HU217448B - General purpose aqueous cleaning composition - Google Patents

Abstract

The aqueous cleaning agent according to the invention contains a) 1-40% by weight of anionic, surfactant system containing surfactants other than alkali metal salts of fatty acids, b) 0.1-5% by weight of 10-22 carbon atoms, monovalent fatty acids, c) 1-30% by weight of eyelash solvent, d ) contains 1-10% by weight polycarboxylic acid or a salt formed with it and e) base, and whose pH is lower than 6. ŕ

Description

FIELD OF THE INVENTION The present invention relates to aqueous detergents, and more particularly to aqueous detergents for general household use.

General purpose household cleaners are commercially available in both powder and liquid form.

Powdered cleaners are mainly composed of systemic or buffering salts such as phosphates, carbonates, silicates and the like. However, the inorganic soiling of such formulations may have a poor cleaning performance against organic impurities such as calcium and / or magnesium salts and fatty or oily impurities typically found in the household. Such formulations are usually solutions buffered by the system builder to alkaline ρΗ. It is generally assumed that the alkaline pH is favorable for the removal of free fatty acids by converting the fatty acids into a suitable soap.

Liquid cleaners generally contain an organic solvent and have the great advantage that they can be applied to solid surfaces when diluted or concentrated, so that relatively high concentrations of surfactant and organic solvent are directly applied to the impurities. These liquid compositions are particularly useful for cleaning solid surfaces such as floors and walls, kitchen or bathroom surfaces, and soft coverings such as upholstery, carpets, curtains and the like. Generally, these formulations are buffered with an alkaline pH, although neutral formulations are known, and some acidic formulations have been marketed, particularly in the form of bathroom cleaners.

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

Surfactants used in commercially available general-purpose cleaners generally contain linear alkylbenzene sulfonates (ABS) and / or secondary alkane sulfonates (SAS).

The incorporation of certain surfactants into such solvent / water formulations does not cause any difficulty when these surfactants are present in relatively low concentrations. EP 0344 847 discloses formulations containing up to 5% by weight of butoxypropanol solvents together with the sodium salt of (C8-C18 straight chain alkyl) benzenesulfonic acid.

Linear alkyl benzene sulfonates, in a mixture of alcohol ethoxylates and optionally small amounts of aliphatic soaps, form the surfactant system used in many successful liquid alkaline commercial products having a pH of 8-11.

In addition to removing greasy / oily soils, it is desirable that household cleaners be able to remove limescale. Limestone is predominantly composed of calcium and magnesium carbonates, which are present in varying amounts in the corresponding hydrocarbonates in natural waters and form carbonates by crystallization or disproportionation. Carbonates are known to be soluble in acidic solutions. However, for the above reasons, acidic formulations are believed to be less effective than alkaline formulations.

A further major technical difficulty with such formulations is that the most commonly used surfactants are less biodegradable and, consequently, less preferred than other surfactant systems from the environmental point of view.

In particular, primary alcohol sulfate (hereinafter "PASS") is an environmentally desirable anionic surfactant due to its readily biodegradable relative to linear alkylbenzene sulfonates and secondary alkanesulfonates, and because of the presence of naturally occurring substances such as coconut oil and other vegetable oils. from its source.

A mixture of primary alcohol sulfate compounds of formula (I)

RO-SO3X (I) wherein

R is a C8-C18 primary alkyl group and X is a solubilizing cation.

Suitable cations are sodium, magnesium, potassium and ammonium ions, TEA and mixtures thereof.

The use of the salts of PÁS known in the art with other surfactants.

EP 125 711 discloses a general purpose detergent comprising nonionic anionic (e.g., Mg-PAS) and partially esterified resin.

GB-2 160 887 discloses a general purpose cleaner comprising a solvent, anionic materials including alkali metal, magnesium, ammonium and TEAPAS salts, and 0.005-3.0% by weight of a non-ionic substance which is a water-insoluble nonionic substance 75- 100% by weight. The most preferred anionic surfactant is the sodium salt of lauryl sulphate _(Na-C12 PAS).

GB-2 144763 relates to a detergent in the form of a microemulsion containing at least 5% solvent and a magnesium salt. Preferred compositions include mixtures of nonionic surfactants, paraffin sulfonates, alkyl sulfates (PAHs), ethoxylated phenols, and ethoxylated alcohols.

EP 107946 (for dishwashers) discloses a liquid detergent comprising 6-18% Mg-PAS together with water-soluble C13-C18 alkane or alkene sulfonate and water-soluble alkyl ether sulfate.

