CA1283511C - Laundry pre-spotter composition providing improved oily soil removal - Google Patents
Laundry pre-spotter composition providing improved oily soil removalInfo
- Publication number
- CA1283511C CA1283511C CA000544828A CA544828A CA1283511C CA 1283511 C CA1283511 C CA 1283511C CA 000544828 A CA000544828 A CA 000544828A CA 544828 A CA544828 A CA 544828A CA 1283511 C CA1283511 C CA 1283511C
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- alcohol
- water
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- carbon atoms
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
- C11D17/0021—Aqueous microemulsions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
LAUNDRY PRE-SPOTTER COMPOSITION
PROVIDING IMPROVED OILY SOIL REMOVAL
ABSTRACT OF THE INVENTION
A clear, single phase, pre-spotting composition is provided in the form of a microemulsion, solution, or gel and which comprises, 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 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 composition being no greater than about 60%; (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 characterized by being infinitely dilutable with water without concomitant phase separation such that the addition of water to said pre-spotting composition in an amount of at least one hundred parts water to one part of said composition results in a diluted composition which is entirely in a clear single phase; and (g) the balance optionally comprising a minor amount of adjuvants.
PROVIDING IMPROVED OILY SOIL REMOVAL
ABSTRACT OF THE INVENTION
A clear, single phase, pre-spotting composition is provided in the form of a microemulsion, solution, or gel and which comprises, 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 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 composition being no greater than about 60%; (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 characterized by being infinitely dilutable with water without concomitant phase separation such that the addition of water to said pre-spotting composition in an amount of at least one hundred parts water to one part of said composition results in a diluted composition which is entirely in a clear single phase; and (g) the balance optionally comprising a minor amount of adjuvants.
Description
.283~
BACKGROUND OF THE INVENTION
This invention relates to laundry pre-spotting compositions which are in the Eorm of clear, stable, micro-emulsions, solu-tions 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 characterized by being "infinitely dilutable" with water, as herein defined, without concomitant phase separation. Thus, the removal of oily stains and soils is effected by 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 composition remains in a clear, sin~le-phase, avoiding the attendant problem of redeposition of the oilv soil on the previously cleaned fabric.
The removal oE oily soils and stains from fabrics has been the focus oE much attention in the laundry art. In particular, emphasis has been placed on pre-treating or pre-spotting articles of laundry which are not uniformly soiled, suchas for 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 pre~spotter prior to being added to the wash bath, as .we~ as formulations intended specifically for oily soil removal which contain one or more organic solvents. While the use of ~,.
', , ' : .: : . . ' ' . :
' . - : - , , ; - . . .. .
- ' ' ~2~335~ 6230l-l434 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 the other hand, the ~nown 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" or extremely diluted with water in the wash bath. In efect, 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 "in~inite dilutability" which is used herein to char~cterize the pre~spotting compositions of the present inventi.on refers to the fact that the pre-spotti.ng compositions are formulated such that when diluted with water in a ratio of at least 100 parts water to 1 part of compositi.on, they are entirely in a clear single phase with no phase separation being present. 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.
- 3 - ~ ~835~1 U. S. Patent 4,180,472 to Mitchell et al is illustrative of a pre-treatment composition for oily 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 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 disclosed.
U. S. Patents 4,093,418 and 4,178,262 to Compton et al describe laundry spot-agent compositions containing a solution of a nonionic surfactant and an isoparaffinic solvent. No water is present in the composition nor is there any indication that such compositions can be readily removed from fabrics by immersion in a wash or rinse bath without the occurrence oE phase separation.
British patent specification 1l518,786, published July 19, 1978 discloses a detergent composition comprising a nonionic detergent, an organic solventl such as, methyl laurate, and water.
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 soilO In example 2 of the publication, the amount of organic solvent in the disclosed composition is '': ' ' : ' ' ~
~ 4 ~ ~ ~3~
3.4~. Further, the disclosed compositions which appear to be in granular form are added directly to the wash bath, according 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 removed there~rom by rinsing with water.
SUMM~RY OF THE INVENTION
_ 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 compris-ing one or more alkanes having from 10 to 18 carbon atoms;
(b) ~rom 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 said alcohol;
(c) from about 0 to 50% of a supplementary nonionic surfactant comprising an amine o~ide ox an alkyl phenol ethoxylate, the total amount of nonionic surfactants in the pre-spotting composition 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 D~
.-.
.
. , ~ . - .
