CZ96995A3 - Aqueous cleansing agent - Google Patents

Abstract

Ideal household cleaning compositions should form a relatively stable foam on application to a surface and rapidly de-foam when rinsed from the surface. The present invention subsists in an aqueous cleaning composition comprising: (a) a surfactant system comprising an anionic surfactant other than an alkali metal salt of a fatty acid, (b) C10-C18 monocarboxylic fatty acid, (c) a semi-polar solvent, (d) a polycarboxylic acid, and (e) a base, said composition having a pH of less than 6. It is believed that the C10-18 fatty acids have a foam boosting effect which improves 'cling' of the foam to sloping or vertical surfaces. When the compositions are diluted during rinsing the fatty acid and the solvent form an antifoam system which defoams the composition.

Description

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The present invention relates to improved household cleaning compositions.

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BACKGROUND OF THE INVENTION

Universal household cleaners are commercially available in both powder and k-form.

Powdered cleaning compositions mainly comprise a bulder or buffer salts such as phosphates, carbonates, silicates, etc. Such compositions well remove inorganic contaminants, but may have insufficient ability to clean organic contaminants such as calcium and / or magnesium salts of fatty acids and fatty / fat contaminants that are typically found in the home. Such compositions generally form solutions buffered to the alkaline pK builder. It is generally believed that alkaline pH improves the free fatty acid detergency by converting the fatty acids into the corresponding soap.

Liquid cleaning compositions generally contain an organic solvent and have the great advantage that they can be applied to hard surfaces in pure or concentrated form such that a relatively high level of surfactant and organic solvent is directly delivered to the impurity. These liquid compositions are particularly useful in cleaning hard surfaces such as floors and walls and kitchen or bathroom surfaces as well as being useful in cleaning soft house furnishings such as upholstery, carpets, curtains, etc. Again, these compositions are generally buffered to alkaline, although known. neutral products and acidic detergents were also available on the market as special cleaning agents for bathrooms.

Both of the above formulation types may contain organic acids such as citric, adipic or glutaric acid.

Typically, surfactants used in commercial universal formulations include one or both linear alkyl benzene sulphonates (ASS) and secondary alkanesulfonates (SAS):

The incorporation of certain surfactants in such solvent / vda compositions does not present any difficulty when these surfactants are present at relatively low concentrations. European Patent No. 0344847 (PandG), for example, discloses compositions containing butoxy-propanol solvents in combination with up to 5 wt. sodium linear C ₁₈ -C _and -alkylbenzensulfonátu.

Mixtures of linear alkylbenzene sulfonates with alkanol ethoxylates and optionally small amounts of fatty soaps contain a surfactant system used in many successful, liquid, alkaline commercial products having an intrinsic pH of the product of 8-11.

In addition to the removal of greasy / fat impurities, it is desirable that household cleaners have the ability to remove limestone deposits. Limestone deposits usually form calcium and magnesium carbonates, which are present as the corresponding bicarbonates at various levels in natural water and form carbonates by crystallization upon disproportionation. It is well known that carbonates are soluble in acidic solutions. However, for the above reasons, it is believed that acid formulations are less effective than alkaline formulations.

Another considerable technical problem associated with such compositions is that the surfactants used

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In particular, primary alkohoisulfate (hereafter referred to as PAS) is more environmentally friendly aionic surfactant, due to its ease of biodegradability compared to linear alkylbenzene sulfonates and secondary alkane sulfonates, and the fact that it can be obtained from natural materials such as coconut oil and other natural oils as a source of fatty acid residues.

Primary alkohoisulfate containing the formula

RO-SC ₂ X alkyl cations mixtures thereof wherein R is C ₈ to C ₁₈ primary bilingual cation. Preferred potassium, ammonium, ΤΞΑ and its mixture confers a group and X is solo include sodium, magnesium,

The use of PAS salts in combination with other surfactants is well known in the literature.

E? 125711 (Clarke: 1984) discloses a GPC containing a nonionic, anionic (examples are Mg-PAS) and a partially esterified resin.

GS-2106887 (Bristol Myers: 1984) discloses GPS containing solvent, anionic agents including alkali metal salts, ammonium and TEA-PAS salts, and 0.005 to 3.0% nonionic surfactants, including 75- 100% water-insoluble non-active substance. The most preferred anionic surfactant is sodium lauryl sulfate (Na-C ₁₂ PAS).

4 GB 2144763 (PAG: 1983) relates to a pure form of a microemulsion comprising at least a magnesium non-ionic salt. Preferred 5% solvent surfactant formulations comprise mixtures of oaraf insulphonates, in alkyl sulfonates (PAS), ethoxylated phenols and ethoxylated alcohols.

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No. 107946 (PandG) relates to liquid detergent compositions containing 6-18 water-soluble C1-C4-alkyl or water-soluble alkyl ether sulfates.

