GB1593108A - Stain-removing compositions - Google Patents

Abstract

A liquid pre-wash spot removing composition which is in the form of a clear, compatible, homogeneous, stable liquid and which is applied to spots or heavily soiled areas of laundry, items of clothing and fabrics before carrying out a customary washing process. It contains (1) 10 to 40 % by weight of benzyl alcohol and/or beta -phenylethyl alcohol as a lubricant or solvent for fats, (2) 5 to 35 % by weight of a chloro-substituted aliphatic hydrocarbon solvent having 1 to 6 carbon atoms, which is liquid at room temperature, and (3) 5 to 40 % by weight of at least one non-ionic surfactant and optionally up to 30 % by weight of an organic solvent and/or up to 40 % by weight of water and/or up to 15 % by weight of at least one anionic surfactant. With the aid of these pre-wash spot removing compositions it is possible to get heavily soiled areas of the fabric perfectly clean without increased amounts of detergents having to be used in the subsequent washing process. This is extremely advantageous taking into account the environmental pollution due to detergents.

Description

(54) STAIN-REMOVING COMPOSITIONS (71) We, COLGATE-PALMOLIVE COMPANY, a Corporation organised under the laws of the State of Delaware, United States of America, of 300 Park Avenue, New York, New York 10022, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to stain-removing compositions, particularly to compositions useful as laundry pre-spotters effective for the removal of stains on fabrics, and to a method of using such compositions.

The removal of certain kinds of stains from fabrics, particularly greasy stains, organic or inorganic, has been and still remains a problem. Suggested solutions have included intensifying the washing conditions, such as increasing the concentration of the detergent, increasing the temperature of the washing solution or increasing the agitation. However, those expedients are not always sufficient; nor are they desirable since they may cause damage to the fabrics. For delicate fabrics, the above-mentioned suggestions cannot be applied since delicate fabrics must be washed at low temperatures and with no more than gentle agitation.

Furthermore, a stain is localized to a particular spot on the fabric and it would be illogical and wasteful to treat the entire item to wash out one stain.

Late in the 1960's, some so-called pre-spotters, which were compositions intended to be applied to stains prior to laundering, appeared on the U.S. market.

Pre-spotters usually contain mixtures of surfactants (surface-active agents) and solvents used for dry cleaning.

The solvent assists in dissolving some components of the stains while the surface-active agent emulsifies or solubilizes the components which are soluble in water but not dissolved by the solvent. The surface-active agent also helps against soil redeposition by modifying the surface tension at the soil-fabric interface.

Most soils or stains deposited on fabrics may be listed in three groups; (i) solvent-soluble soils, e.g. human sebum and its degradation products; (ii) watersoluble soils, e.g. perspiration and some foods; and (iii) insoluble soils, e.g. dust.

This explains why one substance cannot be expected to be efficient on all types of soils.

The present invention provides a stain-removing composition useful as a prespotter composition which is more efficient on a broad spectrum of stain than presently available pre-spotters.

In accordance with the present invention a stain-removing composition comprises: (I) from 10% to 400/, by weight of a solvent for greasy material which is benzyl alcohol or p-phenylethylalcohol or a mixture thereof; (2) from 5% to 35% by weight of a chlorine-substituted hydrocarbon solvent having from 1 to 6 carbon atoms and which is a liquid at room temperature; (3) from 5% to 20% by weight of an additional organic solvent selected from ethylene glycol, propylene glycol, butylene glycol and mixtures thereof; (4) from 5% to 30% by weight of water; (5) from 5% to 40% by weight of at least one nonionic surface-active agent; and (6) optionally up to 10% by weight of at least one anionic surface active agent, the composition being in the form of a clear, homogeneous, stable liquid having a pH in the range from 7 to 9.

Component (1), the solvent for greasy materials, is preferably present in an amount from 20% to 30 /n by weight. Benzyl alcohol is preferred for this component.

Component (2), the chlorinated hydrocarbon solvent, is preferably present in an amount from 10% to 25 /n by weight. Examples of such solvents are methylene chloride; ethylene dichloride; carbon tetrachloride; 1,2-dichloroethane; 1,1,1trichloroethane; 1,3-dichloropropane; chloroform; 1,4-dichlorobutane; perchloroethylene; trichloroethylene and mixtures thereof. Of these, perchloroethylene and 1,1,1 -trichloroethane are preferred, perchloroethylene being most preferred.

Component (3), the additional organic solvent, is preferably present in an amount from 5% to 20% by weight. The preferred additional organic solvent is propylene glycol.

Component (4), water, is preferably deionized or distilled water.

