GB2194547A - Laundry pre-spotter composition providing oily soil removal - Google Patents

Description

1 GB2194547A 1

SPECIFICATION

Laundry pre-spotter composition providing improved oily soil removal The present invention relates to laundry pre-spotting compositions which are in the form of clear, stable, microemulsions, solutions or gels and which are suitable for the treatment of heavily soiled areas of fabrics. More particularly, the invention relates to single-phase pre spotting compositions which are especially effective for the removal of oily stains and soils from fabrics and which are characterised by being "infinitely dilutable" with water, as herein defined, without concomitant phase separation. Thus, the removal of oily stains and soils is effected by 10 the application of the pre-spotting composition to the generally soiled areas of the fabric which solubilizes the oily soil, followed by rinsing with water in a wash or rinse bath wherein the diluted pre-spotting compositions remains in a clear, single-phase, avoiding the attendant prob lem of redeposition of the oily soil on the previously cleaned fabric.

The removal of oily soils and stains from fabrics has been the focus of much attention in the 15 laundry art. In particular, emphasis has been placed on pre-treating or pre-spotting articles of laundry which are not uniformly soiled, such as f, or example, shirt collars and cuffs, as a preliminary stain-removal treatment prior to regular washing. The detergent compositions which have been used and disclosed for pre-spotting have varied considerably encompassing, for example, commercial liquid laundry detergent compositions which are applied to the fabric as a 20 pre-spotter prior to being added to the wash bath, as well as formulations intended specifically for oily soil removal which contain one or more organic solvents. While the use of aqueous liquid laundry detergents has proven successful for cleaning a wide variety of soils, the removal of oily soils, in particular, is often troublesome insofar as such liquid compositions do not generally contain a solvent especially suited for oil solubilization, such as an organic solvent. On 25 the other hand, the known compositions which are specifically formulated for oily soil removal suffer from the fact that they are either impractical to use, or they do not avoid the problem of oily soil redeposition on the fabric in the wash or rinse bath.

The redeposition of oily soil is a problem attributable, in part, to phase separation of the pre spotting composition containing an organic solvent when such composition becomes "infinitely 30 dilutable" with water in the wash bath. In effect, the solubilized oily soil as well as the organic solvent itself become soils to be removed from the fabric when phase separation of the pre spotting composition occurs upon dilution. In this regard, the term "infinitely dilutable" which is used herein to characterise the pre-spotting compositions of the present invention refers to the fact that the pre-spotting compositions are formulated so that when diluted with water in a ratio 35 of at least 100 parts water to 1 part of composition, they are entirely in a clear single phase with no phase separation being present or apparent. This degree of dilutability is significant because it corresponds approximately to the dilution encountered by a pre- spotting composition when applied to a fabric which is subsequently rinsed with water, such dilution being about one hundred to one thousand-fold.

U.S. 4,180,472 to Mitchell et al is illustrative of a pre-treatment composition for oil stain removal which requires a multiple step operation. The patent describes a composition comprising a solvent such as an alkane in combination with a specified surfactant as an emulsifier. The described composition cannot be applied directly to the soiled fabrics, but rather, is added to the wash bath containing the items to be laundered. After oil solubilization from the soiled 45 fabrics is effected, removal of the solvent must be carried out in a second step using a specified surfactant as a solvent stripping agent. No single-phase composition is contemplated or dis closed.

U.S. Patents 4,093,418 and 4,178,262 to Compton et al describe laundry spot-agent compo sitions containing a solution of a nonionic surfactant and an isoparaffinic solvent. No water is 50 present in the composition nor is there any indication that such compositions can be readily removed from fabricq by immersion in a wash or rinse bath without the occurence of phase separation.

British Patent Specification 1,518,786, published July 19, 1978 discloses a detergent compo sition comprising a nonionic detergent, an organic solvent, such as, methyl laurate, and water. 55 The percentage of organic solvent in such composition is severely restricted, however, because according to the disclosure the solvent "tends to act as a load upon the general cleaning performance of the composition". This indicates that the solvent does not remain in solution in the wash bath, but rather, is separated out and acts as a soil. In Example 2 of the publication, the amount of organic solvent in the disclosed composition is 3.4%. Further, the disclosed compositions which appear to be in granular form are added directly to the wash bath, accord ing to the examples, rather than being conveniently applied to the soiled fabrics as a pre spotting composition.

Accordingly there remains a need in the art to provide an improved composition for oily soil removal which can be applied directly to soiled fabrics as a pre-spotter and which can be readily 65 2 GB2194547A 2 removed therefrom by rinsing with water.