- 5 _ ~Z83S1~ 52301-1434 percentages of each component of the composition being such as to forrn a clear, single-phase pre-spotting composition which is further characterizecl by being lnfinitely dilutable with water without concomitant phase separation such that the addition of water to said pre-spotting composition in an amount of one hundred parts wa-ter to one part of said composition results in a diluted composition which is entirely in a clear single phase;
(g) the balance optionally comprising a minor amount of adjuvants, In a preferred embodimen-t of the invention the pre-spotting composition comprises, by weight, about 45%
tridecane, about 29.2% oE a primary alcohol ethoxylate wherein the alcohol has Erom about 9 to 11 carbon atoms and is condensed with 6 moles oE ethylene oxide per mole of alcohol. About 15.8% of a primary alcohol ethoxylate wherein the alcohol has Erom about 14 to about 15 carbon atoms and is condensed with 2.25 moles of ethylene oxide per moLe of alcohol and about 10% water.
In accordance with the process oE the invention, the removal of oi:Ly soils and/or stains from fabrics with a pre-spotting composition is effected by contactiny such stainedfabrics, 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 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.
- 5a ~ 351~ ~2301-1434 In addition to their utility as laundry and pre-spotting compositions, the compositions oE the inven-tion are also partieularly useEul for the removal of oily or greasy soil from hard surEaces such as plastic, vitreous and metal surfaees haviny a shiny Einish. Oily and greasy soils presen-t on such hard surfaces are readily solubilized in microemulsions, solutions or gels in aceordance with the invention and hence such eompositions may be efEectively utilized as clear single phase all purpose cleaning compositions.
~.~
~Z~3~ 62301-1434 ~ he described pre-spotting composition may be formulated as herein described to be in the Eorm of a liquid solution, liquid microemulsion (either water-in oil or oil-in-water type) or a gel, 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 compositions 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 conditi.ons, and thermodynamically stable, are not in accordance with the invention.
The term "microemulsions" as used herein refers to compositions containing two immiscible li~uid phases: a dispersed phase (i.e. micelles) and a continuous phase. The individual droplets of the dispersed phase of the microemulsion generally have an avera~e radius less than about lOOOA, typically between about 50 to 1000 angstroms. In soluti.on form, the dispersed or non-continuous phase is generally below 40A average radius. When the dispersed phase has an average radius greater than about lOOOA, it is no longer a microemulsion but an emulsion which is generally turbld and thermodynamically unstable. The measurement of average radius size of the dispersed phase can be carried out using conventional light scattering techni~ues.
The present invention is predica~d upon the discovery that pre-spotting compositions containing one or more organic solvents for oily soil removal can be formulated to satisfy two , . . ~ .
~.~83511 62301-1434 important requirements for the efEicient 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 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 characteristic 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 weight with water to form a diluted composition which is entirely in a clear, single-phase. Accord-ingly, 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 dil~lted 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 believed that at a condition of infinite dilution, the diluted pre-spottiny compositions of the 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 ' ~ ' '~' :
.
1 ~ ~ 3 5~ 1 62301-1434 -the pre-spotting composi-tions to be readily removed from the treated fabric by rinsing with water without the accompanying problem o~ 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 invention whether a particular pre-spotting formulation is infinitely dilutable in accordance with the following test: tG
one part of the pre-spotting formulation there is added 100 parts or more of water while stirring, both the water and the formula-tion being at room temperature. The resulting diluted mixture is then allowed to stand for at least one hour and then observed for phase separation. I~ 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.
_ AILED DESCRIPTION OF TFIE INVENTION_ _ The pre-spotting compositions of the 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 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 D~ ~
.
.
:
,:
~33~
continuous phase) or gel, and such composition having the ~urther characteristic o~ being infinitely dilutable with wa-ter. The determination of whether a composition is in-finitely dilutable with water is easily carried out in accordance with the test defined above and therefore the formulation of composi-tions which possess this characteristic is readily arrived at by a simple trial and error t~chnique.
