MXPA98000565A - Liqui cleansing compositions - Google Patents

Abstract

An improvement in microemulsion or cleaning compositions for all environmentally friendly purposes is described, which are especially effective in the removal of oily and oily dirt and have a pronounced fat eliminating effect, contain an anionic detergent, an alcohol alkoxylated polyhydric, a hydrocarbon ingredient, and ag

Description

LIQUID CLEANING COMPOSITIONS Field of the Invention The present invention relates to hard surface cleaning compositions containing a complex of an anionic surfactant and a neutral polymer, Lewis base, soluble in water.

Background of the Invention This invention relates to an improved all-purpose liquid cleaner designed in particular to clean hard surfaces and which is effective in removing greasy dirt and / or bathroom soiling and to leave unrinsed surfaces with a shiny appearance. In recent years, liquid detergents have been widely accepted for all purposes to clean hard surfaces, for example, painted wood work and panels, wall tiles, sinks, bath tubs, flooring linoleum or tile, washable wallpaper, etc. Such liquids for all purposes comprise opaque and transparent aqueous mixtures of water soluble synthetic organic detergents and of water soluble detergent builder salts. In order to achieve a cleaning efficiency comparable to that of cleaning compositions for all powder or granular purposes, the use of water insoluble inorganic phosphate builder salts in liquids was favored for all purposes of the prior art. . For example, such phosphate-containing initial compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319 and in British Patent No. 1,223,739.

In view of the efforts of environmentalists to reduce phosphate levels in the earth's water, liquids have appeared for all improved purposes containing reduced concentrations of inorganic phosphate-reinforcing salts or phosphate-free reinforcing salts. A particularly useful self-opacifying liquid of the latter type is described in U.S. Patent No. 4,244,840.

However, those liquid detergents for all purposes containing detergent reinforcing salts or other equivalents tend to leave stains, films or scratches on unrinsed and cleaned surfaces, particularly glossy surfaces. As such, such liquids require a complete rinsing of the cleaned surfaces which is a time-consuming task for the user.

In order to overcome the above disadvantages of the liquid for all purposes of the prior art, U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulphonate and a reduced concentration of inorganic phosphate-reinforcing salt should be employed. . However, such compositions are not completely acceptable from an environmental point of view based on the phosphate content. On the other hand, another alternative to achieve liquids for all phosphate-free purposes has been the use of a major proportion of an anionic and nonionic detergent mixture with minor amounts of glycol ether solvent and organic amine as mixed in the U.S. Patent No. 3,935,130. Again, this approach has not been completely satisfactory nor the high levels of organic detergents needed to achieve cleaning cause foaming which, in turn, leads to the need for a complete rinse which has been found undesirable by current consumers .

Another approach to formulate the liquid detergent composition for all purposes or hard surface where the homogeneity of the product and clarity are important considerations, involves the formation of oil-in-water microemulsions (o / w) which contain one or more surfactant detergent compounds, a solvent immiscible with water (typically a hydrocarbon solvent) water and a "cosurfactant" compound which provides stability to the product. By definition, an oil-in-water microemulsion is a colloidal dispersion that spontaneously forms of "oil" phase particles having a particle size in the range of 25 to 800 A in a continuous aqueous phase.

In view of the extremely fine particle size of the dispersed oil phase particles, the microemulsions are transparent to light and are clear and usually highly stable against phase separation.

Patent disclosures relating to the use of grease removal solvents in oil-in-water microemulsions include, for example, European patent applications EP 0137615 and EP 0137616 by Herbots et al .; European Patent Application EP 0160762 to Johnston et al .; and U.S. Patent No. 4,561,991 issued to Herbots et al. Each of these patent disclosures also teaches the use of at least 5% by weight of a grease removal solvent.

It is also known from the British patent application GB 2144763A granted to Herbots et al., Published on March 13, 1985, that magnesium salts improve the fat removal performance of organic fat removal solvents, such as terpenes, in liquid oil-in-water microemulsion detergent compositions. The compositions of this invention described by Herbots et al. Require at least 5% of the mixture of grease removal solvent and magnesium salt and preferably at least 5% solvent (which can be a mixture of non-polar solvent immiscible in water with a slightly polar and poorly soluble solvent) and at least 0.1% magnesium salt.

However, since the amount of sparingly water-immiscible components which may be present in the oil-in-water microemulsion, with the total active ingredients low without impairing the stability of the microemulsion is rather limited (e.g. , up to 18% by weight of the aqueous phase), the presence of such high amounts of grease removal solvent tend to reduce the total amount of oily and / or oily soils that can be taken by and within the microemulsion and cause a phase separation.

The following representative patents of the prior art also refer to liquid detergent cleansing compositions in the form of oil-pet microemulsions: United States of America patents No. 4,472,291 issued to Rosario; 4,540,448 granted to Gauteer and others; 3,723,330 granted to Sheflin; etc.