The present invention provides a clear, single phase, liquid microemulsion, solution, or gel laundry pre-spotting composition comprising, by weight:

(a) from about 10 to 70% of an organic solvent comprising one or more alkanes having from 10 to 18 carbon atoms; (b) from about 4 to 60% of one or more nonionic surfactants comprising the condensation product of an aliphatic primary or secondary alcohol having from 9 to 16 carbon atoms with from 1 to 7 moles of ethylene oxide per mole of the said alcohol; (c) from about 0 to 50% of a supplementary nonionic surfactant comprising an amine oxide or an alkyl phenol ethoxylate, the total amount of nonionic surfactants in the pre-spotting compo- 10 sition being no greater than about 60%, by weight; (d) from about 0 to 20%, of a co-surfactant comprising an aliphatic primary or secondary alcohol having from 10 to 18 carbon atoms; (e) from about 0 to 10% of a polar organic co-solvent; (f) from about 1 to 80% water, the respective percentages of each component of the composition being such as to form a clear, single-phase pre-spotting composition which is further characterised by being infinitely dilutable with water without concomitant phase separa tion such that the addition of water to the said pre-spotting composition in an amount of at least one hundred parts water to one part of the said composition results in a diluted compo sition which is entirely in a clear single phase; (g) the balance optionally comprising a minor amount of adjuvants.

In accordance with the process of the present invention, the removal of oily soils and/or stains from fabrics with a pre-spotting composition is effected by contacting such stained fabrics, generally in the immediate area of the oily soil, with an effective amount of the above identified liquid or gel pre-spotting composition. This treatment can then be followed by regular 25 washing, if desired, or the treated fabrics can then be simply rinsed with an aqueous liquid, preferably water, to remove the pre-spotting composition containing the solubilized oil.

In addition to their utility as laundry and pre-spotting compositions, the compositions of the present invention are also particularly useful for the removal of oily or greasy soil from hard surfaces such as plastic, vitreous or metal surfaces having a shiny finish. Oily and greasy soils 30 present on such hard surfaces are readily solubilized in microemulsions, solutions or gels in accordance with the invention and hence such compositions may be effectively utilized as clear single phase all purpose cleaning compositions.

The described pre-spotting composition may be formulated as herein described to be in the form of a liquid solution, liquid microemulsion (either water-in-oil or oil-in-water type) or a gel, 35 depending upon the relative proportions of the three principal components of the composition, namely, organic solvent, surfactant and water. For each of these particular forms, the compo sitions of the invention are clear at ambient room temperature, thermodynamically stable and in a single phase. Thus, compositions which are in the form of emulsions, or mixtures which are not otherwise in a single-phase, clear at ambient conditions, and thermodynamically stable, are not in 40 accordance with the invention.

The term "microemulsions" as used herein refers to compositions containing two immiscible liquid phases: a dispersed phase (i.e. micelles) and a continuous phase. The individual droplets of the dispersed phase of the microemulsion generally have an average radius less than about 1000 Angstroms, typically between about 50 to 1000 Angstroms. In solution form, the dispersed or 45 non-continuous phase is generally below 40 Angstoms average radius. When the dispersed phase has an average radius greater than about 1000 Angstroms, it is no longer a microemul sion but an emulsion which is generally turbid and thermodynamically unstable. The measurement of average radius size of the dispersed phase can be carried out using conventional light scattering techniques.

The present invention is predicated upon the discovery that pre-spotting compositions contain- ing one or more organic solvents for oily soil removal can be formulated to satisfy two important requirements for the efficient application of a pre-spotting composition to a soiled fabric and - its efficient removal -therefrom while avoiding the problem of oil redeposition: (1) the pre-spotting composition is in the form of a clear, single-phase composition so as to allow the 55 oily soil upon the fabric to be rapidly solubilized by the pre-spotting composition; and (2) the pre-spotting composition is readily removable from the cleaned fabric by rinsing with water without phase separation occurring in the diluted pre-spotting composition. This latter character- R t istic of the composition is referred to as infinite dilutability with water. More specifically, a composition is considered infinitely dilutable when it can be diluted at least one hundred-fold by 60 weight with water to form a diluted composition which is -entirely in a clear, single-phase.

Accordingly, an essential characteristic of the present pre-spotting compositions is that such compositions regardless of whether in the form of a solution, microemulsion or gel, as well as the infinitely diluted compositions derived therefrom, are formed entirely of a clear, single phase.

