FR2624520A1 - - Google Patents

Abstract

A highly viscous cleaning composition for hard surfaces comprising by weight about 65-80% of an organic liquid vehicle consisting essentially of about 15-35% water-miscible organic solvents and about 35-70% of a surfactant mixture nonionic containing an ethoxylated fatty acid as one of the surfactants and sodium hydroxide which reacts in situ with the ethoxylated fatty acid to form a clear, non-pourable, substantially water-free gelled organic vehicle. A stable suspension of about 10-25% of a water-soluble particulate abrasive builder in said non-pourable organic gel is obtained which is in the form of a viscous cleaning gel. Applications: cleaning products.

Description

The present invention relates to the formulation of a detergent composition

stable for hard surfaces

  in the form of a non-viscous cleaning composition

  pourable, practically free of water, i.e. i having a maximum percentage of water of 6% by weight, which comprises a gelled mixture of an organic liquid vehicle consisting essentially of organic solvents and non-surfactants ionic containing an ethoxylated fatty acid as an essential component in the in situ gelling of said liquid vehicle, after addition of a small amount of about 0.7 to 1.5% by weight of sodium hydroxide. The addition of ingredients insoluble in the gel, in particular a water-soluble inorganic abrasive adjuvant, 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 cleaning products for hard surfaces containing both abrasives and

  in the form of cleaning powders and in liquid form.

  Water-insoluble abrasives as major and primary detergent components in cleaning powders are well known, as described in U.S. Patent 3,850,833. However, it has been found that the use of said water-insoluble abrasives in hard surface cleaning powders leaves an unpleasant ashy residue on the cleaned surface. This problem has been treated in the prior art by replacing all or part of the insoluble abrasive with a water-soluble abrasive, which gives a composition where the water-soluble components are entrained with the rinsing water, leaving practically no residue on the surface. cleaned surface,

  as described in U.S. 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 less than 0.15 mm, and about 8 by weight of the particles. abrasives with a diameter of about 0.037 mm or more for effective cleaning, and a small amount of an organic hydrotropic agent (eg sodium cumene sulfonate) to improve fat removal, as described

in U.S. Patent 4,289,640.

  Likewise, a liquid detergent composition for hard surfaces containing water-insoluble abrasives D suspended in an aqueous medium faces the problem of stability as well as the difficulty of completely removing the insoluble abrasive particles from the cleaned surface. These problems have been dealt with in the prior art by preparing a high performance liquid detergent composition containing a water-soluble adjuvant salt having particles of colloidal size (less than 1 micron and generally 0.1 micron), dispersed in an aqueous medium containing an emulsifier based on fatty acid amide as described in US Pat. No. 4,057,506. Another means of treating the problem of stability is disclosed in US Pat. No. 3,522,186 in which a water-insoluble abrasive dispersed in an aqueous medium containing tetrapotassium pyrophosphate, soda soap, diethanolamide and the like is described. 0.25-1.5% methanol or ethanol to prevent separation of the aqueous liquid into two layers. Another way of tackling the stability problem is disclosed in US Pat. No. 4,051,055, in which an aqueous detergent composition for a hard surface containing a water-insoluble abrasive is suspended in a thickened aqueous medium with at least 1% d clay as thickener, said thickened system pocketing the separation of the abrasive from the liquid medium. The presence of fluorides increases the ability of the system thickened by clay to keep the abrasive particles in suspension. US Pat. No. 4,657,692 also describes a thickened aqueous cleaning product, free from syneresis (separation of solids from the liquid), which contains a water-insoluble abrasive suspended in an aqueous medium containing, as a thickener, an alumina oxide 2 colloidal, inorganic salts of water-soluble alkali metals such as phosphates, polyphosphates, carbonates, etc., and about 0.5-3%

  a surfactant and a halogenS bleach.

  European Patent Application NI 0193.375 relates to the use of a water-soluble salt which functions both as an abrasive and a detergent adjuvant, 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

  from anionic surfactant to nonionic surfactant.

  A cleaning agent for hard surfaces based on water in the form of paste and comprising 50-65% of sodium bicarbonate and 50-35% by weight of water containing sodium chloride and a di & thanolamide of fatty acid (C & 2Cz6 ) is described in the US patent

4,179,414.

