DK175385B1 - Harmless acidic cleanser for hard surfaces and method for removing limestone, soap foam and dirt from hard surfaces - Google Patents

Description

in DK 175385 B1

The present invention relates to a hard surface cleanser such as bathtubs, sinks, tiles, porcelain and enamelled articles which remove soap foam, limestone and grease from such surfaces without damaging them. More particularly, the invention relates to an acidic microemulsion which can be sprayed onto the surface to be cleaned and wiped off without the usual rinsing and yet leaving a cleaned surface clear and shiny. The invention also relates to a method for using such agents.

1 ° Hard surface cleaners, such as bathroom cleansers and abrasive cleansers, have been known for many years. Scouring cleaners usually contain a soap or a synthetic organic detergent or a surfactant and an abrasive. Such products can scratch relatively soft surfaces and eventually cause them to become dull. They are also often ineffective at removing limestone (especially encrusted calcium carbonate and magnesium carbonate) under normal use. Because limestone can be removed by chemical reactions with acidic media, 20 different acidic cleansers have been produced which have had varying degrees of success. In some cases, these cleansers have not been successful because the acid used was too strong and damaged the cleaned surfaces. At other times, the acidic component of the detergent reacted adversely with 25 other components of the product and adversely affected e.g.

the detergent or perfume. Some cleaners required rinsing to avoid leaving troublesome deposits on the cleaned surfaces. As a result of research conducted in an effort to overcome the aforementioned disadvantages, an improved liquid cleaning agent in stable microemulsion form has recently been produced which is an effective cleaning agent for removing soap foam, limestone and greasy dirt from hard surfaces. , such as baby shower surfaces, and which do not require rinsing after use.

One such product is disclosed in U.S. Patent No. 5,476,954. In particular, Example 3 of this specification discloses an acidic clear oil-in-water microemulsion which is described which could be used with good results to purify.

I DK 175385 B1 I

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You see the wall tiles in the showers for limestone and soap foam, which you were

You stuck to it. Such purification was performed by applying I

the cleaning agent on the walls followed by wiping or minimal I

In rinsing, after which the walls were allowed to dry to a good sheen. IN

I 5 -I

In the described microemulsion cleaner in the patent application, I

I effective in removing limestone and soap foam from hard surfaces

In there, and it is easy to apply, but it has been found that its

In mixture of acidic agents (succinic, glutaric and adipic acid) I

I10 could damage the surfaces of some hard fixtures, such as those of I

In materials that are not acid resistant. One such material is I

In an enamel that has been widely used in Europe as I

bathtub coating, and referred to herein

In writing as European Enamel. It has been described as I

In 15 zircon white enamel or zircon white powder enamel and have it I

In favor of being resistant to detergents, which makes it eg

In nets for use in baths, sinks, shower tiles and enamelled

In objects in a bathroom. However, such enamel is felt

You as for acids and are severely damaged by the use of the acidic acid

In 20 coremulsion cleaner based on the three organic carols

In the case of acetic acids mentioned earlier. This problem has been solved

In solution with the present invention, where further acidic I

In materials are incorporated in the detergent together with the organ

In niche acids and instead of exacerbating the problem, you prevent

25 the damage to such European enamel surfaces as a result of I

In the organic acids. A mixture of such additional acids, I

In phosphonic acids and phosphoric acids, surprisingly, I also improves

In the harmlessness of the aqueous cleanser for use on such

In European enamel surfaces and reduces the price of detergent I

For 30 easy. Thus, the present invention enables purification with I

In the invented emulsion of European enamel surfaces as well as I-

turn acid-resistant surfaces of bathtubs and other bathrooms- I

In sea surfaces. However, the product should not be used on different I

In other materials that are particularly sensitive to acid attack I

35 media such as marble. IN

An acidic aqueous cleaner according to the invention for baths and

other hard-surface articles that are acid-resistant or I-resistant

3 DK 175385 B1 clay is of zirconium white enamel which has a pH value in the range of 1 to 4, which removes limestone, soap foam and greasy dirt from the surfaces of such articles without damaging the surfaces, comprising: a purifying amount of a * 5 synthetic organic detergent capable of removing greasy dirt from surfaces, a limestone and soap-scavenging amount of one or more di-carboxylic acids having 2 to 10 carbon atoms, an aminoalkylene phosphonic acid in such amount to prevent damage to zirconium white enamel surfaces of articles to be purified with the dicarboxylic acids when the detergent is used to purify such surfaces, and an aqueous medium for the detergent, dicarboxylic acid or dicarboxylic acids and amoalkylene phosphonic acid.

In the present compositions, the synthetic organic detergent may be any suitable anionic, nonionic, amphoteric, ampholytic, zwitterionic or cationic detergent or mixture thereof, but the anionic and nonionic detergents are preferred just as mixtures thereof. Among the anionic substances, 20 are the more preferred water-soluble salts of lipophilic sulfonic acids and sulfuric acids, whose lipophilic moiety includes long chain aliphatic groups, preferably long chain alkyls having 8 to 20 carbon atoms and more preferably 12 to 18 carbon atoms. Although several different types of solubilizing cations 25 may be present in the detergents, it is generally preferred that they be alkali metal, e.g. sodium, potassium or a mixture thereof, ammonium or lower alkanolamine with 2 or 3 carbon atoms per alkanol moiety. It is a desirable feature of the present invention that sodium may be the alkali metal used and the resulting emulsions will be stable and effective.

