PL202080B1 - Improved detergent composition - Google Patents

Abstract

The invention relates to synergistic concentrated cleaning composition comprising one or more surfactants and one or more water swellable polymers that can absorb more than their weight of water. The composition can be converted into a voluminous paste or thick liquid by the simple addition of water prior to use, to ensure the spreadability of the composition on a large number of surfaces to be cleaned.

Description

Description of the invention

The present invention relates to synergistic cleaning compositions containing surfactants and swellable polymers, compositions suitable for the cleaning of hard surfaces (scouring).

State of the art

Commercially available hard surface cleaning compositions typically contain one or more surfactants and a plurality of abrasive particles dispersed therein. Combinations of surfactants with electrolytes are often used to prepare an abrasive suspending system as is well known in the art.

Various cleaning compositions are available in the form of liquids, pastes, gels, powders and (scouring) bars. Typical abrasives used in such compositions include calcites and dolomites.

Hard surfaces in a household include cookware, kitchen walls and doors, kitchen worktops and sinks, bathroom walls, floors and fittings, other floors, etc. Various types of dirt can be found on these surfaces. The stains generally found on kitchen utensils and worktops are of two types, i.e. movable or greasy stains and resistant, hard-to-remove stains consisting of dried or burnt food. The problem of removing these soils becomes more pronounced as resistant soils build up over time and require considerable effort to remove.

Generally, the amount of surfactant in cleaning compositions is up to about 20%, the balance being other ingredients. Abrasives, builders and fillers are an important part of the formulations. It is necessary to add such ingredients to improve the spreadability of the surfactant on the surfaces to be cleaned, especially in the case of manual cleaning.

Polymers are used in cleaning compositions because they provide various benefits such as structuring and soil release functions. EP 883670 (Unilever, 1998) discloses automatic dishwasher gel dishwashing gel compositions, this gel having a high viscosity. Such compositions comprise a two-component structuring system containing 0.2% to 2% of a cross-linked polycarboxylate and an azole.

Adding a large amount of water together with abrasives, builders and fillers adds bulk to the product and thus increases the cost and difficulty of transporting it from the production site to the application site.

Thus, there is a need to provide a concentrated cleaning composition that the user can transform into a ready-to-use product by adding water. Such a concentrated composition could save shipping and packaging costs compared to a diluted composition.

The present invention provides a synergistic concentrated composition comprising one or more surfactants and one or more water swellable polymers that can absorb water more than its own weight. The compositions can be made into a bulky paste or thick liquid product by simply adding water before use to render the composition spreadable over a wide variety of surfaces to be cleaned.

All parts and percentages mentioned herein are based on the weight of the composition, unless otherwise stated.

The invention relates to a synergistic cleaning composition comprising surfactants and a polymer, comprising:

(a) one or more surfactants in an amount of 5% to 95%, wherein the nonionic surfactant constitutes at least 40% by weight of the total surfactant; and (b) one or more water-swellable polymers absorbing more than their own weight in an amount of 5% to 95%;

wherein the weight ratio of surfactant to water-swellable polymer is in the range of 1: 0.4 to 0.4: 1, and wherein the water-swellable polymer is selected from the group consisting of polyacrylic acids, polyacrylates, cross-linked acrylate polymers , guar gum and its derivatives, starch-acrylic graft copolymers, hydrolysates of graft copolymers of starch acrylonitrile, cross-linked polyoxyethylene, cross-linked carboxymethyl cellulose, partially cross-linked water-swellable polymers such as poly (ethylene oxide) and polyacrylamide, and isobutylene / acid copolymer maleic.

Preferably, the water-swellable polymer is selected from polyacrylic acids or partially neutralized sodium salts of cross-linked polyacrylic acids.

Also preferably, the water-swellable polymer comprises from 5% to 75% of the composition, and more preferably the water-swellable polymer comprises from 5% to 50% of the composition.

Preferably the surfactants are selected from anionic and / or nonionic surfactants, preferably the weight ratio of anionic to nonionic surfactant is in the range 0.1: 1 to 6: 4; especially 1: 1.

Preferably the composition comprises all surfactants in the range 5% to 50% of the composition, especially in the range 5% to 25% of the composition.

Preferably the composition is in the form of a solid powder, tablets, pellets, threads, paste or a gel.