The above-mentioned ABS, SAS and PÁS surfactants are highly effective foaming surfactants. While the formation of foam is desirable for many laundry products, such as shampoo and bar soap, the presence of foam in machine wash and surface cleaning operations is often undesirable since removal of foam after the cleaning operation may be difficult. For this purpose, antifoam agents were incorporated into the compositions. Calcium soaps, ie calcium salts of fatty acids, are known antifoam components in machine wash formulations and for cleaning solid surfaces2

EN 217 448 Β. GB-1 099 562 discloses the use of a combination of hydrocarbons and calcium-sensitive fatty acid soaps as an antifoam system for powder formulations. The cited disclosure discloses detergent compositions comprising anionic sulfate or sulfonate detergents, alkaline polyphosphates, and a "defoamer" mixture of hydrocarbons and C12-C31 fatty acids. Hydrocarbons are broadly defined to include straight or branched chain alkanes (1: 1 mixture of liquid paraffin oils with boiling point> 90 ° C, high melting point paraffin waxes), alkenes, alkylated benzene, anthracene and condensed aromatic compounds such as naphtha alkylated derivatives thereof; and alicyclic hydrocarbons such as terpines and the like. Preferred hydrocarbons include boiling points above 90 ° C, such as paraffin oils and waxes, dodecylbenzene and turpentine oil as mentioned above.

EP 0080 749 discloses the use of a combination of solvents, soaps and selected terpene solvents as antifoam systems in liquid compositions for cleaning solid surfaces. In contrast to, among other things, carpet cleaning compositions, it is preferred in these formulations that the product can be used as desired without the addition of a separate antifoam ingredient.

More specifically, EP 0 080 749 teaches the use of terpenes containing monoquetic isoprene units) or sesqui (containing three isoprene units) with a specific solvent [2- (2-butoxyethoxy) -ethanol commercially available as BUTYL CARE] as an antifoam system, 0.05 to 2% by weight of C 13 -C 24 fatty acids with at least one alkali, ammonium and / or alkanol ammonium soap. According to the cited quotation, these three components interact with each other for antifoaming effect.

According to the above literature, the preferred terpenes among the hydrocarbon-type terpenes are the mono- and bicyclic terpenes, such as terpinene, terpinolene, limonene, pinene and so-called orange terpene, which can be obtained from orange peel. Other terpenes, including terpene alcohols, aldehydes and ketones, are less preferred.

The general disadvantage of terpenes and their related compounds is that they are relatively expensive raw materials, have a pungent odor and generally give the products a pine or lemon scent. It is desirable to have a basic odorless or odorless formulation of detergents. In addition, terpenes may contain traces of so-called "musk xylenes", which have been questioned about the physiological acceptability of these substances.

Products used as bathroom cleaners are expected to form a relatively stable, sticky foam during the initial stages of cleaning. This foam visibly indicates the parts of the surface to which the detergent has already been applied. More importantly, adhesion of the foam to the surface prevents the detergent from running, thereby reducing the amount of desired surfactant containing product and consequently reducing both the cost and the amount of surfactant released into the environment. However, for ease of use and water preservation, it is desirable that the composition be rinsed with as little water and labor as possible.

In view of all of the above, it can be seen that when applied to surfaces, an ideal household cleanser produces a relatively stable foam which disappears rapidly when rinsed from the surface. Such formulations must not contain any components that are environmentally or physiologically unacceptable and may not require the addition of special antifoam components to the rinse water. Although special detergents to meet the specific needs discussed herein have been commercialized or proposed in the literature, there is a need for a general purpose detergent that has the effect of acidic detergents on limescale, but is effective against many varieties of impurities.

Certain fatty acids have been found to have an antifoaming effect in certain concentrated formulations, but when diluted with slightly alkaline water, they have an antifoaming effect. These fatty acids, in combination with polyhydric carboxylic acids, solvents and surfactants at acidic pH, result in substantially simplified component combinations that exhibit excellent cleaning performance and excellent rinsability for a wide range of impurities.

In view of the above, the present invention is an aqueous cleanser which is related to the composition

a) from 1 to 40% by weight of an anionic surfactant system other than an alkali metal salt of a fatty acid,

b) 0.1 to 5% by weight of monovalent fatty acids having from 10 to 22 carbon atoms,

c) 1 to 30% by weight of a semipolar solvent,

(d) from 1 to 10% by weight of polyhydric carboxylic acids or their salts; and

(e) it contains a base and has a pH of less than 6.

As stated above, fatty acids having from 10 to 22 carbon atoms in the detergent according to the present invention have surprisingly antifoaming effect. This is due to the increased adhesion of the foam to oblique or vertical surfaces. The cleaning agents of the invention are therefore particularly suitable for cleaning solid surfaces.

Without adhering to the mechanism of action, it is believed that foaming enhancement can be observed at a pH below _the pKa value of the monovalent fatty acid. In practice, it is difficult to determine _the exact pK _{a of} a fatty acid since under these conditions the fatty acids are not water soluble, although titration gives a good approximation of the pK a. It is also assumed that the pH of the formulation should exceed the polyvalent carbon 3

GB 217,448 Β acid lowest pK _a -value to the polyvalent carboxylic acid partially ionised form.

