SK218492A3 - Cleaning agent and the method of its preparation - Google Patents

Abstract

Problems of stability have bedeviled formulations of aqueous, liquid abrasive cleaning compositions comprising soluble abrasive particles. One factor which can influence the stability of aqueous compositions is the high level of electrolyte present in the compositions: ie. the soluble abrasive is typically immersed in an aqueous medium which is saturated with respect to that abrasive in solution. The electrolyte level varies with temperature and this can have detrimental effects on the product. We have now determined that these problems can be overcome by use of an essentially hydrophobic perfume composition as a stability enhancer in a pourable, aqueous, hard surface cleaning composition comprising water-soluble abrasive. Consequently, the present invention provides a pourable, aqueous, hard-surface cleaning composition comprising a water soluble abrasive, at least part of the abrasive being present as undissolved particles having a mean particle diameter of from 10 to 500 microns, further comprising and essentially hydrophobic perfume composition and a detergent, said composition remaining stable after storage at 37°C for twelve weeks or remaining stable after twelve temperature cycles from -5°C for eight hours to 25°C for sixteen hours.

Description

(57) A cleaning composition intended for cleaning water-based hard surfaces in a liquid state comprises a water-soluble abrasive, at least a portion of which is present in the form of insoluble particles having an average diameter of 10 to 500 µm, at 20 ° C of composition it contains at least 5% by weight of insoluble particles. The composition further comprises a hydrophobic perfume and a wetting agent, typically a mixture of a nonionic and anionic wetting agent. In use, the composition does not leave scratches and, after cleaning the surface, the remainder of the water-soluble salt can be easily removed with clean water.

μη Cleaning agents b i and t techniques

The present invention relates to a detergent composition in liquid form containing abrasive, homogeneous, aqueous surfactant and

- particulate abrasive composition, the composition is suitable for cleaning hard surfaces.

Liquid surfactant compositions for hard surface cleaning can be divided into several groups.

BACKGROUND OF THE INVENTION

One of our groups of hard surface cleaners is aqueous suspensions containing water-insoluble abrasive particles. These compositions may cause stability problems and may also cause the cleaned surface to lose gloss and scratch. They can also arise when rinsing the surface to be cleaned with water, since insoluble particles of abrasive material are usually difficult to remove completely. Other known compositions are liquid compositions which typically contain soap, nonionic surfactants, and non-abrasive particulate alkylbenzene sulfonates.

Liquid formulations of this second type do not act f

However, they have a number of disadvantages which can render consumers unacceptable. For example, they may not adequately clean surfaces that are very dirty, especially in the case of hard water because they do not contain abrasives. folder. In addition, the high concentration of wetting agent required to remove solidified fat may lead to excessive foam formation. so repeated rinsing of the surface is required. Though ^the:: and the formation of foam can be controlled to some degree by the addition of napŕíγί Example of solvents, hydrophobic silica and / or silicone or soap $, these substances may in themselves cause H, <

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- 2 the volatility of the product and its inhomogeneity and, moreover, problems arise from the depositing of insoluble residues on the surface cleaning with subsequent bands or spots after drying.

Another type of liquid surfactant composition has been proposed, for example, in EP 193375 (Unilever PLC, Unilever NV), a liquid aqueous composition containing abrasive and wetting agent, suitable for cleaning hard surfaces and containing water, 1.5 to 30% by weight of surfactant 6 to 45% by weight of a water-soluble salt, of which at least 5% by weight is present at 20 ° C in the form of undissolved particles having a mean diameter of 10 to 500 microns, the salt containing not more than one hydrated group as a crystalline solid in water at a temperature of 10 to 40 ° C in the aforesaid amount or more in a saturated solution at 40 ^° C is less than ten times the amount soluble at 10 ° C, the composition has a viscosity of at least 6500 Pas at 20 ° C; cut 3 x 10 x sec ~ l and maximum 10 pass and cut 21 sec EP 193375 thus describes an abrasive cleaner containing e a water-soluble abrasive in a saturated solution. In use, any undissolved water-soluble abrasive salts on the surface to be cleaned can be easily removed with clean water to dissolve the remaining salt. Accordingly, the composition of this patent can be easily removed from the surface to be cleaned.

Similar compositions containing high amounts of water-soluble salts have been described in US 4,179,414 (Mobil), but they are thick pastes and not liquid compositions. These products are suitable for some uses, but are generally unsuitable for domestic use, for example when the product is to be applied from a plastic container by means of a nozzle. In these products, paste stability is achieved by the interaction of sodium chloride with sodium bicarbonate and certain types of diethanolainides.