Highly preferred salts of lipophilic sulfonic acids are paraffin sulfonates wherein the paraffin group has 12 to 18 carbon atoms, preferably 14 to 17 carbon atoms. Other useful sulfonates are olefin sulfonates wherein olefin starting materials in the alloy have 12 to 18 carbon atoms, e.g. 12 to 15, and linear alkyl benzene sulfonates wherein the alkyl has 12 to 18 carbon atoms, preferably

I DK 175385 B1 I

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In 12 to 1® carbon atoms, e.g. 12 or 13. All such sulphonates will preferably be used as their sodium salts, while other salts are also effective. IN

In 5 Highly preferred salts of lipophilic sulfuric acids are of higher. In I a 1, ethoxy 1 cool to sulfuric acids, which can also be referred to as higher I in all ethyl ether sulfuric acids. The higher alkyls in such compounds have the above chain length for this class I in anionic detergents, 10 to 18 carbon atoms, and preferably I to 10 to 14 carbon atoms, e.g. 12 or 13 carbon atoms. Such compounds should contain from 1 to 10 ethylene oxide groups, preferably 3 to 7 ethylene oxide groups per mol. For example, in I 5. A preferred cation is sodium, the calm of the cations mentioned above for solubilizing I functions can be used in any case. IN

The nonionic detergents useful for the present invention may be any of the nonionic detergents well known (and the same applies to the anionic detergents soro satisfying the conditions which is set out in II of the present description). Many such detergents are described in the text Surface Active Agents (Their Chemistry and I I Technology) by Schwartz and Perry, and in the various annual I I editions of John W. McCutcheon's Detergents and Emulsifiers. However, they will generally be condensation products of a lipophilic crude moiety, such as a higher alcohol or phenol, or a propylene glycol or propylene oxide polymer, with ethylene oxide or 11 liters of ethylene glycol. In some of the condensation products of ethylene I

oxide and higher fatty alcohol or alkyl-substituted phenol I I 30 (wherein the alkyl of the phenol core usually has 7 to 12 carbon-I atoms, preferably 9), some propylene oxide may be mixed I

with the ethylene oxide, so that the lower alkylene oxide component of the I I nonionic detergent is mixed, thereby regulating the hydrophilic-I-I-I-file balance (HLB). Highly preferred nonionic detergents found in the emulsions of the invention will be condensation products 11 of a fatty alcohol of 8 to 20 carbon atoms having from 3 to 20 liters.

B1 mole of ethylene oxide, preferably of a linear alcohol having 9 to 15 carbon atoms, such as 9 to 11 or 11 to 13 carbon atoms, or on average approx. 10 or 12 carbon atoms, red 3 to 15 moles of ethylene oxide such as 3 to 7 or 5 to 9 moles of ethylene oxide; ca. 5 or 7 moles thereof. In place of the higher fatty alcohol, an alkyl phenol such as one having 8 to 10 carbon atoms in a linear alkyl can be used, e.g. nonylphenol, and the phenol may be condensed with from 3 to 20 ethylene oxide groups, preferably 8 to 15. Similarly, nonionic 10 detergents which are polymers of mixed ethylene oxide and propylene oxide can be used at least in part instead. for the other non-ionic substances. Among these are those sold under the Plurafac brand, such as Plurafac® RA-30 and Plurafac LF-400, which are available in BASF. Preferred nonionic substances 15 contain 3 to 10 ethoxy moieties, more preferably approx. 7, and 2 to 7 propoxy groups, more preferably ca. 4, and these are condensed with a higher fatty alcohol of 12-16, more preferably 13-15 carbon atoms, to produce a mole of nonionic detergent.

20

The various nonionic detergents and the anionic detergents are often mixtures which are within the particular designations of the present disclosure. 1 2 3 4 5 6 7 8 9 10 11

The active acidic component of the emulsions is a carboxylic acid 2 which is strong enough to decrease the pH of the emulsion to 3 a value in the range of 1 to 4. Various carboxylic acids 4 may perform this function, but those which have been shown to be effective 5 to best remove soap foam and limestone from bathroom surfaces 6 while not destabilizing the emulsion are 7 polycarboxylic acids, of which the dicarboxylic acids are preferred.

8

Of the dicarboxylic acid group, which includes those with 2 to 10 car 9 bond atoms, from oxalic acid through sebacic acid, cork acid, azelaic acid and sebacic acid have lower solubilities and are therefore not as useful in the present emulsions as the other dibasic aliphatic fatty acids. all of which are preferably saturated and straight-chain. Oxalic and malonic acids, although useful as reducing agents, may be too strong for the purification of sensitive

I DK 175385 B1 I

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In hard surfaces. Preferred dibasic acids are those of the I

In the middle part of the range from 2 to 10 carbon atoms, amber I

In acid, glutaric acid and pimelic acid, especially the first three that heal

In you, industrially available in blend. After you

5 incorporated into the emulsion of the invention, disy

The cores are partially neutralized to give the desired pH

In value in the emulsion to give the greatest functional effect

tivity and harmlessness. IN

I Phosphoric acid is one of the additional acids that can help you

In protecting acid-sensitive surfaces that are cleaned with it

In landscape emulsion cleaner. As it is a tribasic acid, I

It can also be partially neutralized so that an I is obtained

In the pH of the emulsion in the desired range. Eg. can it you

In 15 be partially neutralized to the biphosphate, e.g. NaH2 PO4, I

I or NH 4 H 2 PO 4. IN

In Phosphonic acid, the second of the two additional acids to protect- I

In acid-sensitive surfaces against the dissolving effect of I

In the 20 dicarboxylic acids of the present emulsions, I exist

Apparently only theoretical, but its derivatives are stable and I

You are useful for carrying out the invention. Such derivatives apply- I

You are considered to be phosphonic acids, as used herein

In the present description. The phosphonic acids have structural I

In the trip I

I OH I

I I

I - P = 0, where Y is any suitable substituent, I

I 0H I

I 30. ^ I

but preferably Y is alkylamino or N-substituted alkyl-I

In amino. A preferred phosphonic acid component of the present invention

In emulsions, e.g. aminotris (methylphosphone) acid having I

In the formula N (CH 2 PH 2 O 3). Among other useful phosphonic acids are I

In ethylenediaminetetra (methylene phosphone) acid, hexamethylenediamine I

I 3 5

In tetra (methylene phosphone) acid and diethylenetriamine penta- (methyl I)

In lenphosphonic acid. This class of compounds can be described as I

In aminoalkylene phosphonic acids containing from 1 to 3 amino nitro-I

7 DK 175385 B1 gene atoms, 3 or 4 lower alkylene phosphonic acid groups wherein the lower alkylene has 1 or 2 carbon atoms and 0 to 2 alkylene groups of 2 to 6 carbon atoms each, whichever one or more alkyls are present and linking amino noni 5 when several such amino nitrogen are present in the aminoalkylphosphonic acid. It has been found that such aminoalkylene phosphonic acids, which may also be partially neutralized to the desired pH of the microemulsion detergent, have desired stabilizing and protective effect in the detergent of the invention, especially when present with phosphoric acid. which prevents harmful attacks on European enamel surfaces by the diacid components of the detergent. As a rule, the phosphoric acid salts, if present, will be mono-salts of each of the phosphoric acid groups present and / or phosphoric acid groups.