Domestic drinking water generally contains a certain amount of dissolved calcium from minerals, usually in the range of 20-400 ppm (2-40 French hardness). Waters with a higher calcium content are known, but are relatively rare.

Domestic drinking water is slightly alkaline and has a pH greater than 7.5, typically around 8, due in principle to the naturally occurring dissolved bicarbonate in the water. In some exceptional cases, alkali-forming components, such as calcium oxide, are added to the tap water to neutralize acidic waters and thereby prevent the dissolution of lead and other potentially toxic metals from pipes and fittings.

When multiple volumes of calcium-containing domestic drinking water are added to the detergent according to the invention, the alkalinity of the water is expected to raise the pH of the initially acidic system above _the pKa of the fatty acid and cause dissociation of the fatty acid. . This precipitate is known to have an antifoaming effect and consequently aids in rinsing the product.

solvents

Semi-polar solvents are essential components of the cleaning compositions of the invention. As will be demonstrated in the examples below, the presence of a solvent enables the antifoaming effect of the fatty acid in an acid solution and the antifoaming effect of the fatty acid in an alkaline solution.

Preferred solvents have a dielectric constant of 5-35.

Preferred solvents are: propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, dipropylene glycol mono-tert-butyl ether, diethylene glycol hexyl ether, acetate, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and mixtures thereof.

Thus, glycol ether solvents such as propylene glycol mono-n-butyl ether (commercially available as Dowanol PnB) and diethylene glycol monobutyl ether (commercially available as Butyl Digol or Butyl Carbitol) are preferred solvents. These solvents are particularly advantageous in terms of cost, availability and safety. It has been found that such a choice of solvents for ink and dyes enhances cleaning performance, increases product stability, and improves foam-free behavior during rinsing.

The weight ratio of total surfactant to solvent is preferably in the range 1: 1 to 10: 1, more preferably 2: 1 to 5: 1. A narrower range is advantageous in terms of cost and product stability. In order to obtain an effective solvent concentration during dilution of the concentrate, the typical solvent content of the composition is 1 to 30% by weight, preferably 2 to 20% by weight.

buffers

Buffers are an essential component of the compositions of the invention.

The presence of a buffer is believed to be essential to ensure that the pH of the undiluted composition in the acidic range remains below _the pK _{a of} the fatty acid. However, the pH must not be buffered so strongly that too much water is required to bring the pH above _the pK _{a of} the fatty acid.

In addition, while highly acidic solutions should be avoided to reduce damage to the surfaces to be cleaned, some acidity reserve is required to prevent foam from becoming rapidly unstable due to the formation of insoluble calcium soaps, thereby reducing the descaling effect of the formulation.

A preferred buffer system comprises a polyvalent carboxylic acid and a base, which may be ammonium or alkali metal hydroxide and / or an organic amine. Ammonium hydroxide is particularly advantageous as it aids in the removal of foam formed from calcium soap, although sodium hydroxide also produces good results. The above system preferably buffers the product to a pH of 2 to 6.

Preferably, the buffer system is such that at least 10 times the volume of water is added to the product to achieve a pK _{a of} the fatty acid. The amount of water required to raise the pH above pK _{a is} , to some extent, influenced by the alkalinity and hardness of the added water.

Typically, for a surfactant content of 4-6% by weight of the product, the buffer system is selected such that the pH is higher than the pK _a of the fatty acid when water is added at a volume less than 1000 times.

Particularly preferred products have a pH range of 3.14 to 4.9, most preferably about pH 4, since certain enamels are sensitive to pH less than 3, and low pH products may require too much water due to the low alkalinity of the formulation. to neutralize with water. It provides better foaming when the polyhydric carboxylic acids are present in the form of salts than they are in the form of an acid, so that the pH of the formulation preferably exceeds the lowest pK a of _the polyhydric carboxylic acid present. Citric acid - preferably the polyvalent carboxylic acid - pK _a -values of 3.14, 4.77 and 6.39 and consequently pH above 3.14 are advantageous.

complexing

The essential components of the compositions of the invention are the weak complexing agents present in the form of organic polyhydric carboxylic acids, the presence of which increases the purification efficiency. These components convert weakly bound calcium ions into complex compounds, which play a role in the adhesion of the contaminant to the surface and thus facilitate the removal of these contaminants.

Strong complexing agents may also be present in the composition. However, for environmental reasons, EDTA and similar complexing agents are less advantageous in that such slow biodegradable complexing agents can solubilize heavy metals deposited at the bottom of rivers. In addition, EDTA and other strong complexing agents tend to form compounds complexed with calcium present in domestic drinking water and to inhibit the formation of the foam-inhibiting calcium soap discussed above.