Although the applicant does not wish to be bound to any particular theory of operation, it is 65 3 GB2194547A 3 believed that at a condition of infinite dilution, the diluted pre- spotting compositions of the present invention are in the form of an oil-in-water microemulsion. In such microemulsion, the oil (e.g. organic solvent) is the dispersed phase and is suspended in water which is the continuous phase thereby removing the organic solvent and solubilized oil from contact with the treated fabric. This allows the pre-spotting compositions to be readily removed from the treated fabric 5 by rinsing with water without the accompanying problem of phase separation and oily soil redeposition on the fabric. The formation of an oil-in-water microemulsion at infinite dilution is thus a characteristic of the presently described pre-spotting compositions.

It can be readily determined for purposes of the present invention whether a particular pre spotting formulation is infinitely dilutable in accordance with the following test: to one part of 10 the pre-spotting formulation there is added 100 parts or more of water while stirring, both the water and the formulation being at room temperature. The resulting diluted mixture is then allowed to stand for at least one hour and then observed for phase separation. If no phase separation is present either as a clear phase boundary or by the appearance of cloudiness or opacity, the composition is considered infinitely dilutable.

The pre-spotting compositions of the present invention are essentially comprised of three components: organic solvent, nonionic surfactant and water. In addition to these components, there may also be present, if desired, a co-solvent, a co-surfactant, a supplementary nonionic surfactant as hereinafter defined and adjuvants. The particular components employed and their relative amounts in the pre-spotting composition is determined on the basis of such composition 20 being in a clear single-phase and forming either a microemulsion (oil-in- water or water-in-oil), a solution (water-in-oil type i.e. oil is the continuous phase) or gel, and such composition having the further characteristic of being infinitely dilutable with water. The determination of whether a composition is infinitely dilutable with water is easily carried out in accordance with the test defined above and therefore the formulation of compositions which possess this characteristic is 25 readily arrived at by a simple trial and error technique.

The amount of organic solvent in the composition may vary from 10 to 70%, preferably from about 60 to 80% and most preferably from about 45 to 50%, by weight of the total pre spotting composition. The organic solvent may be comprised of one or more alkanes, straight chain or branched, having from 10 to 18 carbon atoms. Normal dodecane is a preferred solvent 30 for the present pre-spotting composition, with n-decane, n-tridecane and n-hexadecane being also particularly useful.

A polar organic co-solvent may optionally be added to the composition in an amount of up to about 10%, by weight. Among the useful polar co-solvents are the following: low molecular weight alcohols, such as isopropanol and hexanol; benzyl alcohol; oxoalcohol esters, such as the 35 TM Exxates (sold by Exxon); Butyl Carbitol (sold by Union Carbide Corporation); ketones, such as benzophenone; diglyme; dialkyl phthalate esters, such as dibutyl phthalate; esters of monohydric alcohols and fatty acids; esters of glycols and fatty acids; esters of glycerol and fatty acids; and esters of polyglycols and fatty acids.

The nonionic surfactant is preferably comprised of one or a mixture of primary alcohol ethoxy- 40 lates or secondary alcohol ethoxylates. The primary alcohol ethoxylates are represented by the general formula; R-O-(CH2-CH2-0)h-H wherein R represents an alkyl radical having from 9 to 16 carbon atoms and the number of ethoxylate groups, n,. is from 1 to 7. Commercially available nonionic surfactants of this type are sold by Shell Chemical Company under the tradename Neodol and by Union Carbide Corporation under the tradename Tergitol. Especially preferred for use herein are the following: Tergitol 24-L-5, Neodol 91-6, Neodol 45-2.25, and neodol 45-1, the latter, for example, being a 50 Cl,-C,, alcohol condensed with 1 mole of ethylene oxide per mole of alcohol.

The secondary alcohol ethoxylates are represented by the general formula:

CH,-(CHJ,-CH-(C1-12),-CH, 1 55 0 1 (CH,-CH2-0),-H wherein (X+Y) is from 6 to 13 and-the number of ethoxylate groups, n, is from 1 to 7. 60 Commercially available surfactants of this type are sold by Union Carbide Corporation under the tradename Tergitol S series surfactants.

The nonionic surfactants or mixture of surfactants which are useful for the present compo sitions have an HLB (hydrophilic-lypophilic balance) of from about 9 to 13, preferably from about 9 to 11, and most preferably from about 9.5 to 10.5. Generally, if the surfactant or surfactant 65 4 GB2194547A 4 mixture in the composition has an HLB higher than about 12, an oil- soluble fatty alcohol co surfactant (e.g. a C14-Cls alcohol) or a water and oil miscible polar organic cosolvent is required in the composition such as, isopropanol, hexanol or Butyl Carbitol.

In suitable circumstances, other nonionic surfactants can be present in partial replacement or supplementary to the above-defined alcohol ethoxylated surfactants. These supplementary surfac- 5 tants are comprised principally of two types of nonionic surfactants: amine oxides and alkyl phenol ethoxylates.