Preferably the water-swellable polymer is in solid form, in particular in the form of comminuted, granular, pellet, flake or short thread form.

In another embodiment, the composition of the invention further comprises up to 90% inorganic particulates and other conventional ingredients.

Preferably the composition comprises 10% to 90% of the comminuted inorganic phase, and more preferably the comminuted phase is a water-insoluble or partially soluble abrasive.

In the context of the present invention, the expression "cleaning composition" refers to a composition in the form of a solid powder, tablets, pellets or threads, or a paste or gel, which can be converted into a volumizing product by adding water. The product thus obtained can be easily applied to or spread over the surface to be cleaned.

Surfactants

The composition of the invention comprises one or more surfactants which are generally selected from anionic, non-ionic, cationic or amphoteric surfactants. It is preferred that at least 10% of the total amount of surfactant in the composition is nonionic surfactant, and more preferably it is at least 40% of the total surfactant. It is preferred that the surfactant in the composition comprises from 5% to 50%, more preferably 5% to 25% by weight of the composition.

A suitable class of anionic surfactants are the water-soluble salts of organic sulfuric acid monoesters and sulfonic acids having a branched or straight chain structure of an alkyl group containing 8 to 22 carbon atoms, or an alkylaryl group containing 6 to 20 carbon atoms in the alkyl portion.

Examples of such anionic surfactants are water-soluble salts:

long-chain (i.e. 8 to 22 carbon atoms) alcohol sulphates (hereinafter referred to as PAS), especially compounds obtained by sulphonating fatty alcohols prepared from tallow or coconut oil, or synthetic petroleum alcohols;

- alkyl benzene sulfonates, such as those in which the alkyl group has from 6 to 20 carbon atoms;

- secondary alkanesulfonates.

Also suitable are the salts:

alkylglyceryl ether sulphates, in particular fatty alcohol ethers derived from tallow and coconut oil;

- fatty acid monoglyceride sulphates;

ethoxylated aliphatic alcohol sulfates having 1 to 12 ethyleneoxy groups;

- alkylphenol ethyleneoxy ether sulphates having from 1 to 8 ethyleneoxy units per molecule, in which the alkyl groups have from 4 to 14 carbon atoms;

- reaction products of fatty acids esterified with isethionic acid and neutralized with alkali.

A suitable class of nonionic surfactants can be broadly described as compounds prepared by the condensation of common alkylene oxides, which are hydrophilic in nature, with aliphatic or alkyl aromatic hydrophobic compounds with a reactive hydrogen atom. The length of the hydrophilic or polyoxyalkylene chain which is attached to a given hydrophobic group can be easily adjusted so as to obtain a compound with the desired balance

Between the hydrophilic and hydrophobic parts. This allows the selection of a nonionic surfactant with an appropriate HLB value. Specific examples include:

condensation products of aliphatic alcohols with 8 to 22 carbon atoms, both in straight and branched chain configuration, with ethylene oxide, such as coconut alcohol / ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol;

- condensates of alkylphenols having C6 to C15 alkyl groups with 5 to 25 moles of ethylene oxide per mole of alkylphenol;

- condensates of the reaction product ethylene-diamine and propylene oxide with ethylene oxide, condensates having from 40% to 80% by weight of ethyleneoxy groups with a molecular weight of 5000 to 11000.

Other classes of non-ionic surfactants are:

- alkylpolyglucosides, which are the condensation products of long-chain aliphatic alcohols and saccharides;

- tertiary amine oxides of formula RRRNO, where one R is an alkyl of 8 to 20 carbon atoms and the other R's are each alkyl or hydroxyalkyl of 1 to 3 carbon atoms, for example dimethyldodecylamine oxide;

- tertiary phosphine oxides of formula RRRPO, where one R is alkyl of 8 to 20 carbon atoms and the other Rs are each alkyl or hydroxyalkyl of 1 to 3 carbon atoms, for example dimethyl dodecyl phosphine oxide;

dialkyl sulfoxides of formula RRSO, where one R is alkyl of 10 to 18 carbon atoms and the other is methyl or ethyl, for example methyltetradecyl sulfoxide;

fatty acid alkylolamides, such as ethanol amides;

- alkylene oxide condensates with fatty acid alkylamides;

- alkili mercaptans.