The above-mentioned surfactants, A3S, SAS and PAS are very effective foaming surfactants. While foam formation is required for many personal cleansing products, such as shampoos and bar soaps, the presence of foam is often undesirable in fabric washing and surface cleaning as it is difficult to remove the foam after a cleaning operation. For this reason, anti-foaming agents were included in the preparations.

Calcium soaps, i.e., calcium salts of fatty acids, are well known as an antifoam component in fabric washing compositions and hard surface cleaners.

The use of a combination of hydrocarbons and calcium-sensitive fatty acid soaps as antifoam systems for powder systems has been described in GB 1099562 (Unilever: 1964). This reference describes powdered detergent compositions comprising anionic sulfate or sulfonate detergents, alkali polyphosphonates, and antifoam additives of mixtures of hydrocarbons and fatty acids having from 12 to 31 carbon atoms. A hydrocarbon is broadly defined as including straight chain or branched alkanes / liquid paraffinic oils in a 1: 2 mixture with high melting paraffinic waxes having a boiling point above 90 ° C /, alkenes,

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-5-alkylated benzenes, condensed aromatics such as naphthalene and anthracene and their alkylated derivatives and alicyclic hydrocarbons, including terpenes and the like. Preferred hydrocarbons include materials having a boiling point above 90 ° C, such as the aforementioned mixtures of paraffin oils and wax, dodecylbenzene and turpentine oil.

The use of a combination of solvents, soaps and selected terpene solvents as antifoam systems for liquid hard surface cleaners is further described in EP 0080749 (PandG: 1982). In these compositions, unlike, for example, carpet cleaners, it is preferred that the product can be used without the step of adding a separate antifoam component.

More specifically, EP 0080749 describes the use of mono (two isoprene units) or sesqui (three isoprene units) terpenes in combination with a specific solvent (2- (2-butoxyethoxy) ethanol: commercially available as BUTYL CARBITOL (RTM) and 0.05-2% wt. one or more soaps of alkali metals, ammonium or alkanol-ammonium C _{U M} C fatty acids as an antifoam system. This reference states that the three components interact to have antifoam activity.

Preferred terpenes as mentioned in this reference are mono and bicyclic terpenes of a hydrocarbon class of terpenes, such as terpinenes, terpinolenes, limonenes, pinenes, and so-called orange terpenes derived from orange peel. Less preferred are other terpenes, including terpene alcohols, aldehydes and ketones. >

Terpenes and related compounds generally have the disadvantage that they are a relatively expensive raw material and are unpleasantly odorous compounds and generally provide pine or lemon-like odor to the products. It is desirable that

the base of these detergent compositions had little or no odor. In addition, terpenes may contain stoys of so-called musk xylenes and are concerned about the physiological acceptability of these materials.

Products intended for use as bathroom cleaners should form a stable, adhesive foam in the initial cleaning stages. This foam provides a visible indication of the parts of the surfaces to which the cleaner has been applied. More importantly, the foam adheres to the surface and prevents spillage, thereby minimizing the amount of surfactant-containing product required and consequently minimizing both cost and release of surfactants to the environment. However, it is desirable, both for ease of use and for the need for water, that the formulations be as reusable as possible with as little water and effort as possible.

As is apparent from the foregoing, the ideal household cleaning product should be in the form of a relatively stable foam when applied to the surface and should be capable of antifoam when washed from the surface. Such compositions should not contain environmentally unacceptable or physiologically unacceptable ingredients and should not require the addition of special anti-foaming ingredients to the rinse

-7water. Although special cleaning agents that separately meet many of these requirements have been described in the literature and on the market, there is a need for a general purpose cleaner which has the advantages of an acidic cleaner for calcium deposits but which is also effective over a wide range of impurities.

SUMMARY OF THE INVENTION

It has been found that the selected fatty acids have a foam enhancing effect in certain concentrated formulations and a foam suppressing effect when said formulations are diluted with mildly alkaline water. When these fatty acids are combined with polycarboxylic acids, solvents, and surfactants, at an acidic pH, significantly simple combinations of ingredients produce compositions that exhibit excellent cleaning across a wide range of impurities and exhibit excellent rinsing behavior.

Accordingly, the present invention relates to an aqueous cleaning composition comprising:

and / surfactant system comprising an anionic surfactant other than fatty acid salt and an alkali metal, B / C ₁₀ -C _z2 monocarboxylic fatty acid, c / semipolar solvent, d / a polycarboxylic acid or salt thereof ae / base, and said composition having a pH of less than 6a;

As well, the C. foaming expressed in p is vertical so as to change the form of the VVS3 / S OXSXV3, C, fatty acids in the formulations of the present invention as improved adhesion to the surfaces. The compositions are particularly suitable for use in four corners.