The useful amine oxides are represented by the general formula:

R2 1 R'-N,0 1 R3 wherein RI represents an alkyl radical containing from 12 to 18 carbon atoms, and R2 and R3 each represent a methyl, ethyl or hydroxyethyl groups. Commercially available surfactants of this type are sold by Armak under the tradename Aromox surfactant, such as, for example, Aromox DMMC-W the tradename for dimethyl cocoamine oxide.

The alkyl phenol ethoxylates which may be used in the compositions of the present invention 20 include the condensation products of alkylphenol having an alkyl group containing from about 8 to 10 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the said ethylene oxide being present in an amount of 4 to 15 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Tergitol NP surfactant sold by Union Carbide Corporation and Igepal surfactants sold by GAF Corpora tion. Particularly useful is Igepal CO-630 comprised of a C. alkyl phenol ethoxylate with 9 moles of ethylene oxide per mole of phenol.

In general, a supplementary nonionic surfactant may be advantageously used depending upon product economics, surfactant availability or to adjust the HLB of the nonionic surfactant mixture to a desired value.

The total amount of nonionic surfactant in the composition is from about 8 to 60%, preferably from about 15 to 50%, and most preferably from about 30 to 50%, by weight of the compo sition. The percentage of primary or secondary alcohol ethoxylate may vary from about 4 to 60% of the composition. Hence, if the level of the defined alcohol ethoxylates in the compo sition is below about 8%, by weight, we have found that ordinarily it is desirable for a supplementary nonionic surfactant as herein defined to be present in conjunction therewith. The supplementary nonionic surfactant may be present in a ratio of up to 5:1 relative to the alcohol ethoxylates, a ratio of from about 0.5:1 to 3:1 being preferred.

A co-surfactant may optionally be used in the pre-spotting compositions in an amount of up to about 20%, by weight, for purposes of lowering the HLB value of the nonionic surfactant or 40 mixture of n6nionic surfactants to the desired value. The co-surfactant is preferably comprised of a primary or secondary fatty alcohol having from 10 to 18 carbon atoms. Commercially available alcohols of this type are sold under the tradename Neodol by Shell Chemical Company. Neodol 45, a C,,-Cl, alcohol, is particularly useful as a co-surfactant in the compositions of the present invention.

The amount of water in the pre-spotting compositions may vary from about 1 to 80%, by weight, depending upon the desired form of the composition. Water-in-oil microemulsions or water-in-oil solutions are generally favoured when water is present at levels of from about 1 to - 15%, of the composition. Gels which are typically liquid crystalline or isotropic micro-emulsion gels, are generally formed when the amount of water is from about 25% to 50%, by weight. 50 Oil-in-water microemulsions are generally favoured when the water is present at levels of about 50% or higher of the total composition. When the water content is between about 15 to 25%, the resulting compositions will generally define a range of water-solventsurfactant mixtures which are not in a single phase and hence are outside the scope of the present invention.

Various adjuvants may be present in the pre-spotting compositions, such as fluorescent bright eners, bleaches, enzymes, perfumes and colourants. The perfumes that are employed usually include essential oils, esters, aldehydes and/or alcohols, all of which are known in the perfumery art. The colourants may include dyes and water dispersible pigments of various types. The bleach is preferably hydrogen peroxide in an amount of from 0 to 3%, by weight. The enzymes may be protease or amylase enzymes or mixtures thereof. Also present may be builders, such 60 as sodium sesquicarbonate; antiredeposition agents, such as sodium carboxymethyl-cellulose; dispersing agents, such as sodium polyacrylate; bactericides; fungicides; anti-foam agents, such as silicones, anti-soiling agents, such as copolyesters; preservatives such as formalin; and foam stabilizers.

The individual proportion of the aforementioned adjuvants will be less than 3%, by weight, 65 1 GB2194547A often less than 1%, except for builders for which the proportion may sometimes be about 5% or higher. The total percentage of adjuvants will normally be no more than 10%, by weight, of the pre-spotting composition and desirably less than 5% thereof. It is, of course, understood that the adjuvants employed are selected so as not to interfere with the essential physical character istics of the pre-spotting composition as well as the oily soil removal effected by such pre- 5 spotting composition.

The pre-spotting compositions may be prepared by simply mixing the components, the amount of agitation and the order of addition of components not being critical process parameters.

However, to reduce the mixing time and energy required in the manufacturing process the following orders of addition are preferred.