The amount of organic solven-t in the composition may vary from 10 to 70%, preferably from about 45 to 50%, by weight of the total pre-spotting composition. The organic solvent may be comprised o~ one or more al]canes, straigh-t chain or branched, having Erom 10 to 18 carbon atoms. Normal dodecane is a preferred solvent 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 oE up to about 10~, by weight. Among the useful polar co-soLvents are the Eollowing: low molecular weight alcohols, such as isopropanol and hexanol; benzyl alcohol;
oxoalcohol esters, such as the TM Exxates* (sold by Exxon); Butyl Carbitol* (sold by Union Carbide Corporation); ketones, such as benzophenone; diglyme; dialkyl ph-thalate esters, such as dibutyl phthalate, esters of monohydric alcohols and fatty acids; esters of glycols and fatty acids; es-ters of glycerol and fatty acids;
and esters of polyglycols and fatty acids.
*Trade-mark ~L) ''' ~ ' , ' ' - .
~Z8~51~ 62301-1434 The nonionic surfactant is preferably comprised of one or a mixture of primary alcohol ethoxylates or secondary alcohol ethoxylates. The primary alcohols ethoxylates are represented by the general formula:
R~O-(cH2-cH2-O) -H
wherein R is 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 trade~mark Neodol and by Union Carbide Corporation under the trade mark Tergitol. Especially preferred for use herein are the following: Tergitol 24-L-5, Neodol 91-6, Neodol ~5-2.25, and Neodol 45-1, the latter, for example, being a C14-C15 alcohol condensed with 1 mole of ethylene oxide per mole of alcohol.
The secondary alcohol ethoxylates are represented by the general formula:
CH3 - (CH2)X - IH (C~I2)y 3 ( l2 CH2 )n - H
wherein X~Y is from 6 to 13 and the number of ethoxylate groups, n, is from 1 to 7. Commercially available surfactants of this type are sold by Union Carbide Corporation under the trade-mark Tergitol S series surfactants.
The nonionic surfactants or mixture of surfactants which are useful for the present compositions ha~e an HLB
(hydrophilic-lypophilic balance) of from about 9 to 13, preferably " .
133~
from about 9 to 11, and most preferably from about 9.5 to 10.5.
Generally, if the surfactant or surfactant mixture in the composition has an HLB higher than about 12, an oil-soluble fatty alcohol co-surfactant (e.g. a C14~C15 alcohol) or a water and oil miscible polar organic co-solvent is re~uired 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 surfactants 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:
Rl--N--~0 wherein Rl is an al]cyl radical containing from 12 to 18 carbon atoms, and R2 and R3 are methyl, ethyl or hydroxyethyl.
Commercially availabe surfactants of this type are sold by Armak under the trade-mark Aromox surfactant, such as, for example, Aromox DMMC-W the trade-mark for dimethyl cocoamine oxide.
The alkyl phenol ethoxylates which may be used in the present compositions include the condensation products of alkyl-phenol having an alkyl group containing from about 8 to 10 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount of 4 to 15 moles of ethylene oxide per mole of alkyl phenol.
~ - .
::
':
12 - ~ZB35~
623~1-1434 Commercially available nonionic surfactant~ of this type'include *
Tergitol NP surfactant sold by Unlon Carbide Corporation and Igepal surfactants sold by G~F Corporation. Particularly useful is Igepal C0-630 comprised of a C9 alkyl phenol ~thoxylate with 9 moles oE ethylene oxide per mole of phenol, In general, a supplementary nonionic surfactant may be advantageously used dependlng upon product economics, surfactant availability or to adjust the HLB of the nonionic surfactant mixture to a desired value.
The total amount o non:lonic surfactant in the composi-tion is from about 8 to 60%, preferably from about 15 to 50~, and most preferably from about 30 to 50~, by weight of the composition. The percentage of primary or secondary alcohol ethoxyl.ate m~y vary from about 4 to 60~ of the composltion. Hence, if the level of the defined alcohol ethoxylates ln the composition is below about,8'~, hy welght, a supplementary nonionic surfactant as herein ~efi.n~cl mu~ ordlna~lly be present ln conjunction therewith. The supplementary nonlonlc ~urfactant may be present ln a ratio of up to 5:1 relative to the alcohol ethoxylates, a 20 ratio of from about 0.5:1 to 3:1 belng preferred.
A co-surfactant may optionally bs used ln the pre-spotting compositons ln an amount of up to about 20~, by weight, for purposes of lowering the HI,~ value of the nonionic surfactant or mixture of nonionic surfactants to the desired value, The : co-surfactant is preferably comprised of a prlmary or secondary fatty alcohol having from 10 to 18 carbon atoms. Commercially available alcohols of this type are sold under the trade-mark *Trade-mark : D
. , , -.
