JPH07305100A - Acidic microemulsion composition - Google Patents

Abstract

(57) [Abstract] [Purpose] Remove lime scale, soap scum and greasy stains from the surfaces of bathtubs and other hard surface products ranging from acid resistant to zirconium white enamel without damaging the surface. Acidic microemulsion composition for removal. [Structure] A synthetic organic detergent having a pH in the range of 1 to 4 and having a detergency ratio, a lime scale and a soap residue removal ratio α-hydroxy fatty acid, an aminoalkylenephosphonic acid, water, and a fragrance. A microemulsion composition comprising.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention removes soap scum, limescale and grease from hard surfaces such as bathtubs, sinks, tiles, porcelain and enamel products without damaging such surfaces. , A cleaning agent for such hard surfaces. More particularly, the invention relates to acidic microemulsions that can be sprayed onto the surface to be cleaned and wiped off without the usual rinses, leaving a shiny, washed surface that is still shiny. The invention also relates to the use of such compositions.

[0002]

BACKGROUND OF THE INVENTION Hard surface cleaners, such as bathroom cleaners and scouring cleansers, have been known for several years. Scaling cleansers typically include soap or synthetic organic detergents or surfactants and abrasives. Such products can scratch relatively soft surfaces and eventually render such surfaces appear matte. These products are often ineffective in removing limescale (usually crusted calcium carbonate and magnesium carbonate) in normal use. Since limescale can be removed by chemical reaction with acidic media, various acidic cleaners have been produced with varying degrees of success. In some cases,
Such cleaners have failed because the acid used is too strong and damages the surface to be cleaned. In other cases, the problem has been that the acidic components of the cleaner react with other components of the product, adversely affecting the detergent or perfume. Some cleaners required a subsequent rinse to avoid leaving problem deposits on the cleaned surface. As a result of research conducted in an effort to overcome the above drawbacks, it is an effective cleaner for removing soap scum, lime scale and greasy dirt from hard surfaces such as bathroom surfaces, and rinsing after use. Improved stable liquid detergent compositions in the form of stable microemulsions have been produced which do not require. Such a product is described in US Patent Application No. 120,2 for a stable microemulsion detergent composition filed Nov. 12, 1987 by Loth, Blancalet and Valenge.
No. 50 (this application is hereby incorporated by reference). Example 3 of this application discloses a clear acidic oil-in-water emulsion, which is said to be successfully used to remove limescale and soap scum deposited on it from shower wall tiles. Has been. Such cleaning is carried out by applying a cleaner to the wall and then wiping or minimally rinsing, after which the wall dries and obtains a good gloss.

The above-mentioned microemulsion cleaner of this patent application is effective in removing limescale and soap scum from hard surfaces and is easy to use, but its acidic agents (succinic acid, glutaric acid and adipic acid) Some rigid fixtures, such as mixtures made of materials that are not acid resistant
It has been found possible to damage the surface of the (fixture). One such material is enamel, which is used extensively in Europe for bathtub coatings (herein referred to as European enamel).
Is. It is described as zirconium white enamel or zirconium white powder enamel and has the advantage of being resistant to detergents, which makes it suitable for use in tubs, sinks, shower tiles and bathroom enamel products. . However, such enamel is acid sensitive and is severely damaged by the use of the previously described microemulsion acidic cleaners based on the three organic carboxylic acids.

This problem is related to European patent 033687
8A2 has been resolved. In this patent, an additional acidic substance is added to the cleaner along with an organic acid, without exacerbating the problem, which prevents any such organic acid from damaging such a European enamel surface. Also, such additional acids (phosphonic acid and phosphoric acid)
Surprisingly further improves the safety of an aqueous cleaner for use on such European enamel surfaces and reduces the cost of the cleaner.

[0005]

The composition of the present invention enables the cleaning of European enamel surfaces as well as other acid resistant surfaces of bathtubs and other bathroom surfaces. The product can also be used for various other substances which are particularly susceptible to the action of acidic media, for example marble. The composition of the present invention replaces the mixture of succinic acid, glutaric acid and adipic acid previously used in acidic microemulsions with α-hydroxyaliphatic acids. The compositions of the present invention using an α-hydroxy aliphatic acid are less harmful than a mixture of succinic acid, glutaric acid and adipic acid on the surface of European enamel or other acid sensitive surfaces (eg marble). In addition, the composition of the present invention
Co-pending US Patent Application No. 07 / 950,370
It is believed that xanthan gum as described in the publication can thicken.

