HU226238B1 - Cleaning composition comprising saturated dialkyl cationic surfactant and process for its use - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to a hard surface cleanser comprising a fully saturated dialkyl cationic surfactant and a nonionic surfactant.

Conventional cleaning of hard surfaces, such as wood, polished tiles, painted metal surfaces, uses surface-active or solvent-based compositions to remove contaminants, and in a separate operation coat the surface with lacquer, wax, or polish to protect the surface and reduce the buildup of contaminants. This two-step cleaning and protection procedure is very time consuming and complex.

Surfactant-based formulations are known to incorporate components that form a protective layer once deposited on the surface.

GB 152 85 92 discloses an alkaline floor cleaning agent comprising an organic polycarboxylic acid soluble in an aqueous solution having a molecular weight of 8.000 to 250000 at pH 8.5 or higher. These polymers are commercially available.

GB 153 47 22 discloses granular compositions for hard surface cleaning comprising a surfactant and a polyvinyl alcohol or pyrrolidone and a biopolysaccharide as a "soil remover". Such polymers are commercially available with molecular weights of about 500-360,000. The compositions described above can be used to obtain alkaline solutions.

U.S. Patent Application Serial No. 07 / 297,807, EP 0 467 472 A2 (EP 379256) discloses a hard surface cleaning composition which is associated with a mixed nonionic surfactant system in 2.3%, 15-20% poly [ Beta (methyl diethylammonium) ethyl methacrylate] in an aqueous solution containing a cationic polymer. A previously cleaned and cleaned ceramic tile surface can be easily cleaned with this product.

EP 0 467 472 A2 discloses that soil release polymers such as cationic poly [beta (methyl diethylammonium) ethyl methacrylate] can be used effectively in combination with anionic and cationic surfactants. It is claimed in this application that the "soil release polymer" forms a hydrophilic layer which remains on the surface of the soil so that the subsequent deposition of dirt on the surface requires much less work than without the surface remaining on the surface. The molecular weight of the polymers is 4000-100,000, but polymers with a molecular weight above 50,000 are less preferred in terms of solubility.

EP 0379 256 discloses compositions similar to those described above which, in a system having a pH of 2-4 and containing 2-4% by weight of a nonionic surfactant, contain up to 2% by weight, optionally quaternized, of 2000-500,000 molecular weight. containing an antistatic polymer. The examples described relate to compositions comprising 2.2% by weight of a mixed nonionic system and 0.07% by weight of a given cationic polymer in a pH 2.5 medium. The modified polymer is described as being used as a soil release agent.

U.S. Patent 4,065,409 discloses a detergent mixture comprising a nonionic surfactant (which may be ethoxylated alcohol) and a cationic surfactant (quaternary alkyl) ammonium halide. There is no mention in the document of the soiling ability of the composition, which may be related to the use of different structure nitrogenous compounds as cationic surfactants in the present invention, which are tertiary, preferably dialkyl quaternary compounds.

WO 94/06899 and WO 86/05199 disclose compositions comprising a non-ionic surfactant of the glycoside type. It is emphasized in the documents that no residue is present on the cleaned surface (while the present invention is characterized by the retention of a subsequent soil release surfactant layer, see below).

U.S. Patent No. 4,606,842 discloses a spray and wipe glass cleaner comprising a low molecular weight pollacrylic acid resin as a building material. U.S. Pat. No. 4,690,779 discloses hard surface cleaning compositions comprising polyacrylic acid polymers having a molecular weight of less than 5000 in combination with certain nonionic surfactants. In these formulations, the polymer is primarily used as a builder.

It can be seen from the foregoing that certain polymers are generally used in combination with alkaline hard surface cleaners to achieve a primary cleaning effect when first used in the formulation, or to modify the surface to prevent dirt deposition or otherwise to promote secondary cleaning.

Other surface treatment agents, including some special cationic cleaners, deserve attention. WO 91/09930 discloses ETHOQUAT, a commercially available agent for cleaning aluminum, for example, on metal surfaces in vehicles.

It is an object of the present invention to provide improved compositions for both cleaning the surface and providing a layer of cationic surfactant deposited on the surface to aid in loosening the surface after cleaning.