Liquid detergent compositions which include terpenes, such as d-limonene, or another class of grease removal solvent, even if not described to be in the form of oil-in-water microemulsions, are the subject of the following representative patent documents: European patent application 0080749; British patent descriptions Nos. 1,603,047; 4,414,128; and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly discloses a liquid detergent composition characterized by weight by: (a) from 1% to 20% of a synthetic, nonionic, amphoteric or zirionionic anionic surfactant or mixtures thereof; (b) from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, at a weight ratio of (a): (b) being in the range of 5: 1 to 1: 3; Y (c) from 0.5% to 10% of a polar solvent having a solubility in water at 15oC in the range of 0.2% to 10%. Other ingredients present in the formulas described in this patent include from 0.05% to 2% by weight of the alkali metal, ammonium or alkanolammonium soap of a C13-C24 fatty acid; a calcium sequestrant of from 0.5% to 13% by weight; non-aqueous solvent, for example, alcohols and glycol ethers of up to 10% by weight; and hydrotropes, for example, urea, ethanolamines, salts of alkylaryl sulfonates up to 10% by weight. All of the formulas shown in the examples of this patent include relatively large amounts of detergent builder salts which are detrimental to surface gloss.

U.S. Patent No. 5,082,584 discloses a microemulsion composition having an anionic surfactant, a cosurfactant, a non-ionic surfactant, perfume and water; however, these compositions do not possess the ecotoxicity and improved interfacial tension properties as exhibited by the compositions of the present invention.

A neutral pH microemulsion composition based on paraffin sulphonate and ethoxylated nonionic surfactant is capable of delivering improved fat cleaning against the reinforced alkaline compositions. In addition to improved fat cleaning, this approach is much safer for surfaces as well as less aggressive to the consumer's hands (Loth et al., United States of America No. 5,075,026).

The technology of the microemulsion provides a surprising capacity of taking of oil due to the adjustment of the curvature of the micelles of surfactant by the molecules of the cosurfactant. Rod-type micelles are preferred since they can "swallow" the oil to become globular without increasing the contact surface between the hydrophobic core of the micelle and the hydrophilic continuous phase.

In diluted use, however, the microemulsion state is usually lost and the cleaning operation relies on the adsorption efficiency and leaving the character of the surfactant system. Nonionic surfactants work very well on fat, since they are excellent fat solubilizers. Currently, they spontaneously form swollen micelles. In moderate-sized countries such as the northern states of the United States, North America, and northern European countries, dirt on hard surfaces contains many greasy materials. It is therefore not surprising that microemulsion based on nonionic anionic surfactant is so efficient in these countries. In countries with a hot climate, however, the amount of particulate dirt is more important (since the doors and windows remain open and the classic microemulsion shows weakness over this type of dirt which is a dirt of mixed particle-fat nature .

The present invention solves this problem by delivering a significant amount of negative charges on the solid polar surface to ensure adequate dispersion of particulate dirt in the wash liquor. The problem is that the anionic surfactants r.o are absorbed spontaneously on the surfaces of silica type. Nonionic surfactants provide but do not provide sufficient "starting" character.

The present invention teaches that neutral Lewis-based polymers exhibit the ability to bind an anionic surfactant to a silica type surface while maintaining the negative charge of the anionic present on the surface. This characteristic leads to a tremendous increase in the density of negative charge on the silica surface, resulting in surprising water dispersibility.

In addition, this property manifests itself on mineral, high-energy and clean surfaces, such as glass, ceramics and enamel. In practice, this results in additional surface benefits such as grease release, the lowest residue, the best draining (no rinsing required), anti-fog and anti-static.

Synthesis of the Invention The present invention provides a clear and improved liquid cleaning composition having an improved interfacial tension which improves the cleaning of hard surfaces such as plastic, vitreous and metal surfaces having a glossy finish, oil-stained floors, engines automotive and other machines. More particularly, the improved cleaning compositions exhibit good grease removal properties due to the improved interfacial tensions, and leaves the surfaces cleaned bright without the need of or requiring only a minimum additional rinsing or cleaning. The latter feature is evidenced by the fact that there are very few or no visible residues on the cleaned unrinsed surfaces and, therefore, one of the disadvantages of the prior art products is overcome. The present compositions exhibit a fat release effect in the sense that the present compositions prevent or diminish the anchoring of oily dirt on the surfaces that have been cleaned with the compositions present as compared to the cleaned surfaces with a commercial cleaning composition. which means that the dirty surface of grease is easier to clean with the subsequent cleanings.

Surprisingly, these desirable results are achieved even in the absence of polyphosphate or other organic or inorganic detergent builder salts and also in the complete absence or in the essentially complete absence of the grease removal solvent.

In one aspect, the invention generally provides a hard surface cleaning composition, for all purposes, transparent and stable especially effective for the removal of oily and greasy dirt, the cleaning composition includes, on a weight basis: from 0.1% to 30% of an anionic surfactant; from 0.1% to 10% of a neutral Lewis-based polymer; from 0 to 50% of a water-miscible cosurfactant having either limited ability or essentially no ability to dissolve oily or greasy dirt; from 0% to 2.5% of a fatty acid; from 0 to 15% of a magnesium sulfate heptahydrate; from 0 to 10.0% of a perfume or a water-insoluble hydrocarbon; Y the rest being water, said proportions being based on the total weight of the composition.