[0006]

According to the present invention, an acidic aqueous cleaner for bathtubs and other hard surface articles which is acid resistant or made of zirconium white enamel, in the range of 1 to 4 A cleaner that has a pH and that removes limescale, soap scum and greasy dirt from the surface of such items without damaging such surface will remove greasy dirt from such surfaces. Detergency rate of at least one synthetic organic detergent which can be removed; Lime scale and soap scum removal rate of α-hydroxy fatty acid having 3 to 5 carbon atoms; Zirconium white of article cleaned by α-hydroxy fatty acid Aminoalkylenephosphonic acid in a proportion that prevents damage to the enamel surface; phosphoric acid; detergent, α-hydroxy fatty acid, phosphoric acid and And a water-based medium for aminoalkylenephosphonic acid.

The thickened acidic microemulsions of the present invention have approximately the following components: (a) C ₁₄ -C ₁₇ alkali metal or ammonium sulfonate; C ₈ -C ₁₈ alkali metal or ammonium alkyl sulfate or C ₈ Anionic surfactant such as -C ₁₈ alkali metal or ammonium ethoxylated alkyl ether sulfate 1-9
%; (B) For example, C ₁₃ -C ₁₅ fatty alcohol EO7: 1 / P
Nonionic surfactants such as O4: 1 0-5%; (c) Preservatives such as alkali metal benzoates (eg sodium benzoate) 0-0.7%; (d) For example Merck. About 1,000,000 ~ like Kelzan T sold by Merck & Co.
Xanthan gum thickener having a molecular weight of 10,000,000 0-1.0%; (e) Alkyl metal hydroxide 0-0.3%; (f) Phosphoric acid 0-1.0% and more Preferably 0.05
(G) aminotrimethylphosphonic acid 0-0.5%, more preferably 0.01-0.3%; (h) dye 0-0.1%; (i) fragrance 0 to 0.1%; (j) at least one C2-C6 α-hydroxy fatty acid 2 to 9%; and (k) water balance, the composition comprising from about 1 to about 4%. More preferably, at a pH of about 2.7 to about 3.3 and at room temperature (RT) using a # 2 spindle and 50 rpm, about 5 to 1,000 cp.
s, more preferably about 30 to about 600 cps Brookfield viscosity.

In the composition of the present invention, the synthetic organic detergent is a suitable anionic, nonionic, zwitterionic, ampholyti.
c, zwitterionic) or cationic detergents, or mixtures thereof, but anionic and nonionic detergents and mixtures thereof are preferred.

The nonionic surfactant that can be used in the liquid detergent composition of the present invention is about 0-5% by weight of the composition, preferably 0.5-4.5%, most preferably 1-4. It is present in the amount of wt% and gives good soil removal performance.

The water-soluble nonionic surfactants used in the present invention are commercially well known and include primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates, primary alkanols and ethylene oxide-propylene. Includes oxide condensates (eg, Plurafacs (BASF)) and condensates of ethylene oxide with sorbitan fatty acid esters (Tweens) (ICI). Nonionic synthetic organic detergents are generally condensation products of organic aliphatic or alkylaromatic hydrophobic compounds with hydrophilic ethylene oxide groups. In fact, hydrophobic compounds containing carboxy, hydroxy, amido or amino groups with free hydrogen bonded to the nitrogen are treated with ethylene oxide or its polyhydration (p
olyhydration) product (polyethylene glycol) can be condensed to form a water-soluble nonionic detergent.
In addition, a length of polyethenoxy hydrophobic and hydrophilic elements can be formed.

Types of nonionic detergents include higher alcohols (eg, higher alcohols) condensed with about 5 to 30 moles of ethylene oxide.
A straight or branched chain alkanol having about 8 to 18 carbon atoms)
Condensation products of, for example, ethylene oxide (EO) about 16
Lauryl or myristyl alcohol condensed with moles, E
Coconut oil fatty alcohol containing tridecanol condensed with about 6 moles of O, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, and a mixture of fatty alcohols having an alkyl chain of 10 to about 14 carbons in length. And a tallow alcohol ethoxylate containing 6 EO to 11 EO per mole of alcohol, the condensation product of the cut with EO (this condensate contains about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol). Including.