- 13 ~ 3~
Neodol by Shell Chemical Company. Neodol 45, a C14-C15 alcohol, is particularly useful as a co-surfactant in the present compositions.
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 isfrom about 25~ to 50%, by weight. Oil-in-water microemulsions are generally favoured when the water lS present at levels of about 50% or higher o the total composition. When the water content is between about 15 to 25~, the resulting compositions will generally ~eine a range of water-solvent-surfactant 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 1uorescent brighteners, 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 watex 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. A]so present may be builders, such as sodium sesquicarbonate; antiredeposition agents, such as sodium ~3~ 62301-1434 carboxymethyl-cellulose; dispersing agents, such as sodium polyacry]ate; bactericides; funyicides; 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, 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 characteristics of the pre-spotting composition as well as the oily soil removal effected by such pre-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 micro-amulsions 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.
D
~",...
. . . . .
- -, . . - ,: .
- 15 ~ 35~1 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.
Illustrative of the pre-spotting compositions of the invention, Compositions 1 through 21 were prepared in accordance with the above-described method of preparation. The particular form of the pre-spotting composition is indicated for each composition described.
~,. ' ~Z83~ 62301-1434 WT. PERCENT
1- n-Dodecane 42.0 Alcohol (Cg-Cll) 42.0 (Neodol 91-6) ethoxylate (EO 6) Alcohol (C14 C15) 11.2 (Neodol 45-1) ethoxylate (EO 1) Water 4.8 Form: water-in-oil solution 100.0 (a) The names in par~ntheses represent the commercial trade-marks of the alcohol ethoxylates marketed by Shell Chemical Company 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.
WT. PERCENT
2- n-Dodecane 30%
ohol (C12-C14 ) ethoxylate (EO 5) Water 40 -Form: gel 100%
n-Hexadecane 15.4%
Alcohol (Cg-Cll) 9 5 ethoxylate (EO 6) Alcohol (C14-C15) 4-~
ethoxylate (EO 1) Water 70.3 Form: oil-in-water (o/w) microemulsion 100.0 `~'.,' ~,~ 1).
':.' ' ~ . .
- 17 - ~ ~3S~
WT. PERCE~T
BACKGROUND OF THE INVENTION
This invention relates to laundry pre-spotting compositions which are in the Eorm of clear, stable, micro-emulsions, solu-tions 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 characterized by being "infinitely dilutable" with water, as herein defined, without concomitant phase separation. Thus, the removal of oily stains and soils is effected by 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 composition remains in a clear, sin~le-phase, avoiding the attendant problem of redeposition of the oilv soil on the previously cleaned fabric.
The removal oE oily soils and stains from fabrics has been the focus oE much attention in the laundry art. In particular, emphasis has been placed on pre-treating or pre-spotting articles of laundry which are not uniformly soiled, suchas for 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 pre~spotter prior to being added to the wash bath, as .we~ as formulations intended specifically for oily soil removal which contain one or more organic solvents. While the use of ~,.
', , ' : .: : . . ' ' . :
' . - : - , , ; - . . .. .
- ' ' ~2~335~ 6230l-l434 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 the other hand, the ~nown 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" or extremely diluted with water in the wash bath. In efect, 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 "in~inite dilutability" which is used herein to char~cterize the pre~spotting compositions of the present inventi.on refers to the fact that the pre-spotti.ng compositions are formulated such that when diluted with water in a ratio of at least 100 parts water to 1 part of compositi.on, they are entirely in a clear single phase with no phase separation being present. 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.
- 3 - ~ ~835~1 U. S. Patent 4,180,472 to Mitchell et al is illustrative of a pre-treatment composition for oily 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 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 disclosed.
U. S. Patents 4,093,418 and 4,178,262 to Compton et al describe laundry spot-agent compositions containing a solution of a nonionic surfactant and an isoparaffinic solvent. No water is present in the composition nor is there any indication that such compositions can be readily removed from fabrics by immersion in a wash or rinse bath without the occurrence oE phase separation.
British patent specification 1l518,786, published July 19, 1978 discloses a detergent composition comprising a nonionic detergent, an organic solventl such as, methyl laurate, and water.
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 soilO In example 2 of the publication, the amount of organic solvent in the disclosed composition is '': ' ' : ' ' ~
~ 4 ~ ~ ~3~
3.4~. Further, the disclosed compositions which appear to be in granular form are added directly to the wash bath, according 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 removed there~rom by rinsing with water.