The cleaning composition may be in the form of a microemulsion in which case the concentration of the mixable cosurfactant in water is from 0 to 50.0% by weight, preferably from 0.1% by weight to 20% by weight and the concentration of the perfume or the Water insoluble hydrocarbon is 0.4% by weight to 10.0% by weight. The dispersed oil phase of the oil-in-water microemulsion is essentially composed of a perfume immiscible with water or hardly soluble in water. Very surprisingly, even when the perfume is not, by itself, a solvent for oily or oily dirt, even though some perfumes may, in fact, contain as much as 80% of terpenes which are known as good fat solvents - the inventive compositions in diluted form have the ability to solubilize up to 10 times or more of the weight of the oily and oily dirt perfume, which is removed or released from the hard surface by virtue of the action of the anionic surfactant, said dirt being taken by the oil phase of the oil-in-water microemulsion.

In the second aspect, the invention generally provides highly concentrated microemulsion compositions in the form of any or an oil-in-water microemulsion. (o / w) or a water-in-oil microemulsion (w / o) which when diluted with additional water before use can form dilute oil-in-water microemulsion compositions. Broadly, concentrated microemulsion compositions contain, by weight, 0.1% to 30% of an anionic surfactant, 0.1% to 10% of a neutral Lewis-based polymer, 0% to 5% of a fatty acid, 0.4 % to 10% perfume or a hydrocarbon insoluble in water having 6 to 18 carbon atoms, 0 to 50% of a cosurfactant, and the remainder being water.

Detailed description of the invention The present invention relates to a stable hard surface cleaning composition of approximately by weight: from 0.1% to 30% of an anionic surfactant, from 0 to 50% of a cosurfactant, from 0% to 2.5% of a fatty acid, of 0.1% to 10% of a neutral Lewis-based polymer, 0 to 10% of a water-insoluble hydrocarbon or perfume and the remainder being water, wherein the cleaning composition may be in the form of a microemulsion in which case, the concentration of the mixable cosurfactant in water is from 0 to 50% by weight, preferably from 1.0% by weight to 25% by weight and the concentration of the perfume or the water-insoluble hydrocarbon is from 0.4% to 10.0% by weight.

One of the objects of the present invention is to deliver higher proportions of anionic surfactant in the adsorbed layer in the solid-water interface. This is due to an increased adsorption tendency and a narrower 2-D package by means of the neutralization between the negative charge of the anionic surfactant and the positive charge of the zwitterionic surfactant that is used in combination with the anionic surfactant in the present compositions Two anionic surfactants can be used in the composition wherein one of the anionic surfactants is preferably and very possibly associated with the zirutionic surfactant through the electrostatic interactions. If two anionic surfactants are present, can make a hydrophilic-lipophilic interaction between the two anionic surfactants which will contribute to the 2-D packaging in the water-solid interface. To an optimized surface package there is a minimum interfacial tension arising from the maximum adhesion stress measured in the wetting line between the liquid composition containing surfactant and the solid surface. The liquid compositions present exhibit an adhesion tension of one gram of the liquid composition-liter of water on a bright and flat solid layer of tripalmitin (glyceryl tripalmitate) at 25 ° C of more than 18 mN / m, more preferably higher. at 20 mN / m and more preferably greater than 21 mN / m.

As is known in the art of adhesion, stress is defined as the net force exerted by a solid on a liquid in the wetting line and depends on the contact angle? which makes the liquid on the solid substrate in equilibrium. The adhesion stress is defined as the cosine of the contact angle? that the liquid composition makes with the substrate times the surface tension of the liquid composition? L as measured at 25 ° C on a weakly polar solid substrate which is glycerol tripalmitate. The liquid compositions of the present invention exhibit a minimum adhesion tension of 17 mN / m, more preferably 18 mN / m and more preferably 19 mN / m as measured at 25 ° C for one gram of the liquid composition (liter of water on a solid layer of glycerol tripalmitate The wetting of the substrate increases with increasing adhesion tension.

The wetting parameter (mN / m) of the liquid composition is defined as? L (1-cos?) Measured at 25 ° C per one gram of the liquid composition per one liter of water as measured on glycerol tripalmitate. The wetting parameter is linked to the propensity of the liquid composition to spread on the substrate. The lower the value of the wetting parameter, the lower the interfacial tension in the water-glycerol tripalmitate interface. The wetting parameter of the present compositions measured under said conditions has a value of less than 15 mN / m, more preferably less than 11 mN / m and more preferably less than 7 mN / m.

The contact angle of the liquid composition present at a concentration of 1 gram / liter of water as measured at 25 ° C on a flat and bright glycerol tripalmitate substrate is less than 60o, more preferably less than 50o and more preferably less than 45 °.

According to the present invention, the role of the hydrocarbon is provided by a perfume not soluble in water. Typically, in the aqueous-based compositions the presence of solubilizers, such as the aryl hydrotrope of aryl lower alkyl of alkali metal, triethanolamine, urea, etc., is required for the dissolution of the perfume, essentially at perfume levels of 1% and above, since perfumes are generally a mixture of fragrant essential oils and aromatic compounds which are generally not soluble in water. Therefore, by incorporating the perfume in the aqueous cleaning composition as the oil (hydrocarbon) phase of the latter oil-in-water microemulsion composition, several different important advantages are achieved.

First, the cosmetic properties of the final cleaning composition are improved: the compositions are both clear (as a consequence of the formation of a microemulsion) and highly perfumed (as a consequence of the level of perfume).