A preferred group of the above nonionic surfactants is Neodol ethoxylates (She
ll Co.)), which is, for example, a C ₉ -C ₁₁ alkanol condensed with 8 mol of ethylene oxide (Neodol 91-
8), C ₁₂ -C condensed with 6.5 mol of ethylene oxide
₁₃ alkanol (Neodol 23-6.5), C ₁₂ -C ₁₅ alkanol condensed with 12 mol ethylene oxide (Neodol 25-12), C ₁₄ -C ₁₅ alkanol condensed with 13 mol ethylene oxide (Neodol 45-
13) and the like, which are higher aliphatic primary alcohols having about 9 to 15 carbon atoms condensed with ethylene oxide. Such an ethoxamer has an HLB of about 8-15.
Etoxamers having a (hydrophobic-lipophilic equilibrium) value and producing a good O / W emulsification but having an HLB value of less than 8 contain less than 5 ethylene oxide groups and lead to insufficient emulsifier and insufficient detergent. Tends to become.

Another satisfactory water-soluble alcohol / ethylene oxide condensate is a second straight or branched chain carbon number about 8-18 condensed with 5-30 moles of ethylene oxide.
It is a condensation product of an aliphatic alcohol. Examples of commercially available non-ionic detergents of the above type are those sold by Union Carbide, condensed with 9EO (Tergitol 15-S-9) or 12
Condensed with EO (Tergitol 15-S-1
2), a C ₁₁ -C ₁₅ second alkanol.

Other suitable nonionic detergents are polyethylene oxide condensates of about 5 to 30 moles of ethylene oxide and 1 mole of an alkylphenol having a straight or branched chain alkyl group of about 8 to 18 carbon atoms. A specific example of an alkylphenol ethoxylate is nonylphenol 1
Nonylphenol condensed with about 9.5 moles of EO per mole, dinonylphenol condensed with about 12 moles of EO per mole of phenol, and EO per mole of phenol
About 15 mol of condensed diisooctylphenol. A commercially available nonionic surfactant of this type is Igepal CO-630 (nonylphenol ethoxylate) sold by GAF Corporation.

A satisfactory nonionic detergent is a water-soluble condensation product of a heteroic mixture of ethylene oxide and propylene oxide with a C ₈ -C ₂₀ alkanol, the weight ratio of ethylene oxide to propylene oxide being in this case. 2.5: 1 to 4: 1, preferably 2.8: 1
Is about 3.3: 1, and the total of ethylene oxide and propylene oxide (including a terminal ethanol or propanol group) is 60 to 85% by weight, preferably 70 to 80% by weight. Such a detergent is BASF-Vandotte (W
Particularly preferred detergents commercially available from Yandotte) are C with ethylene oxide and propylene oxide.
A ₁₀ -C ₁₆ alkanol condensate, the weight ratio of ethylene oxide to propylene oxide is 3: 1, total alkoxy content is about 75 wt%.

2 to 30 moles of ethylene oxide and sorbitan mono- and tree C _10- with HLB 8 to 15
Condensates of C ₂₀ alkanoic acid esters are also used as nonionic detergent components in already described shampoo. These surfactants are well known and are available from Imperial Chemical Industries under the trade name Tween. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate. There is.

Although not preferred, other suitable water soluble nonionic detergents are sold under the tradename "Pluronics". This compound is formed by the condensation of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol.
The molecular weight of the hydrophobic portion of this molecule is about 950 to 4000, preferably 200 to 2,500. Addition of polyoxyethylene radicals to this hydrophobic moiety tends to increase the solubility of the entire molecule and render the surfactant water soluble. The molecular weight of this block polymer is 1,000 to 1.
It is in the range of 5,000 and the polyethylene oxide content accounts for 20-80% by weight. Preferably, these surfactants are in liquid form and satisfactory surfactants are available as grades L62 and L64.

The anionic surfactant used in the microemulsion comprises about 1-9% by weight, preferably 2-8% by weight, most preferably 2-7% by weight.

The anionic surfactants used in the microemulsion detergents of the present invention are water soluble, such as triethanolamine salts, and C ₈ -C ₁₈ alkyl sulfates, such as lauryl sulfate, myristyl sulfate and the like. sodium, potassium, ammonium and ethanol ammonium salt; C ₈ -C ₁₈ ethoxylated alkyl ether sulfates; linear C ₈ -C ₁₆ alkyl benzene sulphonate; C ₁₀ -C ₂₀ paraffin sulfonates; about the carbon number 10 to 24 of α- olefin sulfonates; C ₈ -C ₁₈ alkyl sulfoacetates; C ₈ -
C ₁₈ alkyl sulfosuccinate esters; C ₈ -C ₁₈
Including and C ₈ -C ₁₈ acyl taurates; acyl isethionates. The preferred anionic surfactant is a water soluble alkyl sulphate.