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Soluble abrasive compositions are also known in the art

C ⁽ 3 1 370 377 (Procter and Gambia), a non-aqueous, abrasive, concentrated abrasive surfactant suitable for washing dishes after dilution with water) containing a water-miscible liquid medium such as glycerol, a water-soluble solid particulate inorganic salt, sodium chloride, a solid anionic surfactant, and a suspension aid such as starch Other ingredients such as bactericides, enzymes, dyes and perfumes may be included.

^! U.S. Pat. 3,577,347 (Procter and

Gambia), a variety of abrasive agents are disclosed, typical compositions include sodium bicarbonate, sodium cetylbenzenesulfonate, chlorinated sodium phosphate, and perfume.

Further, for example, U.S. Pat. No. 4,057,506 (Colgate) discloses a sodium polyphosphate composition having a particle size that no longer causes scratching of the surface. These particles have a colloidal particle size, i.e. less than 1 µm, and are kept in suspension by means of an emulsifier.

'. For particulate hard surface cleaners, it must be ensured that the particles remain in the suspension formulation. In some groups, the surfactant also acts as a suspending agent, usually in combination with an electrolyte.

Wetting agents which may be used for this purpose in abrasive-containing liquid cleaning compositions are, for example, alkylbenzene sulfonates, alcohol ethoxylates, alkyl amidoethoxylates, aliphatic acid soaps and secondary alkyl sulfonates. Mixtures of these surfactants together with electrolytes may also be used to form a suspension.

The fine structure of these systems in suspension is usually: formed by spherical structures with a diameter of 0.05 to 10 micro-;

average to average. These structures appear to contain concentric

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- 4 layers in which the surfactant molecules alternate, separated by a thin layer of water. A suspension system is not merely a structure that can be formed by wetting agents in the presence of water. Micelles may also be formed which are viscous but not capable of forming particles in suspension. In addition, wetting agent and water compositions may be separated into two or more mixing phases with different physical properties.

In the case of liquid cleaners containing abrasives and wetting agents as a suspending system, it is important that the suspension is stable within the intended temperature range of use and that the abrasive particles remain in suspension for a variety of monitoring and use applications. It is also important to consider the possibility of the interaction of various other components with the surfactant, especially the electrolyte.

Despite the great attention paid to the stability problems, the compositions on the aqueous substrate containing the abrasive substances have low stability. One factor that can affect the stability of aqueous compositions is the high amount of electrolyte in the composition. The soluble abrasive composition is typically found in an aqueous medium saturated with the composition. However, the composition of the saturated solution is highly temperature dependent and the electrolyte concentration will vary depending upon storage and / or use conditions. These changes in electrolyte concentration may affect the stability of the suspension and, under certain conditions, cause instability of the compositions.

The only liquid formulation available on the market is a formulation containing soluble abrasive particles about 200 microns in size, but it is known that the product decomposes into individual storage phases and produces layers containing higher or lower amounts of particles as a result of the particles are suspended due to instability. This leads to the cleaning ability of the track, as it is not possible to empty the entire contents of the package.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid composition without the above disadvantages.

It has been found that all of the above problems can be overcome by using a substantially hydrophobic perfume as a stabilizer for water-based hard surface cleaners containing water-soluble abrasive particles.

Although perfumes have previously been added to said cleansing compositions, it has never been considered that these perfumes could increase the durability of such compositions.

The present invention provides a liquid aqueous hard surface cleaning composition comprising a water-soluble abrasive, at least a portion of which is in the form of undissolved particles having a mean diameter of 10 to 500 microns, the composition comprising a substantially hydrophobic perfume and a wetting agent. storage at 37 ° C for 12 weeks or after 12 cycles of temperature change, alternating 8 hours at -5 ° C and 16 hours at 25 ° C.

The amount of perfume used ranges from 0.1 to 10 hours by weight, based on the total weight of the compositions.

The water-soluble abrasive comprises at least one compound selected from sodium bicarbonate, potassium sulfate, sodium phosphate hexahydrate and sodium tetraborate decahydrate.

The water-soluble abrasive is preferably in an amount of 6 to 75 hours by weight based on the total amount of the composition.

Typically, the storage liquid is a stable, homogeneous, abrasive, wetting agent-containing aqueous composition suitable for cleaning hard surfaces containing water and inimoto.