Foaming has now been the effect of promoting the invention.

Foam to oblique cdie presented by P-Ostrec.

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Without limiting the invention to any theory of operation, it is believed that in the case which is below the pK of the monocarboxylic fatty acid, a foam-promoting effect is observed. The exact pK of the fatty acid is difficult to confirm in practice because the fatty acids are not soluble in water under these conditions, although the oK determination can be obtained by titration. Also with

and expects the pH of the composition to be greater than about pX.

polycarbonyl acids, so that polycarbonyl acid exasts into the castone in an ionized form.

general households contains some calcium, derived from minerals ty20 to 400 ppm / 2-40 frane.stupňů, i.e. 0,2-4,0.1O ^'J or higher levels of calcium are known but

Water supplied to the amount of dissolved furnace at levels ranging from Ca ² ', Mg ² '. The waters having are relatively rare

Household water typically has a weakly alkaline pH above 7.5, typically around 8, and essentially due to dissolved bicarbonate, which naturally occurs in water. In rare instances, alkalizing components such as calcium oxide may be added to the water to be supplied by neutralizing acidic water and thereby preventing the dissolution of lead and other potentially toxic to the pipes and equipment.

By adding a certain amount of calcium containing alkaline domestic water to the compositions of the present invention, it is believed that the alkalinity of the water reaches the pK of the original acidic system in the delivery above the pK of the fatty acid and causes ionization

-9 fatty acids while forming a fatty acid precipitate with soap. This precipitate has suffered as a result of which it is expected to produce a limestone effect in the known manner which will aid the oiling of the product.

Solvents

Semi-polar solvents are essential components of the present invention. As will be seen later in the examples, the presence of a solvent is considered to suppress the foaming effect of the fatty acid in acidic solution and potentiate the antifoaming effect of the fatty acid in an alkaline solution.

Preferred solvents have a dielectric constant of from 5 to 35.

Preferably, the solvent is selected from propylene glycol mono-n-butyl ether, dipro n-butyl ether, propylene glycol mono-tert.

groups including pylene glycol monobutyl ether, dipropylene glycol mono-tert-butyl ether, diethylene glycol hexyl ether, ethyl acetate, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and mixtures thereof.

Preferred solvents are glycol ether solvents and these are preferably selected from the group consisting of propylene glycol mono-n-butyl ether (available as Dowanol PnB (RTM) and diethylene glycol monobutyl ether (available as Butyl Digol (RTM) or Butyl Carbitol (RTM)). These solvents are particularly preferred due to cost, availability and safety. This selection of solvents has been found to provide improved cleaning performance in terms of inks and dyes and improved product stability as well as potentiating the antifoam behavior of the rinsing compositions.

The preferred range of total surfactant: solvent ratios ranges from 1: 1 to 10: 1, preferably 2: 1 to 5: 1. A narrower ratio is preferred for cost reasons and sufficient solvent contents are 1-30% by weight of the composition, preferably 2 to 20% by weight. of the composition to achieve an effective solvent concentration upon dilution of the concentrate.

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Buffers are essential components of the compositions of the present invention.

It is believed that the presence of a buffer is essential to ensure that the pH of the undiluted composition is maintained in the acidic pH range, below the pX of the fatty acid. However, pd may not be so strongly buffered that excess water is required or an increase in cH over the oK fatty acid.

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In addition, while strongly acidic solutions should be avoided because they damage the surfaces to be cleaned, some cuts are required so that the foam is not so rapidly destabilized by the formation of insoluble calcium soaps to reduce the calcium deposition effect of the compositions of the invention.

A preferred buffer system comprises a polycarboxylic acid and a base selected from ammonium hydroxide or alkali metal hydroxides and / or organic amines, which may also be used. Ammonium hydroxide is particularly preferred and is believed to increase the removal of calcium soap deposits, although sodium hydroxide also provides good results. Preferably such a system will buffer the product to a pH of 2-6.

and will have a certain pH above pK.

Particularly preferred is most preferably the pH range of the product is pH 3.14-4.9, pH around 4, since certain enamels are sensitive to pH below 3 and products having a low pH may cause excessive rinsing to neutralize the composition

boxylic acid, has a pK of 3.14, 4.77 and 6.39, and

of this, pH above 3.14 are preferred.

Sequestrants

Weak sequestrants in the form of organic polycarboxylic acids are essential components of the compositions of the present invention. The presence of these weak sequestrants improves cleaning performance. These sequestering components are believed to weakly bind calcium ions which are involved in attaching the impurity to the surface and thereby facilitate removal of such impurities.