SUMM~RY OF THE INVENTION
_ 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 compris-ing one or more alkanes having from 10 to 18 carbon atoms;
(b) ~rom 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 said alcohol;
(c) from about 0 to 50% of a supplementary nonionic surfactant comprising an amine o~ide ox an alkyl phenol ethoxylate, the total amount of nonionic surfactants in the pre-spotting composition 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 D~
.-.
.
. , ~ . - .
- 5 _ ~Z83S1~ 52301-1434 percentages of each component of the composition being such as to forrn a clear, single-phase pre-spotting composition which is further characterizecl by being lnfinitely dilutable with water without concomitant phase separation such that the addition of water to said pre-spotting composition in an amount of one hundred parts wa-ter to one part of said composition results in a diluted composition which is entirely in a clear single phase;
(g) the balance optionally comprising a minor amount of adjuvants, In a preferred embodimen-t of the invention the pre-spotting composition comprises, by weight, about 45%
tridecane, about 29.2% oE a primary alcohol ethoxylate wherein the alcohol has Erom about 9 to 11 carbon atoms and is condensed with 6 moles oE ethylene oxide per mole of alcohol. About 15.8% of a primary alcohol ethoxylate wherein the alcohol has Erom about 14 to about 15 carbon atoms and is condensed with 2.25 moles of ethylene oxide per moLe of alcohol and about 10% water.
In accordance with the process oE the invention, the removal of oi:Ly soils and/or stains from fabrics with a pre-spotting composition is effected by contactiny such stainedfabrics, 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 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.
- 5a ~ 351~ ~2301-1434 In addition to their utility as laundry and pre-spotting compositions, the compositions oE the inven-tion are also partieularly useEul for the removal of oily or greasy soil from hard surEaces such as plastic, vitreous and metal surfaees haviny a shiny Einish. Oily and greasy soils presen-t on such hard surfaces are readily solubilized in microemulsions, solutions or gels in aceordance with the invention and hence such eompositions may be efEectively utilized as clear single phase all purpose cleaning compositions.
~.~
~Z~3~ 62301-1434 ~ he described pre-spotting composition may be formulated as herein described to be in the Eorm of a liquid solution, liquid microemulsion (either water-in oil or oil-in-water type) or a gel, 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 compositions 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 conditi.ons, and thermodynamically stable, are not in accordance with the invention.
The term "microemulsions" as used herein refers to compositions containing two immiscible li~uid phases: a dispersed phase (i.e. micelles) and a continuous phase. The individual droplets of the dispersed phase of the microemulsion generally have an avera~e radius less than about lOOOA, typically between about 50 to 1000 angstroms. In soluti.on form, the dispersed or non-continuous phase is generally below 40A average radius. When the dispersed phase has an average radius greater than about lOOOA, it is no longer a microemulsion but an emulsion which is generally turbld and thermodynamically unstable. The measurement of average radius size of the dispersed phase can be carried out using conventional light scattering techni~ues.
The present invention is predica~d upon the discovery that pre-spotting compositions containing one or more organic solvents for oily soil removal can be formulated to satisfy two , . . ~ .
~.~83511 62301-1434 important requirements for the efEicient 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 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 characteristic 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 weight with water to form a diluted composition which is entirely in a clear, single-phase. Accord-ingly, 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 dil~lted 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 believed that at a condition of infinite dilution, the diluted pre-spottiny compositions of the 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 ' ~ ' '~' :
.
1 ~ ~ 3 5~ 1 62301-1434 -the pre-spotting composi-tions to be readily removed from the treated fabric by rinsing with water without the accompanying problem o~ 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 invention whether a particular pre-spotting formulation is infinitely dilutable in accordance with the following test: tG
one part of the pre-spotting formulation there is added 100 parts or more of water while stirring, both the water and the formula-tion being at room temperature. The resulting diluted mixture is then allowed to stand for at least one hour and then observed for phase separation. I~ 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.
_ AILED DESCRIPTION OF TFIE INVENTION_ _ The pre-spotting compositions of the 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 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 D~ ~
.
.
:
,:
~33~
continuous phase) or gel, and such composition having the ~urther characteristic o~ being infinitely dilutable with wa-ter. The determination of whether a composition is in-finitely dilutable with water is easily carried out in accordance with the test defined above and therefore the formulation of composi-tions which possess this characteristic is readily arrived at by a simple trial and error t~chnique.