Second, the need for uec of solubilizers, which do not contribute to cleaning operation, is eliminated.

Third, an improved fat release effect and improved fat removal capacity can be obtained in pure (undiluted) use of the diluted aspect or after dilution of the concentrate without detergent buffers or buffers or fat removal solvents conventional at a neutral or acidic pH and at low levels of active ingredients while also achieving an improved cleaning performance in diluted use.

As used herein and in the appended claims, the term "perfume" is used in its ordinary sense to refer to and include any substance or mixture of fragrant substances not soluble in water including natural substances (eg obtained by the extraction of flowers, herbs , flowers or plants), artificial (for example, mixtures of natural oils or oil constituents) and synthetically produced substances. Typically, perfumes are complex mixtures of combinations of various compounds such as alcohols, aldehydes, ethers, aromatics and varying amounts of essential oils (e.g., terpenes), such as from 0% to 30%, usually from 10% to 70% by weight. The essential oils themselves are volatile odoriferous compounds and also serve to dissolve the other components of the perfume.

In the present invention, the precise composition of the perfume is not of particular consequence for cleaning operation as long as it meets the criterion? And immiscibility in water and having a pleasant smell. Naturally, of course, especially for the cleaning compositions intended for use in the home, the perfume, as well as the other ingredients, must be cosmetically acceptable, for example, non-toxic, hypoallergenic etc.

The hydrocarbon such as the perfume is present in the hard surface cleaning composition in an amount of from 0 to 10% by weight, preferably from 0.4% to 10% by weight and more preferably from 0.4% to 3.0% by weight, special and preferably from 0.5% to 2.0% by weight. If the hydrocarbon (perfumes added) in amounts of more than 10% by weight, the cost is increased without any additional cleaning benefit and, in fact, with some decrease in cleaning performance with respect to the total amount of oily or oily dirt that it can be taken in the oil phase of the microemulsion which will decrease proportionally.

In addition, even when superior grease removal performance for perfume compositions containing no terpene solvents will be achieved, it is apparently difficult for perfumers to formulate sufficiently inexpensive perfusion compositions for products of this type (e.g. to the consumer very sensitive to cost) which include less than 20%, usually less than 30% of such terpene solvents.

Therefore, merely as a practical matter, based on an economic consideration, the microemulsion composition of the present invention can frequently include as much as 0.2% to 7% by weight, based on the total composition, of the terpene solvents introduced into the composition. through the perfume component. However, even when the amount of terpene solvent in the cleaning formula is less than 1.5% by weight, such as up to 0.6% by weight or 0.4% by weight or less, an oil removal capacity is provided. and satisfactory grease removal by the diluted microemulsions of the invention.

Therefore, for a typical formula of diluted microemulsion according to this invention, a sample of 20 milliliters of microemulsion containing 1% by weight of perfume will be able to solubilize, for example, up to 2 to 3 millimeters of oily dirt and / or oily, while retaining its cc-or microemulsion form, regardless of whether the perfume contains 0%, 0.1 *, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, or 0.8% by weight of the solvent of terpene.

Instead of the perfume one can employ a paraffin or isoparaffin insoluble in water having from 6 to 18 carbon atoms at a concentration of 0 to 8.0% by weight, preferably from 0.4 to 8.0% by weight, more preferably from 0. 4 to 3.0% by weight.

In relation to the anionic surfactant present in the cleaning composition, any of the anionic water-soluble anionic surfactants conventionally used or mixtures of said anionic surfactants and anionic surfactants can be used in this invention. As used herein, the term "anionic surfactant" is intended to refer to the class of mixed anionic and anionic-nonionic detergents providing a detersive action.

The water-soluble organic surfactant materials which are used to form the final cleaning compositions of this invention can be selected from the group consisting of anionic non-soap and water-soluble surfactants blended with a fatty acid and a partially esterified ethoxylated glycerol.

Suitable anionic, non-soap water-soluble surfactants include those surfactant or detergent compounds which contain an organic hydrophobic group generally containing from 8 to 26 carbon atoms and preferably from 10 to 18 carbon atoms in its molecular structure and at least one water solubilizing group selected from the sulfonate group, sulfate and carboxylate as to form a water soluble detergent. Usually, the hydrophobic group will include or comprise an alkyl, C8-C22, alkyl or acyl group. Such surfactants are used in the form of water-soluble salts and the salt-forming cation is usually selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di-, or tri-alkanolammonium C2-C3 with the sodium, magnesium and ammonium cations being preferred.

Examples of suitable sulfonated anionic surfactants are the well-known higher alkyl mononuclear aromatic sulphonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, the sulfonates C8-C15 alkyl toluene and the C8-C1S alkyl phenol sulfonates.

A preferred sulfonate is a linear alkyl benzene sulfonate having a higher content of 3- (or higher) phenyl isomers and a correspondingly lower content (well below 50%) of 2- (or lower) phenyl isomers, that is, in where the benzene ring is preferably held in place. part in position 3 or higher (for example, 4, 5, 6 or 7) of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low. Particularly preferred materials are set forth in U.S. Patent No. 3,320,174.