  A water-based gel containing at least 40% anionic surfactant and 210% water-soluble adjuvant salts is described in U.S. Patent 4,107. 067 as a laundry detergent composition under

form of a flowable gel.

  ir, U.S. Patent 4,257,908 also describes a laundry detergent composition in a stable flowable form, containing 25-55% of a phosphate-type adjuvant salt, 5-40% of an anionic surfactant in -50%. an aqueous medium containing alcohol according to

  a water: alcohol weight ratio of 5: 1 to 20: 1.

  US Pat. No. 3,981,826 also describes non-aqueous pitous or gelatinous liquid detergent compositions having cleaning properties and comprising a dispersion of a normally solid anionic surfactant 2 of a water-soluble inorganic salt (adjuvant salt) in solid particles and a suspending agent such as very bulky 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 possibly a lower mono-alcohol (ethanol, methanol, etc.). Another detergent composition for hard surfaces, gelled or grabbed & base of organic solvent, pourable and pourable, is described in U.S. Patent 3,865. 756 and comprises a gelling agent which acts as an abrasive such as collotdale silica, an alkaline adjuvant salt such as water-soluble phosphates and silicates, a surfactant, a water-insoluble abrasive, eg calcium silicate, and about 55-90% of an organic cleaning solvent such as a large amount of a mineral oil based on aliphatic hydrocarbons mixed with 4-7% of ethylene glycol monobutyl ether. U.S. Patent 2,864,770 also describes a water-soluble aqueous thixotropic liquid detergent composition based on organic and pourable solvent which contains glycols and glycerol as the organic solvent, an anionic surfactant, and a suspended phosphate builder. However, none of the above mentioned patents

  describes a viscous detergent composition not

  pourable for hard surfaces, practically free of water, and comprising a gelled mixture of an organic liquid vehicle consisting essentially of 23 water-soluble organic solvents and nonionic surfactants containing an ethoxylated fatty acid as one of the surfactants, and a small amount of sodium hydroxide that reacts in situ with the acid

  ethoxylated fat to form a clear non-organic gel

  2 pourable, and about 10 to 25% of an abrasive additive

  water-soluble in suspension in said gelled vehicle.

  It has now been found that the formulation of the new 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 new formulation is

  the incorporation of a water-soluble abrasive material in-

  the organic gelling mixture. This allows the preparation of viscous products containing inorganic solids suspended in an organic gelifib vehicle. While this abrasive is insoluble in the gelified vehicle, it becomes soluble by diluting the product with water. Cleaning with the undiluted product is helped by the weak abrasive action of the abrasive, especially sodium pyrophosphate. The overall product dissolves in water, leaving no ash 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 a significantly improved cleaning power due to the triple action of the solvent.

  organic, non-ionic detergent and abrasive.

  In the diluted product, the abrasive dissolves in water and becomes an emergency aid. The organic viscous product for hard surfaces according to the present invention can function as a sprayed detergent, degreasing cream and multi-use maintenance product for floors and walls. Simulated floor cleaning tests show that, at 3 g / l of this cleaning product, the result is better than with the product "commercially available" at -15 g / l. This translates to the fact that 5 bottles of the equivalent commercial product

  1 bottle of this cleaning product.

  Consequently, the first object of the present invention is to provide a new viscous organic cleaning product for hard surfaces which comprises a fatty acid Mthoxylè and sodium hydroxide dissolved in an organic vehicle which reacts in

  situ to form a gelified vehicle.

  Another object of this invention is to provide a new viscous organic cleaning composition containing an inorganic water-soluble particulate abrasive suspended in the organic vehicle gel. Yet another object of the present invention is to provide an organic gel containing an abrasive which dissolves in water leaving no residue

  ashy on or around cleaned surfaces.

  Yet another object of this invention is to provide a multipurpose cleaning product having

a triple cleaning action.