The water used to prepare the present microemulsions may be tap water, but it preferably has low hardness, usually less than 150 parts per million hardness such as 20 calcium carbonate. Useful cleansers can still be made from higher hardness tap water up to 300 ppm like CaCO 3. Most preferably, the water used will be destined for 11 hours or 1 is deionized water, in which the content of hardness ions is less than 25 ppm, usually zero. Use of such an ionized water enables the preparation of a product of consistently good properties, regardless of the hardness variations in the aqueous medium.

Various other components may conveniently be found in the detergents of the invention, including preservatives, antioxidants or corrosion inhibitors, co-solvents, other surfactants, multivalent metal ions, perfumes, coloring agents and terpenes (and terpineols), but various other additives traditionally used in liquid detergents and hard surface cleaners may also be present, provided they do not interfere with the cleansing and antifouling and stone removing functions of the cleanser.

Of the various additives (identified thus,

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because they are not necessary for the production of an effective

In detergent, although they may be very desirable components of I

In this) the most important are considered to be perfumes which, together with I

In terpenes, terpineols and hydrocarbons (which may be used in I)

δ site of the perfumes or added to them), seems special

In equally effective solvents for greasy dirt on hard I

In surfaces that are cleansed, forming the dispersed phases of I

oil-in-water (o / w) microemulsions. Of functional importance you are

Also in surface - active agents and polyvalent metal ions,

In 10, the former helps to stabilize the microemulsion, I

The latter and the latter help to improve the cleaning performance, especially to the

In stirrer, diluents are diluted and when the polyvalent salts of I

In the anionic detergent used, stirrers are effective detergents I

In the face of the greasy dirt that appears during use. IN

I 15 I

The various perfumes that have been found to be useful to you

In forming the dispersed phase of o / w roicroemulsion purifier I

In the clay, may be those commonly used in cleaning products, and

Preferably, they are usually in liquid state. They include

In 20 esters, ethers, aldehydes, alcohols and alkanes used in par- I

In the fumery, but of the greatest importance are the essential oils which you

You have a high terpene content. It appears that terpenes (and I

terpineols) react with the purifying components of I

In microemulsions to improve the purity of the agents according to I

In the invention, in addition to forming the stable disperse phase I

I of the microemulsions. In the present invention, it has:

It has been found that especially when using a pine-like perfume, you can

Reducing the amount of relatively expensive such perfumes

You can compensate for this with α-terpineol, and in some cases I

In 30 with other terpenes. For every 1% perfume, for example, Are you

In states from 60 to 90% of it, e.g. ca. 80%, with α-terpineol I

Generally, you get the same piney scent with good cleansing

In and stability of the microemulsion. Similarly, I-I

In des terpenes and other terpenic compounds and derivatives,

In 35 but a-terpineol is considered to be the best. IN

The polyvalent metal ion contained in the detergents of I

In the invention, any such ion, including magnesium (i

(Aluminum, copper, nickel, iron or calcium), and the ion or mixture thereof may be added in any suitable form, sometimes as a hydroxide, but usually as a water-soluble salt. It appears that the polyvalent metal ion reacts with the anion of the anionic detergent (or replaces the detergent cation, or creates an equivalent solution in the emulsion), which improves the purity and generally improves other properties of the product as well. If the polyvalent metal ion reacts with the anion 10 of the detergent to form an insoluble product, such a polyvalent ion must be avoided. Eg. For example, calcium reacts with the paraffin sulfonate anion to form an insoluble salt, and therefore calcium ions, as obtainable from calcium chloride, will be omitted by emulsion cleaners of the invention containing paraffin sulfonate as a detergent. Similarly, the polyvalent ions or other components of the agents of the invention which will react adversely with other components will also be omitted. As previously mentioned, the polyhydric metal ion will preferably be magnesium and it will be added to the other emulsion components as a water-soluble salt. One such preferred salt is magnesium sulfate, usually used as its heptahydrate (Epsom salt), but other hydrates thereof or the anhydride may also be used. In general, the sulfates of the polyvalent metals will be used because the sulfate anion thereof is also the anion of some of the anionic detergents and is found in some such detergents from the neutrons of the sat ion.

The co-surfactant component (s) of the microemulsion cleaners reduce the interface voltage or surface tension between the lipophilic droplets and the continuous aqueous medium to a value often close to 10 "3 dynes / cm, resulting in spontaneous decay of the spheres in the dispersed phase. until they become so small that they are invisible to the human eye and form a clear microemulsion. In such a microemulsion, the surface area of the disperse phase grows greatly and its solubility and ability to remove fat also increases, so that the microemulsion is significantly more

I DK 175385 B1 I

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In effective as a grease removal agent, I