Strong sequestrants may also be present. However, sequestrants such as EDTA are less environmentally preferable because it has been confirmed that such &lt;

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-12 Poor biodegradable sequestrants can solubilize heavy metals from sediments on the bottom of rivers. In addition, EDTA and other strong sequestrants have a glass to camplex the calcium present in domestic water and prevent the formation of antifoam calcium soap as mentioned above.

Preferably, the sequestrant is selected from citric, adipic, succinic, maleic, glutaric acid, and mixtures or salts thereof. Typical levels of the sequestrant range are between 1 to 10 wt%, preferably 3 to 6 wt%. product.

Most preferably, the sequestrant is citric acid or a salt thereof. Citric acid is a weak sequestrant for calcium available from renewable sources and is rapidly bioavailable.

Citric acid is particularly preferred both as a sequestrant and as a component of a buffering system, at preferred levels contained in the product of 3 to 6% by weight of the product.

Fatty acids ^C io ^"C 22 fatty acids are essential components of the compositions of the present invention.

It is expected that shorter-chain fatty acids will not form sufficiently soluble calcium soaps and longer-chain fatty acids should be sufficiently insoluble in the composition to act as an antifoam component. Moreover, these average chain length fatty acids are commercially available at affordable cost and are obtained from renewable sources.

The fatty acids may be linear or branched, saturated or unsaturated, but linear fatty acids obtained from nature are preferred.

C ₂ -C ₆ , preferably C ₄ , represents the average chain length of the linear fatty acid (derivable cd of lauric acid oils such as coconut oil and palm kernel fats) are particularly preferred. Long chain soaps are less soluble in the absence of costly hydrotropes or organic solvents.

Typical levels of fatty acids are between 0.1 and 3% based on the product, with a range of 0.5 to 1% by weight. as particularly preferred.

It is important that the pH of the composition is below the pK of the cL fatty acid used. Generally, pKa will be C. ₂ -C. _with fatty acids as close as possible to 4.9, as a result, the pH of the compositions will be below this value. In accordance with the requirement that the pH is above the pK of the polycarboxylic acid, the composition will generally be in the range of 3.14 to 4.9.

Surfactants (surfactants)

At least one anionic surfactant other than soap is an essential component of the compositions of the present invention.

Preferably, the surfactant comprises one or more groups including primary and secondary alcohol sulphates, alkoxyalkoxy sulphates, primary and secondary alkanesulphonates, and alkylarylsulphonates. In the absence of an anionic surfactant in the products of the present invention, less effective adhesion occurs.

AND

Preferably, the ratio of fatty acid to anionic surfactant falls within the range of 1: 4 to 1:20, with a particularly preferred range of about 1: 5 to 1:10, expressed as% wt. % fatty acids to% wt. anionic surfactants in the product. In this way a good balance is achieved between foaming and cleaning efficiency.

Preferably, the anionic surfactant is alkanol sulphate (PAS), a foaming, readily biodegradable, breeding active agent.

primary coatingPreferred primary alkanol sulphate mixture of materials of general formula:

/ PAS / contains

SC-RO, Χ wherein R is Cg to C _lg primary alkyl group and X is a solubilising katicnt. Suitable cations include sodium, magnesium, potassium, ammonium, and mixtures thereof.

It has been found that compositions containing magnesium PAS and partially neutralized organic acid have improved cleaning performance, particularly with respect to heavy soaps and lime deposits, while maintaining cleaning performance against greasy / fat impurities. Consequently, the preferred embodiments of the present invention contain magnesium in a molar ratio of 0.1 to 0.8 moles of Mg per mole of primary primary alkanol sulphate.

It should be noted that the use of magnesium alone as a counterion for PAS can lead to difficulties in the presence of polycarboxylic acid, so it is preferred that the molar ratio of the counterions for PAS be such that the ratio of Mg to other counterions does not exceed about 5: 1. MgPAS to NaPAS ratios greater than 1: 1 but less than 2: 1 are preferred.

Especially preferred are those PAS molecules having a major proportion of C 1 -C 6 alkyl residues.

As mentioned above, these surfactants can be obtained by forming the primary alkanol sulphate of the fatty acids obtained from renewable sources is coconut oil, although they can also be obtained from the tetanol. These surfactants have very acceptable biodegradation behavior.

substances from z as sources show syn

Suitable additional surfactants are selected from cationic, nonionic, amphoteric and zwitterionic surfactants as well as mixtures thereof.

The presence of nonionic surfactants is particularly preferred. Preferred nonionic surfactants are alkoxylated alcohols and preferred alkoxylated alcohols are selected from the group consisting of ethoxylated alcohols of formula

R 1 - (OCH-CH 2) -CH 1 of 2 m wherein R 1 is straight or branched, C 1 -C 4 alkyl or hydroxyalkyl and the average degree of ethoxylation m is 1 to 14, preferably 3 to 10, for good greasy dirt detergency.