Component (5), the nonionic surface-active agent(s), is preferably present in an amount from 10% to 30% by weight. The choice of particular nonioinc surface active agents is not critical, e.g. any of the well-known nonionic surface-active agents may be used. Examples of conventional nonionic surface-active agents include those nonionic detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or amino with an alkylene oxide, e.g. ethylene oxide, or with the polyhydration product thereof, e.g.

polyethylene glycol. As examples of such nonionic surface-active agents there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g. the reaction product of nonyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to 15 ethylene oxide units; condensation products of fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydroic alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol monooleate and mannitan mono palpitate, and the condensation products of polypropylene glycol with ethylene oxide.Other suitable nonionic surface-active agents include alkylolamine condensates of fatty acids, such as lauric and myristic mono- and di-ethanolamine; alkyl amine oxides such as lauryl dimethyl amine oxide and lauryl bis(hydroxy ethyl) amine oxide; and alkyl mono- and di-sulphoxides and phosphine oxides.

Among the above-listed nonionic surface-active agents, those of the ethoxylated alcohol type are preferred. Most preferred is an ethoxylated alcohol having 12 to 15 carbons and an ethylene oxide ratio of about 7:1.

Although it is preferred to use only nonionic surface-active agents, the composition may optionally include as component (6) at least one anionic surfaceactive agent, in an amount up to 10% by weight. In this instance, the anionic surface-active agent merely acts as a booster. The choice of anionic surface-active agents is not critical. Useful anionic surface-active agents include those detergent compounds which' contain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulphonate, sulphate, carboxylate, phosphonate and phosphate.Examples of suitable anionic detergents include soaps such as the water-soluble salts of fatty acids or rosin acids such as may be derived from fats, oils and waxes of animal, vegetable or mineral origin, e.g. the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and sulphated and sulphonated synthetic detergents, particularly those having at least 8 and up to 30, preferably from 12 to 22, carbon atoms in the molecular structure.As examples of suitable synthetic anionic detergents there may be cited higher-alkyl mononuclear aromatic sulphonates such as higher-alkyl benzene sulphonates containing from 10 to 16 carbon atoms in the higher-alkyl group in a straight or branched chain, e.g. the sodium salts of higher-alkyl benzene sulphonic acids or of higher-alkyl toluene, xylene and phenol sulphonic acids; other alkyl toluene, xylene and phenol sulphonates; alkyl naphthalene sulphonates; ammonium diamyl naphthalene sulphonate; and sodium dinonyl naphthalene sulphonate. The higher-alkyl groups may be mixed long chain alkyls derived from coconut oil fatty acids and tallow fatty acids, while cracked paraffin wax olefins and polymers of lower monoolefins may also be used as higher-alkyl sources. In one preferred type composition there is used a linear alkyl benzene sulphonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers; in other terminology the benzene ring is preferably attached in large part at the 3 or higher (e.g. 4, 5, 6 or 7) position of the alkyl group and the content of isomers at which the benzene ring is attached at the 2 to 1 position is correspondingly low. Other suitable anionic detergents are olefin sulphonates including long chain alkene sulphonates, long chain hydroxy alkane sulphonates or mixtures of alkene-sulphonates and hydroxy alkane-sulphonates.These olefin sulphonate detergents may be prepared in known manner by the reaction of sulphur trioxide with long chain olefins (of 8 to 25 and preferably of 12 to 21 carbon atoms) of the formula RCH=CH R1 where R is alkyl and R, is alkyl or hydrogen to produce a mixture of sultones and alkene sulphonic acids, which mixture is then treated to convert the sultones to sulphonates.

Especially good characteristics are obtained by the use of a feed stock containing a major proportion, i.e. above 70% and preferably above 90%, of alpha olefins.

Examples of such products are C14 alpha olefin sulphonate and C,6 alpha olefin sulphonate. Examples of other sulphate or sulphonate detergents are paraffin sulphonates such as the reaction products of alpha olefins and bisulphites (e.g.

sodium bisulphite), for instance primary paraffin sulphonates of 10 to 20, preferably 15 to 20, carbon atoms, such as sodium n-pentadecane sulphonate and sodium noctadecyl sulphonate; sulphates of higher alcohols; and salts of alphasulpho fatty esters (e.g. of 10 to 20 carbon atoms, such as metal alpha-sulpho myristate or alpha sulpho tallowate).Examples of sulphates of higher alcohols are sodium lauryl sulphate, sodium tallow alcohol sulphate; turkey red oil or other sulphated oils, and sulphates of mono- or di-glycerides of fatty acids (e.g. stearic monoglyceride monosulphates), sulphates of alkyl condensation products of ethylene oxide and lauryl alcohol (e.g with 1 to 20 ethylene oxide groups per molecule) and sulphates of condensation products of ethylene oxide and nonyl phenol (e.g. having 1 to 10 ethylene oxide groups per molecule and usually from 2 to 10 such groups). The suitable anionic detergents include also acyl sarcosinates (e.g. sodium lauroyl sarcosinate); acyl esters (e.g. oleic acid ester) of isethionates; and acyl N-methyl taurides (e.g. potassium N-methyl lauroyl or oleoyl tauride).In each instance, the acyl moieties will usually be in the range from C10 to C20, preferably C,2 to C,6. The most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono, di- and tri-ethanolamine), alkali metal (such as sodium and potassium), and alkaline earth metal (such as calcium and magnesium) salts, of the higher alkyl benzene sulphonic acids, olefin sulphonic acids and higher alkyl sulphuric acids. Among the above-listed anionic surface-active agents, the most preferred are the sodium alkyl benzene sulphonates (LAS).