To form water-in-oil solutions, water-in-oil microemulsions or gels, the organic solvent and surfactant are combined followed by the addition of water. When two or more surfactants are used, the more oil soluble (i.e. hydrophobic) surfactant is combined with the solvent prior to adding the more water soluble (i.e. hydrophilic) surfactant, with water then being added to the resulting mixture.

To form oil-in-water microemulsions, the order of addition is reversed. Thus, the surfactant or surfactant mixture is first added to water followed by addition of the organic solvent. If a polar organic co-solvent is employed, it should be combined with the organic solvent prior to being added to the water-surfactant mixture. Where two or more surfactants are to be used, the more hydrophilic surfactant is first added to the water followed by addition of the more hydrophobic surfactant. If water-soluble adjuvants are to be used, they are the first components dissolved in the water before addition of the other components.

The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples. All parts and percentages are by weight unless otherwise specified.

EXAMPLE 1. 1- 1.21 Illustrative of the pre-spotting compositions of the present invention, Compositions 1 to 21 were prepared in accordance with the above-described methods of preparation and are set out as Examples 1.1 to 1.21 below. The particular form of the pre-spotting composition is indicated 30 for each composition described.

Example 1. 1

Ingredients WT. PERCENT n-Dodecane 42.0 35 Alcohol (C,-C,J ethoxylate 42.0(Neodol 91-6) (EO 6) Alcohol (C,,-C,J ethoxylate 11.2(Neodol 45-1) (EO 1) Water 4.8 40 wz, Form: water-in-oil solution 100.0 The names in parentheses in the Tables represent the commercial tradenames of the ingredients 45 marketed by their manufacturers and used in the composition. Neodol 91-6, for example, is an ethoxylated alcohol having from 9 to 11 carbon atoms with 6 moles of ethylene oxide per mole, of alcohol.

Example 1.2 50 Ingredients WT. PERCENT N-Dodecane 30 Alcohol (C12-C,J ethoxylate 30 (EO 5) Water 40 55 Form: gel 6 GB2194547A 6 Example 1.3

Ingredients WT. PERCENT n-Hexadecane 15.4 Alcohol (C9-CJ ethoxylate 9.5 (EO 6) Alcohol (C11-CA ethoxylate 4.8 (EO 1) Water 70.3 100.0 Form: oil-in-water (o/w) microemulsion 15 Q Example 1.4

Ingredients WT. PERCENT n-Dodecane 35.3 Alcohol (C,-C,,) ethoxylate 37.9 (EO 6) 20 Alcohol (C,-C,,) ethoxylate 4.3 (EO 2.25) Benzyl alcohol 6.9 Water 15.6 25 Form: water-in-oil (w/o) microemulsion 100.0 30 Example 1. 5

Ingredients WT. PERCENT n-Dodecane 15.0 Secondary alcohol (C,,) 15.0(Tergitol ethoxylate (EO 7) 15-S-7) 35 Alcohol (C,,-C,j ethoxylate 2.0 (EO 1) Benzyl alcohol 3.0 Water 65.0 40 Form: o/w microemulsion 100.0 Example 1. 6 - 45 Ingredients WT. PERCENT n-Dodecane 10.0 Secondary alcohol (C,j 10.0 ethoxylate (EO 5) Alcohol (C,,-C,j ethoxylate 2.0 50 (EO 3) Benzyl alcohol 2.0 Water 76.0 ------------- 100.0 55 Form: o/w microemulsion 7 GB2194547A 7 Example 1. 7

Ingredients WT. PERCENT n-Dodecane 24.0 Butyl Carbitol (Union 6.0 5 Carbide TM) Alcohol (C14-C15) ethoxylate 8.0 (EO 2.25) Dimethyl cocoamine oxide 10.0 Water 52.0 10 Form: o/w microemulsion 100.0 15 Example 1. 8

Ingredients WT. PERCENT PEG 400 Distearate 5.6 n-Dodecane 22.2 Alcohol (C147-Clj ethoxylate 7.4 20 (EO 2.25) Dimethyl cocamine oxide 7.4 Butyl carbitol 7.4 Water 50.0 25 Form: o/w microemulsion Example 1.9

Ingredients n-Dodecane Alkyl (CJ phenol ethoxylate (EO 9) Alcohol (C14-Clj ethoxylate 21.0 (EO 2.25) Water 100.0 WT, PERCENT 48.0 30.0 (lgepal CO-630) 1.0 100.0 Form: w/o solution 40 Example 1. 10

Ingredients WT. PERCENT n-Dodecane 10.0 45 Alkyl (C.) phenol ethoxylate 5.0 (EO 9) Alcohol (C14-Cls) ethoxylate 5.0 (EO 2.25) Butyl carbitol 5.7 50 Water 74.3 Form: o/w microemulsion 100.0 8 GB2194547A 8 Example 1. 11