Accordingly, the present invention relates to an aqueous composition for cleaning a hard surface comprising a surfactant composition having the following composition;

HU 226 238 Β1

(a) at least 65% by weight of the total surfactant obtained by condensation of hydrophilic alkylene oxides with a hydrophobic aliphatic or alkyl aromatic compound as detailed below;

(b) less than 1% by weight of total surfactant anionic surfactant; and

c) 0.1% to 35% by weight of the total cationic surfactant, which is a dialkyl cationic ammonium compound containing ethylene groups.

The cationic dialkylammonium compound which is useful in the compositions of the present invention can be of many kinds. These alkyl chains of compounds containing C = O groups do not contain C = C bonded groups, i.e., their ethylene groups are saturated. It is important that the molecule contains at least two moderately long alkyl chains, but these alkyl chains may be present in greater numbers. At least two alkyl chains of the compounds useful in the present invention will generally have 8 or more carbon atoms.

The cationic surfactant is typically a [R ₁ R ₂ R ₃ N® _{(CH2) n} CH (O (OC) R ₄₎ - _{(CH2) m} O (OC) R ^{_5], the} compounds of formula X wherein

R 1, R ₂ and R ₃ are each independently C 1 -C 6 alkyl or hydrogen, n and m are 0-4,

-O (OC) R ₄ and -O (OC) R ₅ are C 8 -C ₂₆ fatty acid residues and

X is the equivalent of a monovalent anion.

More typically, the cationic surfactant comprises a cation of the general formula described above wherein m = 1 and n = 1.

Preferably, the cationic surfactant comprises a cation of the general formula described above wherein R ₁ = R ₂ = R ₃ = CH ₃ . More preferably, R ₄ and R ₅ are independently 12 to 20 carbon atoms.

The fully saturated dialkylammonium compound may also be a compound of the formula X® [CH ₃ (CH ₂ ) _n (CO) NH (CH ₂ ) _m ] ₂ .NR ₁ R _{2 in} which

· R! and _R2 are independently hydrogen, C1-4 alkyl, C1-4 hydroxy alkyl residue and polymers thereof, n is from 8 to 26 alkylene glycol;

m is 1-4; and

X is the equivalent of a monovalent anion. Preferably, R 1) is methyl and R ₂ is - (CH ₂ CH ₂ O) _X H or methyl.

The fully saturated dialkyl ammonium compound can be a X® [CH ₃ (CH _{2) n} (CO) O _{(CH2) m] 2} N®R _one R ₂ is Compounds of formula I wherein

R ₁ and R ₂ are each independently hydrogen, C 1-4 alkyl, C 1-4 hydroxyalkyl, alkylene glycol residues, and polymers thereof, n is from 8 to 26;

m is 1-4; and

X is the equivalent of a monovalent anion.

Preferably R ι is methyl, R ₂ represents a (CH ₂ CH ₂ O) _x H group of the formula wherein x has an average value of 1-2, or a methyl group and m is the second

A fully saturated dialkyl quaternary ammonium compound is one

ΧθΙΟΗ ^ ^ may also ΟΗ -Ν® ^ compounds of formula I wherein Ri and _R2 are independently hydrogen, C1-4 alkyl, C1-4 hydroxy alkyl residue and polymers thereof, n is from 8 alkylene glycol -26; and

X is the equivalent of a monovalent anion. Preferably R 1 is methyl, R ₂ is - (CH ₂ CH ₂ O) _X H, where x is an average of 1 to 2, or methyl. The value of n is preferably chosen so that the distribution of the longer alkyl chain is similar to that of tallow.

The compositions of the invention may be acidic, alkaline or neutral.

The pH of the compositions of the present invention when the surfactant contains an ester group is typically less than 7.5, and if the cationic surfactant does not contain an ester linking group, the pH may be greater than 7.5.

Preferably, the cationic surfactant is a compound of the formula [(CH ₃ ) ₃ N -CH ₂ -CH (O (OC) R ₄ ) -CH ₂ O (OC) R ₅ ] X X where R ₄ and R ₅ are independently C12-20 alkyl and the composition is substantially free of anionic surfactant. Such materials are manufactured by Hoechst. Preferably R ₄ and R ₅ are alkyl moieties of a fatty acid group having a chain length distribution similar to that of tallow.