Other suitable anionic surfactants are olefin sulfonates, including long chain alkene sulphonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulphonates and hydroxyalkane sulphonates. These olefin sulfonate detergents can be prepared in a known manner by the reaction of the sulfur trioxide (S03) with the long chain olefins containing from 8 to 25, preferably from 12 to 21 carbon atoms and having the formula RCH = CHR1 wherein R is an upper alkyl group of 6 to 23 carbons and x is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and sulphonic acid alkene which is then treated to convert the sultones to sulfonates. Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the alkyl group R and are obtained by sulfonating an α-olefin.

Other examples of suitable anionic sulphonate surfactants are paraffin sulfonates containing 10 to 20, preferably 13 to 17, carbon atoms. The primary paraffin sulfonates are made by reacting the long chain alpha olefins and the paraffin bisulfites and sulfonates having the sulfonate group distributed together with the paraffin chain are shown in US Pat. Nos. 2,503,280; 2,507,088; 3,260,744; 3,372,188; and in German Patent No. 735,096.

Examples of the satisfactory anionic sulfate surfactants and the salts of alkyl sulfate Ca-C18 and the salts of C3-C18 alkyl sulfate and the salts of polyethenoxy sulfate of C8-C18 alkyl ether having the formula R (OC2H4) n OS03M wherein n is from 1 to 12, preferably from 1 to 5 and M is a metal cation selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- and triethanolammonium ions. The alkyl sulphates can be obtained by sulfating the alcohols obtained by reducing the glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resulting product.

On the other hand, the alkyl ether polyethenoxy sulphates are obtained by sulfating the condensation product of the ethylene oxide with a C 8 -C 18 alkanol and neutralizing the resulting product. The alkyl sulphates can be obtained by sulfating the alcohols obtained by reducing the glycerides of coconut or tallow oil or mixtures thereof and neutralizing the resulting product. On the other hand, the alkyl ether polyethenoxy sulphonates are obtained by sulfating the condensation product of ethylene oxide with a C8-C18 alkanol and neutralizing the resulting product. The alkyl ether polyethenoxy sulfates differ from one another in the number of moles of ethylene oxide reacted with an alkanol template. Preferred alkyl sulfates and preferred alkyl ether polyethenoxy sulfates contain from 10 to 16 carbon atoms in the alkyl group.

The polyethenoxy sulfates of C8-C12 alkylphenyl ether containing from 2 to 6 moles of ethylene oxide in the molecule are also suitable for use in the compositions of the invention. These surfactants can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfatar and neutralizing the resulting ethoxylated alkyl phenol.

Other suitable anionic surfactants are the polyethenoxy carboxylates C9-C15 alkyl ether having the structural formula R (OC2H4) nOX COOH wherein n is a number from 4 to 12, preferably from 5 to 10 and X is selected from the group consisting of CH2, (C (0) R1 and wherein Rx is an alkylene group ^^ 3. Preferred compounds include polyethenoxy C9-C11 alkyl ether (7-9) C (0) CH2CH2C00H, and polyethenoxy C13-C15 alkyl ether (7-9) and C10-C12 alkyl ether polyethenoxy (5-7) CH2C00H. These compounds can be prepared by considering the ethylene oxide with appropriate alkanol and reacting this reaction product with the chloroacetic acid to make the carboxylic acids as shown in U.S. Patent No. 3,741,911 or with the succinic anhydride or with the phthalic anhydride. Obviously, these anionic surfactants will be present either in acid form or in salt form depending on the pH of the final composition, with the salt forming cation being the same as for the other anionic surfactants.

Of the above non-soap anionic surfactants, the preferred surfactants are the C9-C15 linear alkyl benzene sulphonates and the C13-C17 alkane or paraffin sulphonates. Particularly, the preferred compounds are sodium C 10 -C 13 alkyl benzene sulfonate and sodium C 13 -C 17 alkane sulfonate.

Generally, the proportion of the anionic-non-soapy surfactant will be in the range of 0.1% to 30.0% by weight, preferably from 1% to 7%, by weight of the diluted cleaning composition.

The present compositions contain from 0.1% by weight to 10% by weight, more preferably from 0.5% by weight to 8% by weight of a neutral Lewis base polymer which is soluble in water and has either a nitrogen or an oxygen atom with a pair of free electrons so that the neutral Lewis base polymer can be electronically associated with the anionic surfactant or an active ingredient such as a perfume or an anti-microbial agent such as triclosan or an insect repellent such as MNDA wherein the base Lewis, the neutral polymer is deposited and anchored on the surface of the surface being cleaned thereby holding the anionic surfactant or active ingredient in close proximity to the surface being cleaned and in the case of the active ingredient ensuring that the properties that are being imparted by the active ingredient last longer.

The Lewis base, the neutral polymer are selected from the group consisting of an alkoxylated polyhydric alcohol and a polyvinyl pyrrolidone.

The alkoxylated polyhydric alcohol is shown by the following formula: wherein w equal to one the four and x, y and z have a value between 0 and 60, more preferably from 0 to 40, provided that (x + y + z) is equal 2 to 100, preferably 4 to 24 and more preferably from 4 to 19 and where R 'is either a hydrogen atom or a methyl group.