Ingredients n-Dodecane Alkyl (CJ phenol ethoxylate (EO 9) Alcohol (C,4-C,,) ethoxylate 14.0 (EO 2.25) Water Form: w/o microemulsion Example 1. 12

Ingredients n-Dodecane Alcohol (C,-C,,) ethoxylate (EO 6) Alcohol (C14-Cl.) ethoxylate 4.5 (EO 1) Water WT. PERCENT 54.0 30.0 2.0 100.0 WT. PERCENT 17.0 9.7 68,8 Form: o/w microemulsion 100.0 Example 1. 13

Ingredients n-tridecane Alcohol (C,-C,,) ethoxylate (EO 6) Alcohol (C14-Clj ethoxylate 4.8 (EO 1) Water WT. PERCENT 15.4 9.5 70.3 Form: o/w microemulsion Example 1. 14 Ingredients n-Hexadecane Alcohol (C,-C,,) ethoxylate (110 6) 100.0 WT. PERCENT 48.0 31.8 Alcohol (C14-C,j ethoxylate 16.9 (EO 1) Water 3.3 ------------- 100.0 50 Form: w/o solution Example 1. 15

Ingredients WT. PERCENT 55 n-Dodecane 35.1 Alcohol (C9-C,j ethoxylate 51.3 (EO 6) Alcohol (C14-Cl.) 9.1 Water 4.5 60 Form: w/o solution 11 100.0 9 I GB2194547A 9 Example 1. 16

Ingredients WT. PERCENT n-Dodecane 14.8 Oxohexyl acetate 0.2 5 Alcohol (Q,-C,,) ethoxylate 22.0 (EO 6) Alcohol (C,,-CJ 3.0 Water 60.0 10 ------------- 100.0 Form: o/w microemulsion Example 1. 17 15 Ingredients WT. PERCENT n-Dodecane 30.0 Alcohol (C12-C14) ethoxylate 20.0 (EO 5) Water 50.0 20 Form: gel 100.0 25 Example 1. 18

Ingredients WT. PERCENT n-Dodecane 25.0 Alcohol (C,-C,,) ethoxylate 37.3 (EO 6) 30 Alcohol (C,,-ClEi) 5.1 (Neodol 45) Oxyhexyl acetate 0.4 Water 32.2 ------------- 100.0 35 Form: gel Example 1. 19

Ingredients n-Decane Alcohol (C,-C,j ethoxylate (EO 6) Alcohol (C14-C15) ethoxylate (EO 1) Water WT. PERCENT 40.9 23.6 11.0 24.5 100.0 Form: gel 50 Example 1.20 Ingredients n-Dodecane 55 Alcohol (C12-C,j ethoxylate (EO 5) Water Form: obin-water microemulsion WT. PERCENT 10.0 10.0 80.0 100.0 GB2194547A 10 Example 1.21

Ingredients WT. PERCENT n-Dodecane 45.0 Alcohol (C12-C14) ethoxylate 45.0 5 (EO 5) Water 10.0 Form: water-in-oil microemulsion 100.0 EXAMPLES 2.1 TO 2.3 The compositions of Examples 2.1 to 2.3 described below are illustrative of formulations which were all in the form of clear single-phase solutions yet were not infinitely dilutable as herein defined, and hence are not in accordance with the invention.

Example 2.1

Ingredients WT. PERCENT n-Dodecane 58.8 20 Alcohol (C12-Clj ethoxylate (EO 5) 39.2 Water 2.0 Form: w/o solution 100.0 Example 2.2

Ingredients WT. PERCENT n-Tridecane (Norpar 13) 50.0 Alcohol (C,-Cjethoxylate (EO 6) 22.2 Alcohol (C,,-Cj ethoxylate (EO 2.25) 17.8 Water 10.0 4' Q1 ------------- 100.0 35 Form: w/o solution Example 2.3

Ingredients WT. PERCENT 40 n-Tridecane 40.0 Alcohol (C,C,j ethoxylate (EO 6) 27.8 Alcohol (C,-C,j ethoxylate (EO 1) 22.2 Water 10.0 45 Form: w/o solution 100.0 EXAMPLE 3

Shown below is a composition, similar to the compositions of Examples 2.1 to 2.3 but 50 significantly different insofar as it is formulated to be infinitely dilutable and hence in accordance with the invention.