Preferably, the cationic surfactant may also be a compound of the formula X® [CH ₃ (CH ₂ ) _n CO.NH (CH ₂ ) ₂ ] ₂ .NR ₁ R ₂ wherein n is 11-19;

R 1 is methyl and

R ₂ is - (CH ₂ CH ₂ O) _X (wherein x is

1-2), hydrogen or methyl.

Examples include ACCOSOFT 440/75 manufactured by Stepen.

In the above compositions, the x ethoxylation number is preferably from 1.5 to 2.0; for example 1.7.

The cationic surfactants in the compositions of the invention are believed to modify the surface energy of the treated surfaces by increasing the contact angle of the deposition on the modified surface after treatment. On the surface treated with the preferred cationic surfactants, the contact fluid angle of the test fluid is significantly increased. For example, the contact angle of 10 liters of dodecane droplet on a plate of untreated glass microscope is 10 °; if the plate with a composition according to the invention, i.e. 5% by weight nonionic and 1% by weight cationic surfactant

When treated with a composition containing a substance, as will be described in more detail below, the contact angle of the dodecan droplet typically increases to above 20 °.

It is a further object of the present invention to provide a method for cleaning hard negatively charged hard surfaces comprising the step of treating the surface with a composition of the invention.

It is important that the compositions of the invention contain a nonionic surfactant. The presence of nonionic surfactants significantly increases the cleaning effect of the compositions of the invention.

Nonionic detergent surfactants prepared by condensation of alkylene oxide groups of a hydrophilic nature with an aliphatic or aromatic hydrophobic compound are suitable.

The length of the hydrophilic or polyoxyalkylene moiety to be condensed with a particular hydrophobic group can be readily adjusted to obtain a water-soluble compound of the desired degree of hydrophilic-lipophilic equilibrium.

Examples of such compounds are the condensation products of straight or branched aliphatic alcohols having from 6 to 22 carbon atoms with ethylene oxide, such as coconut oil ethylene oxide condensate containing from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; and alkyl phenols having from 6 to 12 carbon atoms having from 5 to 25 moles of ethylene oxide per condenser of alkyl phenol

Particularly preferred are non-ionic surfactants having from 6 to 14 carbon atoms having 2-9 moles of ethoxylation degree. Of these, for example, IMBENTIN 91/35 OFA, which is a product of 10 carbon atoms with an average degree of ethoxylation of 5 ml, is suitable.

Several other known nonionic surfactants obtained by condensation of alkylene oxides with an aliphatic or alkyl aromatic compound are described in M. J. Schick, Nonionic Surfactants, Marcel Dekker (1967) and later editions.

The amount of nonionic detergent surfactant used in the compositions of the invention is generally from 1 to 30% by weight, preferably from 2 to 20% by weight and more preferably from 5 to 10% by weight.

The ratio of nonionic, anionic and cationic surfactants is particularly preferably such that more than 75% of the total amount of surfactant present in the composition is nonionic surfactant.

It is important that the compositions of the present invention contain only a small amount or practically no anionic detergent surfactant (i.e., the composition is substantially free of anionic surfactant). It is believed that the anionic surfactant complexes with the cationic surfactant, which reduces the efficacy of the formulations.

The total surfactant content of the compositions of the invention is generally from 1 to 30% by weight.

The compositions of the present invention optionally contain hydrophobic oils. Suitable oils which are rapidly soluble in triglyceride are suitable. Optional oils include, but are not limited to, limonene, paracimol, dibutyl ether and butyl butylate.

The compositions of the present invention may also contain other additives which enhance their cleaning effect.

The compositions may also contain, for example, detergent building materials. Suitable materials include carbonates and bicarbonates, nitrilotriacetates, polycarboxylates, cifrates, dicarboxylic acids, water-soluble phosphates, in particular polyphosphates, ortho- and pyrophosphate mixtures, zeolites and mixtures thereof. Such building materials (especially phosphates and carbonates), if present in greater than their water-soluble proportions, may also act as abrasives, but the compositions of the present invention preferably do not contain abrasive particulate materials. The amount of building material is generally 0.1 to 25% by weight of the composition.