The paraffin sulfonate is a monosulfonate or a disulfonate and usually has 10 to 2 carbon atoms.
These mixtures are obtained by sulfonation of paraffin of 0. The preferred paraffin sulfonate is C
Paraffin sulfonates ₁₂ -C ₁₈ chains, more preferably paraffin sulfonates of C ₁₄ -C ₁₇ chain.
Paraffin sulfonates having sulfonate groups distributed along the paraffin chain are described in US Pat. No. 2,503,28.
No. 0, No. 2,507,088, No. 3,260,744
And 3,372,188 and German Patent No. 7
35,096. Such compounds may be prepared according to the specification, and the content of paraffin sulfonates outside the C _{14 to} C ₁₇ range, as well as the content of poly-sulfonates, is preferably and minimized.

Other examples of suitable sulfonated anionic detergents are, for example, higher alkylbenzene sulphonates containing higher or lower alkyl groups having 9 to 18 carbon atoms, preferably 9 to 10 to 15 to 16 carbon atoms, in straight-chain or branched form. C ₈ -C _15, such as an alkyl toluene sulfonate is a well known higher alkyl mononuclear aromatic sulfonates. Preferred alkylbenzene sulphonates have a high content of 3 (or higher) -phenyl isomers and a correspondingly low content (50%).
% (Well below%) 2 (or less)-
A linear alkyl benzene sulphonate having a phenyl isomer, for example a benzene ring bonded predominantly at the 3 or higher position of the alkyl group (eg 4, 5, 6 or 7) and a benzene ring bonded at the 2 or 1 position. Sulfonates with a correspondingly low content of isomers. Preferred materials are described in U.S. Pat. No. 3,320,174, especially those where the alkyl has 10 to 13 carbon atoms.

The higher alkyl ether sulphate used in the present invention has the formula: RO (C ₂ H ₄ O) _n SO ₃ H [wherein R is 10 to 18 carbon atoms, preferably 12 carbon atoms].
-14, most preferably a linear or branched primary or secondary alkyl group having 12 to 13 carbon atoms]. M is an alkali metal or ammonium cation and n is 1-10, preferably 1-6, especially 2 or 3. These detergents are prepared by sulfating the corresponding ether alcohol and neutralizing the resulting sulfate ester. Particularly preferred are the sodium and ammonium salts of ether sulphate.

The alkyl sulphate anion detergent composition useful in the present invention has an alkyl group having 6 to 18 carbon atoms and has the following general formula: R ² SO ₄ M [wherein R ² has 6 to 8 carbon atoms]. Chain length, especially 8 to 14 carbon atoms
A straight or branched chain of chain length, M is an alkali metal or ammonium cation, especially sodium]
Represented by Straight-chain alkyl groups are preferred.

The active acidic component of the acidic emulsion is α-hydroxyacetic acid, which is strong enough to reduce the pH of the microemulsion to 1 in the range of 1-4. A variety of such carboxylic acids have been found to be able to perform this function, but have been found to be effective in best removing soap scum from the surface of the bathroom and yet not destabilize the emulsion. The carboxylic acid has the structural formula:

[Chemical 1] [Y is selected from the group consisting of hydroxy and COOH groups, X is (CH ₂ ) _n W, where W is selected from the group consisting of CH ₃ and COOH, and n is 0, 1 or 2. Yes] is an α-hydroxy fatty acid. Preferred α-hydroxy fatty acids are citric acid, lactic acid and malic acid, but a mixture of lactic acid and malic acid is preferred, in which case the weight ratio of lactic acid to malic acid is from about 5: 1 to about 1: 1. It is preferably about 4: 1 to about 1: 1 and more preferably about 1: 1. At least one α-hydroxy fatty acid is included in the composition in an amount of about 2 to about 9% by weight, more preferably about 2 to about 7% by weight.

The .alpha.-hydroxy fatty acids are partially neutralized after incorporation in the acidic emulsion, safely yielding a preferred pH for maximum functional effect.

Phosphoric acid is one of the additional acids that helps protect the acid sensitive surfaces cleaned by the emulsion cleaners of this invention. Since phosphoric acid is a tribasic acid, it partially neutralizes phosphoric acid, so that the emulsion p in the preferable range is
H can be obtained. For example, it may be partially neutralized to give a phosphate such as NaH ₂ PO ₄
Or it can be NH ₄ H ₂ PO ₄ .