  Other objects, advantages and new features of the invention will appear for

  part in the description which follows, and partly to

  considering the following description or may be

  taught by practicing the present invention. In order to achieve the above and other 2D objects according to the present invention, the non-pourable organic gel detergent composition for hard surfaces of the invention contains about 65%. by weight of an organic liquid vehicle consisting essentially of about 15 to 35% by weight of an organic solvent miscible with water, about 35 to 70%

  of a surfactant mixture ncn-iaiqo.emtena-xtuna = i gras-

  ethoxylated as one of the surfactants, and a small amount of about 0.7 to 1.5% by weight of sodium hydroxide, which reacts in situ with ethoxylated fatty acid to form a clear, non-flowable gelled vehicle , practically 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 to% 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 70% by weight of a nonionic surfactant mixture containing an ethoxylb fatty acid as one of the surfactants, approximately 0.7 to 1.5% by weight of sodium hydroxide, gelled by in situ reaction of the ethoxylated fatty acid with sodium hydroxide; and about 10 to% by weight of a particulate water-soluble inorganic abrasive (adjuvant salt) in uniform suspension in the

gelled vehicle.

  The water-miscible organic solvent is chosen from glycol ethers alkylated by lower alkyl groups, monoalcohols alkylated by it from lower alkyl groups, diols alkylated by

  lower alkyl groups, and mixtures thereof.

  The detergents for hard surfaces of the present invention described are pastes & thick (viscous), clear, non-pourable and stable, having a minimum viscosity of approximately 14,000-15,000 cps (14 Pa.s) measured with the Brookfield HATD viscometer. The viscosity of the gelified product gives a stable suspension of relatively large particles of water-soluble abrasives, that is to say larger than the 2 particles of colloidal dimension. 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 baths, and as a stain remover for hard soiled surfaces, producing a triple cleaning action due to the combined action of organic solvent, non-ionic detergent and abrasive, without leaving the usual ash residue with abrasive detergents. The new organic pastes of the present invention diluted with water can be used as a maintenance product for floors and walls. The new organic detergent pfttes of the present invention can also be used as anhydrous detergents for the hands, in particular for mechanics and gardeners; for cleaning cooking vessels, pots etc. industrialists and communities. The major essential component of the present non-pourable viscous detergent composition is the nonionic surfactant system which constitutes approximately

  at 70% by weight of a mixture of non-surfactants

  ionic containing approximately 6 to 38% of an ethoxylated fatty acid, and approximately 10 & 64% of the other non-ionic ethoxylated surfactants which can be a fatty alcohol, an alkylphenol, a product of condensation

  propyl ne - propyl neglycol, or a mixture thereof.

  More specifically, the additional non-ionic ethoxylated surfactant can be chosen from a polyethylene oxide condensate of an alkylphenol having an alkyl group having 6 to 12 carbon atoms, a polyethylene oxide condensate of an aliphatic alcohol containing about 8 to 22 carbon atoms, a polyethylene oxide condensate of the condensation product of propylene oxide with propylene glycol with a molecular weight of about 1500 to 1800, and mixtures thereof. Typical examples of polyethylene oxide condensates of alkylphenol 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 ethoxylated alcohols include: about 6 moles of ethylene oxide condensed with one mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide, a C0- fatty alcohol Cl4 condensed with

  about 6 moles of ethylene oxide, a C1- alcohol

  C.4 condensed with 5 moles of ethylene oxide per mole of alcohol (Alfonic 1012-60). Examples of polyethylene oxide condensates with the condensation product of propylene oxide with propylene glycol are commercially available as Pluronic surfactants marketed by the Wyandotte Chemicals Corporation. The liquid nature of this product is maintained up to the point where the polyoxyethylene content is approximately 50% of the total weight of the condensation product. Examples of ethoxylated fatty acids include lauric, palmitic, stearic acids, etc., ethoxylated with approximately 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 ethoxylated fatty acid in the organic vehicle is essential for the formation of the gel, 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 media. body fluids. A small

  amount of sodium hydroxide causes different hydrolysis

  fée followed by the g] lificaticn of 'vhie perting to the fatty étnoxy.é.

  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 the gelling of the organic medium. Suitable water-miscible organic solvents include monoalcohols alkylated by lower alkyl groups, diols alkylated by lower alkyl groups (glycols), ethers of alkylated glycols

  by lower alkyl groups, and mixtures thereof.

  Examples of water-soluble lower monoalcohols are ethanol, isopropanol and butanol. Examples of suitable glycols are ethylene glycol,

  diethylaneglycol (Carbitol), and propylene glycol.