The compositions of the invention may optionally contain metal ion sequestering agents (e.g. sequestering agents), such as ethylenediaminetetraacetates, amino polyphosphonates (DEQUEST) and phosphates, as well as a variety of other polyfunctional organic acids and salts.

The compositions of the invention may optionally contain antifoam agents. These agents are used when the formulations have a high tendency to foam during use. Such materials include, for example, organic solvents, hydrophobic silica, silicone oils or hydrocarbons.

The compositions of the invention may optionally contain solvents. Optional solvents are preferably those

Compounds of formula Ri-O- (EO) _m - (PO) _n -R _{2 in} which

R-ι and R ₂ are each independently C 2 -C 6 alkyl or hydrogen, but may not be both hydrogen, and m and n are each independently 0-5. More preferably, these solvents are diethylene glycol mono (n-butyl) ether, mono (ethylene glycol) mono (n-butyl) ether, propylene glycol n-butyl ether, isopropanol, ethanol, butanol and mixtures thereof. Pyrrolidones such as N-methylpyrrolidone may also be used as a solvent.

In addition to the additives described above, the compositions of the invention may optionally contain other additives, such as pH-adjusting agents, coloring agents, optical brighteners, suspending agents, cleaning enzymes, compatible bleaching agents, gel control agents, anti-freeze-thawing stabilizers, bactericides, preservatives, hydrotropic substances, perfumes and opacifiers.

The compositions of the present invention which are contaminated by burnt or otherwise crosslinked webs4

It is intended to remove alcohols, and most preferably also contains from 2 to 6% by weight of alkanolamine. Suitable alkanolamines include 2-amino-2-methyl-1-propanol, monoethanolamine and diethanolamine.

It has been found that the compositions of the present invention, when applied as a relatively fine mist, should preferably contain a polymer which prevents the formation of extremely fine droplets.

Suitable polymers include polyvinylpyrrolidone, a product commercially available from Polymer PVP K-90. The amount of PVP polymer used is at least 50 ppm, more preferably 300-2000 ppm.

The compositions of the present invention may be alkaline, acidic or neutral, preferably having a pH greater than 6, generally alkaline, to remove kitchen impurities.

Particularly preferred formulations have a pH greater than 10 and include the following in admixture with water:

a) from 3 to 15% by weight of a nonionic surfactant (preferably from 9 to 12 carbon atoms EO5-8 nonionic surfactant);

b) 2-10% by weight of solvent [preferably diethylene glycol mono (n-butyl) ether;

c) 2-6% by weight of alkanolamine (preferably 2-amino2-methyl-1-propanol);

d) 0-5% by weight of buffer / alkali (preferably an alkali metal carbonate);

e) 0-2000 ppm polymer (preferably PVP); and

f) 0.1 to 2% by weight of such

A compound of the formula wherein R ₁ and R ₂ are each independently hydrogen, C 1-4 alkyl, C 1-4 hydroxyalkyl, alkylene glycol residues, and polymers thereof;

n is from 8 to 26;

m is 1-4; and

Χ ^θ is the equivalent of a monovalent anion.

Preferably, this composition is packaged in a container capable of dispensing 0.1 to 1.5 mL of product per spraying operation. The average droplet size of the spray is 30-300 µm.

The following examples illustrate the compositions of the invention in more detail.

Examples

Aqueous formulations containing a nonionic surfactant and a relatively small amount of a cationic surfactant are prepared using the composition described in Tables 1 and 2 from the following materials (weight percent unless otherwise stated):

WOMAN: IMBENTIN 91/35 OFA (manufactured by Dr. W. Kolb SA);

CTAB: Cetyltrimethylammonium bromide;

HEQ [(CH3) _{3N-CH2-CHOOCR4} -OOCR _5] ®C | Q, wherein -OOCR ₅ -OOCR ₄ and the presence of the corresponding tallow chain fatty group (manufactured by Hoechst).

ACCO: ACCOSOFT 440/75 (Stepan). Chemical name: methylbis (hydrogenated tallow20 amidoethyl) -2-hydroxyethylammonium methylsulfate.

The formulations are prepared at room temperature by mixing the components except HEQ and ACCO. The latter two components at 70 ° C

It is dissolved in 3 parts of propylene glycol and then added to water with stirring at 70 ° C.