A specific group of surfactants are tertiary amines obtained by condensation of ethylene and / or propylene oxide with long-chain aliphatic amines. Such compounds behave as nonionic surfactants in an alkaline environment and as cationic surfactants in an acidic environment.

Optionally, amphoteric, cationic or zwitterionic surfactants may be included in the compositions of the invention.

Suitable amphoteric surfactants that may optionally be used are derivatives of aliphatic secondary and tertiary amines containing alkyl groups of 8 to 18 carbon atoms, and an aliphatic radical substituted with an anionic water-solubilizing group, e.g. sodium 3-dodecylamino propionate, 3 sodium dodecylaminopropanesulfonate, and sodium N-2-hydroxydodecyl-N-methyl taurate.

Examples of suitable cationic surfactants can be found among quaternary ammonium salts having one or two alkyl or aralkyl groups of 8 to 20 carbon atoms and two or three small aliphatic (e.g. methyl) groups, e.g. cetyltrimethylammonium bromide.

Examples of suitable zwitterionic surfactants can be found among the aliphatic derivatives of the quaternary ammonium, sulfonium and phosphonium compounds, with an aliphatic group of 8 to 18 carbon atoms, and an aliphatic group substituted with a water-solubilizing group, e.g. Betaine dimethyl N-hexadecylammonium propane-1-sulfonate, betaine 3- (dodecylmethylsulfonio) propane-1-sulfonate and betaine 3- (cetylmethylphosphonio) ethanesulfonate. Other well known betaines are alkylamidopropyl betaines, for example those in which the alkylamido group is derived from coconut fatty acids.

Further examples of suitable surfactants commonly used as surfactants are given in the well known textbooks "Surface Active Agents Vol. 1, by Schwartz and Perry, Interscience 1949; Surface Active Agents vol. 2 by Perry and Berch, Interscience 1958; the current issue of "McCutcheon's Emulsifiers and Detergents published by Manufacturing Confectioners Company; "Tenside-Taschenbuch, by H. Stache, 2nd edition, Carl Hauser Verlag, 1981.

It is particularly preferred that the surfactant is a mixture of anionic and nonionic surfactants in a ratio ranging from 1: 0.1 to 1:10, more preferably ranging between 1: 0.1 and 1: 1.

PL 202 080 B1

Swelling polymers

Water-swellable polymers are polyacrylic acids and polyacrylates, cross-linked acrylate polymers, guar gum and its derivatives, starch-acrylic graft copolymers, hydrolysates of starch-acrylonitrile graft copolymers, cross-linked polyoxyethylene, cross-linked carboxymethylcellulose, partially water-swellable cross-linked polyoxide polyacrylamide, isobutylene / maleic acid copolymers, etc. For the present invention particularly preferred water-swellable polymers are polyacrylic acids, and cross-linked polyacrylic acids partially neutralized to sodium salts are most preferred. Water-swellable polymers suitable for use in the invention are available as solids and liquids, preferably solids such as particulates, granules, pellets, flakes, short threads and the like.

It is preferred that the water-swellable polymer in the composition comprises from 5% to 75%, more preferably 5% to 50% by weight of the composition.

The ratio of surfactant to polymer is preferably in the range 1: 0.1 to 0.1: 1, more preferably 1: 0.4 to 0.4: 1.

Other ingredients

Inorganic particulate substances

A particulate, insoluble solid phase is an optional ingredient in the composition of the invention.

Preferably, the particulate phase contains an abrasive that is insoluble in water. Alternatively, the abrasive may be soluble to some extent, and may be present in relation to the water present in the composition when mixed with water before use to such an excess that the solubility of the abrasive in the aqueous phase will be exceeded and consequently the abrasive is present in the water phase. solid in the swollen mixture.

The ability of the swellable polymers to form a gel or paste may be reduced in the presence of certain electrolytes. For example, calcium ions reduce the swelling capacity of cross-linked polyacrylic acid, which is a water-swellable polymer. Therefore, when selecting abrasives and inorganic particulates, care should be taken to avoid such materials. If their use is absolutely necessary, they must be present in minimal amounts.

Suitable abrasives can be selected from comminuted zeolites, calcites, dolomites, feldspars, silicas, silicates, other carbonates, aluminates, bicarbonates, borates, sulfates, and polymeric materials such as polyethylene.

Preferred abrasives for use in general purpose cleaning compositions have a Moh's hardness of 2 to 6, although higher hardness abrasives may be designed for specific applications.