Phosphonic acid, the other of the two additional acids to protect the acid-sensitive surface from the dissolving action of the dicarboxylic acids of the thickened emulsions of the present invention, appears to exist only theoretically, but its derivatives. Is stable and useful in the practice of the invention. When the term phosphonic acid is used in this specification, such is considered a phosphonic acid. Phosphonic acid has the following structure:

[Chemical 2] [Wherein Y is a suitable substituent, but preferably Y is alkinoamino or N-substituted alkylamino]. For example, a preferred phosphonic acid component of the thickened acidic emulsion of the present invention is aminotri (methylenephosphonic) acid represented by the formula: N (CH ₂ PH _x O ₃ ).
ethylenephosphonic) acid). Other useful phosphonic acids are ethylenediaminetetra (methylenephosphonic) acid, hexamethylenediaminetetra (methylenephosphonic) acid, and diethylenetriaminepenta (methylenephosphonic) acid. Compounds of this kind have a range of 1 to 3 amino nitrogens, 3 or 4 lower alkylenephosphonic acid groups in which lower alkylene has 1 to 2 carbon atoms, and an alkylene group having 2 to 6 carbon atoms, respectively. .About.2 aminoalkylenephosphonic acid, and when a plurality of such amino nitrogens are present in the aminoalkylenephosphonic acid, the alkylene present is bonded to the amino nitrogen. Such aminoalkylenephosphonic acids, which may be partially neutralized at the desired pH of the microemulsion cleaner, especially when present with phosphoric acid, provide the desired stabilizing and protective action of the cleaners of the present invention. Has been found to protect the deleterious effects of the cleaner's α-hydroxyaliphatic component on the surface of European enamel.

An optional thickening agent in the acidic microemulsion is xanthan gum, called Kelzan T, sold by Merck. This xanthan gum has a molecular weight of about 1,000,000 to 10,000,000.
Is an excellent heteropolysaccharide having about 0 to about 1.0% by weight, more preferably about 0.1 to about 0.7% by weight, most preferably 0.2 to 0.6% by weight. To be When used at these concentration levels, the composition retains its microemulsion properties in that essential micellar aggregates are retained. The composition is still sprayable and adheres well to vertical walls. Furthermore, the composition with the incorporated xanthan gum is shear thinning, which means that the composition is easily removed from the cleaned surface without significant mechanical action. Other cellulose,
Hydroxypropyl cellulose, polyacrylamide and polyvinyl alcohol produce a shear thickening composition.

The water used to prepare the microemulsions of the present invention preferably has a low hardness, usually 15
The hardness is less than 0 ppm. Still useful cleaners can be produced from tap water with high hardness up to 3000 ppm. Most preferably, the water used is distilled or deionized water having a hardness ion content of less than 25 ppm.

Various other ingredients are preferably present in the cleaners of the present invention, such ingredients including preservatives such as sodium benzoate, antioxidants or anticorrosive agents, cosolvents. , Cosurfactants (cosurfac
tant), polyvalent metal ions, fragrances, colorants and terpenes (and terpineol), but various other auxiliaries commonly used in liquid detergents and hard surface cleaners also have cleaning and scumming and descaling functions. Can exist unless it interferes with Of the various adjuncts (these are highly desirable ingredients of cleaners, but are not necessarily required for the production of effective cleaners, they are so distinguished) the most important is considered perfume. The perfume, together with talpenes, terpenes and hydrocarbons (used in place of or in addition to perfume), acts as a particularly good solvent for greasy stains on leaned hard surfaces. To form the dispersed phase of the oil-in-water (o / w) microemulsion. Also, cosurfactants and polyvalent metal ions are functionally important, the former helps to stabilize the microemulsion, the latter promotes improved washability, especially for leaner cleaners,
The polyvalent salts of the anionic detergents used in this case are effective detergents for the greasy soils encountered during use.

The various perfumes that have been found to be useful in forming the dispersed phase of thickened acidic microemulsion cleaners are those commonly used in cleaner products and are usually preferred in the liquid state. These include esters, ethers, aldehydes, alcohols and alkanes used in perfumery, but essential oils with a high terpene content are the most important. The terpenes (and terpineol) cooperate with the detersive component of the microemulsion to form a stable dispersed phase of the microemulsion as well as improve the detergency of the compositions of the present invention. In the composition of the present invention, especially pine tree (pin
ey) It turns out that when using fragrances, the proportion of such fragrances, which is relatively expensive, can be reduced and α-terpineol can be used in its place and in some cases other terpenes can be used. is doing. For example, with 1-% of the perfume instead of 60-90%, eg about 80%, of α-terpineol, one obtains essentially the same pinewood aroma with good detergency and microemulsion stability. it can. Similarly, terpenes and other terpene-like compounds and derivatives can be used,
α-Terpineol is considered the most suitable.