Ingredients WT. PERCENT n-Tridecane 45.0 55 Alcohol (C,-C,,) ethoxylate (EO 6) 25.0 Alcohol (C11-C15) ethoxylate (EO 2.25) 20.0 Water 10.0 ------------- 100.0 60 Form: w/o solution EXAMPLE 4

The following procedure was followed in evaluating the efficacy of prespotting compositions in accordance with the invention relative to the performance of commercial liquid compositions 65 P 11 GB2194547A 11 intended for oily soil removal.

The stained swatches to be cleaned were 3" x 4" (7.6 x 10.2cms) and consisted of the following:

1- Dirty motor oil on Dacron double knit (DMO); 2- Barbecue sauce on Dacron double knit (BBQ); 3- Carbon black in olive oil on cotton percale (EMPA); and 4- Artificial sebum/particulate on a blend of 65% Dacron/35% cotton (SEBUM).

An initial reflectance reading (Rd initial) of the stained swatches was recorded. A duplicate of 10 each stained swatch was used in the test. To each swatch there was applied 0.2 gram of the particular pre-spotting fluid which was then allowed to soak for four (4) minutes. The treated swatches were then added to a Tergotometer vessel with each bucket thereof containing the stained swatches to be tested in duplicate (a total of 8 stained swatches) for a particular pre- spotting composition. Each bucket of the Tergotometer contained one litre of water having dissolved therein 1.3 grams of a commercial powder laundry detergent composition, the water hardness being 150 ppm of artificial hardness as calcium carbonate. After adding the treated stained swatches to the wash liquor, the swatches were washed for 12 minutes at 100'F (38'C) while agitated at 100 rpm. The wash liquor was then discarded and replaced with one litre of water at 100'F (38'C) containing 150 ppm of artificial hardness. The swatches were then rinsed 20 for 5 minutes at 100 rpm, removed from the rinse water and allowed to air dry. The reflectance reading of each of the washed swatches (Rd final) was then recorded.

The percent soil removal (% SR) was calculated using the following equation:

Rd final-Rd initial % SR= X 100 92-Rd initial An oil-in-water microemulsion (Composition A) and a water-in-oil solution (Composition B), 30 compositions in accordance with the invention, were formulated as shown below:

COMPOSITION A (Example 4. 1) Ingredients WT. PERCENT n-Dodecane 15 Alcohol (C,-C,,) ethoxylate (EO 6) 15 35 Alcohol (C,,-C15) ethoxylate (EO 1) 4 Water 66 Form: o/w microemulsion COMPOSITION 8 (Example 4.2) 100.0 Ingredients WT. PERCENT n-Dodecane 44.0 45 Alcohol (C,-C,,) ethoxylate (EO 6) 44.0 Alcohol (C14-CJ ethoxylate (EO 1) 11.0 Water 1.0 ------------100.0 50 Form: o/w microemulsion Compositions A and B were evaluated for soil removal in accordance with the procedure described above as were the following four commercial formulations: a pre-spotter; a liquid laundry detergent composition; a pine oil-based liquid cleaner containing about 30% pine oil; and 55 a petroleum-based all purpose cleaner containing about 40% petroleum distillates. The results of the soil removal tests are shown In Table 1 below indicating the % SR achieved for each composition. A difference of about 5% SR units is considered to be the minimum that can be visually detected in a side-by-side comparison of two fabric.

12 GB2194547A 12 TABLE 1 % SR Prespotter DMO BBQ EMPA SEBUM 5 Composition A (o/w microemulsion) 8.2 55.9 30.1 73.4 Composition B 10 (o/w solution) 42.2 57.5 50.2 68.1 i Prespotter 7.3 39.6 49.0 63.5 1 ii Liquid laundry detergent 5.1 49.7 37.6 72.3 15 i iii Pine oil-based cleaner 9.8 63.6 55.3 66.5 iv Petroleum-based cleaner 15.9 61.3 52.9 67.1 As shown in the Table, the solution form of the present pre-spotting compositions (Compo- sition B) was markedly superior in performance relative to all four of the commercial pre-spotting and cleaning compositions with regard to removal of the DMO stain. The o/w microemulsion composition (Composition A) was essentially equivalent in performance to the commercial pre spotter and liquid laundry detergent but slightly inferior overall to the pine oil-based cleaner and 25 the petroleum-based cleaner. The pine oil-based cleaner and the petroleum based cleaner be come increasingly susceptible to problems of redeposition of the organic solvent, particularly at higher temperatures, such as above 100'F (38'C).

EXAMPLE 5 -

The procedure of Example 4 was followed to evaluate Composition C, a water-in-oil solution in accordance with the present invention, relative to a commercial liquid pre-spotting composition and a commercial liquid laundry detergent. Tap water at 114'F (45,C) was used in place of 100'F (35'C) water containing 150 ppm hardness. The stains tested were DIVIO, BBW and EMPA as previously described.