A preferred ethoxylated polyhydric alcohol is glycerol 6EO designated as Gly »6E0.

Polyvinyl pyrrolidone is shown by the formula wherein m is 20 to 350, more preferably 70 to 110.

A cosurfactant can optionally be used in the formation of the microemulsion composition. Three major classes of compounds have been found to provide highly suitable cosurfactants over temperature ranges ranging from 5 C to 43 C for example; (1) C3-C4 alkanols soluble in water, polypropylene glycol of the formula HO (CH3CHCH2) nH wherein n is a number from 2 to 18 and the copolymers of ethylene oxide and propylene oxide and monoalkyl ethers C1-C And esters of ethylene glycol and propylene glycol having the structural formulas R (X) nOH and R ^ XJnOH wherein R is C1-C6 alkyl, Rx is C2-C4 acyl group, X is (OCH2 (CH2) or (OCH2 (CH3) CH) and n is a number from 1 to 4; (2) aliphatic mono- and di-carboxylic acids containing from 2 to 10 carbon atoms, preferably from 3 to 6 carbons in the molecule; and (3) triethyl phosphate. Additionally, mixtures of two or more of the three classes of cosurfactant compounds can be employed where specific pHs are desired.

When the mono- and di-carboxylic acid cosurfactants (Class 2) are used in the microemulsion compositions present at a concentration of 2 to 10% by weight, the microemulsion compositions can be used as cleaners for bath tubs and other surface articles. hard, which are acid-resistant, thus removing the lime scale, soap scum and oily dirt from the surfaces of such articles by damaging such surfaces. If these surfaces are white zirconium enamel, these can be damaged by these compositions.

An aminoalkylene phosphoric acid at a concentration of 0.01 to 0.2% by weight can optionally be used in conjunction with the mono- and di-carboxylic acids, wherein the aminoalkylene phosphoric acid prevents damage to the white zirconium enamel surfaces. Additionally, 0.05 to 1% phosphoric acid may be used in the composition.

Representative members of polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, for example, polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether, triethylene glycol monobutyl ether, mono, di, tripropylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoacetate and dipropylene glycol propionate.

Representative members of the aliphatic carboxylic acids include monobasic acids of C3-C6 alkyl and alkenyl such as acrylic acid and propionic acid and dibasic acids such as glutaric acid and mixtures of glutaric acid with adipic acid and succinic acid, as well as mixtures of the above acids.

Although all of the aforementioned glycol ether compounds and acid compounds provide the stability described, the most preferred cosurfactant compounds of each type, on the basis of cost and cosmetic appearance (particularly odor) are diethylene glycol monobutyl ether and a admixture of adipic, glutaric and succinic acids, respectively. The proportion of acids in the above mixture is not particularly critical and can be modified to provide the desired odor. Generally, to maximize the water solubility of the acid mixture, the glutaric acid, the most water soluble of these three saturated aliphatic dibasic acids, will be used as the main component.

Generally, the proportions by weight of adipic acid: glutaric acid: succinic acid is 1-3: 1-8: 1-5, preferably 1-2: 1-6: 1-3, such as 1: 1: 1 , 1: 2: 1, 2: 2: 1, 1: 2: 1.5, 1: 2: 2, 2: 3: 2, etc. they can be used with equally good results.

Still other classes of cosurfactant compounds providing stable microemulsion compositions at low and elevated temperatures are the mono-, di- and triethyl esters of phosphoric acid such as triethyl phosphate.

The amount of cosurfactant which may be required to stabilize the microemulsion compositions will, of course, depend on such factors as the surface tension characteristics of the cosurfactant, the type and amounts of the primary surfactants and the Lewis base polymer and perfumes, and the type and amounts of any other additional ingredients which may be present in the composition and which have an influence on the thermodynamic factors listed above. Generally, amounts of the cosurfactant in the range of from 0.1% by weight to 50% by weight, preferably from 0.5% by weight to 15% by weight, especially preferably from 1% by weight to 7% by weight, provide stable diluted oil-in-water microemulsions for the above-described levels of primary and perfume surfactants and any other additional ingredients described below.

As will be appreciated by the practitioner, the pH of the final microemulsion will depend on the identity of the cosurfactant compound, with the choice of the cosurfactant made by cost and cosmetic properties, particularly the odor. For example, microemulsion compositions which have a pH in the range of 1 to 10 may employ any of the cosurfactant of class 1 or class 4 as the sole cosurfactant, but the pH range is reduced from 1 to 8.5 when the polyvalent metal salt is present. On the other hand, the cosurfactant of class 2 can only be used as the only cosurfactant in which the pH product is below 3.2. However, where the acidic cosurfactants are employed, in combination with a glycol ether cosurfactant, the compositions can be formulated at an essentially neutral pH (eg, pH of 7 ± 1.5, preferably of 7 ± 0.2).

The ability to formulate neutral and acidic products without boosters having grease removal capabilities is a feature of the present invention because the prior art oil-in-water microemulsion formulas are more usually highly alkaline or highly reinforced or both .

The final essential ingredient in the hard surface compositions of the invention having improved interfacial tension properties is water. The proportion of water in the hard surface cleaning compositions will generally be in the range of 20% by weight to 97% by weight, preferably from 70% by weight to 97% by weight of the usual hard surface cleaning composition.