(i) at least 0.1 ¾ by weight of a substantially hydrophobic perfume; (ii) 1.5 to 30% by weight of a surfactant; (iii) a water-soluble salt of which at 20 ° C is at least 5% by weight based on the total weight of the composition; the mean particle diameter is 10 to 50 microns, the salt contains at most one hydrated group in solid crystalline form in water at a temperature of 10 to 40 ° C in an amount in excess of that required to form a saturated solution; at a temperature of 40 ° C is less than ten times the solubility at 10 ° C and the solubility of the salt in water at 10 ° C is at least 1.2 g per liter.

Preferably, the composition has a viscosity at 20 ° C of at least 6,500 Pas of 3 x 10 shear and at most 10 Pas of shear 21 sec. As measured by a rotating viscometer.

Surfactant

The composition of the invention will comprise a surfactant which may be selected from anionic and nonionic surfactants.

Suitable anionic surfactants are the water-soluble salts of sulfur-containing organic substances having alkyl radicals of 8 to 22 carbon atoms in the molecular structure

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- 7 and a sulphonic acid residue or a sulfuric acid ester or a mixture of these residues. Examples of anionic surfactants are sodium and potassium alcohol sulphates, especially those obtained by sulphating higher alcohols obtained by reducing glyceride of tallow fat or coconut oil. They may also be sodium and potassium alkylbenzene sulphonates, for example having an alkyl group of 9 to 15 carbon atoms, secondary sodium and potassium alkanesulphonates, sodium alkylglyceryl ether sulphates, in particular higher alcohol ethers, derived from tallow fat and coconut oil, aliphatic coconut oil aliphatic sulphate monoglyceride sulphates. the sodium and potassium salts of the sulfuric acid ester, i. reaction products of 1 mole of a higher aliphatic alcohol and 1 to 6 moles of ethylene oxide, sodium and potassium salts of 1 to 3 units of ethylene oxide with alkyl residues of 4 to 14 carbon atoms, and may also be a reaction product of aliphatic acids esterified with isethionic acid and neutralized with hydroxide sodium, wherein the aliphatic acids may be derived from coconut oil, mixtures of these may also be used.

Preferred water-soluble synthetic anionic surfactants are ammonia and substituted ammonia, for example mono-, di- and triethanolamine, as well as salts of higher alkylbenzene sulfonates with alkali metals such as sodium and potassium and alkaline earth metals such as calcium and magnesium, olefinsulfonate and higher alkylsulfonates and also monoglycerisulfate of higher aliphatic acids. The most preferred anionic surfactants are higher alkyl laromatic sulfonates, for example higher alkylbenzene sulfonates of 6 to 20 carbon atoms in straight or branched chain alkyl groups, for example the sodium salts of higher alkylbenzene sulfonate or alkyltoluenesulfonate, xylenesulfonate or phenylsulfonate or phenylsulfonate

- 8 sulfonates, ammonium diamylnaphthalenesulfonate and sodium dinonylnaphthalenesulfonate.

The amount of synthetic anionic surfactant is usually in the range of 1 to 25, preferably 2 to 20, and in particular 2 to 15 ⁵ % by weight.

Suitable nonionic surfactants may be described as compounds formed by the condensation of alkylene oxide groups of substantially hydrophilic nature with an organic hydrophobic compound, which may be aliphatic or alkylaromatic in nature. The length of the hydrophilic or polyoxyalkylene chain fused to a particular hydrophobic group can readily be adjusted to obtain a water-soluble compound with the desired degree of equilibrium between the hydrophilic and hydrophobic element. An example is the condensation product of aliphatic alcohols having 8 to 22 carbon atoms in a straight or branched chain with ethylene oxide, for example ethylene oxide and coconut oil condensate containing 2 to 15 moles of ethylene oxide per mole of coconut alcohol alcohol. These may include alkylphenol condensates containing alkyl groups of 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkyl phenol, reaction products of ethylenediamine and propylene oxide with ethylene oxide containing from 40 to 80% by weight of polyoxyethylene residues and having molecular weights 5000 to 11 000, tertiary amine oxides of the formula R 1 NO, where one R group is an alkyl of 8 to 18 carbon atoms and the remaining R groups are methyl, ethyl or hydroxyethyl, such as dimethyldodecylamine oxides, tertiary phosphine oxides of formula RP 0, where one R group is an alkyl group of 10 to 18 carbon atoms and the other R groups are alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms each, for example dimethyldodecylphosphine and may also be dialkyl sulfoxides of formula R2SO, where one R is alkyl of □ 10 to 18 carbon atoms and the other is j

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Methyl or ethyl, for example methyltetradecylsulfoxide, can also be alkylolamides of aliphatic acids, condensates of alkylene oxide and alkylolamides of aliphatic acids and alkylmercaptan.