If than the balls in the disperse phase have the usual emulsion I

In size. Among the surfactants useful I

I in the detergents of the invention are: water soluble lower I

5 alkanols having 2 to 4 carbon atoms per molecule (sometimes I

Preferably 3 or 4); polypropylene glycols of 2 to 18 l

In propoxy units; monoalkyl lower glycol ethers of formula I

In RO (X) nH where R is C 1-6 alkyl, X is CH 2 CH 2 O, CH 2 CH 2 CH 2 O or I

CH (CH 3) CH 2 O and n is from 1 to 4; monoalkyl esters of formula I

In 1 ° R * O (X) nH, where R * is C2-4 acyl and X and n are as described in

In the immediate front; aryl-substituted alkanols having 1 to 4 l

In carbon atoms; propylene carbonate; aliphatic mono-, di- and tri-I

In carboxylic acids having 3 to 6 carbon atoms, mono-, di- and tri-I

In hydroxy substituted aliphatic mono-, di- and tricarboxylic acids I

In 15 with 3 to 6 carbon atoms; higher alkyl ether poly-lower alkoxy- I

In carboxylic acids; lower alkyl mono-, di- and triesters of phos- I

In phoric acid, wherein the lower alkyl has 1 to 4 carbon atoms; and in

In mixtures thereof. IN

I Representatives of such surfactants are amber I

In acid, glutaric and adipic acid, diethylene glycol monobutyl ether, I

In dipropylene glycol monobutyl ether and diethylene glycol monoisobutyl I

In lether that is considered to be the most effective. IN

In the preceding discussion of useful cooverf 1 adeact in ve I

substances in the present cleaning agents, it appears that ravsy- I

re, glutaric and adipic acid and a mixture of such compo- I

Agents are useful for lowering the pH of the product, so-

You are led to remove soap foam and limestone easily from surfaces, I

For 30 **, they must be cleaned and at the same time they act as cooverf1adactive I

In substances that improve the appearance of the product and make it more I

In effectively removing fat from such surfaces. Light I

Reducing dual effects can be achieved by removing others from I

In said acidic materials having co-surfactant properties

I 35 here in the cleansers described. IN

Although it is highly preferred that the present cleaning agents I

is in the form of aqueous microemulsion ions, it is within op

In the finding of using less preferred emulsions (in which the spheres 1 of the disperse phase are larger in size), in such cases the product's purity will be less because there will be no good contact of the detergent with the surface being treated. . Although microemulsions are very preferred embodiments of the invention, other emulsions and other forms of the agent may also be used, such as gels, pastes, solutions, foams and "aerosols" containing aqueous media.

In the detergents of the invention, it is important that the amounts of the components be at certain intervals so that the product can be most effective in removing greasy dirt, limestone and sap foam and other deposits from the hard surfaces undergoing treatment and to protect these 15 surfaces during treatment. As previously mentioned, the detergent should be present in a cleansing amount sufficient to remove the greasy and oily dirt. The amount of carboxylic acid or carboxylic acid must be sufficient to remove soap foam and limestone, phosphonic acid or phosphoric acid 20 and the phosphonic acid mixture must be sufficient to prevent damage to acid sensitive surfaces with the carboxylic acid and the aqueous medium should be a solvent and suspending medium for the necessary components. and for any ten Insertions that may also be present. Typically, these 25 percent of components will be 2 to 8% synthetic anionic organic deteroent to 6% synthetic organic nonionic detergent, 2 to 6 or 10% aliphatic carboxylic acid (preferably diacids), 0.05 to 5% phosphoric acid, or monosaltic acid. thereof and 0.005 to 2% phosphonic acid, aminoalkylene phosphonic acid or monophosphonic acid salt thereof, and the remainder is water and any additives. Among the carboxylic acids, it is preferred to use a mixture of succinic, glutaric and adipic acids, and their ratio will most preferably be in the range 1-3: 1-6: 1-2, with 1: 1: 1 and ea. 2: 5: 1 ratios are the most preferred. The ratios of phosphonic acid (preferably aminoalkylene phosphonic acid) to phosphoric acid and aliphatic carboxylic diacids (or carboxylic acids) are generally approx. 1: 1-20: 20-500, preferably 1: 2-10: 10-200, and more preferably 1: 4: 25, 1: 7: 170 and 1: 3.26, respectively.

Η I

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In three representative compositions. However, intervals as wide as 1: 1- I may be

In 2000: 10-4000, and sometimes the preferred range is between dicarboxylic acid and I

In phosphonic acid 5: 1 to 250: 1. Similarly, a mixture of succinic acid, glutaric acid and adi I

In pinic acid the ratio is 0.8-4: 0.8-10: 1 and the ratio of dicarboxylic acid to I

In 5 phosphoric acid may be 5: 2 to 25: 1. IN

As a rule, there will be found in the detergent, especially when paraffin sulfate