The amount of organic solven-t in the composition may vary from 10 to 70%, preferably from about 45 to 50%, by weight of the total pre-spotting composition. The organic solvent may be comprised o~ one or more al]canes, straigh-t chain or branched, having Erom 10 to 18 carbon atoms. Normal dodecane is a preferred solvent 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 oE up to about 10~, by weight. Among the useful polar co-soLvents are the Eollowing: low molecular weight alcohols, such as isopropanol and hexanol; benzyl alcohol;
oxoalcohol esters, such as the TM Exxates* (sold by Exxon); Butyl Carbitol* (sold by Union Carbide Corporation); ketones, such as benzophenone; diglyme; dialkyl ph-thalate esters, such as dibutyl phthalate, esters of monohydric alcohols and fatty acids; esters of glycols and fatty acids; es-ters of glycerol and fatty acids;
and esters of polyglycols and fatty acids.
*Trade-mark ~L) ''' ~ ' , ' ' - .
~Z8~51~ 62301-1434 The nonionic surfactant is preferably comprised of one or a mixture of primary alcohol ethoxylates or secondary alcohol ethoxylates. The primary alcohols ethoxylates are represented by the general formula:
R~O-(cH2-cH2-O) -H
wherein R is 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 trade~mark Neodol and by Union Carbide Corporation under the trade mark Tergitol. Especially preferred for use herein are the following: Tergitol 24-L-5, Neodol 91-6, Neodol ~5-2.25, and Neodol 45-1, the latter, for example, being a C14-C15 alcohol condensed with 1 mole of ethylene oxide per mole of alcohol.
The secondary alcohol ethoxylates are represented by the general formula:
CH3 - (CH2)X - IH (C~I2)y 3 ( l2 CH2 )n - H
wherein X~Y is from 6 to 13 and the number of ethoxylate groups, n, is from 1 to 7. Commercially available surfactants of this type are sold by Union Carbide Corporation under the trade-mark Tergitol S series surfactants.
The nonionic surfactants or mixture of surfactants which are useful for the present compositions ha~e an HLB
(hydrophilic-lypophilic balance) of from about 9 to 13, preferably " .
133~
from about 9 to 11, and most preferably from about 9.5 to 10.5.
Generally, if the surfactant or surfactant mixture in the composition has an HLB higher than about 12, an oil-soluble fatty alcohol co-surfactant (e.g. a C14~C15 alcohol) or a water and oil miscible polar organic co-solvent is re~uired 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 surfactants 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:
Rl--N--~0 wherein Rl is an al]cyl radical containing from 12 to 18 carbon atoms, and R2 and R3 are methyl, ethyl or hydroxyethyl.
Commercially availabe surfactants of this type are sold by Armak under the trade-mark Aromox surfactant, such as, for example, Aromox DMMC-W the trade-mark for dimethyl cocoamine oxide.
The alkyl phenol ethoxylates which may be used in the present compositions include the condensation products of alkyl-phenol having an alkyl group containing from about 8 to 10 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount of 4 to 15 moles of ethylene oxide per mole of alkyl phenol.
~ - .
::
':
12 - ~ZB35~
623~1-1434 Commercially available nonionic surfactant~ of this type'include *
Tergitol NP surfactant sold by Unlon Carbide Corporation and Igepal surfactants sold by G~F Corporation. Particularly useful is Igepal C0-630 comprised of a C9 alkyl phenol ~thoxylate with 9 moles oE ethylene oxide per mole of phenol, In general, a supplementary nonionic surfactant may be advantageously used dependlng upon product economics, surfactant availability or to adjust the HLB of the nonionic surfactant mixture to a desired value.
The total amount o non:lonic surfactant in the composi-tion is from about 8 to 60%, preferably from about 15 to 50~, and most preferably from about 30 to 50~, by weight of the composition. The percentage of primary or secondary alcohol ethoxyl.ate m~y vary from about 4 to 60~ of the composltion. Hence, if the level of the defined alcohol ethoxylates ln the composition is below about,8'~, hy welght, a supplementary nonionic surfactant as herein ~efi.n~cl mu~ ordlna~lly be present ln conjunction therewith. The supplementary nonlonlc ~urfactant may be present ln a ratio of up to 5:1 relative to the alcohol ethoxylates, a 20 ratio of from about 0.5:1 to 3:1 belng preferred.