Starting materials for the synthesis of these ethoxylated alcohols, a minor component of the surfactant system, are available from both natural and synthetic sources.

The most preferred surfactant system comprises a mixture of primary alcohol sulfates and alkoxylated alcohols. For the purposes of this disclosure, alkoxylated alcohols are those which

-16 include alkyl or hydroxyalkyl ethoxylated alcohols.

Preferably, the primary alkanol sulfates and alkoxylated alcohols are from about 3: 1 to about 1: 1, and most preferably about 2: 1.

The compositions contain 15 to 30% and 5 to 10% non-ionic surfaces. Relatively punching the level of PAS and flavoring agents is desirable for formulations which may be less requiring less packaging material.

Particularly preferred primary alkanol sulfates in the active ingredients. These nonionic surfactants concentrated more effectively a

Preferred levels of 1-40 wt. 20% to 40%, more preferably surfactants of up to 10% by weight are preferred for unconcentrated products;

Levels 25 up to concentrates, although foaming components may be at levels of surfactants.

surface 35%

Components present in small quantities and other non-essential components

The compositions of the invention may further comprise other minor ingredients selected from the group consisting of perfumes, dyes and colorants, hygiene agents, viscosity modifiers, and mixtures thereof. In some embodiments of the invention, it is desirable to include additional foam control agents in the composition.

Preferably, the additional foam control agents comprise hydrophobic oils. More preferably, the hydrophobic oil is a straight or branched chain hydrocarbon or silicone oil, a more preferred hydrophobic oil is paraffin.

Most preferably, the hydrophobic oil is paraffin with 50¾ wt. a loss at boiling point in the range of 170 to 300 Y'-rzz 507 a loss in boiling point means that 50% by weight of paraffin can be distilled off at a temperature in this range. In general, the boiling point limits of paraffins suitable for use in the composition of the present invention lie between 171 and 250 ° C. Iscaparaffins, i.e. branched paraffins, have been found to be particularly effective when compared to other hydrophobic oils such as n-decane and n-tetradecane.

The content of the solubilized hydrophobic oil in embodiments of the present invention is typically in the range of 0.2 to 5 wt%, preferably 1.0 to 2.0 wt%. When a hydrophobic oil is present, the preferred ratio of fatty acid to hydrophobic oil is in the range of 0.5 to 1: 1 to 0.5, preferably about 1: 1. These ratios form a particularly effective antifoam syst

Preferably, the compositions of the present invention are homogeneous, more preferably translucent and most preferably transparent. Typical viscosities are 1 to 2000 m 2 / s at a shear rate of 21 s 1 measured at 25 ° C.

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Packing

It is preferred that the compositions of the present invention are provided in a package adapted to produce a product spray, preferably a foam spray, although the possibility of other dispensing and delivery systems is not excluded.

AND

In view of all the above, preferred embodiments of the present invention comprise an acidic aqueous cleaning composition:

and / 2 to 40 wt. surfactants, wherein the surfactant comprises primary alcohol sulfate and preferably one or more nonionic surfactants, wherein at least 50 wt. % of the surfactant that is present is the primary alcohol sulfate as the basic surfactant; c, _o- c ₁₈ unbranched fatty acids as a foam-promoting agent under acidic conditions and antifoaming agents under alkaline conditions; c / at least one solvent selected from the group of glycol ether and alcoholic solvents of 1 to 5 carbons, in an amount where surfactant: solvent ratios % in the range of 1: 1 to 10: 1, d / 1 to 10 wt. a water-soluble organic acid selected from citric, adipic, succinic, glutaric, maleic, their salts or mixtures thereof, such as calcium and magnesium sequestrants and a buffer component, and e / a sufficient base to be present in the formulation in the range of 3.14 to 4; 9.

For a better understanding of the invention, it will be further illustrated by way of examples and with reference to the accompanying drawings.

Description of the figures in the attached drawings:

Giant. 1 - represents the effect of the composition on the number of rinses required to reduce the foam volume with waters of different hardness.

-19Cbr. 2- represents the effect of pH on foam volume with water of different hardness.

DETAILED DESCRIPTION OF THE INVENTION

Examples 1 to 2

The formulations were prepared according to Table 1 below. All ingredients were mixed at room temperature and filled into containers fitted with spray heads. The nonionic surfactant was DC3ANCL 23-6.5 EO (RTM from SHELL), PAS bvl DACPCN-27L (3TM cd DAC). Butyl Carbitol is a trademark of Union Carbide. The fatty acid was PSIFAC 7S01 (RTM from Unichema).