The polyvalent metal ion present in the cleaner of the present invention is any suitable ion including, but not limited to, magnesium (usually preferred), aluminum, copper, nickel, iron or calcium. The ion or mixture of ions is usually added as a water-soluble salt, although it can be added in any suitable form, sometimes as an oxide or hydroxide. The polyvalent metal ion reacts with the anion of the anionic detergent (or displaces the cation of the detergent, or forms an equivalent solution in the emulsion) to improve detergency and generally other properties of the product as well. Seems to do.
If the polyvalent metal ion reacts with the anion of the detergent to form an insoluble product, such polyvalent ion should be avoided. For example, calcium reacts with the paraffin sulfonate anion to form an insoluble salt,
Calcium ions, such as those obtained from calcium chloride, should be excluded from the microemulsion cleaners of the present invention, including paraffin sulfonate detergents. Similarly, polyvalent metal ions or other components of the compositions of the present invention that adversely react with other components should also be removed. As mentioned above, the polyvalent metal ion is preferably magnesium and such an ion is added to the other emulsion components as a water-soluble salt. Such a preferred salt is magnesium sulfate, commonly used as its heptahydrate (Epson salt), although other hydrates or anhydrides can be used. Generally, polyvalent metal sulfates are used because their sulfate anions are also the anions of some anionic detergents and are found in such detergents as neutralization by-products.

The cosurfactant component in the acidic cleaner reduces the interfacial or surface tension between the lipophilic droplets and the continuous aqueous medium, often to a value close to 10 ^-3 dynes / cm to disperse. The microspheres are allowed to spontaneously collapse until they are invisible to the human eye, forming a clear microemulsion. In such microemulsions, the surface area of the dispersed phase is greatly increased and its solvent powe
Since r) and fat removal capacity are also increased, this acidic microemulsion is clearly more effective as a cleaner for removing greasy soil than when the dispersed phase globules are of normal emulsion size. Cosurfactants useful in the cleaners of the present invention include 2 to 4 carbon atoms per molecule.
(Sometimes preferably having 3 or 4 carbon atoms) water-soluble lower alkanol; polypropylene glycol having propoxy units 2 to 18; formula: RO (X) _n H (wherein R is C ₁ -C ₄
Alkyl, X is CH ₂ CH ₂ CH ₂ O or CH (CH ₃ ) C
H ₂ O, n is 1 to 4), a monoalkyl lower glycol ether represented by the formula; R is C ₂ -C ₄ acyl, and X
And n are as just described, a monoalkyl ester of the above formula; an aryl-substituted alkanol having 1 to 4 carbon atoms;
Propylene carbonate; C2-C6 mono-, di- and trihydroxy-substituted aliphatic mono-, C2-C6 α-hydroxy aliphatic acids such as di- and tricarboxylic acids; lower alkyl mono-, di- and phosphoric acid Triesters (lower alkyl has 1 to 4 carbon atoms); and mixtures thereof.

It is also clear that the other surfactants mentioned above can be used in combination with the α-hydroxyaliphatic acid which functions as a cosurfactant. These non-acidic co-surfactants are usually combined with the α-hydroxyaliphatic acid in an amount of about 0.1 depending on the concentration of the α-hydroxyaliphatic acid.
To about 5% by weight, more preferably about 0.5 to about 4.0% by weight.

Typical of such cosurfactants are lactic acid, malic acid, citric acid, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and diethylene glycol monoisobutyl ether, which are considered to be the most effective. .

From the above discussion of co-surfactants useful in the cleaners of the present invention, malic acid, lactic acid and citric acid, and mixtures of such elements, readily remove soap scum and lime scale from the surface to be cleaned. As well as lowering the pH of the product, at the same time they function as co-surfactants, improving the appearance of the product and making it more effective for removing fat from such surfaces. It is clear that The same dual effect can be obtained by using other acidic substances having the action of cosurfactant in the cleaner.