The amount of nonionic surfactant in the composition will generally be in the range of 0.5 to 15, preferably 1 to 10, and especially 1 to 8% by weight. Preferably, the composition comprises both anionic and non-ionic wetting agents to provide a liquid composition having a certain density without the need for a thickener.

The weight ratio of anionic surfactant to nonionic surfactant will depend on the nature of these agents and will vary from 1.9 to 9: 1, preferably 1: 4 to 4: 1.

According to a preferred embodiment, the composition will comprise from about 2% to about 10% by weight of a water soluble salt of a synthetic anionic sulphate or solfonate having an alkyl radical of from about 8 to about 22 carbon atoms per molecule and from about 0.5 to about 3% by weight of an alkylene oxidized nonionic surfactant. condensate of an aliphatic alcohol of 8 to 22 carbon atoms with ethylene oxide, for example a condensate containing 2 to 15 moles of ethnylene oxide per mole of aliphatic alcohol.

Optionally, amphoteric, cationic or amphoteric ionic surfactants may also be added to the compositions of the invention.

Suitable amphoteric substances which may be used in the present invention are derivatives of secondary and tertiary aliphatic amines having alkyl radicals of 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic group, acting as solubility in water, for example 3-dodecylaminopropionate sodium, 3-dodecylaminopropanesulfonate and sodium 2-2-hydroxydodecyl-N-methyltaurate.

Appropriate. cationic surfactants are quaternary ammonium salts with aliphatic radicals having 8 to 18 carbon atoms, for example sets 1 trimethylammonium bromide.

Suitable amphoteric ionic surfactants which may be used are derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium compounds having an aliphatic radical of 8 to 18 carbon atoms and an aliphatic radical substituted with an anionic solubilizing group in water, for example 3- ( N, N-dimethyl-N-hexadecylammonium) propane-1-sulfonate betaine, 3- (dodecylinethylsulfonium) propane-1-sulfonate betaine and 3- (cetylmethylphosphonium) ethanesulfonate betaine.

Other examples of suitable surfactants are those commonly used as surfactants and are listed in conventional textbooks, for example, Surface Active Agents, Vol. I (Schwartz and Perry) and Surface Active Agents and Detergednts, Vol. II (Schwartz, Perry and Berch).

The total amount of wetting agent in the composition of the invention will generally be in the range of 1.5 to 30, preferably 2 to 15, 5% by weight.

Water soluble salt

The composition according to the invention preferably also contains 6 to 75, preferably 6 to 40% by weight of at least one water-soluble salt. The salt is present in the composition in an amount exceeding the solubility of the substance in solution and is therefore present both in dissolved and undissolved state. Thus, it is a saturated aqueous solution of the salt, wherein at least 5 hours by weight of the composition is at 20 ° C a solid phase of particles of the salt having a mean diameter of 10 to 500, preferably 15 to 300 and especially 20 to 100 micrometers.

Particular attention should be paid to particle size at higher abrasive content, in particular in the range of 45 to 75% by weight.

EP 193375 (Unilever) describes how it is necessary to adjust the size and distribution of the abrasive in the range of 45-75% by weight.

The water-soluble salt, preferably the inorganic salt, does not contain more than one hydrated form under normal conditions. when present in water as a crystalline substance at a temperature of 10 to 40 ° C in an amount in excess of that required to form a saturated solution. The water permeability of the salt in a saturated solution at 40 ° C should be less than 10 times, preferably less than 8 times, and particularly less than twice the solubility at 10 ° C. It is needed for the reason that the country-? the size, shape and quantity of the crystalline abrasive particles did not substantially change over the normal temperature range in use. This ensures also good environmental efficiency. Obviously, the choice of a salt with the indicated properties will ensure that, when the composition has the desired viscosity and is formed by the respective anionic and nonionic surfactants selected, it will remain stable without substantial changes in viscosity.

The water-soluble salt preferably has a hardness (Moh) of less than 3 and the water solubility at 10 ° C at saturation does not exceed 15% by weight.

The salt should also have a water solubility of at least 1.2 g, preferably at least 5 g / liter at a temperature of 10 ° C to ensure that any excess salt can readily be purified from the salt. Rinse hard surface. In this way, the surface remains free of spots or strips.