The composition may further contain (7) a solubilizer in such an amount as to keep the liquid mixture stable, homogeneous and transparent when aged at temperatures ranging from -40C to 430 C. Examples of suitable solubilizers are urea, sodium xylene sulphonate and sodium cumene sulphonate, urea being preferred since it ensures better stability at low temperatures. The amount of solubilizer used in the composition may be up to 10% by weight, preferably about 6% by weight.

Various supplemental ingredients, which are optional but desirable, can be included in the pre-spotter composition. These comprise, for example, germicides, colouring dyes and perfumes, all of which, when utilized, are employed in small amounts, most of them below 1% by weight of the composition.

The composition can be formed by mixing the above-mentioned ingredients in any sequence. However, the following sequence is preferred. The nonionic surface active agent (5) is mixed with the organic solvent (3). The anionic surface active agent (6), if used, is dissolved in some of the water (4). This anionic/water solution is then mixed with the nonionic/organic solvent solution. To the resulting solution, the solvent for greasy materials (1) is added. The solubilizer (7), if used, is then dissolved in the remainder of the water (4) and added to the mixture. Lastly, the chlorinated solvent (2) is added to form the final product.

The above composition may be aplied to the fabric by any of a number of methods. The composition may be sprayed onto the fabric by means of either a mechanical spraying apparatus including a pump or an aerosol spray wherein the composition includes a small portion of an aerosol propellant, for example, nitrous oxide, carbon dioxide, isobutane, and polar hydrocarbon and chlorinated hydrocarbon propellants. The composition may also be sprinkled on the fabrics although an even, finely dispensed spray is preferred. The composition is sprayed onto the fabric either covering the entire fabric if the same is heavily soiled or only upon those areas which require special pre-treatment. Subsequent to the spraying, the fabrics may be washed in any conventional manner utilizing either nonionic, cationic or anionic detergents or soaps.

Although it is preferred to use the composition as a prespotter, i.e. for treating the stain just prior to washing, the composition may also be used simply as a stainremover. In this instance, the composition is applied to the stain on the fabric and the solvents are allowed to evaporate.

The following Examples illustrate the invention.

EXAMPLES 1--15 A composition embodying the present invention and having the ingredients shown in Table I was formed by mixing the ingredients in the same order as they are listed (Formula I).

TABLE I

Ingredients Weight, % "Dobanol 25-7"* (5) 15.6 Propylene glycol (3) 13.8 Water (part of 4) 10.8 "LAS" (6) 2.1 Benzyl alcohol (1) 26.1 U rea (7) 6 Water (remainder of 4) 10 Perchloroethylene (2) 15.6 *an ethoxylated alcohol having 12 to 15 carbons and an ethylene oxide ratio of 7:1.

Dobanol is a trade mark.

A 10x12 cm cotton swatch was artificially soiled in a uniform way. Fifteen commonly encountered stains were deposited on the swatches. Then, 0.12 g of Formula I was applied to the swatches. After a contact time of IT minutes, the swatches were laundered in a Tergotometer (300 ppm water, 2 g/l of French Gamma detergent, wash temperature at 800C for 10 minutes and 4 swatches per beaker). After rinsing and drying, the swatches were read on a Gardner Reflectometer at two places, one where the pre-spotter had been applied (D1) and the other where the pre-spotter had not been applied (D2). Stain removal due to the pre-spotter was expressed by A=D1-D2.

Comparative experiments were conducted with a commercially available prespotter composition containing 150it nonionics (ethoxylated fatty alcohol) and 85% petroleum distillated (Formula II). The procedure used in Examples 1--15 was repeated with the exception that Formula II was used.

The results are summarized in Table II, where "comparative efficiency" of the formulae was used in order to eliminate the effects of the concentration of the soil.

In Table II, the following code was used: ++ positive effect, superior to that of other product.

+ positive effect 0 no effect - negative effect, stain reset by the prespotter.

TABLE II Example Stains Formula I Formula II 1 Ink ++ + 2 Shoe Polish + + + 3 Blood ++ + 4 Spangler Soil* + + 5 Tomato Sauce + + 6 Gouache Lilac + 7 Gouache Pink + 8 Chocolate+Milk + 9 Coffee+Milk + 0 10 Gravy + 0 11 Wine + 0 12 Apricot + 0 13 Black Currant + 0 14 Raspberry + 0 15 Grapes + 0 *A synthetic sebum which simulates soil on collars derived from perspiraton in the neck area.