Preferably, the average particle size of the abrasive is in the range 0.5 to 400 microns, with values of about 5 to 200 microns being preferred.

Other optional ingredients

The composition of the invention may contain other ingredients to aid in cleaning performance. For example, the composition may contain detergent builders such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates (such as polyphosphates, mixtures of ortho- and pyrophosphates), zeolites, and mixtures thereof. The compositions of the invention may also contain, in addition to those already mentioned, various other optional ingredients such as solvents, colorants, whitening agents, optical brighteners, soil suspending agents, enzyme washing agents, compatible bleaching agents (in particular hypohalides), and preservative.

Inorganic particulates and other optional ingredients may be present in up to 90% of the composition.

Thus, according to a preferred aspect of the invention, it provides a synergistic cleaning composition comprising:

(a) 5% to 50% of one or more surfactants, wherein at least 10% by weight of the total surfactants is nonionic surfactant;

(b) 5% to 75% of one or more water-swellable polymers absorbing more water than it weighs; and

(C) optionally up to 90% by weight of inorganic particulates and other conventional ingredients.

Thus, according to a more preferred aspect, the invention provides a synergistic cleaning composition comprising:

(a) 5% to 25% of one or more surfactants, wherein at least 40% by weight of all surfactants are in the form of non-ionic surfactant;

(b) 5% to 50% by weight of one or more water-swellable polymers absorbing more water than it weighs; and (c) 10% to 90% by weight of inorganic particulates and other conventional ingredients.

The invention will now be illustrated with reference to the following non-limiting examples.

Examples

i. Effect of polymer-surfactant interaction on gel formation: Compositions with the compositions shown in Table 1 were prepared by mixing surfactant and polymer. The obtained products were in the form of a powdery mass. 50 g of water was added to each of these products and allowed to stand for 1 to 2 minutes. Table 1 also shows the results of the visual appearance of the products after the addition of water and the volume of gel produced.

Measurement of the gel volume (ml) after addition of excess water: The pastes / thick liquids having compositions according to Examples 1 to 6 below were transferred to separate 250 ml graduated cylinders, and water was added to a volume of 250 ml. The contents of the cylinders were stirred for a minute and allowed to settle overnight and then observed. The contents of the cylinders separated into two phases (in the compositions of Examples 1, 2, 3 and 6). The gel formed by the swellable polymer solidified at the bottom, and the water layer was at the top. The volume of the gel layer was measured. The volumes of the gels (in the presence of excess water) indicate the gel-forming ability of the swellable polymer in the presence of a surfactant. It was concluded that the greater the volume of the gel, the lower the negative effect of the surfactant on the swellable polymer.

T a b e l a 1

Composition Weight in grams Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Linear alkyl benzene sulfonate 0.5 - 0.25 0.5 - - 7EO fatty alcohol (carbon chain length C12 to C18) - 0.5 0.25 - 0.5 - Cross-linked polyacrylic acid GE 500F Kolon Chemicals 0.5 0.5 0.5 - - 0.5 Water added 50 50 50 50 50 50 Product properties Physical appearance after adding 50 ml of water Soft gel Good solid like a gel Gel Liquid Liquid Soft gel Gel volume (ml) after addition of excess water 58 68 60 0 0 75

The data presented in Table 1 shows that the polymer is essential for gel formation and that the polymer forms a good solid-like gel in the presence of nonionic surfactants. This shows that the choice of surfactant is important in determining gel strength and volume, which in turn determines the consistency of the paste produced.

ii. Effect of Surfactant Nature on Gel Formation: Anionic surfactant and nonionic surfactant were tested in various ratios in the compositions described in Table 2 to determine their effect on gel formation. The product was mixed with water and the nature of the gel produced was examined. Following the procedure described above, the gel volume (ml) was measured after the addition of excess water. The performance was also assessed by considering the cleaning efficiency.

PL 202 080 B1

Measurement of cleaning efficiency: 1 g of gel, made by adding 100 grams of water to 7.5 g of powder, was drawn up with an apparatus and the soiled plate was cleaned with it. During the cleaning operation, various cleaning parameters and performance properties were determined. Based on the overall benefit, cleaning performance was rated on a scale of 1 to 5 where "1 corresponds to" poor and "5 refers to" good cleaning performance.