  Examples of lower alkyl glycol ethers are the diethylene glycol monobutyl ether of formula: C4HeOCH2CH = OCHmCH20H also known as Butyl Carbitol (Union Carbide), the monobutyl ether of ethylene glycol of formula: C4H.OCH2CH.OH etc. It is preferred to use a mixture of monoalcohols and diols, and even better 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 quantity

  from about 10 to 25% by weight of the total composition.

  The abrasive is insoluble in gel but soluble in water. The water-soluble abrasive particles are relatively large particles of about 1/2 mm in size.

  diameter. The viscosity of the glifqe vehicle is one

  run from 14,000 to 15,000 cqs (14 to 15 Pa.s), is to keep large particles in suspension. Suitable water-soluble abrasives 2 are chosen from phosphates, polyphosphates and carbonates of alkali metals. Examples of suitable water-soluble abrasives include pyrophosphates such as tetrasodium and tetrapotassium pyrophosphates, tripolyphosphates, tetrapolyphosphates, carbonates, etc. This abrasive becomes a surfactant adjuvant when the product is used diluted and is easily removed from the cleaned surface leaving no ash residue. Preferred abrasives include

  tetrasodium pyrophosphate and sodium carbonate.

  The hard surface cleaning composition of the present invention may also contain minor amounts of conventional additional components to introduce any desirable characteristic, components which 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 organic water-miscible solvent components with an ethoxylated fatty acid and at least one nonionic surfactant component to form a transparent, low viscosity liquid vehicle; adding a solution of sodium hydroxide to the clear liquid vehicle and mixing until the liquid is gified, which can last from a few minutes to several hours, depending on the quantities of components; and finally

  by adding to the gelled vehicle the roel1Ibte arasif, tn oio-

  rait, rm e totatre iniEntaittia usl1, JiUS 'until the abrasive is uniformly dispersed within the gelled vehicle and a fart is formed. The detergent composition is packaged in any suitable container, whether rigid or flexible. The fart can be extruded from a compressible container. The final gelled cleaning product is a stable hard surface detergent with a thick creamy (viscous) appearance, practically anhydrous and having a pH

  alkaline in the range of about 8 to 11.

  It can be applied to the surface to be cleaned in any suitable way, that is to say with a sponge or cloth, then rinsing the surface with water, without leaving

ash residue.

  The following nonlimiting examples illustrate the invention. All the amounts of the different ingredients in the examples and elsewhere in the

  description are by weight unless indicated

opposite.

Example 1

  Ingredients Lauric acid ethoxylate (9OE) 28, -30 D Tetrasodium pyrophosphate 20.00 Diethylene glycol monobutyl ether 14.00 Ethanol 14.00 Alcohol C ^ o-Co DE 5: 1 10.00 Propyldneglycol 6.00 Deionized water 4 .00 Caustic soda (50%) 3.00 Blue Graphtol 1% 0.40 Perfume 0.30 pH (1%) = 10.9 The ingredients of the vehicle, namely ethoxylated lauric acid, ethoxylated alcohol, butylcarbitol, ethanol and propylene glycol and perfume are 2 mixtures to form a clear mobile liquid. NaOH is added to this liquid until the vehicle is ghlified and a solid gel is formed. After 5 minutes of gel aging, the tetrasodium pyrophosphate is mixed with the dark gel to form a cream (bud). The blue pigment is then dispersed within the cream. This formulation provides a blue cleaning product with superior cleaning properties and leaving no ash residue on the surface

cleaned.

Example 2

  Incredients Lauric acid ethoxylate (90E) 28.00 Sodium carbonate 23.00 Clo-C alcohol * DE 5: 1 21.00 Ethanol 12.5 Diethylene glycol monobutyl ether 7.00 Propylene glycol 5.00 Caustic soda 38% 3 .00 Perfume 0.30 Lemon colored solution 0.20 This product is prepared according to the

Example 1.

  This product is a viscous colored paste

  with superior cleaning properties.