In the following table, preferred salts are listed together with the amount of salt in a saturated solution in water and the hydration of these salts. Mixtures of the salts may also be used.

hydration

- 40 ° C solubility ° C g / 100 ml at ° C

sodium bicarbonate NaHCO? 8 13 sodium phosphate hexahydrate ^clay 5 ^P 3 ° 10 · ^6H 2 ° 14 14 sodium tetraborate decahydrate Ua 3 ₄ 0 _? .10H ₂ 0 l 1.2 ? 5

Sodium llydrogen carbonate is a particularly preferred salt for the following reasons:

(i) it is cheap and readily available; (ii) it is non-toxic and does not harm the skin; (iii) its solubility in water does not change much at normal storage temperatures of 0 to 40 ° C; temperature of 40 ° C is 13, iv) the amount in water at saturation of the solution at 10 ° C is approximately 8% by weight, which guarantees an undissolved excess and thus abrasive properties of the composition, on the other hand the water solubility is sufficient for

- 13 dissolution of any excess of this undissolved salt when rinsing the hard surface with water after cleaning with a composition according to the invention,

v) in the temperature range of 10 to 40 ° C, this salt exists in only one crystalline form and does not exist in hydrated form, i.e. it does not contain crystalline water and its crystalline structure thus remains unchanged when stored according to the invention at normal temperatures; ) the crystalline form is hard enough for a good cleaning effect, but since it is somewhat lower than the hardness of the calcite, i. less than 3 on the Moh scale, there is less risk of damage to the hard surface than using similar products containing water insoluble abrasives, for example calcite having a Moh scale hardness.

All of the above properties have no other material with abrasive properties.

Fine sodium bicarbonate particles can be obtained by grinding, sodium bicarbonate, commercially available or by purchasing sodium bicarbonate with extra fine particles, available under the designation extra-fine (Orunner-Mond, formerly ICI). It is particularly preferred to use a salt with a particle size of less than 80 microns, especially in the range of 1 to 3 microns.

The total amount of the water-soluble salt in the composition according to the invention in dissolved and undissolved state is in the range of 6 to 45, preferably 10 to 40 and especially 15 to 40% by weight. At least 5% by weight of the water-soluble salt should be present at a conventional storage or use temperature of 10 to 40 ° C in the form of solid particles having the above mean diameter and other properties.

In addition to sodium bicarbonate, potassium sulfate, sodium tripolyphosphate hexahydrate, and sodium tetraborate decahydrate, the composition of the present invention may also contain other water-soluble inorganic salts or organic salts of magnesium, sodium, potassium and calcium. Each of these optional salts may be present in the composition below or above saturation. Mixtures of these salts may also be used.

Hydrophobic compound

The composition of the invention also comprises at least 0.1% by weight of a substantially hydrophobic compound or mixtures thereof.

When the hydrophobic compound is p and r, it is preferably present in an amount of 0.1 to 2.0% by weight, based on the total weight of the composition. By perfume is meant a substantially water-insoluble volatile substance or sines of such substances, predominantly natural, artificial and synthetic fragrances. It is a complex mixture of organic compounds, for example, fragrant or flowable essential oils, resins, resinous substances, ester, ether, aldehyde, alcohol, hydrocarbons, ketone, lactone, pyrrone and pyrrole. Examples of these perfumes are:

(i) essential oil: pine oil, balsam, citrus oil, magnolium oil, jasmine, lily oil, rose oil and ylang ylang; (ii) esters: phenoxyethyl isobutyrate, benzyl acetate, p-tert-butylcyclohexyl acetate, guaiac resin acetate, linalyl acetate, dimethyl, dimethyl, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycidate, allylcyclohexanepropionate, styrallylpropionate and benzyl salicylate; , citral, citronelal, citronellyloxyacetaldehyde, cyclaenenaldehyde, hydroxycitronellal and Ulial,

(v) alcohols: anethole, citronellol, eugenol, geraniol, linalool, phenylethylalkonol and terpineol; (vi) hydrocarbons: balsams and terpenes; (vii) ketones: ionones, alpha-isomethylionone and methylenedryl-ketone; (viii) lactones: gamma-alkyllakila (C8 -C14), (ix) pyrrones: lower hydroxyalkylpyrrones having an alkyl moiety of 1 to 4 carbon atoms; and

(x) pyrroles: benzpyrrole.