Preferred complexing agents are citric acid, adipic acid, succinic acid, maleic acid, glutaric acid, mixtures of these acids and

HU 217 448 Β salts. The usual amount of complexing agent is 1-10% by weight, preferably 3-6% by weight of the product.

Most preferably, the complexing agent is citric acid or salts thereof. Citric acid is available from renewable sources as a weak complexing agent for calcium and is rapidly biodegradable.

Citric acid is particularly preferred both as a complexing agent and as a component of the buffer system, preferably in an amount of 3-6% by weight of the product.

fatty acids

C 10 -C 22 fatty acids are an essential component of the composition of the invention.

Shorter-chain fatty acids would not be sufficiently insoluble in calcium soaps, and longer-chain fatty acids would be too insoluble in the formulation to act as an antifoam component. In addition, these short-chain fatty acids are commercially available at a reasonable price and are derived from renewable sources.

The fatty acids may be straight or branched chain saturated or unsaturated compounds, but straight-chain fatty acids of natural origin are preferred.

Particularly preferred are straight chain fatty acids having an average chain length of 12 to 16 carbon atoms, more preferably 14 carbon atoms (which may be prepared from lauric acid oils such as coconut and palm kernel fats). Longer chain soaps are poorly soluble without expensive hydrotropic compounds or organic solvents.

The product generally contains from 0.1 to 5% by weight, preferably from 0.1 to 3% by weight, particularly preferably from 0.5 to 1% by weight of fatty acids.

It is important that the pH of the formulation is lower than the pK a of _the fatty acid used. The pK _{a of C} 12 -C 16 fatty acids is generally close to 4.9 and consequently the pH of the formulations will be lower. In view of the fact that the pH exceeds the pK _a polyvalent carboxylic acid Rf, the pH of the composition is generally in the range 3.14-4.9.

Surfactants

An essential component of the compositions of the invention is at least one anionic surfactant other than soap.

The surfactant comprises at least one compound of primary and secondary alcohol sulfates, alcohol alkoxysulfates, primary and secondary alkanesulfonates, and alkylarylsulfonates. Without the anionic surfactant, the compositions of the invention exhibit less effective adhesion.

The ratio of fatty acid to anionic surfactant in the product, expressed as a ratio by weight of the components, is preferably from 1: 4 to 1:20, particularly preferably from 1: 5 to 1:10. Thus, a favorable balance between foaming and cleaning ability is achieved.

Preferably, the anionic surfactant is primary alcohol sulfate (PAS), which is a highly foaming, readily biodegradable surfactant.

The preferred primary alcohol sulfate is a mixture of compounds of formula I

RO-SO ₃ X (I) wherein

R is a C8-C18 primary alkyl group and X is a solubilizing cation.

Suitable cations include sodium, magnesium, potassium and ammonium ions, and mixtures thereof.

It has been found that formulations containing magnesium PAS and an organic acid partially neutralized with a base exhibit improved cleaning performance, particularly with respect to lime soaps and limescale, while retaining their cleaning effectiveness against fatty and oily impurities. Consequently, particularly preferred embodiments of the invention contain from 0.1 to 0.8 moles of magnesium per mole of primary alcohol sulfate.

It should be noted that the use of magnesium alone as a counter ion to the PAS can lead to difficulties in the presence of polyvalent carboxylic acid, so it is preferable that the ratio of magnesium to other counterions for PAS counterions does not exceed 5: 1. The MgPAS: NaPAS ratio is preferably in the range 1: 1-2: 1.

Particularly preferred are the PASS molecules which predominantly contain a C 10 -C 14 alkyl group.

As noted above, these surfactants may be prepared from primary sources of primary alcohol sulfate from fatty acids derived from coconut oil, but may also be prepared from synthetic alcohol. These surfactants exhibit very favorable behavior in terms of biodegradation.

Suitable additional surfactants are selected from cationic, nonionic, amphoteric and inner salt surfactants, and mixtures thereof.

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

R [- (OCH ₂ CH ₂ ) _m -OH (II) wherein

R 1 represents a straight or branched alkyl or hydroxyalkyl group containing from 8 to 18 carbon atoms and m represents the average degree of ethoxylation of

-14, preferably 3-10 for good lipolytic activity.

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

Most preferably, the surfactant system comprises a mixture of primary alcohol sulfates and alkoxylated alcohols. As used herein, alkoxylated alcohols include alkyl or hydroxyalkyl derivatives of ethoxylated alcohols.

In the compositions of the invention, the weight ratio of primary alcohol sulfates to alkoxylated alcohols is preferably from 3: 1 to 1: 1, particularly preferably about 2: 1.