At night, the detergent is 0.05 to 5%, and preferably 0.1 to 0.3% I

In polyvalent ion, preferably magnesium or aluminum, and more

In preferred magnesium. The percentage of perfume will also usually I

You will be in the range of 0.2 to 2%, preferably in the range of 0.5 L

I to 1.5% and of this perfume is at least 0.1% terpene or ter- I

pineol. The terpineol is α-terpineol and preferably I was added

To allow a reduction in the amount of perfume,

In 15 total amounts of perfume (including the α-terpineol), 50 to 90% are I

In terpineol, preferably approx. 80% thereof. IN

For preferred compositions of the present cleaners, I

You are different in that one contains two anionic parts

In 20 tergents and the other only one, the latter will contain 3 to 1

5% sodium paraffin sulfonate wherein the paraffin is C14-17 »2 to 1

In 4% nonionic detergent, which is a condensation product of an I

In fatty alcohol having 9 to 15 carbon atoms with 3 to 15 moles of ethyl I

In lenoxide per mole of higher fat alcohol, 3 to 7% of a 1: 1: 1 or I

In a 2: 5: 1 mixture of succinic, glutaric and adipic acid, 0.1 to 1

In 0.3% phosphoric acid, 0.03 to 0.1% aminotris- (methylene phosphone-I

In acid), 0.1 to 0.2% magnesium ion, 0.5 to 2% perfume, of which 50 I

I to 90% thereof are α-terpineol, 0 to 5% additives and 75 to 1

In 90% water. More preferably, such a cleaning agent will comprise I

In 30 or consisting essentially of approx. 4% sodium paraffin I

In (Cj4_i) sulfonate, ca. 3% of the nonionic detergent, approx. 5% I

In 2: 5: 1 mixture of dicarboxylic acids, ca. 0.2% phosphoric acid, approx. IN

In 0.05% aminotris (methylene phosphonic acid), ca. 1% perfume which I

You contain approx. 0.8% α-terpineol, ca. 0.7% magnesium sulfate (water · I

In 35 free), approx. 3% additions and approx. 83% water. IN

In the second preferred composition, 0.5 to 2% comprises sodium I

In umparaffin sulfonate, wherein the paraffin is 024-17 »2 to 4% Na

—— - '----- -: -: 13 Triumethoxylated higher fatty alcohol sulfate, wherein the higher fatty alcohol has 10 to 14 carbon atoms and contains 1 to 3 ethylene oxide groups per mole, 2 to 4% non-ionic detergent , which is a condensation product of fatty alcohol having 9 to 5 carbon atoms with 3 to 15 moles of ethylene oxide per mole of fatty carbon, 3 to 7 »of a 1: 1: 1 mixture of succinic, glutaric and adipic acid, 0.1 to 0.3 % phosphoric acid, 0.01 to 0.05% aminotris (methylene phosphonic acid), 0.09 to 0.17% magnesium ion, 0.5 to 2% perfume, of which at least 10% is terpene and / or terpine-10ol , 0 to 5% additions and 75 to 90% water. More preferably, such a detergent having two anionic detergents will comprise or consist essentially of ca. 1% sodium paraffin (C 1-4) sulfonate, ca. 3% sodium ethoxylated higher fatty alcohol sulphate, wherein the higher fat alcohol is lauryl alcohol and the degree of ethoxylation is 2 moles of ethylene oxide per mole, approx. 3% nonionic detergent, which is a condensation product of a Cg-u linear alcohol and 5 moles of ethylene oxide, approx. 5% of a 1: 1: 1 mixture of succinic, glutaric and adipic acid, approx. 0.2% phosphoric acid, approx. 0.03% aminotris (methylene phosphonic acid), approx. 0.7% magnesium sulfate (anhydrous), approx. 2% additions and approx. 84% water.

The pH of the various preferred microemulsion cleaners is usually 1-4, preferably 2.5-3.5, e.g. 3. The water content of the microemulsions will usually be in the range of 25 to 75%, preferably 80 to 85%, and the content of additives will be from 0 to 5%, usually 1 to 3%. If the pH is not in the desired range, it will usually be adjusted with either sodium hydroxide or an appropriate acid, e.g. sulfuric acid, but usually the pH will be raised, not lowered, and if reduced, more of the dicarboxylic acid mixture may be used instead.

The cleaning agents of the invention in microemulsion form are clear o / w emulsions and exhibit stability at room temperature and at elevated and reduced temperatures from 10 to 50 ° C. They are easily pourable and have a viscosity in the range of 2 to 150 or 200 centipoise, e.g. 5 to 40 centipoise, as desired, the viscosity being adjustable, partly by addition to the medium.

I DK 175385 B1 I

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In light of a thickening agent such as lower alkyl celluloses, I

eg. methyl cellulose, hydroxypropyl methyl cellulose or I

In water-soluble resin, e.g. polyacrylamide, polyvinyl alcohol. IN

Any tendency of the product to foam too much can counteract

5 is effected by incorporation into the composition of free fatty acid e1-I

You clay soap in smaller quantities, as is known in the art

In the detergent industry (at a low pH value, the soap becomes sys- I

In re). IN

The liquid detergents can be prepared by simply mixing the I

In various components thereof, the order of addition I

You are not essential. However, it is desirable that the various I

In water-soluble components are mixed together, the oil-soluble I

In components are mixed together in a separate operation and the two I

In 15 mixtures, mix together, adding the oil-soluble portion

to the water-soluble portion (in the water) with stirring. In some I

In such cases, such a procedure may be varied to prevent

In any undesired reactions between components. Eg. Will you

concentrated phosphoric acid is not added directly to the stomach

In 20 nium sulphate or to a dye, but these additions will

Be of aqueous solutions, preferably diluted by compo-

In the near future. IN

The cleaning agent can conveniently be packed in manually operated I

In 25, ice dispensing containers which are generally and preferably are, are sprayed

Made of synthetic and organic polymeric plastic material,

I such as polyethylene, polypropylene or polyvinyl chloride (PVC). IN

Such containers also preferably include nylon or other

In the non-reactive plastic closure, dip pipes and associated I

In 30 dispensing parts, and the resulting packaged cleaner is I

Ideal for use in spraying and wiping. In some I

In cases such as when limestone and soap foam deposits are heavy, I

You can leave the cleaner on items until you have it

You dissolved or loosened the deposits, and can then be wiped off, or

I 35 can be rinsed off or multiple applications can be made

In pursuit of several removals until the deposits are gone. To you

In spray applications, the viscosity of the microemulsion (or I)

In a conventional emulsion, if used instead)

It is useful to increase the liquid so that the liquid adheres to the surface to be cleaned, which is especially important when this surface is vertical, to prevent immediate run-off of the cleaner and consequent loss of efficiency. About 5 times, the product can be formulated as a spray-type aerosol so that its foam discharged from the aerosol container will adhere to the surface to be cleaned. At other times, the aqueous medium may be such as to provide a gel or paste deposited on the surface by hand application, preferably with a sponge or cloth, and removed by a combination of rinsing and wiping, preferably with a sponge. , after which it can be left to dry to a gloss, or can be dried with a cloth. Of course, when feasible, the cleaned surface can be shined to remove all traces of acid 15 from it.

The following examples illustrate but do not limit the invention. All parts, quantities, and percentages in the Examples, description and claims are by weight and all temperatures are in CC, 20 unless otherwise noted.