The present invention also relates to a stable concentrated microemulsion or an acidic microemulsion composition comprising approximately by weight: (a) from 1 to 30% of an anionic surfactant; (b) 0.1% 10% of a neutral Lewis base polymer; (c) from 0 to 2.5% of a fatty acid; (d) from 2 to 30% of a cosurfactant; (e) from 0.4 to 10% of a hydrocarbon insoluble in water or perfume; (f) from 0 to 18% of at least one dicarboxylic acid; (g) from 0 to 1% phosphoric acid; (h) from 0 to 0.2% of an aminc alkylene phosphoric acid; (i) from 0 to 15% magnesium sulfate heptahydrate; Y (j) the rest being water.

Such concentrated microemulsions can be diluted by mixing with up to 20 times or more, preferably 4 to 10 times their weight of water to form oil-in-water microemulsions similar to the dilute microemulsion compositions described above. Although the degree of dilution is suitably chosen to give an oil-in-water microemulsion composition after dilution, it should be recognized that during the course of dilution both the microemulsion and the non-microemulsions can be found successively.

In addition to the essential ingredients described above required for the formation of the microemulsion or cleansing composition for all purposes, the compositions of this invention can frequently and preferably contain one or more additional ingredients which serve to improve the functioning of the product in general. .

One such ingredient is an organic or inorganic oxide salt of a multivalent metal cation, particularly Mg ++. The metal or oxide salt provides several benefits including improved cleaning performance in diluted use, particularly in areas of mild water, and minimized amounts of the perfume required to obtain the microemulsion state. Magnesium sulfate, either anhydrous or hydrated (eg, heptahydrate), is especially preferred as the magnesium salt. Good results have also been obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used with formulas at a neutral or acidic pH since the magnesium hydroxide will not precipitate at these pH levels.

Although magnesium is the preferred multivalent metal from which salts (including oxide and hydroxide) are formed, other polyvalent metal ions can also be used provided their salts are non-toxic and are soluble in the aqueous phase of the system at a desired pH level.

Therefore, depending on such factors as the pH of the system, the nature of the surfactants, base polymer Lewis and cosurfactant, as well as the availability of cost factors, other suitable polyvalent metal ions include aluminum, copper, nickel, iron, calcium, etc. It should be noted, for example, that the preferred paraffin sulfonate will precipitate the calcium salts of anionic detergent and should not be used. It has also been found that the aluminum salts work best at a pH below 5 or when a low level, for example, of 1% by weight, of citric acid is added to the composition which is designed to have a neutral pH. Alternatively, the aluminum salt can be added directly as the citrate in such a case. As the salt, the same general classes of anions as mentioned for the magnesium salts, such as halide (eg, bromide, chloride), sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc. can be used.

Preferably, in the diluted compositions the metal compound is added to the composition in an amount sufficient to provide at least one stoichiometric equivalent between the anionic surfactant and the multivalent metal cation. For example, for each gram-ion Mg ++ there will be 2 grams moles of paraffin sulphonate, alkyl benzene sulfonate, etc., while for each gram-ion of A13 + there will be ge 3 gram moles of anionic surfactant. Thus the proportion of the multivalent salt will generally be selected such that one equivalent of the compound will neutralize from 0.1 to 1.5 equivalents, preferably from 0.9 to 1.4 equivalents, of the acid form of the anionic surfactant. At higher concentrations of anionic surfactant, the amount of roullivalent salt will be in the range of 0.5 to 1 equivalent per equivalent of anionic surfactant.

Hard surface cleaning compositions may optionally include from 0 to 2.5% by weight, preferably from 0.1% by weight to 2.0% by weight of the composition of a fatty acid soap or C8-C22 fatty acid as a foam suppressant. . The addition of the fatty acid or fatty acid soap provides an improvement in the rinsing of the composition whether it is applied in pure or diluted form. Generally, however, it is necessary to increase the level of the cosurfactant to maintain the stability of the product when the fatty acid or soap is present. If more than 2.5% by weight of the fatty acid is used in the present compositions, the composition will become unstable at low temperatures as well as that which will have an objectionable odor.

As an example of the fatty acids which can be used as such or in the form of soap, mention can be made of fatty acids of coconut oil distilled "mixed vegetables" such as fatty acids (eg, a high percent of C8 chains). mono- and / or polyunsaturated, saturated); oleic acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty acids having from 8 to 22 carbon atoms being acceptable.

The liquid emulsion or microemulsion composition for all purposes of this invention can, if desired, also contain other components either to provide an additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: colors or dyes in amounts of up to 0.5% by weight; bactericides in amounts of up to 1% by weighing-condoms or antioxidant agents, such as formalin, 5-chloro-2-methyl-4-isotaliazolin-3-one, 2,6-di-tert .butyl-p-cresol, etc. ., in amounts up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide as required. In addition, if the opaque compositions are desired, up to 4% by weight of an opacifier can be added.

In the final form, clear or liquid cleaning microemulsions for all purposes exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 4oC to 50oC, especially 10oC to 43oC. Such compositions exhibit a pH in the acid or neutral range depending on the intended end use. The liquids are easily pourable and exhibit a viscosity in the range of 6 to 60 milliPascals »Second (mPas) as measured at 25oC with a Brookfield RVT viscometer using a # 1 spindle rotating at 20 revolutions per minute. Preferably, the viscosity is maintained in the range of 10 to 40 mPas.