Table 1 Example 1 Example 2

citric acid 4.00 % 4.00 % passport 4.00 % 4.00 % / anionic / non-ionic active substance 2.00 % 2.00 % butylcarbitol 2.00 % 2.00 % / solvent perfume 0.50 % 0.50 % sodium hydroxide 1.20 % 1.20 % protective substances 0.015% 0.015 % fatty acid - 0.5 % water to 100 % to 100 % pH 4.3 4.3 adhesion 2.7 3.6

Efficacy was evaluated by spraying the products onto a non-horizontal surface and rinsing with hard water (typically above 2.6 x ¹⁰ -3 moLt ¹ Ca ² * or Mg ² *). Adhesion was evaluated

using 20 experienced technicians instructed in evaluating the foam adhesion in the adhesion test on a scale of 1 to 5, where 1 represents a back adhesion and 5 an excellent adhesion.

Example 1 is a commercially available product selected as a comparative example; the effectiveness of this product was good.

Example 2 is an example of the present invention, the composition exhibiting more bulk and adhesive foams that were particularly effective in adhering to inclined or vertical surfaces. While the composition of Example 1 exhibits an acceptable adhesion and can be washed without separate pigments, it has been found that the composition of Example 2 exhibits improved adhesion and washing is particularly easy.

Examples 3 to S

Giant. 1 shows the effect of the composition on the amount of rinsing needed to reduce the foam volume with water of different hardnesses.

The measurements were performed as follows: 5 mg of the product was diluted to 50 ml with water of stated hardness in a calibrated tap funnel closed. The vial was manually shaken vigorously for approximately ten seconds to form a foam, and the initial foam volume was recorded after the excess liquid was drained by the tap. Aliquots of 50 ml of water were used for each rinsing by addition to the funnel, an additional shaking cycle and a further measurement of the foam volume after liquid removal, this process was repeated until no more foam remained. The above compositions in Examples 1 and 2 were used, with a fatty acid level of 0.5 wt.

It can be seen from the figure that the addition of a fatty acid to the comparative example leads to a reduction in the number of rinsing cycles required in all cases and that there was an improvement

-21. z represents the influence of pri on the volume of oer.v with water of hardness. Said pH is the pH of the liquid obtained during the flushing cycles described above. It can be seen as the rinsing proceeds, rises with the liquid. Furthermore, it can be seen that in the case of always containing an exceptionally high level of calcium, the effect of the fatty acid is very noticeable.

For most common vcd the foam volume decreases rapidly and at a rate above 6.5 from the orododuct, the 10% dilution of the ore 4-5.

From the above examples, the formulation examples show both improved rinsing compared to the state of the art.

it can be seen that said improved adhesion of the foam thus with the composition of the prior art

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Examples 9 to 15

Table 2 further provides values for the compositions of Example 2 in which the average fatty acid chain length was varied. The values for the composition of Example 1, without fatty acid, are given for comparative purposes. The cumulative foam volume (CFV) is measured in cubic centimeters for the standard initial volume and shaking procedure as above with reference to Examples 3 to 8.

CFV represents the total volume of foam obtained in the rinsing process using water with a hardness of 2.6. 10 ' ³ moLT ¹ Ca ²⁺ or Mg. The number of rinses required to remove the foam was determined as above.

- 1Ί -

Table 2 fatty acid ina CFV colachy 4950 * r - ? 13 C ₃ 3025 3.5 ₃ .HC _{; 3} 2400 8.0 Ex.12 C. ₂ 2525 5.0 Ex.13 C _u 400 4.0 steed. 14 C. _e 375 6.0 Ex 15 Ά 975 6.0 From the above data can be seen t that greasy an acid having a length chains above C; significantly decrease CFV. It should be noted that e fatty acids, having a length

re-ez cs load. C-, were insoluble in the composition.

Example 16/19

The effect of the sequestrant type is demonstrated in Table 3 below, in which the sequestrant type was changed in the presence and absence of fatty acid (FA). The cumulative foam volume (CFV) is measured in cubic centimeters for the standard initial volume, and the shaking protocol is described above in Examples 3 to 8. CFV is the total foam volume obtained in the flushing process using water having a hardness of 2.6 x 10 -1 mol.I ⁴ Ca čiMg '. The number of rinses required to remove the foam bvl was determined as described above.

-23p. 19 Dec

FA

- / Ex.1 / 0.5 / Ex.2 /

0.5

EDTA CFV% -3300% -337c% 3 3 5 0% 3400

3.5 Ξ / o

7.5

5.5

It can be seen from Table 3 above that better results are obtained in the presence of fatty acid and sequestrants.

Examples 20 to 25

The influence of the primes is demonstrated with reference to the values given in Table 4 below. CFV and rinse measurements are performed as above, using water at 12.10 ^-3 and 2.6. 10 ' ³ moLT ¹ Ca ² ' or Mg ² '. The results are generally 2.6. 10 ^'3 mol.r ¹ Ca ²⁺ CImg ² if it were similarly obtained with the softer water / Examples 25 and 25 /. 20, 22 and 23 are comparative examples.