Particularly preferred formulations contain from 15 to 30% by weight of primary alcohol sulfate and from 5 to 15% by weight of nonionic surfactant. The PAS and the non-ionic

Such relatively high concentrations of surfactant are desirable to provide concentrated formulations that are more economically transportable and require less packaging.

The total amount of surfactant is preferably 1-40% by weight of the product, while the non-concentrated composition for household use preferably contains 2-10% by weight of the surfactant. In the case of concentrates, 20-40% by weight, preferably 25-35% by weight, of surfactant is preferred, although additional antifoam components may be required at the highest concentrations of surfactant.

Used in small quantities and other ingredients

The compositions of the invention may also contain other minor components, such as perfume additives, pigments and dyes, hygiene agents, viscosity modifying additives, and mixtures thereof. In certain embodiments of the invention, additional foaming agents are useful in the formulation.

Other foaming agents are preferably hydrophobic oils. The hydrophobic oil is more preferably a straight or branched hydrocarbon or silicone oil, the hydrophobic oil is more preferably a paraffinic oil.

Most preferably, the hydrophobic oil is a paraffinic oil having a boiling point with a loss of 50% by weight in the range of 170-300 ° C. By "boiling point" with a loss of 50% by weight, it is understood that within this temperature range, 50% by weight of paraffin can be removed by distillation. Suitable paraffin formulations for use in the compositions of the present invention generally have a boiling range of 171 ° C to 250 ° C. It has been found that isoparaffins, i.e. branched paraffins, are particularly effective when compared to other hydrophobic oils such as n-decane and n-tetradecane.

In the embodiments of the invention, the solubilized hydrophobic oil generally contains from 0.2 to 5% by weight, preferably from 1.0 to 2.0% by weight. If a hydrophobic oil is present, the preferred weight ratio of fatty acid to hydrophobic oil is 0.5-1: 1-0.5, preferably about 1: 1. These ratios provide a particularly effective antifoam system.

The compositions of the present invention are preferably homogeneous, more preferably translucent, most preferably transparent. Typical viscosity at 25 ° C at a shear rate of 21 S measured in a ¹ 1 to 2000 mPas.

Stripping

The compositions of the present invention are preferably packaged in a package that provides a spray, preferably a foam, of the product, although other delivery and delivery systems are not excluded.

In view of all of the above considerations, the present invention is an acidic aqueous cleanser comprising:

a) from 2 to 40% by weight of a surfactant comprising a primary alcohol sulfate and preferably at least one nonionic surfactant, wherein at least 50% by weight of the surfactant is a primary alcohol sulfate,

b) 0.2-5% by weight of a C10-C18 straight chain fatty acid in an acidic medium as an antifoaming agent in an alkaline medium,

c) at least one solvent selected from glycol ether and C 1 -C 5 alcohols, wherein the weight ratio of surfactant to solvent is from 1: 1 to 10: 1,

d) 1-10% by weight of water-soluble organic acid as citric acid, adipic acid, succinic acid, glutaric acid, maleic acid, salts thereof or mixtures thereof as a complexing agent for calcium and magnesium and as a buffering agent; and

e) an appropriate base to provide a pH of the detergent in the range of 3.14 to 4.9.

The invention is further illustrated by the following examples, with reference to the accompanying drawings.

Figure 1 shows the effect of formulation with water of varying hardness for rinsing to reduce the volume of foam.

Figure 2 shows the effect of pH on foam volume for water of varying hardness.

The abbreviations used in the figures are explained below.

11 'FH: 11 French hardness water (of Wirral origin)

26 'FH: 26 French hardness (of Prenton origin) 48' FH: 48 French hardness (of Haubourdin origin)

1-2. example

The formulations of Table 1 were prepared (data by weight). All components were mixed at room temperature and filled into a pressurized spray bottle. The nonionic surfactant was DOBANOL 23-6.5 EO (manufactured by SHELL) and PÁS DACPON-27L (manufactured by DAC). Butyl Carbitol is a registered trademark of Union Carbide. The fatty acid was sold under the tradename PRIFAC 7901 (manufactured by Unichema).

Table 1

Example 1 Example 2 Citric acid 4.00 4.00 PAS 4.00 4.00 (Anionic) Non-ionic 2.00 2.00 Butyl Carbitol 2.00 2.00 (solvent) perfumes 0.50 0.50 NaOH 1.20 1.20 preservatives 0,015 0,015 Fatty acid - 0.5 Water 100% 100% PH 4.3 4.3 Adhesion 2.7 3.6

HU 217 448 Β

The suitability of the formulations was determined by spraying the products on a non-horizontal surface and rinsing with hard water (generally above 26 French degrees of hardness). Adhesion was determined by 20 skilled technicians by placing the coded test samples on a scale of 1 to 5, where 1 indicates poor adhesion and 5 excellent adhesion.