The results in Table II show that Formula I was efficient on all listed stains whereas Formula II was less efficient in Examples 1--3, had no effect in Examples 9-15, and an undesirable effect in Examples 8 where the stains were reset rather than removed.

The results of Table II clearly indicate the superiority of Formula I, the composition of the present invention.

WHAT WE CLAIM IS: 1. A stain-removing composition comprising: (1) from 10% to 40 /n by weight of a solvent for greasy material which is benzyl alcohol or ,B-phenylethylalcohol or a mixture thereof; (2) from 5% to 35 /n by weight of a chlorine-substituted aliphatic hydrocarbon solvent having from 1 to 6 carbon atoms and which is a liquid at room temperature; (3) from 5% to 20% by weight of an additional organic solvent selected from ethylene glycol, propylene glycol, butylene glycol and mixtures thereof; (4) from 5% to 30% by weight of water; (5) from 5% to 40% by weight of at least one nonionic surface-active agent; and (6) optionally, up to 10% by weight of at least one anionic surface active agent; the composition being in the form of a clear, homogeneous, stable liquid having a pH in the range from 7 to 9.

2. A composition as claimed in Claim 1 wherein component (2) is selected from methylene chloride; ethylene dichloride; carbon tetrachloride; 1,2dichloroethane, I,l,l-trichloroethane; 1,3-dichloropropane; chloroform, 1,4dichlorobutane; perchloroethylene; trichloroethylene; and mixtures thereof.

3. A composition as claimed in Claim 1 or Claim 2 wherein the amounts by weight of the components present are: component (1) from 20% to 30 /n; component (2) from 10% to 250/, and is perchloroethylene or l,l,l-trichloroethane; component (3) from 10% to 20% and component (4) from 10% to 30%.

4. A composition as claimed in any of the preceding Claims wherein component (1) is benzyl alcohol, component (2) is perchloroethylene, and component (3) is propylene glycol.

5. A composition as claimed in any of the preceding claims which also contains (7) up to 10% by weight of a solubilizer.

6. A composition substantially as hereinbefore described as Formula I.

7. A process for removing stains and soil from a fabric, comprising first treating the fabric with a composition as claimed in any of the preceding Claims as a pre-spotter, and then laundering the fabric using a detergent composition.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (7)

**WARNING** start of CLMS field may overlap end of DESC **. The results in Table II show that Formula I was efficient on all listed stains whereas Formula II was less efficient in Examples 1--3, had no effect in Examples 9-15, and an undesirable effect in Examples 8 where the stains were reset rather than removed. The results of Table II clearly indicate the superiority of Formula I, the composition of the present invention. WHAT WE CLAIM IS:

1. A stain-removing composition comprising: (1) from 10% to 40 /n by weight of a solvent for greasy material which is benzyl alcohol or ,B-phenylethylalcohol or a mixture thereof; (2) from 5% to 35 /n by weight of a chlorine-substituted aliphatic hydrocarbon solvent having from 1 to 6 carbon atoms and which is a liquid at room temperature; (3) from 5% to 20% by weight of an additional organic solvent selected from ethylene glycol, propylene glycol, butylene glycol and mixtures thereof; (4) from 5% to 30% by weight of water; (5) from 5% to 40% by weight of at least one nonionic surface-active agent; and (6) optionally, up to 10% by weight of at least one anionic surface active agent; the composition being in the form of a clear, homogeneous, stable liquid having a pH in the range from 7 to 9.

2. A composition as claimed in Claim 1 wherein component (2) is selected from methylene chloride; ethylene dichloride; carbon tetrachloride; 1,2dichloroethane, I,l,l-trichloroethane; 1,3-dichloropropane; chloroform, 1,4dichlorobutane; perchloroethylene; trichloroethylene; and mixtures thereof.

3. A composition as claimed in Claim 1 or Claim 2 wherein the amounts by weight of the components present are: component (1) from 20% to 30 /n; component (2) from 10% to 250/, and is perchloroethylene or l,l,l-trichloroethane; component (3) from 10% to 20% and component (4) from 10% to 30%.

4. A composition as claimed in any of the preceding Claims wherein component (1) is benzyl alcohol, component (2) is perchloroethylene, and component (3) is propylene glycol.

5. A composition as claimed in any of the preceding claims which also contains (7) up to 10% by weight of a solubilizer.

6. A composition substantially as hereinbefore described as Formula I.

7. A process for removing stains and soil from a fabric, comprising first treating the fabric with a composition as claimed in any of the preceding Claims as a pre-spotter, and then laundering the fabric using a detergent composition.