The results of the Examples were hardly reported

Table 4

FA pH CFV rinsing 20 - / BC / 4.3 3800 6.5 př.21 0.5 / Ex.2 / 4.3 3375 5.5 př.22 - 10.5 3625 9.0 př.23 0.5 10.5 1400 3.0 24 0.5 c.2,5 2325 5.5 Ex 25 0.5 4.3 3400 6.0 ex 26 0.5 c.2,5 5100 9.0

The results shown above show a significant effect on the products, and these alkaline compounds do not remove effective calcium deposits. Examples 24 and 26 show the effect of purging the alkaline (NaCH) powder from the composition. The composition of Example 24 shows similar behavior of the compositions of the invention in hard water, but is too acidic to use on some surfaces. Examples 25 and 25, with soft leads, at 1.2. 1O ^'J moths' ^{1 Ca> eimai>} show that embodiments of the present invention / Example 25 / exhibit acceptable rinsing whereas in r.epřípufrovac:

Component (Example 26) shows apparent orotio-efficacy,

It should also be noted that foams at about 2.5 have low adhesion and efficiency.

Prepared products are checked

Examples 27 to 30

In Examples 27-30, as shown in Table 5, the synergistic relationship of solvent and antifoam fatty acid is shown. The results were obtained as described above.

Table 5

FA solvent CFV Ex 27 - / BC / 2% 3800 Ex 23 0.5 / Ex.2 / 2% 3375 př.29 - - 2325 eg 30 0.5 - 2750

rinsing

8.5

5.5 7.0 7.0

AND

From the above results, it can be seen that the presence of a solvent is essential because the fatty acid has an antifoam effect on dilution. In the absence of a solvent (Comparative Examples 29 and 30), a poor low-adhesion foam is obtained. In the presence of a solvent, the foam is stabilized when the fatty acid is omitted (Comparative Example 27). Only in the presence of both a fatty acid and a solvent, both high foam volumes and rapid rinses were obtained (Example 28).

Examples 31 to 36

In Examples 31-36, as shown in Table 5, the synergistic effect of changes in the surfactant world on product properties is presented. The results were obtained as described above using water with a hardness of 2.6. 10 &quot; mol.l · ¹ Ca &quot;

Table 6

FA anionic nonionic CFV rinsing př.31 - / BC / 4% 2% 3800 8.5 32 0,5 /př.2/ 4% 2% 3375 5.5 eg 33 - - 2% 150 3.0 Example 34 0.5 - 2% 0 0.0 35 - 4% - 4700 7.0 př.36 0.5 4% - 3900 4,5 Comparative Examples 33 and 34 show that in nepitom-

Anionic surfactant has little or no foam formation, allowing the product to fall off quickly from surfaces to which it has adhered during cleaning operations.

Examples 35 and 36 show the effect of omitting any nonionic surfactant present in embodiments

-27rabulka 7

p *** η * 37 33 o 9 Tncnssium PAS 13.5 - - PAS (sodium salt) - 2.5 - SAS (sodium salt) - - t, u nonionic substance 9.5 - »Í \ i ř solvent 8.0 - - fatty acid 0.7 - - isoparaff in 0.75 - - ammonia 1.1 0.75 - organic acid 5.0 5.0 5.2 minority components tracks tracks tracks VOG 3. to 100 % dol00% dc 100% pH 4.0 sour kvselv dirt / contact time kitchen 15s 4 3 2 greasy dirt 15s T 3 3 30s 3 3 3 60s 4 4 3 soap sediment 180s 3 1 0

240s 4 21

Table 7 sets forth two comparative examples (examples 38 and 39) of current, commercially available acidic bathroom cleaners. These compositions were obtained by analysis of these compositions. In composition 39, the organic acids are a mixture of succinic, glutaric, adipic and

% Azide in a total amount of 6.2 wt. In Examples 27 and 33, citric acid was used. It will be appreciated that the center of Example 33 differs from the present invention in that it does not use the magnesium salt of PAS and there is no fatty acid or solvent present.

In order to evaluate the compositions of Examples 27, soiled tiles have been prepared wherein the dirt is a synthetic soap deposit, greasy dirt, and kitchen dirt.

The soap deposit consists essentially of calcium, applied to the enamelled steel by spraying a suspension of calcium stearate in isohalcohol. The tiles were baked at 13 ° C after dirt application.

álsždicorccv1—

Op 3-i

The greasy dirt comprises a mixture of fatty acids and para-nano applied to the ceramic tile by spraying the composition in an oetrol ether.

Kitchen dirt contains a mixture of fats, fatty acids, paraffin and clay, applied to a ceramic tile by forcing oetrol ether.