In Example 1, a commercially available product was selected for comparative study; the suitability of this product was good.

In Example 2, the formulation of the present invention was selected which resulted in a larger volume and adhesive foam which was particularly effective in adhering to oblique or vertical surfaces. As long as it is

The comparative composition of Example 1 exhibited acceptable adhesion and was easy to rinse, the composition of the present invention used in Example 2 showed increased adhesion and was extremely easy to rinse.

3-8. examples

Figure 1 shows the effect of formulation on the number of rinses required to reduce foam volume with water of varying hardness.

For the measurements, 5 g of the product was diluted in a 50 ml graduated separatory funnel of water of specified hardness, the stopcock of which was closed. The funnel was shaken vigorously by hand for 10 seconds to produce foam, and the initial foam volume was recorded after the excess liquid was drained through the tap. For each rinse, 50 mL of water was used, which was added to a separatory funnel for an additional shaking cycle, and the foam volume was determined after removing the liquid. This procedure was repeated until no foam remained. The formulations of Examples 1 and 2 were used in the tests at 0.5% by weight of fatty acids.

It can be seen from the figure that the addition of fatty acids to the comparative formulation resulted in a reduction in the number of rinsing cycles required, and the improvement was more pronounced for hard waters.

Figure 2 shows the effect of pH on the foam volume for waters of different hardness. In this case, pH is the pH of the liquid obtained during the above rinsing cycles. The results show that the pH of the liquid increases with the rinsing process. It can also be seen that the effect of fatty acids is extremely significant in the case of exceptionally high calcium water. For more common waters, the foam volume decreases rapidly when the pH is raised from 4-5 to over 6.5 when diluted with 10 times the original product.

From the examples above, it can be seen that, compared to a known composition, the composition of the present invention exemplified has increased foam adhesion and at the same time improved rinsability.

9-15. examples

Table 2 shows data for the compositions of Example 2 wherein the average chain length of the fatty acid varies from 8 to 22 (C8-C22) needles. For comparison, data for the composition of Example 1 are provided without the use of fatty acids. 3-8 described above. The cumulative foam volume (CFV) was measured in cm ^{3 to a} standardized initial volume of ¹⁵ units. The cumulative foam volume represents the total volume of foam generated in the flushing process using 26 French hardness water. The number of rinses required to remove the foam was determined as described above.

Table 2

Pclda number Fatty acid CFV rinse number 9th Example 1 4950 9.5 10th C8 3025 8.5 11th CIO 2400 8.0 12th C12 2525 5.0 13th C14 400 4.0 14th C18 375 6.0 15th C22 975 6.0

From the above data it can be seen that fatty acids with a chain length of more than 12 carbon atoms significantly reduce CFV. It is noted that fatty acids having a chain length of more than 22 carbon atoms were insoluble in the composition.

16-19. examples

The data in Table 3 illustrate the effect of the complexing agent type, where the complexing agent type was varied in the presence and absence of fatty acid (FA). 3-8 described above. cumulative foam volume to a standardized initial volume in cm ^{3 was} determined. The cumulative foam volume represents the total volume of foam generated in the flushing process using 26 French hardness water. The number of rinses required to remove the foam was determined as described above. (% In the table refers to% by weight.)

Table 3

Pclda number Fatty acid Citrate EDTA CFV Number of rinses 16th - (Example 1) 4% - 3800 8.5 17th 0.5% (Example 2) 4% - 3375 5.5 18th - - 4% 3850 7.5 19th 0.5% - 4% 3400 5.5

HU 217 448 Β

From the data in Table 3, it can be seen that the composition containing fatty acid and complexing agent gives better results.

20-26. examples

The data in Table 4 illustrate the effect of pH. As described above, cumulative foam volume and rinsability were investigated using 12 and 26 French hardness water. The results are generally reported for water of French hardness 26, although similar results were obtained for softer water (Examples 25 and 26). Examples 20, 22 and 23 are comparative examples. % In the table refers to% by weight.)

Table 4

Example number Fatty acid PH CFV rinse number 20th (Example 1) 4.3 3800 8.5 21st 0.5% (Example 2) 4.3 3375 5.5 22nd - 10.5 3625 9.0 23rd 0.5% 10.5 1400 3.0 24th 0.5% C. 2.5 2325 5.5 25th 0.5% 4.3 3400 6.0 26th 0.5% C. 2.5 5100 9.0

The above data show that the antifoaming effect of fatty acid in alkaline products is very pronounced. However, these alkaline formulations do not effectively remove limescale. Examples 24 and 26 show the effect of removing the alkaline buffer component (NaOH) from the formulation. The composition of Example 24 exhibits similar behavior in hard water to the composition of the present invention, but is too acidic to be used on certain surfaces. Examples 25 and 26 with softer water at 12 French degrees of hardness show that the compositions of the invention (Example 25) can be rinsed in an acceptable manner, while without the alkaline buffer component (Example 26) there is little antifoaming.