Composition C was comprised of the following:

COMPOSITION C Ingredients WT. PERCENT n-Dodecane 48.2% 40 Oxohexyl alcohol 0.8 Alcohol (C,-C,,) ethoxylate (EO 6) 34.2 Alcohol (C14-C15) ethoxylate (EO 1) 14.8 Water 2.0 45 Form: w/o solution 100.0 The results of the cleaning tests are shown in Table 2 below:

TABLE 2 % SR Pre-Spotter DMO BBQ EMPA 55 Composition C 30.1 66.1 42.1 Commercial pre-spotter 6.4 41.5 37.5 Liquid laundry detergent 3.2 47.0 35.6 60 As shown in Table 2 above, Composition C was markedly superior as a pre- spotting composition relative to the commercial compositions.

Claims (11)

13 GB2194547A 13 1. A clear, single phase, liquid microemulsion, solution, or gel cleaning composition compris ing, by weight:

(a) from about 10 to 70% of an organic solvent comprising one or more alkanes having from to 18 carbon atoms; (b) from about 4 to 60% of one or more nonionic surfactants comprising the condensation 5 product of an aliphatic primary or secondary alcohol having from 9 to 16 carbon atoms with from 1 to 7 moles of ethylene oxide per mole of the said alcohol; (c) from about 0 to 50% of a supplementary nonionic surfactant comprising an amine oxide or an alkyl phenol ethoxylate, the total amount of nonionic surfactants in the pre-spotting compo- sition being no greater than about 60%, by weight; (d) from about 0 to 20%, of a co-surfactant comprising an aliphatic primary or secondary alcohol having from 10 to 18 carbon atoms; (e) from about 0 to 10% of a polar organic co-solvent; (f) from about 1 to 80% water, the balance optionally comprising a minor amount of adju- 1 vants, the respective percentages of each component of the composition being such as to form 15 a clear, single-phase pre-spotting composition which is further characterised by being such that dilution at 25"C of the said pre- spotting composition with water in an amount of one hundred parts water to one part of the said composition results in a diluted composition which is entirely clear when observed one hour after the dilution.

2. A cleaning composition as claimed in Claim 1 in which the amount of water is from about 20 1 to 15%, by weight of the composition.

3. A cleaning composition as claimed in Claim 1 or Claim 2 in which the organic solvent is ndodecane.

4. A cleaning composition as claimed in any one of Claims 1 to 3 in which the nonionic surfactant is the condensation product of a primary alcohol having from 12 to 14 carbon atoms 25 with five moles of ethylene oxide per mole of the said alcohol, and in which the said pre spotting composition is substantially free of the said co-surfactant.

5. A cleaning composition as claimed in any one of Claims 1 to 4 in which the HLB value of the nonionic surfactant or surfactant mixture in the pre-spotting composition is from about 9 to 11.

6. A cleaning composition as claimed in any one of Claims 1 to 5 which contains a supplementary nonionic surfactant comprised of an alkyl phenol ethoxylate.

7. A cleaning composition as claimed in any one of Claims 1 to 6 which contains a supplementary nonionic surfactant comprised of an amine oxide.

8. A cleaning composition as claimed in Claim 1 in the form of a water-inoil solution 35 comprising, by weight, about 45% tridecane; about 29.2% of a primary alcohol ethoxylate wherein the alcohol has from about 9 to 11 carbon atoms and is condensed with 6 moles of ethylene oxide per mole of alcohol; about 15.8% of a primary alcohol ethoxylate wherein the alcohol has from about 14 to 15 carbon atoms and is condensed with 2.25 moles of ethylene oxide per mole of alcohol; and about 10% water.

9. A cleaning composition as claimed in Claim 1 substantially as specifically described herein with reference to the accompanying examples 1, 3, 4 or 5.

10. A cleaning composition as claimed in any one of Claims 1 to 9 in the form of a laundry pre-spotting composition.

11. A process of spotting and laundering fabrics containing an oily soil and/or stain compris- 45 ing:

(1) contacting the soiled fabrics with an effective. amount of a clear, single-phase, liquid microemulsion, solution, or gel laundry pre-spotting composition as claimed in Claim 10, (2) rinsing the fabrics treated in step (1) with an aqueous liquid so as to remove the pre- spotting composition from said fabrics and thereby recovering the laundered fabrics sub,stantially 50 free of the said oily soils and/or stains.

Published 1988 at The Patent Office, State House, 66/71 High Holborn, London WC1R 4TP. Further copies may be obtained from The Patent Office, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Burgess & Son (Abingdon) Ltd. Con. 1/87.