To evaluate the efficacy of the composition, 0.5 ml of the compositions of Examples 37-39 were applied to each of the soiled tiles and left in contact with the tile for the time indicated in Table 7 as the contact time. The tiles were then mechanically cleaned with a cleaning cloth in one direction at a constant pressure. The residual spin is evaluated visually by a six-point scale of 0 to 5, where 0 means no soil removal and 5 means complete soil removal as indicated by soot removal.

From the above results, the present invention is equivalent to removing dirt, but they are kitchen soils and in particular soaps.

it will be appreciated that the compositions below the known compositions are somewhat better when removing deposits

UJ.

Examples 39 to 43

Examples 39 to 44 uv illustrate the effect of porn changes for PAS surfakta.nt, in high examples they are similar to the simple difference that the MG: Na ratio of PAS

** below in Table 3 to Na as the counterion. Everything in Example 37 with it

Table

Example Mc? AS: For? AS 3 9 10.5: 3.0 srabilni 40 11.0: 7.5 c - = Γ) -i 1 n ' 41 18.5: 0.0 unstable 42 17.7: 1.0 Π3S u302.1Π1 43 15.0: 3.5 unstable

In Examples 41-43, as a precipitant of product p, the compositions of Examples 39-40 and above were found to be magnesium storage while stable storage.

The products of Examples 41-43 are otherwise acceptable

Claims (15)

DO-metal-fatty acids, b / C _a to C ₂₂ fatty acid monokarboxylcvcu c / semipolar solvent, d / polykarboxylcvou acid or its salt ae / base, said composition having a pH less than the sixth 2. The composition of claim 1 wherein the semipolar solvent has a dielectric constant of 5 to 35. 3. A composition according to claim 1 wherein the semipolar solvent is selected from the group consisting of propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, dipropylene glycol. mono-tert-butyl ether, diethyl ether hexyl ether, ethyl acetate, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and mixtures thereof. 4. The composition of claim 3 wherein the semipolar solvent is a glycol ether solvent. The composition of claim 4, wherein the semipolar solvent is selected from the group I glycolminobutyl ether. Composition according to claim 1, characterized in that the level of the solvent is from 1 to 30% by weight of the product. 7. The composition of claim 1 wherein the total surfactant: solvent weight ratio is in the range of 2: 1 to 5: 1. 8. A composition according to claim 1 comprising from about 1% to about 10% polycarboxylic acids or salts thereof. The composition of claim 8, wherein the polycarboxylic acid is selected from the group consisting of citric, adipic, succinic, maleic, glutaric, their salts and mixtures of acids and their salts. 10. The composition of claim 1 wherein the acidic reserve of the composition is such that the pH exceeds pX of the monocarboxylic acid with the addition of more than ten volumes of water having a pH of at least 7.5 per volume of product. The composition of claim 1, wherein the acidic reserve of the composition is such that the pH is raised above the βX monocarboxylic acid when less than 1000 volumes of water having a pH of at least 7.5 is added to one volume of product. -7712. 14. se vyb ^! 3. A composition according to claim 1 having a pH of from 3.14 to 4.9. A composition according to claim 1, wherein the level of the carboxylic acid is bound to oro. A composition according to claim 1, wherein the at least one up-surfactant 32 comprises primary and secondary alcohol nolethoxysulfates, primary and secondary alkanilyl aryl sulfonates, and mixtures thereof. ía of sx. sulfates, alkoxysulfates, al 15. The composition of claim 1, further comprising a nonionic surfactant. 15. A composition according to claim 1, comprising a surfactant selected from a propanol alcohol and an alkyl benzene sulfonate together with an alkoxylated alcohol in a ratio of 3: 1 to 1: 1. 17. A composition according to claim 1, wherein the monocarboxylic acid to anionic surfactant is in the range of 1: 4 to 1:20. 18. A composition according to claim 1 wherein the level of surfactant in the product is 2 to 10 wt. 19. The composition of claim 1, wherein the level of surfactant is from 20 to 40% by weight. product. A composition according to claim 1 in a package adapted to produce a product spray. 21. An acidic aqueous cleansing composition according to claim 1, comprising from a / 2 to 40 wt. a surfactant, wherein said surfactant comprises a primary alcohol sulfate and preferably one or more nonionic topcoats, wherein at least 50 wt. % of the surfactant present is the primary alcohol sulfate, b) 0.2 to 5 wt. Nos. ₀ -C ₈ unbranched fatty acid, c / at least one solvent selected from the group consisting of glycol ether and 1-5 carbon alcohol solvents, in an amount such that the ratio of surfactant: solvent are in the range 1: 1 to 10 % D: 1 to 10 wt. a water-soluble organic acid selected from citric, adipic, succinic, glutaric, maleic, their salts or mixtures thereof and e / an amount of base sufficient to bring the pH of the composition to within the range of 3.14 to 4.9.