Other fragrance materials that may also be used are, for example, pine oil, lemon oil, lime oil, orange oil, bergamot oil, sweet orange oil, bigarad oil, rosmarin oil, methyl anthranilate, dimethylanthranilate, indole, jasmine oil, patchouli oil, bourbon oil, vanillin, ethylvanillin, coumarin, 3-methylnonan-3-yl acetate, methyionone, synthetic lily oil, synthetic red rose oil, 3-methylnonan-3-ol, cinnamic acid amylaldehyde, methyl salicylate, amyl salicylate, lavandine, isobutylheptenone, cedrylacetate, ethyllinalylacetate, nerylacetate, nerol, d-limonene, cutin aldehyde, linalylpropionate, nerolidyl acetate, nerolidyl formate, alpha-pinene, isobutyllineool, methylnaphthylketone, linalyl isobutyrate, paracresyl acetate, paracresyl acetate , angelic pepper oil, peual balsam, clove oil , nutmeg, methanol, matt oil and almond oil.

Water

The means of the invention comprises a share of the water, which usually constitutes 25 to 92.4, preferably 40 to 00 and separate 50 to 70 ^5; by weight of the composition.

Possible components

The composition according to the invention may contain other ingredients which may increase the cleaning effect. , special polyphosphates, mixtures of ortho- and pyrophosphates, zeolites, and mixtures of these substances. These materials may have an additional function as abrasives when present in an amount greater than that required to saturate the solution in water, as discussed above. Usually, when used, these substances are present in an amount of 0.1 to 25 hours by weight, based on the weight of the compositions of the invention.

Further, the composition may contain metal ion sequestering agents, for example, ethylenediaminetetraacetates, aminopolyphosphonates such as Dequesi and phosphates, and a wide variety of agents. poly functional organic acids and salts.

A further optional component may be a suds controlling agent, which may be used in compositions which could form too much foam when used. For example, soaps. The soaps are salts of aliphatic acids, for example with alkali metals, which may be sodium, potassium or ammonium salts or else alkanolammonium salts of higher aliphatic acids having 3 to 24, preferably 10 to 20 carbon atoms. Particularly suitable are the sodium and potassium salts and the mono-, di- and triethanolamine salts with mixtures of aliphatic acids,

- 17 derived from coconut and peanut oil. The amount of soap may be at least 0.005, preferably 0.5 to 2 hours, by weight of the composition. Other suitable materials for use herein may be organic solvent, hydrophobic silica and silicone oil or hydrocarbons.

The composition according to the invention may also contain other substances which adjust the consistency of the composition and guarantee suitable rheological properties so that the undissolved salt or salts are evenly distributed in the composition and do not adhere too much to the hard surface to be cleaned. Preferred substances for use herein are polysaccharides such as sodium carboxymethylcellulose and other chemically modified cellulose-based materials, xanthan gum and other non-flocculants such as the PS87 Biopolymer described in US 4,329,448. Also, some polymers such as acrylic acid polymer may be used. polyfunctional crosslinking agents such as Carbopol. The amount of agents to maintain the desired structure is, when used, from 0.001%, preferably at least 0.01%, by weight of the composition.

The composition of the invention may also contain at least a partial esterified resin, for example at least a partial esterified resin and unsaturated di-carboxylic acid or anhydride addition product thereof or at least partially esterified derivatives of mono-unsaturated aliphatic, cycloaliphatic or aromatic monomers without carboxy groups and dicarboxylic acids or anhydrides thereof.

Typical examples of suitable copolymers of this type are copolymers of ethylene, styrene and vinyl methyl ether with maleic acid, fumaric acid, itaconic acid, citraconic acid and the like or with anhydrides thereof. Especially preferred are copolymers of styrene and maleic anhydride.

F

Usually, the compositions according to the invention may optionally contain 0.005 to 20, preferably 0.1 to 15, and in particular 0.5 to 10 ⁹ % by weight of at least partially esterified resin.

In addition to the above substances, the compositions of the invention may also contain various other optional ingredients such as pH regulators, dyes, optically brighteners, agents, emulsifying impurities, enzymes, compatible bleaching agents, substances preventing gel formation or repeated freezing and thawing, bactericides, preservatives, hydrotropic surfactants and opacifiers.

The compositions of the present invention typically contain at most about 10%, preferably at most about 5%, by weight of a water insoluble abrasive, such as calcite, since these materials may leave residues on the surface after cleaning the hard surface, even if the surface is thoroughly rinsed. water.