It is further noted that the foam formed from formulations having a pH of about 2.5 was slightly adherent and the purification efficiency was poor.

27-30. examples

27-30 shown in Table 5. Examples 1 to 4 show a synergistic interaction between the solvent and the antifoaming fatty acid. The results were obtained as described above.

Table 5

Example number FA Solvent CFV rinse number 27th - (Example 1) 2% 3800 8.5 28th 0.5% (Example 2) 2% 3375 5.5 29th - - 2325 7.0 30th 0.5% - 2750 7.0

From the above results it can be seen that the presence of a solvent is essential for the fatty acid to exert antifoaming effect upon dilution. Without solvent (Comparative Examples 29 and 30), little foam was obtained with poor adhesion. In the presence of a solvent, the foam stabilized when fatty acid was omitted (Comparative Example 27). Only in the presence of fatty acid and solvent do the advantages of high initial foam volume and rapid rinsing occur (Example 28).

31-36. examples

31-36 in Table 6. Examples 1 to 4 show the synergistic effect of changes in the surfactant system on product properties. The results were obtained as described above using 26 French hardness water.

Table 6

Pclda FA anionic Non-ionic CFV rinse number surfactant number 31st - (Example 1) 4% 2% 3800 8.5 32nd 0.5% (Example 2) 4% 2% 3375 5.5 33rd - - 2% 150 3.0 34th 0.5% - 2% 0 0.0 35th - 4% - 4700 7.0 36th 0, 5% 4% - 3900 4.5

Comparative Examples 33 and 34 show that, with or without anionic surfactant, little or no foam is formed, which allows the product to quickly run off sloping surfaces during cleaning operations. Examples 35 and 36 show the effect of omitting the nonionic surfactant optionally used in embodiments of the invention. Comparative Example 35 shows that nonionic surfactants exhibit some antifoaming activity, but their presence increases the rinse time. These results show that while fatty acid and at least one additional anionic surfactant

The nonionic surfactant is an optional component.

37-39. examples

37-39 below. Examples (see Table 7) compare the suitability of the formulations of the present invention with commercial formulations.

Table 7

Pclda number 37th 38th 39th Magnesium PAS 18.5 - - PÁS (sodium salt) - 3.5 - SAS (sodium salt) - - 4.0 Non-ionic 9.5 - 4.0 Solvent 8.0 - - Fatty acid 0.7 - - isoparaffin 0.75 - - ammonium L1 0.75 - Organic acid 6.0 6.0 6.2 Small amount of creators traces traces traces Water 100% 100% 100% pH 4.0 acidic acidic Contamination / contact time Kitchen dirt 15 s 4 3 2 fat Contamination 15 sec 3 3 3 30 sec 3 3 3 60 sec 4 4 3 Soap foam 180 s 3 1 0 240 sec 4 2 1

Table 7 shows two comparative examples (Examples 38 and 39) of the currently available acidic bathroom cleaners. These formulations were obtained by analysis. In the composition of Example 39, the organic acids were a mixture of succinic acid, glutaric acid, adipic acid and benzoic acid, amounting to 6.2% by weight. In Examples 37 and 38, citric acid was used. The composition of Example 38 is noticeably different from the composition of the present invention in that it does not use the magnesium salt of PAH and is free of fatty acids or solvents.

37-39. For the preparation of the compositions of Examples 1 to 4, contaminated tiles were prepared which were coated with synthetic soap, grease and kitchen dirt. For the purpose of visualization, each contaminant contained visible soot.

The soap foam was essentially calcium stearate, which was applied by spraying a suspension of calcium stearate in isopropyl alcohol onto an enameled steel sheet. After application of the impurities, the samples were heat-treated at 180 ° C for 30 minutes.

The grease impurity consisted of a mixture of fatty acids and paraffin applied to the ceramic tiles by spraying the composition in light petroleum.

The kitchen dirt contained a mixture of fats, fatty acids, paraffin and clay, which was applied to the ceramic tiles by spraying the composition in light petroleum. To determine the efficacy of the composition, see Figures 37-39. Examples 1 to 5 were applied to the contaminated tiles in 0.5 ml and allowed to remain in contact with the tiles for the time indicated in Table 7. The tile was then mechanically wiped with a clean, damp cloth that was used once at a specified pressure. Residual impurities were visually determined using a 0-5 scale of 0-5, where 0 indicates no dirt was removed, and 5 indicates complete removal of dirt as indicated by the removal of soot.

From the above results it can be seen that the compositions of the present invention are equivalent to known compositions for the removal of grease impurities, but far superior to those for kitchen impurities and especially soap foam.