25 1 35

I DK 175385 B1 I

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In Example 1 I

Component% (by volume I

Sodium paraffin sulphonate (1.00 I paraffin

Sodium lauryl ether sulfate (2 moles of ethylene oxide 3.00 l

I [EtOJ per mole) I

In c9-ll linear alcohol ethoxylate nonionic 3.00 I

In detergent (5 moles EtO per mole) I

In Magnesium Sulfate Heptahydrate (Epsom Salt) 1.35 I

I 10 succinic acid 1.67 I

In Glutaric Acid 1.67 I

In Adipic Acid 1.67 I

In Aminotris (methylene phosphonic acid) 0.03 I

Phosphoric acid 0.20 I

I 15 Perfume (contains about 40% terpenes) 1.00 I

In Dye (1% aqueous solution of blue dye) 0.10 I

Sodium hydroxide (50% aqueous solution;

I is reduced by the amount of NaOH solution used)

I Water (of ionized) 85.31 I

I 20 _ I

I 100.00 I

The Microemulsion cleaner is prepared by dissolving the detergent

In the terns in the water, after which the rest of the water-soluble materials

25 clays are added to the detergent solution with stirring, except I

In the perfume and the agent for adjusting the pH (sodium hy- I

In droxide solution). The pH is adjusted to 3.0 and then I

You immerse perfume in the aqueous solution and develop momentarily

preferably the desired microemulsion, which is clear blue, and with an I

In viscosity in the range of 2 to 20 centi poise. If we skosi tea- I

It is lower, or if it is considered desirable that it be

If increased, approx. 0.1 to 1% I

I of one suitable rubber or resin such as sodium carboxymethane

In yl cellulose or hydroxypropyl methyl cellulose, or poly-I

In acrylamide or polyvinyl alcohol, or a suitable mixture I

In that. IN

I The acidic cleaner is packed in polyethylene squeeze bottles

I controlled with polypropylene spray nozzles which can be set to I

17 DK 175385 B1 positions closed, syringe and outflow. In use, the microemulsion is sprayed onto bathtubs on a bathtub, which also contains limestone in addition to soap foam and greasy dirt. The amount applied is approx. 5 ml per 5 m ring (about 3 cm wide).

5 After application and a waiting time of approx. After 2 minutes, wipe the ring with a sponge and wash off with water. It turns out that the greasy dirt, soap foam, and even limestone have been effectively removed, in cases where the limestone is particularly thick or adherent, another application may be desirable, but this is not considered normal.

The surface of the bathtub can be rinsed because it is so easy to rinse a bathtub (or shower), but no such rinse is required. Sometimes dry wiping will be sufficient, but if you want to remove any acid residue, the surface can be wiped with water or wiped with a wet cloth, but in that case it is not necessary to use more than 10 times the weight of the applied detergent. In other words, the surface does not need to be thoroughly dipped 20 or rinsed with water and it will still be clean and shiny (provided it was originally shiny. In other uses of the detergent it can be used to clean tile in shower, floor tiles in bathroom , kitchen tiles, sinks and enamelled items, generally without damaging the surfaces.

25 It is recognized that many of such surfaces are acid resistant, but a commercial product must be able to be used without damage to even less resistant surfaces, such as European white enamel (often cast iron or steel plate), often referred to as zircon white powder enamel. It is a feature of the above-described detergent (and other detergents of the invention) that they clean hard surfaces effectively, but contain ionizable acids and should therefore not be applied to acid-sensitive surfaces. Yet, it has been found that they do not damage European white enamel bathtubs, in this example, which are severely affected by cleaning with preparations exactly like the one in this example except the omission of phosphonic acid or the mixture of phosphonic acid and phosphoric acid.

I DK 175385 B1 I

I 18 I

I The main component of the preparation which protects European enamel- I

In you, the phosphonic acid is, and in the composition, the amount of it is

I ne acid has been reduced below the minimum normally required

at a pH of 3. Although 0.5% is the normal minimum when I

I present the phosphoric acid which is ineffective in itself by I

At this pH, it nevertheless exacerbates the effect of phosphone I

acid and allows a reduction in the amount of the more expensive phosphorus

In phonic acid. IN

In 10 variations of the composition described, all compositions are kept

In ponents at the same and in the same quantities except the water, and

In the phosphonic acid and the phosphoric acid. In experiment 1a, 0.05% I is used

amino tris- (methylene phosphonic acid) and the phosphoric acid is omitted. I I

In experiment 1b, 0.5% ethylene diamine tetra- (methylene phosphone-I) is used

In 15 acid) without any phosphoric acid. In experiment 1c, 0.5% hexa- I is used

'Ethylenetetra- (methylene phosphonic acid) without any phosphoric acid. IN

In experiment 1d, there is 0.4% diethylenetriamine penta-methylene phosphorus I

phonic acid) present without phosphoric acid, and in experiment le I is used

In 0.10% diethylenetriamine penta- (methylene phosphonic acid) together with I

In 0.60% phosphoric acid. The purity of compositions ld and le are I

In approximately equivalent, showing that the presence of I

the phosphoric acid, which is essentially inactive as a protector I

I of surfaces against the effects of the carboxylic acids found in

In the composition, the amount of phosphonic acids decreases to be I

In 25 protection of the surfaces to 1/4 of the former

I needed. Similar effects can be obtained when phosphoric acid I

I is used in compositions 1b and 1c for approx. the same quantities as I

In Example 1 and Example 1c. IN

I 30 If excessive foaming occurs when using the detergent I

You can add an anti-foaming agent such as a silicone or an I

In coconut fatty acid. Alternatively, coconut diethanolamide may be added

In to increase foaming. IN

I 35 I

------------ - '1' "» * '·' · _ »*« - r-T 'etc. ·' ItlMIUHlll Jl DK 175385 B1 19 EXAMPLE 2

Component% (on guard)

Sodium paraffin sulphonate (paraffin with C₂4_j) 4.00 5 Nonionic detergent (condensation product of 3.00 one mole of fatty alcohol and 5 moles of EtO)