In case it does not include a means výhodnejšírn the stage ¹ of the invention from water-insoluble abrasives.

Typically, the water and optional ingredients form the difference between the subtraction of the surfactant content, the water-soluble salts and the perfume from the total amount of the compositions.

PH

The compositions of the present invention typically have an alkaline pH of from about 7 to about 13, preferably from about 7 to about 11. If sodium bicarbonate is used as a water-soluble abrasive, the pH should be in the range of about 0.0 to about 9, 5th Within this range, sodium bicarbonate either decomposes to release carbon dioxide or is converted to carbonate. Alkaline substances such as sodium hydroxide or sodium carbonate may be used to adjust the pH.

- 19 Keeping the suspension still

An important property of the composition according to the invention is the suspension stability of the undissolved particles of the soluble abrasive salt so that the consumer is not forced to agitate the composition by shaking, for example, to resuspend the suspension and redistribute the deposited particles before use. To that end, had to have a means at 20 ° C a viscosity of at least 6500 Pas at a shear 3 x 10 ^- ^ sec ^, to nedocnázelo deposition of particulate abrasive soluble salts of standing at 20 ° C by more than 1 cm months.

While it is necessary to ensure that the composition of the present invention has a viscosity sufficient to prevent substantial deposition of the undissolved particles of the abrasive water-soluble salt during storage, the composition should remain liquid at the same time so that it can be removed from the container or container. use easy to pour out. For this purpose, at a temperature of 20 ° C, the viscosity composition should have a maximum viscosity of 10 Pas at a shear of 21 sec. Preferably, the viscosity is at most 5 Pas at shear of 21 sec.

Appropriate ideological properties corresponding to these criteria can be ensured by the appropriate choice of anionic and nonionic surfactants to obtain a liquid with suitable properties in suspension and / or by adding an appropriate amount of a suitable substance which can provide the desired consistency of the composition as described above. .

Preferred embodiment

A particularly preferred embodiment of the present invention is suitable for cleaning hard surfaces on an aqueous basis having a viscosity at 20 ° C of at least 6500 Pas per shear 3 x 10 -5 sec-l and at most 10 Pas per shear 21 sec. the device contains:

i) 0.1 to 2% by weight of a substantially hydrophobic perfume; ii) 4 to 20 hours by weight of a wetting agent, a mixture of a nonionic and anionic surfactant in a ratio of 1; And (iii) sodium bicarbonate in an amount at which at least 5% by weight of the undissolved particles of the salt, based on the total weight of the formulation, is present at 25 ° C, the mean particle diameter being 10 to 500 microns.

Method of manufacture of the composition

Since the composition of the invention is in liquid form, it can be prepared simply by mixing the base and optional ingredients with water.

Packaging and use of the product

The composition of the invention is a pourable liquid and is therefore preferably stored in a sealable container, which is most convenient in terms of storage, transport and sale, so as not to spill the composition.

The composition according to the invention is particularly suitable for cleaning contaminated hard surfaces, for example in households in kitchens or bathrooms. The composition is ready for use so that it can be used undiluted or it can be first diluted with water before use on a hard surface to which the composition can be applied, for example, with a cloth, brush or sponge. After use, any excess of the undissolved abrasive water-soluble salt remaining on the cleaned surface can be removed by washing with clean water to dissolve the remaining salt.

Surfaces cleaned with the compositions of the present invention do not have the stains or streaks that occur on them from cleaning compositions containing water-insoluble abrasives such as calcite.

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EXAMPLES Certain commercial products are used in the following examples, the composition of which will be explained hereinafter.

B

DO3S 102: Linear alkylbenzene sulfonate, obtained as an alkylate (Shell) followed by sulfonation.

DOOS 113: Linear alkylbenzene sulfonate, obtained as an alkali (Shell) followed by sulfonation prior to manufacture, according to the invention.

PETRALAO 550: Linear alkylbenzene sulfonate, obtained as: alkylate (Petresa) followed by sulfonation prior to manufacture of the compositions of the invention.

OOBALOL 3 (6.5 EO): The ethoxylated alcohol (Shell) which was used as such.

; TRIFAC 7901: Aliphatic acids (Onichema) were used as sodium salts after neutralization with HaOH.

LEMONSTAR: Perfume (Firmenich, CH).

3UPPA: Perfume composition (Firmenich, CH).

Dowanol Pn9: n-butoxypropanol (Oow).

Isopar L: Isoparaffin (Exxon).