39-43. examples

39-43 in Table 8. In the examples, the effect of the change in Mg: Na ratio at high concentrations is shown as counterions of the PÁS surfactant. All of the exemplary formulations were similar to the formulation of Example 37 except that the Mg: Na ratio of the PAS surfactant was varied.

Table 8

Example number MgPAS NaPAS 39th 10.5: 8.0 stabile 40th 11.0: 7.5 stabile 41st 18.5: 0.0 unstable 42nd 17.7: 1.0 unstable 43rd 15.0: 3.5 unstable

41-43. In Examples 1 to 4, magnesium citrate was precipitated from the product during prolonged storage, while the compositions of Examples 39 and 40 were stable in storage. 41-43. The formulations of Examples 1 to 4 were otherwise acceptable.

Claims (21)

An aqueous detergent, characterized in that it relates to the composition a) from 1 to 40% by weight of an anionic surfactant system other than an alkali metal salt of a fatty acid, HU 217 448 Β b) 0.1 to 5% by weight of monovalent fatty acids having from 10 to 22 carbon atoms, c) 30% by weight of a semipolar solvent, (d) from 1 to 10% by weight of polyhydric carboxylic acids or their salts; and (e) it contains a base and has a pH of less than 6. Cleaning agent according to claim 1, characterized in that it contains a semi-polar solvent having a dielectric constant of 5 to 35. The detergent according to claim 1, wherein the semipolar solvent is propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, dipropylene glycol mono-tert-butyl ether. , diethylene glycol hexyl ether, ethyl acetate, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or a mixture thereof. 4. The cleaning agent of claim 3, wherein the semipolar solvent comprises glycol ether. 5. A detergent composition according to claim 4 wherein the semipolar solvent is propylene glycol mono-n-butyl ether or diethylene glycol monobutyl ether. The detergent according to claim 1, characterized in that it contains from 1% to 30% by weight of the solvent. The detergent according to claim 6, characterized in that it contains a surfactant and solvent in a weight ratio of 2: 1 to 5: 1. 8. A detergent composition according to claim 1, characterized in that it contains from 1 to 10% by weight of polyvalent carboxylic acid or a salt thereof. Cleansing agent according to claim 8, characterized in that the polyvalent carboxylic acid comprises citric acid, adipic acid, succinic acid, maleic acid, glutaric acid, salts thereof or a mixture of these acids and their salts. 10. The detergent composition of claim 1, wherein it has an acidity content such that at least 10 volumes of water having a pH of at least 7.5 are added to one volume of the product to a pH greater than the pK _a of the monovalent carboxylic acid. 11. A detergent composition according to claim 1, characterized in that it has an acidity content such that at least 1000 volumes of water having a pH of at least 7.5 are added to one volume of the product and the pH is greater than the pK _a of the monovalent carboxylic acid. 12. The cleaning agent of claim 1, wherein the detergent has a pH in the range of 3.14 to 4.9. 13. The detergent composition of claim 1, wherein the product contains from 0.1 to 3% by weight of a monovalent fatty acid. Cleaning agent according to claim 1, characterized in that the at least one anionic surfactant is primary and / or secondary alcohol sulfate (s), alcohol ethoxysulfate (s), primary and / or secondary alkane sulfonate (s). or an alkylaryl sulfonate (s) or a mixture thereof. 15. The detergent composition of claim 1, further comprising a nonionic surfactant. 16. The detergent composition of claim 1, wherein the surfactant is selected from the group consisting of primary alcohol sulfate or alkylbenzene sulfonate and alkoxylated alcohol in a weight ratio of 3: 1 to 1: 1. The detergent according to claim 1, characterized in that it contains monovalent fatty acids and anionic surfactants in a weight ratio of 1: 4 to 1:20. 18. The detergent composition of claim 1, wherein the detergent comprises from 2% to 10% by weight of the total surfactant. 19. The detergent composition of claim 1, wherein the detergent comprises 20-40% by weight of the total surfactant. 20. The cleaning agent of claim 1, wherein the product is packaged in a spray package. A detergent according to claim 1, characterized in that it comprises the following components: a) from 2 to 40% by weight of a surfactant comprising a primary alcohol sulfate and preferably at least one nonionic surfactant, wherein at least 50% by weight of the surfactant is a primary alcohol sulfate, b) 0.2-5% by weight of straight chain fatty acids having from 10 to 18 carbon atoms, c) at least one solvent selected from glycol ether and C 1 -C 5 alcohols, wherein the weight ratio of surfactant to solvent is from 1: 1 to 10: 1, d) 1-10% by weight of polyvalent carboxylic acid, citric acid, adipic acid, succinic acid, glutaric acid, maleic acid, salts thereof or mixtures thereof; and e) an appropriate base to provide a pH of the detergent in the range of 3.14 to 4.9.