The results in Tables 1 and 2, designated "ETh" and "EPh", are described below. CTAB, which is typically a monoalkyl cationic surfactant, is used as a control which has a substantially lower effect on the contact angle of the dodecan droplet on a glass slide treated with a 5% w / w aqueous solution of 1% dialkyl cationic surfactant solution on a glass slide. .

The surface energy (Gamma _s ) of the microscope slides treated with the CTAB composition was 25 mN.m ^-1 (as measured by the Griflaco, Good Fowkes and Young method40, see Physical Chemistry of Surfaces, AA, Adamson, Wiley, New York). 1990)], while the surfaces containing the cationic surfactant of the present invention treated with similar solutions are less than 25 mN.m ^-1 .

Table 1

Examples preparation 1 2 3 4 5 GROW 5t% 5t% 5t% 5t% 5t% CTAB - 1% - - - HEQ - - 0.01% 0.1% 1/0% ETh * * * 2140 2119 EPH 2634 1697 - 896 776 Gamma _e > 25 25 - - 23.1

* meaning that the tile did not clear in 2 minutes, ie the cleaning power was probably around 10,000 Ns.

HU 226 238 Β1

Table 2

Examples preparation 6 7 8 9 GROW 101% 101% 101% 101% AMP 4% 4% 4% 4% K ₂ CO ₃ 1.2% 1.2% 1.2% 1.2% digol 8% 8% 8t% 8% Prop G - - 0.61% 3.01% CTAB - 1% - - ACCO - - 0.21% 1.01% ETh 930 469 189 137

AMP: amino-2-methyl-1-propanol.

Digol: n-butyl diethylene glycol ether (Butyl Digol ^R , Union Carbide).

Weigh 100 g of anhydrous castor oil (manufactured by NICHEMA) into a glass crucible. To this was added 0.2 g of Fata Red (SIMGA) dye and the mixture was vigorously stirred (2000 rpm) with a Heidolph mixer. The mixture is refrigerated until use.

Glass enamel tiles (380-300 mm) are cleaned by first using a freshly moistened J-CLOTH cloth and then a JIF LAC liquid hand dishwashing detergent and calcite powder. After drying, the remaining calcite is removed with a paper towel.

The cleaned tiles are wiped with J-CLOTH wipes freshly moistened with 1 ml of the formulations of Table 1. Excess formulations are removed by rinsing with tap water for 15 seconds and the tiles are allowed to dry. The tiles are contaminated in an area of 215 * 150 mm. The contamination is performed with a gravity-fed spray gun (MODEL MPS-514/515), commercially known as DeVilbiss, at a pressure of 137.8 kPa from 27 cm to 35 s. Contaminated tiles are placed horizontally in an oven at 85 ° C, then heat-aged for 2 hours, then stored overnight or in daylight

It is subjected to photochemical aging for 3-6 days. The tiles are cleaned again with wet J-wipes or 1-2 ml of a control composition containing the mixture described in Table 3 for the compositions of Table 1.

Table 3

control Products

5t% GROW 3.4% AMP 0.2 M K ₂ CO ₃ 5t% N-methylpyrrolidone

The force given in Table 1 for purification is "ETh" for heat-aged tiles, and "EPh" for photochemically-aged tiles.

The cleaned tiles are wiped with a freshly moistened J-CLOTH cloth with 2 ml of the preparation of Table 2. The tiles are contaminated and aged as previously described and cleaned with pretreatment formulations instead of the control formulation.

The results reported in Tables 1 and 2 show that the compositions of the present invention significantly reduce the purification power relative to comparative formulations that do not contain a cationic surfactant or other than a saturated dialkyl cationic surfactant.