Magnesium sulfate heptahydrate 1.50

Mixed succinic acid, glutaric acid and adipic acid (1: 1: 1) 5.00

Aminotris (Raethylene Phosphonic Acid) 0.03 Phosphoric Acid 0.20

Perfume 1.00

Dye (1% aqueous blue dye solution) 0.05

Sodium hydroxide (50% aqueous solution;

is reduced by the amount of NaOH solution used) Water (deionized) 85.22 100.00

The agents in this example are prepared in the same way as in Example 1 and are tested in the same way with similar good results. The microemulsions are clearly pale blue and the pH is set to 3.0. The cleaners lightly remove soap foam and greasy dirt from hard surfaces and loosen and facilitate the removal of limestone with minimal rinsing or sponge treatment as in Example 1. The presence of the amino tri (methylene phosphonic acid) prevents damage to acid sensitive surfaces as a result of the carboxylic acids and the presence of the phosphoric acid allows reduction in the amount of aminotris (methylene phosphonic acid). In Example 2a, without any phosphoric acid, it requires e.g. 0.10% of 30 ami notri s- (methylene phosphonic acid) to prevent damage to European enamel as a result of the detergent. Similarly in Example 1b, where the composition is the same except that the phosphonic acid and the phosphoric acid are replaced by 0.20% phosphonic acid (diethylenetriamine penta- (methylphosphonic acid)) and 0.6% phosphoric acid, European enamel is undamaged, whereas to achieve the same desirable effect without the phosphoric acid, 0.5% of the phosphonic acid is required. Similar results are obtained when the 0.5% phosphonic acid is replaced by the same amount of ethylene diamine.

I DK 175385 B1 I

I 20 I

In tetra (methylene phosphonic acid) or hexamethylenedia, nintetra- I

I (methylene phosphonic acid), with and without supplementary phosphoric acid. IN

I From this example {and Example 1) it is seen that phos- I

In 5 phoric acid which is essentially ineffective in protecting I

In acid-sensitive surfaces against the effects of carboxylic acids in the I

In the present cleansers, the protective effects I improve

I of phosphonic acids, and do so to a considerable extent for European I

In bath enamel. IN

I I

In Example 3 I

I Component% (by weight! I

In Deionized Water 82,339 I

In C14-17 paraffin sodium sulfonate (60% active, 6,670 I)

In Hostapur SAS) I

I * Mixture of glutaric, succinic and adipic acid 5,000 I

Manufactured by GAF Corp.)

I Non-ionic detergent (Plurafac RA-30, ethoxyprop- 3,000 I

In 20 oxy higher fatty alcohol, manufactured by BASF-Wyandotte) I

In Epsom salt 1,500. IN

In Aminotris (methylene phosphonic acid) 0.050 I

In Phosphoric Acid (85%) 0.230 I

Perfume (pine scent, containing terpenes) 0.200 I

In α-terpineol (perfume replacement) 0.800 I

I Formalin (preservative) 0.200 I

In 2,6-di-tert-butyl para-cresol (antioxidant) 0.010 I

I Cl Acid Blue 104 Dye 0.001 I

I 30 100,000 I

In * 57.5% glutaric acid, 27% succinic acid and 12% adipic acid. IN

I The above composition is prepared on the previous batch

In 35 written manner and tested in a similar manner and proved to- I

In pacifiers to clean acid-sensitive hard surfaces, I-

You as a bathtub and sinks of cast iron and steel plate coated with I

In European enamel, for the greasy dirt thereon and to facilitate removal

21 DK 175385 B1 of soap foam and limestone from these surfaces. When the phosphonic acid and the phosphoric acid are omitted by the composition, or when only the phosphonic acid is omitted, the detergent attacks these surfaces and dissolves them. The presence of the phosphoric acid allows a reduction in the amount of phosphonic acid needed to inhibit the detergent so that it does not attack European enamels, and this reduction is significant, especially for economic reasons but also functionally, the o-terpineol replaces somewhat of the perfume and helps to form the microemulsion while not destroying the pleasant scent that the perfume imparts to the product, and these results can be obtained with other pine-type perfumes, the o-terpineol, as well as the terpene components of a pine-type perfume, facilitates the formation of the microemulsion, but the terpineol is even more active because it is essentially 100% terpene-type compound, whereas the perfumes are generally less than 50% terpene.

EXAMPLE 4 20 When variations are made in the above compositions by using various anionic and nonionic detergents of the types described in the present specification, using (or omitting other) polyvalent salts, using other phosphonic acids with or without phosphoric acid, and by varying the amount of the components ± 10%, 20% and 30%, within the ranges specified in the specification, useful microemulsion cleaners can be obtained which can satisfactorily clean hard surfaces and remove 30 soaps and limestone from them, without damaging them, even if they are of European enamel. The products preferably contain phosphoric acid which enhances the protective effect of the phosphonic acid component, but it is within the scope of the invention to omit the phosphoric acid if deemed desirable and feasible. The detergents are preferably in microemulsion form, but although the microemulsion should "break" into a conventional emulsion, the product will be useful as an effective detergent, and such emulsions are therefore also within the scope of the invention.