T a b e l a 2

Composition Weight in grams Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Linear alkyl benzene sulfonate 1.5 - - 1.5 - 1.35 0.9 Fatty alcohol ethoxylate C12 to C18 3EO - 1.5 - - 1.5 0.15 0.6 Cross-linked polyacrylic acid GE 500F 1.5 1.5 1.5 - - 1.5 1.5 Sodium tripolyphosphate 0.2 0.20 0.2 0.2 0.2 0.2 0.2 Alkali silicate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Inorganic particulate substances 4.4 4.4 4.4 4.4 4.4 4.4 4.4 Water added 100 100 100 100 100 100 100 Product properties Physical appearance Gel The best solid gel Gel Liquid Liquid Gel Good solid gel Gel volume (ml) 98 142 152 0 0 126 100 Cleaning action 5 3 0 1 1 4 4

The data presented in Table 2 shows that the polymer is important to obtain a coherent gel but performs poorly with respect to cleaning (Example 9). If the surfactant is present in the absence of polymer, no gel is obtained and the cleaning efficiency is lower (Examples 10 and 11) because the polymer helps to distribute the active ingredient. The performance of the compositions as in Examples 7, 8, 12 and 13 in terms of gel formation and cleaning performance demonstrates that the correct combination of surfactant and polymer is important to obtain a composition with both optimal cleaning performance and the formation of a gel of adequate strength.

Claims (15)

1. A synergistic cleaning composition containing surfactants and a polymer characterized in that: (a) the one or more surfactants are present in an amount of 5% to 95%, wherein the nonionic surfactant is at least 40% by weight of the total surfactant; and (b) the one or more water-swellable polymers absorbing more water than it weighs, is present in an amount of 5% to 95%; wherein the weight ratio of surfactant to water-swellable polymer is in the range 1: 0.4 to 0.4: 1, and wherein the water-swellable polymer is selected from the group consisting of polyacrylic acids, polyacrylates, cross-linked acrylate polymers , guar gum and derivatives thereof, starch-acrylic graft copolymers, hydrolysates of graft copolymers of starch acrylonitrile, cross-linked polyoxyethylene, cross-linked carboxymethyl cellulose, partially cross-linked water-swellable polymers such as polyethylene oxide and polyacrylamide, and isobutylene / maleinic acid copolymer. PL 202 080 B1 2. A composition according to claim 1 The method of claim 1, wherein the water-swellable polymer is selected from polyacrylic acids or partially neutralized sodium salts of cross-linked polyacrylic acids. 3. A composition according to p. The composition of claim 1 or 2, wherein the water-swellable polymer comprises 5% to 75% of the composition. 4. A composition according to p. The composition of claim 3, wherein the water-swellable polymer comprises from 5% to 50% of the composition. Composition according to any one of claims 1 to 4, characterized in that the surfactants are selected from anionic and / or non-ionic surfactants. 6. A composition according to p. The method of claim 5, wherein the weight ratio of anionic to nonionic surfactant is in the range 0.1: 1 to 6: 4. 7. The composition according to p. The method of claim 6, wherein the weight ratio of anionic to nonionic surfactant is 1: 1. 8. A composition according to any one of the claims 1-7; The composition of any one of claims 1 to 7, characterized in that it contains all surfactants in the range 5% to 50% of the composition. 9. A composition according to p. The composition of claim 8, wherein the surfactants are in the range 5% to 25% of the composition. Composition according to any one of claims 1 to 10 The composition of any one of claims 1 to 9, characterized in that the composition is in the form of a solid powder, tablets, pellets, threads, paste or a gel. 11. A composition according to any one of claims 1 to 11 The water-swellable polymer of any of claims 1 to 10, wherein the water-swellable polymer is in a solid form. 12. A composition as claimed in p. The method of claim 11, wherein the water-swellable polymer is in the form of a particulate, granulate, pellets, flakes or short threads. 13. A composition according to any one of claims 1 to 13, The composition of any one of claims 1 to 12, characterized in that the composition additionally comprises up to 90% inorganic particulates and other conventional ingredients. 14. A composition according to any one of claims 1 to 14, The composition of any one of claims 1 to 13, characterized in that the composition comprises 10% to 90% of the comminuted inorganic phase. 15. A composition as claimed in p. The process of claim 13 or 14, characterized in that the particulate phase is a water-insoluble or partially soluble abrasive.