Sodium bicarbonate was used in extra-fine form (3runner Mond.).

Table 1 below lists the compositions used in the Examples and Comparative Examples. The compositions were suitable for cleaning hard surfaces such as sinks, work surfaces, l

bathrooms and floors.

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The statement is expressed in the following way:

S: The abrasive did not settle after storage for 12 weeks at 37 ° C or after 12 temperature cycles for 3 hours at -5 ° C and 16 hours at 25 ° C.

F: The abrasive material settled in the course of 12 temperature cycles for 3 hours -5 ° C and 16 hours 25 ° C.

II: The abrasive was not stable for 12 weeks when stored at 37 ° C.

In Examples 1 to 4, the compositions of the invention are mentioned and it is evident that under the selected storage conditions, the compositions are still present. In Examples A to D, the compositions are comparative, which are unstable in the absence of perfume and are only partially still in the presence of organic solvents other than perfumes. Compositions A to C were unstable under conditions similar to those during the zinc moons in the temperate zone.

Although the cause of the stability is not yet well known, it is likely that the hydrophobic compound aids in the formation of the lamellar phase by spherulinity by associating with a wetting agent and thus increasing the volume of the lamellar phase.

represents:

'i an attorney

I • 1: Γ ί (* / / / / / / / <

- 24 PATENT TOOLS 0

Claims (12)

Use of substantially hydrophobic pacifiers for enhancing the stability of liquid water-based cleaning compositions containing water-soluble abrasives for cleaning hard surfaces. Use according to claim 1, in which the composition comprises from 0.1 to 10% by weight of the composition. Use according to claim 1 or 2, wherein the water-soluble abrasive is at least one of sodium bicarbonate, potassium sulfate, sodium phosphate hexahydrate and sodium tetraborate decahydrate. Use according to claim 1, 2 or 3, wherein the water-soluble abrasive is present in an amount of 6 to 75% by weight, based on the narcotic weight of the compositions. Use according to claim 4, wherein the water-soluble abrasive is present in an amount of 6 to 45% by weight. 6. A liquid-based water-based cleaning agent for cleaning hard surfaces, comprising a water-soluble abrasive, at least a portion of which is present in the form of undissolved particles having a mean diameter of 10 to 500 microns; The composition comprises a substantially hydrophobic perfume and a wetting agent, the composition being stable for 12 weeks at 37 ° C or after 12 temperature cycles, each for 8 hours at -5 ° C and then 16 hours at 25 ° C. A detergent composition according to claim 6, comprising: • i i) at least about 0.1 by weight EXAMPLE ⁵ substantially hydrophobic l (ii) 1.5 to 30% by weight of the surfactant; and (iii) a water-soluble salt in an amount at which at least about 5 hours by weight of undissolved ^{1 part} of the salt is present in the composition, based on the total potency of the composition. wherein the mean diameter of said particles is 10 to 500 microns, the salt contains at most one hydrated form when present as a crystalline solid in water at a temperature of 10 to 40 ° C in an amount in excess of that required to form a saturated solution; the salt in a saturated solution in water at 40 ° C is less than ten times the solubility of the salt at 10 ° C and the water solubility of the salt at 10 ° C is at least I, 2 g / liter. A cleaning composition according to claim 7, wherein its viscosity at 20 ° C: * is at least 6500 Pas at 3 x 10 sec. measured in a rotary viscometer. > · 9. A detergent composition according to claim 7 comprising 6 to 45% by weight of the water-soluble salt (iii). A detergent composition according to claim 7 comprising 45 to 75% by weight of the water-soluble salt (iii), wherein the salt is in particulate form with a volume distribution of less than 80 microns and within the range; li to 3. II. A detergent composition according to claims 6 to 10 wherein the water-soluble salt is selected from the group consisting of sodium bicarbonate, sodium phosphate hexahydrate, sodium tetraborate decahydrate and mixtures thereof. 12. A detergent composition according to claim 11 wherein the water-soluble salt comprises sodium bicarbonate. 13. A cleaning composition according to claim 6, comprising: i) 0.1 to 2 ° with a substantially hydrophobic perfume, ii) 4 to 20% by weight of a wetting agent, a mixture of a nonionic and anionic wetting agent in a ratio of 1:10 to 10: 1, and iii) an amount of sodium bicarbonate, however, at 20 ° C, at least 5 parts by weight of the undissolved particles are present in the composition, based on the weight of the composition, the mean diameter of said particles being 10 to 500 microns.