The compositions are directly ready for use or can be diluted as desired and in any case no rinse or only a minimum is required and virtually no residues or scratches are left. In addition, because the compositions are free of detergent builders such as alkali metal polyphosphates these are environmentally acceptable and provide a better "shine" on the cleaned hard surfaces.

When intended for use in the pure form, the liquid compositions may be packaged under pressure in an aerosol container or in a pump-type sprayer for the so-called spraying and cleaning type of application, Because the compositions as prepared are aqueous liquid formulas and because no particular mixing is required to form the microemulsion or cleaning compositions for all purposes, the compositions are easily prepared simply by combining all the ingredients in one suitable container. The order of the mixing of the ingredients is not particularly important and generally the various ingredients can be added in sequence or all at the same time or in the form of aqueous solutions of each or all of the primary detergents and the cosurfactants can be prepared separately and combine with each other and with the perfume. The magnesium salt or other multivalent metal compound, when present, may be added as an aqueous solution thereof or may be added directly. It is not necessary to use high temperatures in the formation step and the room temperature is sufficient.

The microemulsion or cleaning compositions for all the present purposes explicitly exclude alkali metal silicates and alkali metal reinforcing agents such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates. because these materials, if used in the present composition will cause the composition to have a high pH as well as that which will leave a residue on the surface being cleaned.

The present compositions explicitly exclude the use of either a nonionic surfactant or an alkyl polyglucoside surfactant both of which, if added to the composition, can cause the composition to exhibit a decrease in the removal of particulate soiling from oil-kaolin. in comparison to a composition containing the Lewis base neutral polymer complex and anionic surfactant which does not contain a nonionic surfactant or an alkyl polyglucoside surfactant.

It is contemplated within the scope of the present invention that the present complexes of anionic surfactant and Lewis base, neutral polymer, can be employed in hard surface cleaning compositions such as wood cleaners, window cleaners and liquid cleaners. light work.

The following examples illustrate the liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the description are by weight.

Example 1 The following formulas were prepared and tested: (a) The release of grease was evaluated through the ease of removing dirt from a treated tile (TP) against an untreated tile (NTP). The lower the number the better the fat release effect. (b) The kaolin particulate soil composition: 70g of mineral oil, 35g of kaolin and 35g of tetrachloroethylene as solvent carrier, the tetrachlorethylene is removed in an oven at 8O0C before running the test. Kaolin is a Chinese clay of average particle size of BCC International - class E powder - 65% minimum below 10 microns, with 0.05% maximum above 53 microns.

Example 2 The following formulas were prepared and tested: (a) adhesion stress and contact angle measured at a concentration of one gram of surfactant per liter of water at 25oC on glycerol tripalmitate.

Example 3 The following formulas were prepared and tested: (a) the adhesion stress and the contact angle measured at a concentration of 1 gram of surfactant per liter of water at 25oC on glycerol tripalmitate.

Claims (10)

R E I V I N D I C A C I O N S

1. A cleaning composition comprising: a) from 0.1 to 10% by weight of Lewis base, neutral polymer, which is a polyvinyl pyrrolidone; b) from 0.1% to 30% by weight of an anionic surfactant; c) from 0 to 50% by weight of a cosurfactant; d) from 0 to 10% by weight of a hydrocarbon insoluble in water or a perfume; Y (e) the rest being water.

2. The cleaning composition as claimed in clause 1, which also contains a salt of a multivalent metal cation.

3. The cleaning composition as claimed in clause 2, characterized in that the multivalent metal cation is magnesium or aluminum.

4. The cleaning composition as claimed in clause 2, characterized in that said composition contains from 0.9 to 1.4 equivalents of said multivalent cation per equivalent of anionic surfactant.

5. The cleaning composition as claimed in clause 3, characterized in that said multivalent salt is magnesium sulfate or magnesium oxide.

6. The cleaning composition as claimed in clause 1, characterized in that it includes a fatty acid which has from 8 to 22 carbon atoms.

7. The cleaning composition as claimed in clause 1, characterized in that it contains from 0.1% by weight to 25% by weight of said cosurfactant and from 0.4% by weight to 10% by weight of said hydrocarbon.

8. The cleaning composition as claimed in clause 1, characterized in that the cosurfactant is a water-soluble glycol ether.

9. The cleaning composition as claimed in clause 8, characterized in that the cosurfactant is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol having an average molecular weight of from 200 to 1,000 and dipropylene glycol monomethyl ether, propylene glycol tert.butyl ether, mono, di, tri propylene glycol monobutyl ether.

10. The cleaning composition as claimed in clause 9, characterized in that the glycol ether is ethylene glycol monobutyl ether or diethylene glycol monobutyl ether. SUMMARY An improvement in microemulsion or cleaning compositions for all environmentally friendly purposes is described, which are especially effective in the removal of oily and oily dirt and have a pronounced fat eliminating effect, contain an anionic detergent, an alcohol alkoxylated polyhydric, a hydrocarbon ingredient, and water.