I DK 175385 B1 I

I 22 I

In the framework of the part. It may be preferable to dispense the detergent I

In from a syringe bottle, but it can also be packed in usual I

In bottles. It can be made in paste or gel form, so I

In that it is more easily adhered to surfaces as applied to it

I 5 on so that it will remain there and attack the limestone of I

Instead of running down the surface. Although there have been you

I mentioned blends in the present specification, even where they are

Moreover, you were not specifically mentioned, it is to be understood that mention I

I of a single component includes reference to mixtures I

10 of such components in the cleaning agents of the invention. IN

I 15 I

I I

I I

I 30 I

1 35 i

Claims (10)

1. Acidic aqueous cleanser for bathtubs and other hard surfaces that are acid resistant or of zircon white enamel, ^. said detergent having a pH in the range of 1 to 4, which removes limestone, soap foam and greasy dirt from surfaces of such articles without damaging the surfaces, characterized in that it comprises a purifying amount of a synthetic organic detergent contained in capable of removing greasy dirt from the surfaces, a limestone and soap scavenging amount of dicarboxylic acids of 2 to 10 carbon atoms, an aminoalkylene phosphonic acid in such amount as to prevent damage to the zircon white enamel surfaces of articles to be cleaned when dicarboxylic acids the detergent is used to clean such surfaces, and an aqueous medium for the detergent, dicarboxylic acid and aminoalkylene phosphonic acid. 20. Acidic aqueous cleaner according to claim 1, characterized in that the dicarboxylic acid or acids are aliphatic and have a carbon atom content in the range of 3 to 8, the aminoalkylene phosphonic acid contains 1 to 3 amino nitrogen, 3 or 4 lower alkylene phosphonic acid groups and 0 to 2 lower alkyl groups having 2 to 6 carbon atoms each, which alkylene is present and combines amino nitrogen when more than one such nitrogen is present in the aminoalkylene phosphonic acid. IN Acidic aqueous emulsion cleaner according to claim 2, characterized in that it is in liquid emulsion form, wherein the ratio of dicarboxylic acid to aminoalkylene phosphate Ionic acid is in the range of 5: 1 to 250: 1. I Η I Acidic aqueous emulsion detergent according to claim 3, characterized in that the synthetic organic detergent is II a mixture of anionic and nonionic detergents, wherein in the anionic detergent (s) are water-soluble salts of II lipophilic organic sulfonic acids and / or water-soluble salts I of lipophilic organic sulfuric acids, the nonionic detergent II 15 is a condensation product of a lower alkylene oxide lipophilic alcohol or phenol I, wherein the aminoalkylene phosphonic acid is II selected by the group consisting of aminotris (methylene phosphonic acid), ethylene diamine tetra - (methylene phosphonic acid), hexamethylene-II diamine tetra- (methylene phosphonic acid) and diethyl entriamine penta-I (methylene phosphonic acid) and mixtures thereof. IN Acidic aqueous emulsion cleaner, characterized in that it also contains phosphoric acid, which improves the action of the aminoalkylene phosphonic acid to protect enamel surfaces of zircon white on articles being purified against the action of the dicarboxylic acids, wherein the amount of phosphoric acid II is in the range of 2: 1 to 10: 1 relative to the aminoalkylenephosphonic acid, and the ratio of dicarboxylic acid to phosphoric acid II is in the range of 5: 2 to 25: 1. I I 30 I Acidic liquid emulsion cleaner according to claim 5, ke η - II characterized in that it comprises 2 to 8 til synthetic organic ionic detergent, 1 to 6% synthetic organic non-ionic detergent, 2 to 10% aliphatic carboxylic acids, 0.05 to II 35 in% phosphoric acid and 0.01 to 0.2% aminolecylphosphonic acid. IN Acidic liquid emulsion cleaner according to claim 6, ke η - II, characterized in that the synthetic organic anionic detergent is selected from the group consisting of water-soluble higher paraffin sulfonate and water-soluble ethoxylated higher fatty alcohol sulphate to 1 10 ethylene oxide groups per mole, and mixtures thereof, the nonionic detergent is a condensation product of a 9 to 15 carbonator fatty alcohol having from 3 to 15 moles lower alkylene oxide per mole higher fatty alcohol, the succinic, glutaric and adipic acid mixture is one having the proportions of 0.8-4: 0.8-10: 1, the aminoalkylene phosphonic acid is aminotris (methylene phosphonic acid), wherein 0.05 to 0.5% of magnesium and / or aluminum ion and 0.2 to 2 are present in the detergent. % perfume material containing at least 0.1% terpene and / or terpineol, which is a microemulsion form cleaner. Acidic liquid roemic emulsion cleaner according to claim 7, 15, characterized in that it has a pH in the range of 2.5 to 3.5 and comprises 3 to 5% sodium paraffin sulfonate wherein the paraffin is ¢ 74-17, 2 to 4 % nonionic detergent, which is a condensation product of a fatty alcohol having 9 to 15 carbon atoms with 3 to 15 moles of lower alkylene oxide per mole of higher fatty alcohol, 3 to 7% of the mixture of succinic, glutaric and adipic acid, 0.1 to 0.3% phosphoric acid, 0.03 to 0.1% aminotris (methylene phosphonic acid), 0.1 to 0.2% magnesium ion, 0.5 to 2% perfume, 50 to 90% of which is α-terpineol , 0 to 5% additions and 75 to 90% water. 25 Acidic liquid microemulsion detergent according to claim 7, characterized in that it comprises 0.5 to 2% sodium pairs of affine sulfonate, wherein the paraffin is ¢ 74-77, 2 to 4% sodium unethoxylated higher fatty alcohol sulfate, wherein the higher fatty alcohol has 10 to 14 carbon atoms and containing from 1 to 3 ethylene oxide groups per mole, 2 to 4% non-ionic detergent, which is a condensate in on-product of fatty alcohol with 9 to 15 carbon atoms with 3 to 15 moles of ethylene oxide per mole of higher fatty alcohol, 3 to 7 % of an approx. 1: 1: 1 mixture of succinic acid, glutaric acid and adipic acid, 0.1 to 0.3% phosphoric acid, 0.01 to 0.05% aminotris (methylene phosphonic acid), 0.09 to 0.17% magnesium ion, 0 , 5 to 2% perfume, of which at least 10% is terpene and / or terpineol, 0 to 5% additives and 75 to 90% water. I DK 175385 B1 I I 26 I 10. A process for removing limestone, soap foam and / or IH greasy dirt from bathtubs and other hard surface articles which are acid-resistant or of zircon-white enamel, characterized in that such a surface is applied II 5 an agent according to claim 1, and this agent and the limestone I and / or soap foam and / or greasy dirt are removed from the II surface. I I io I I I I 20 I I I I 30 I 35