7.0</td>

<td>propylene glycol</td><td>-</td><td>6.0</td><td>6.0</td>

<td>ethanol</td><td>8.0</td><td>14.0</td><td>14.0</td>

<td>Water and dye</td><td>0.9</td><td>5.9</td><td>5.9</td>

<td>NaOH</td><td>0.7</td><td>1.5</td><td>1.5</td>

<td>tetrasodium</td><td></td><td></td><td></td>

<td>pyrophosphate</td><td>12.0</td><td>20.3</td><td>23.0</td>

<td>Perfume</td><td>0.5</td><td>0.3</td><td>0.3</td>

1. C10 to Cu alcohol condenses with 5 moles of ethylene oxide per mole of alcohol

Second Lauric acid condenses with 9 moles of ethylene oxide per mole of acid

Third Low foaming polyol: propylene oxide and

Ethylene oxide polycondensates of propylene glycol

4th High foaming polyol: propylene oxide and

Ethylene oxide polycondensates of propylene glycol.

The detergents were prepared according to the method of Example 1.

The finished products were viscous hard surface cleaners that could be easily removed by water without leaving a grainy residue.

All of the undiluted cleaning pastes described above could be diluted with water for equally effective cleaning of hard surfaces. The paste product dissolved completely in water, which left no granular residue of abrasive particles on the cleaned surfaces.