Examples 3-5

3 4 5

  Alfonic 1012-60 '48.0 10.0 14.0 Alkasurf L-92 6.0 28.3 21.0 Plurafac RA403 - - 7.0

Pluronic L-644 15.5 - -

  2 Butyl Carbitol 8.0 14.0 7.0 Propyl neglycol - 6.0 6.0 Ethanol 8.0 14.0 14.0 Water and dye 0.9 5.9 5.9 NaOH 0.7 1.5 1,5 Tetrasodium pyrophosphate 12,0 20,0 23,0 Perfume 0,5 0,3 0,3 l. CzoC alcohol, DE 5: 1 2. Lauric acid OE 9: 1 3. Low foaming polyol: polycondensates propylene oxide and ethylene oxide and propylene glycol. 4. Strong foaming polyol: These compositions are prepared according to the process

from example 1.

  The final products are viscous cleaning compositions for hard surfaces, easily removable by rinsing with water without leaving an ashy residue. All the undiluted cleaning agents mentioned above can be diluted with water for equally effective cleaning of hard surfaces. The fizzy product dissolves completely in water without leaving an ashy residue, i.e. abrasive particles, on or around the cleaned surfaces.

Claims (16)

Claims   1. An organic cleaning composition of high viscosity for hard surfaces, characterized in that it comprises by weight approximately 65 to 80% of an organic liquid vehicle consisting essentially of approximately 15 to 35% of an organic solvent miscible with   water, about 35 to 70% of a non-surfactant mixture   ionic containing an ethoxylated fatty acid as one of the surfactants, and about 0.7 to 1.5% sodium hydroxide, gelled by the in situ reaction of ethoxylated fatty acid with sodium hydroxide to form a clear and non-flowable gelled vehicle, practically anhydrous; and about 10 to 25% by weight of a water-soluble inorganic particulate abrasive incorporated in the gelled vehicle.   2. Composition according to claim 1, characterized in that the water-miscible organic solvent is chosen from an alkyl glycol ether & by lower alkyl groups, an alkyl monoalcohol & by lower alkyl groups, an diol alkylated by   lower alkyl groups and mixtures thereof   this. 3. Composition according to claim 2, characterized in that the water-soluble particulate abrasives have particles of dimensions   higher than those of the colleges.   4. Composition according to claim 1, characterized in that the detergent pastes have a minimum viscosity of approximately 14,000 to 15,000 cps (14 to   Pa.s) measured with the Brookfield HATD viscometer.   5. Composition according to claim 1, characterized in that the ethoxylated fatty acid represents   about 6 to 38% by weight of the composition.   6. The composition according to claim 1, 1-7 characterized in that the nonionic surfactant in the mixture with the ethoxylated fatty acid can be chosen from a condensate of polyethylene oxide not with an alkyl (CrC ==) phenol, a polyethylene condensate with a Ca-C = m aliphatic alcohol, a polyethylene oxide condensate with the propylene oxide condensate with propylene glycol having a molecular weight of about 1500 to 1800, and their mixtures. 7. Composition according to claim 1, characterized in that the ethoxylated fatty acid is lauric acid having 9 ethylene oxide units by mole of lauric acid.   8. Composition according to claim 2, characterized in that the miscible solvent & water is a mixture of a monoalcohol, a dialcohol and an ether glycol.   9. Composition according to claim 8, characterized in that the organic solvent miscible with water is a mixture of ethanol, propylAneglycol and   diethylene glycol monobutyl ether.   10. Composition according to claim 2, characterized in that the organic solvent miscible with water is a mixture of ethanol and monobutyl ether 2 of diethylene glycol.   11. Composition according to claim 6, characterized in that the nonionic surfactant is   a polyethylene Clo -C.4 alcohol (5 EO).   12. Composition according to claim 3, characterized in that the water-soluble particulate abrasive is chosen from phosphates,   polyphosphates and carbonates of alkali metals.   13. Composition according to claim 12, characterized in that the water-soluble abrasive is tetrasodium pyrophosphate.   14. Composition according to claim 12, characterized in that the water-soluble abrasive is sodium carbonate.   15. Composition according to Claim 14, characterized in that the organic solvent miscible with water is a mixture of ethanol, propylene glycol and monobutyl ether of diethylene glycol, and the nonionic surfactant mixture consists of an alcohol. in Cio-Ci4 DE 5: 1 and of lauric acid * thoxylb 9 DE. 16. Composition according to claim 13, characterized in that the organic solvent miscible with water is a mixture of & thanol, propylGneglycol and monobutyl ether of diethylene glycol, and the nonionic surfactant mixture consists of a   ethoxylated fatty acid and an ethoxylated fatty alcohol.