In the cleaner of the present invention, the ratio of the components is
Within a certain range, which is most effective for removing greasy dirt, limescale and soap scum and other deposits from hard surfaces to be treated and protecting such surfaces during such treatment. Is important. As mentioned above, the detergent should be present in a sufficient detergency rate to remove greasy and greasy soils; the proportion of α-hydroxyaliphatic acid should be sufficient to remove soap scum and lime scale. Should be; phosphonic acid or a mixture of phosphoric acid and phosphonic acid should be sufficient to prevent acid-sensitive surface damage by α-hydroxyaliphatic acids; the aqueous medium for the necessary ingredients and It should be a solvent and suspending medium for any auxiliaries that may be present. Such proportions of ingredients are typically 0-1.0% by weight xanthan gum.
1 to 9% by weight of synthetic anionic organic detergent, 0 to 5% by weight of synthetic organic nonionic detergent, and α-hydroxyaliphatic acid 2
~ 9 wt% and phosphoric acid or its monosalt 0.05
~ 0.6 wt% and phosphonic acid 0.005-2 wt%
And 0 to 0.6% by weight of aminoalkylenephosphonic acid or its monophosphonate, the balance water and auxiliary agents, if present. For the α-hydroxy aliphatic acid, it is preferable to use a mixture of lactic acid and malic acid.

The ratio of α-hydroxyaliphatic acid to aminoalkylenephosphonic acid in the composition of the present invention is from about 5: 1 to about 2.
50: 1, preferably about 2: 1 to about 10: 1, α
The ratio of hydroxyaliphatic acid to phosphoric acid is about 5: 2 to about 2
It is 5: 1.

Usually, 0.05 to 5%, preferably 0.1 to 3.0% of polyvalent ions (preferably magnesium or aluminum, more preferably, especially in the presence of anionic surfactants in the cleaner. Is magnesium). The proportion of the fragrance is usually in the range of 0.2 to 2%, preferably 0.5 to 1.5%, and at least 0.1% of the fragrance is terpene or terpineol. Terpineol is α-terpineol and is preferably added at 50-90% α-terpineol, especially about 80% thereof, of the total perfume (including α-terpineol) to reduce the perfume.

The pH of various preferred microemulsion cleaners is usually 1 to 4, preferably 1.5 to 3.5.
(For example, 3). The water content of the microemulsion is about 7
It is 5 to 90%, preferably about 80 to 85%, and the auxiliary content is 0 to 5%, usually about 1 to 3%. If the pH is not within this preferred range, the pH can be adjusted with sodium hydroxide or a suitable acid (eg sulfuric acid) solution, but it is common to increase the pH rather than decrease it. If desired, larger amounts of α-hydroxyaliphatic acid mixture can be used instead.

Liquid cleaners can be produced by simply mixing the various ingredients, the order of addition being immaterial. However, the optionally added xanthan gum is first mixed with water, the various water-soluble components are mixed together in the xanthan gum solution, the oil-soluble components are mixed together during the fractionation operation, and the oil-soluble part is mixed with the water-soluble part ( It is preferred to mix these two mixes in water) with stirring or other agitation.

In some cases, such manipulations can be modified to prevent undesired reactions between the components. For example, concentrated phosphoric acid is not added directly to the magnesium sulphate or dye, but such an addition is carried out by means of an aqueous solution, preferably by dilution of the components.

The manually operated spray dispenser, preferably the cleaner is usually made of a synthetic organic polymer plastic material such as polyethylene, polypropylene or polyvinyl chloride (PVC).
It is preferably filled in an ed spray dispensing container). Such containers preferably also include nylon or other non-reactive plastic closures, spray nozzles, dip tubes, and associated dispensing portions, and the resulting packaged cleaner is a "spray and wipe".
ay and wipe) ". However, in some cases where the deposits of limescale and soap dregs are severe, in some cases the cleaner will be deposited until it dissolves or relaxes. It can be left on and then wiped or rinsed, or it can be applied multiple times and removed multiple times until the deposit disappears.

[0044]

The following examples illustrate the invention,
It is not limited. All parts, percentages and percentages in the examples, the description and the claims are by weight and all temperatures are in ° C unless otherwise stated.

[0045] Example 1 Ingredient Weight% A B C Sodium lauryl sulfate 4.00 3.00 4.0 C ₁₃ -C ₁₅ benzoate Na 0.30 0.3 0.3 Magnesium sulfate heptahydrate 1.50 1.5 1.5 Malic acid 2.0 2.0 - lactic acid 2.0 3.0 - Citric Acid --- 4.0 Aminotrimethylphosphonic acid 0.25 0.25 0.25 Phosphoric acid 0.425 0.425 0.425 Fragrance (containing about 40% terpene) 0.8 0.8 0.8 Dye 0.002 0.002 0.002 Water balance balance balance pH 3.0 3.0 3.0 Brookfield viscosity 10 10 10 (RT, # 2 Spindles) Sorpins (cps) balance 100.00 Dissolve any xanthan gum and benzoate in water, then dissolve detergent, then remove perfume and modifier (sodium hydroxide solution), The rest of the water-soluble substance is added to the detergent solution with stirring. The pH is adjusted to 3.0 and the perfume is added to this aqueous solution with stirring, which immediately gives the desired microemulsion in clear blue color.