Claims (13)

PATENT CLAIMS An aqueous composition for cleaning a hard surface comprising a mixture of surfactants, characterized in that the composition of the surfactant mixture is as follows: (a) by weight of total surfactant 45 at least 65% nonionic surfactants selected from ethylene oxide condensates of C 6 -C 22 aliphatic alcohols and 5 to 25 mol of ethylene oxide condensates per alkylene phenol of C 6 -C 12 alkyl phenols; 50 b) less than 1% by weight of total surfactant anionic surfactant; and c) 0.1% to 35% by weight, based on the total weight of the surfactant, of an ethylenically saturated dialkyl cationic surfactant containing at least two, Contains 55 alkyl groups having at least 8 carbon atoms: i) X ^e [R ₁ R ₂ R ₃ N®- _{(CH2) n} CH (O (OC) R ₄₎ - (CH _{2) m} O (OC) R _5] A compound of formula I wherein R _1t R ₂ and R ₃ are independently C 1 -C 6 alkyl or hydrogen; N and m are 0-4; -O (OC) R ₄ and -O (OC) R ₅ are C 8 -C ₂₆ fatty acid residues; and Χ ^θ is the equivalent of a monovalent anion; ii) X® [CH ₃ (CH ₂ ) _n (CO) NH (CH ₂ ) _m ] ₂ .N® R ₁ R _{2 in} which Ri and _R2 are independently selected from the group consisting of hydrogen, C1-4 alkyl, C1-4 hydroxy alkyl and alkylene glycol residues or polymers thereof; n is from 8 to 26; m is 1-4; and X® is the equivalent of a monovalent anion; iii) X ^Q [CH ₃ (CH ₂ ) _n (CO) O (CH ₂ ) _m j ₂ .N R ₁ R _{2 in} which R ι and R ₂ are independently selected from the group consisting of hydrogen, C1-4 alkyl, C1-4 hydroxyalkyl and residues or polymers of alkylene glycol n is from 8-26; m is 1-4; and Χ ^θ is the equivalent of a monovalent anion. Composition according to Claim 1, characterized in that it contains a total of 1 to 30% by weight of a surfactant. Composition according to claim 1 or 2, characterized in that the saturated dialkyl cationic surfactant is one X @ CH ₃ (CH ₂ ) _n (CO) NH (CH ₂ ) _m ] ₂ .N * R ₁ R ₂ wherein R ₃ and R ₂ are independently selected from hydrogen, C 1-4 alkyl, C 1-4 hydroxyalkyl, and alkylene glycol moieties or polymers; n is from 8 to 26; m is 1-4; and X® is the equivalent of a monovalent anion. The composition of claim 3, wherein the cationic surfactant comprises a cation wherein m = 1, n = 1 and R ₁ = R ₂ = R ₃ = CH ₃ . Composition according to claim 1 or 2, characterized in that the saturated dialkyl cationic surfactant is X (R ₁ R ₂ R ₃ N - (CH ₂ ) _n -CH (O (OC) R ₄ ) - (CH ₂ ) _m O (OC) R ₉ ) wherein R ₄ , R ₂ and R ₃ are each independently C 1 -C 6 alkyl or hydrogen; n and m are 0-4; -O (OC) R ₄ and -O (OC) R ₅ are C 8 -C ₂₆ fatty acid residues; and X® is the equivalent of a monovalent anion. 6. The composition of claim 5, wherein the cationic surfactant comprises a cation wherein R ₁ = CH ₃ and R ₂ = - (CH ₂ CH ₂ O) _X H, wherein x is an average of 1-2, or CH ₃ . 7. A composition according to claim 1 or 2, wherein the saturated dialkyl cationic surfactant is X® [CH ₃ (CH ₂ ) _n (CO) O (CH ₂ ) _m J ₂ .NR ₁ R _{2 in} which R ₂ and R ₂ are each independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, alkylene glycol residues, and polymers, n is from 8 to 26; m is 1-4; and X® is the equivalent of a monovalent anion. The composition of claim 7, wherein R ₃ is methyl and R ₂ is - (CH ₂ CH ₂ O) _X H (where x is an average of 1 to 2) or methyl and m is 2. 9. Composition according to any one of claims 1 to 3, characterized in that it also contains from 1 to 10% by weight of alkanolamine. 10. Composition according to any one of claims 1 to 3, characterized in that it contains essentially no anionic surfactant. 11. Composition according to any one of claims 1 to 3, characterized in that it has a pH greater than 6. 12. Composition according to any one of claims 1 to 3, characterized in that it also contains a building material component selected from the group consisting of carbonates and bicarbonates, nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates, in particular polyphosphates, ortho and mixtures thereof. 13. A process for cleaning hard negatively charged hard surfaces, comprising the step of treating the surface with a composition according to any one of the preceding claims.