This acidic cleaner is a polyethylene squeeze bottle (squeeze bottle) equipped with a polypropylene spray nozzle that can be adjusted to a spray closed position and a flow position.
bottole). At the time of use, the microemulsion is sprayed onto a "bathtub" on the bath which also contains lime scale as well as soap scum and greasy soil. The coating rate is ring (approx. 3 cm)
Width) About 5 ml per 5 m. After application, after waiting for about 2 minutes, the ring was wiped off with a sponge and washed with a sponge moistened with water. It was observed that fatty stains, soap scum and even lime scale were effectively removed. A second application is desirable in cases where the lime scale is particularly thick or tacky, but this is considered standard.

Rinsing the bathtub (or shower) is so easy that the tub surface can be rinsed, but such rinsing is not necessary.

Sometimes dry wiping is sufficient, but if it is desired to remove acidic residues, the surface can be washed with a water-moistened sponge or wiped with a damp cloth, but this In such a case, it is not necessary to use more than 10 times the coating weight of the cleaner. In other words, the surface is still clean and shiny (if initially shiny) without the need to be completely wetted with water or rinsed with water. Other uses of this cleaner include this cleaner for shower tiles, bathroom floor tiles,
It can generally be used for cleaning kitchen tiles, sinks and enamel products without damaging these surfaces. Although many of these surfaces are found to be acid resistant, commercial products have low resistance surfaces such as European enamel (often on cast iron or sheet steel bases) sometimes referred to as zirconium white powder enamel. Should also be usable without damage. It is one of the features of the above cleaners (and other cleaners of the invention) that they clean hard surfaces but do not apply to acid sensitive surfaces because they contain ionizable acids. Nevertheless, in this example, these cleaners were severely decontaminated by a formulation exactly similar to the cleaner of the present invention except that the cleaner of the present invention omitted the phosphonic acid or phosphoric acid-phosphonic acid mixture. It was found not to damage the infested European white enamel bathtub.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C11D 3:36) (72) Inventor Claude Blancvale Belgium 4031 Angleur, Liu Bossi 61

Claims (8)

[Claims] 1. Removal of lime scale, soap scum and greasy dirt from the surfaces of bathtubs and other hard surface articles, from acid resistant to zirconium white enamel, without damaging such surfaces. An acidic microemulsion composition for such articles, having a pH in the range of 1 to 4, capable of removing greasy soil from such surfaces, detergency synthetic organic The above composition comprising a detergent, a lime scale and soap scum removal rate α-hydroxy fatty acid, aminoalkylenephosphonic acid, water, and a fragrance. 2. The α-hydroxy fatty acid has 2 carbon atoms.
To 6 and the aminoalkylenephosphonic acid has 1 to 3 amino nitrogens, 3 or 4 lower alkylenephosphonic acid groups each having 2 to 6 carbon atoms, and 0 to 2 lower alkylene groups. The composition of claim 1 having alkylene, wherein the alkylene present when a plurality of such nitrogens are present in the aminoalkylenephosphonic acid connects with the amino nitrogen. 3. A composition according to claim 2, wherein the ratio of the α-hydroxy fatty acid to the aminoalkylenephosphonic acid is in the range of 5: 1 to 250: 1. 4. The composition of claim 3 wherein the synthetic organic detergent is a C ₈ -C ₁₈ alkyl sulfates surfactants. 5. Phosphoric acid is also present which improves the action of the aminoalkylenephosphonic acid, which protects zirconium from the action of α-hydroxy fatty acids when the enamel surface of the article is cleaned, the ratio of phosphoric acid to aminoalkylenephosphonic acid being present. Is in the range of 2: 1 to 10: 1, and α-
The composition of claim 1 wherein the ratio of hydroxy fatty acid to phosphoric acid is in the range of 5: 2 to 25: 1. 6. A synthetic organic anionic detergent 1-9%, a synthetic organic anionic detergent 1-6%, and an α-hydroxy fatty acid 2
6. The composition of claim 5 comprising .about.9%, phosphoric acid 0.05-1%, and aminoalkylenephosphonic acid 0.01-0.3%. 7. The composition according to claim 1, wherein the α-hydroxy fatty acid is a mixture of malic acid and lactic acid. 8. The composition according to claim 1, wherein the α-hydroxy fatty acid is citric acid.