A co-surfactant may optionally bs used ln the pre-spotting compositons ln an amount of up to about 20~, by weight, for purposes of lowering the HI,~ value of the nonionic surfactant or mixture of nonionic surfactants to the desired value, The : co-surfactant is preferably comprised of a prlmary or secondary fatty alcohol having from 10 to 18 carbon atoms. Commercially available alcohols of this type are sold under the trade-mark *Trade-mark : D
. , , -.
- 13 ~ 3~
Neodol by Shell Chemical Company. Neodol 45, a C14-C15 alcohol, is particularly useful as a co-surfactant in the present compositions.
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 isfrom about 25~ to 50%, by weight. Oil-in-water microemulsions are generally favoured when the water lS present at levels of about 50% or higher o the total composition. When the water content is between about 15 to 25~, the resulting compositions will generally ~eine a range of water-solvent-surfactant 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 1uorescent brighteners, 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 watex 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. A]so present may be builders, such as sodium sesquicarbonate; antiredeposition agents, such as sodium ~3~ 62301-1434 carboxymethyl-cellulose; dispersing agents, such as sodium polyacry]ate; bactericides; funyicides; 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, 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 characteristics of the pre-spotting composition as well as the oily soil removal effected by such pre-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 micro-amulsions 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.
D
~",...
. . . . .
- -, . . - ,: .
- 15 ~ 35~1 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.
Illustrative of the pre-spotting compositions of the invention, Compositions 1 through 21 were prepared in accordance with the above-described method of preparation. The particular form of the pre-spotting composition is indicated for each composition described.
~,. ' ~Z83~ 62301-1434 WT. PERCENT
1- n-Dodecane 42.0 Alcohol (Cg-Cll) 42.0 (Neodol 91-6) ethoxylate (EO 6) Alcohol (C14 C15) 11.2 (Neodol 45-1) ethoxylate (EO 1) Water 4.8 Form: water-in-oil solution 100.0 (a) The names in par~ntheses represent the commercial trade-marks of the alcohol ethoxylates marketed by Shell Chemical Company 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.
WT. PERCENT
2- n-Dodecane 30%
ohol (C12-C14 ) ethoxylate (EO 5) Water 40 -Form: gel 100%
n-Hexadecane 15.4%
Alcohol (Cg-Cll) 9 5 ethoxylate (EO 6) Alcohol (C14-C15) 4-~
ethoxylate (EO 1) Water 70.3 Form: oil-in-water (o/w) microemulsion 100.0 `~'.,' ~,~ 1).
':.' ' ~ . .
- 17 - ~ ~3S~
WT. PERCE~T
4- n-Dodecane 35.3%
( 9 11 ethoxylate (EO 6) Alcohol (Cg-Cll) 4.3 ethoxylate (EO 2.25) Benzyl alcohol 6.9 Water 15 6 Form: water-in-oil (w/o) 100.0 microemulsion 5- n-Dodecane 15.0%
Secondary alcohol (C15) 15.0 (Tergitol 15-S-7) ethoxylate (EO 7) Alcohol (C14 C15) 2.0 ethoxylate ~EO 1) Benzyl alcohol 3.0 Water 65.0 Form: o/w microemulsion 100.0%
( 9 11 ethoxylate (EO 6) Alcohol (Cg-Cll) 4.3 ethoxylate (EO 2.25) Benzyl alcohol 6.9 Water 15 6 Form: water-in-oil (w/o) 100.0 microemulsion 5- n-Dodecane 15.0%
Secondary alcohol (C15) 15.0 (Tergitol 15-S-7) ethoxylate (EO 7) Alcohol (C14 C15) 2.0 ethoxylate ~EO 1) Benzyl alcohol 3.0 Water 65.0 Form: o/w microemulsion 100.0%
6- n-Dodecane 10.0%
Secondary alcohol (C15) 10.0 ethoxylate (EO 5) Alcohol (C12 C15) 2.0 ethoxylate (EO 3) ; Benzyl alcohol 2.0 Water 76.0 Form: o/w microemulsion 100.0 ~,, ~ .
, , .' : .
1283~ 62301-1434 WT. PERCENT
Secondary alcohol (C15) 10.0 ethoxylate (EO 5) Alcohol (C12 C15) 2.0 ethoxylate (EO 3) ; Benzyl alcohol 2.0 Water 76.0 Form: o/w microemulsion 100.0 ~,, ~ .
, , .' : .
1283~ 62301-1434 WT. PERCENT
7- n-Dodecane 24.0%
Butyl Carbitol (Union Carbide T~) 6.0 Alcohol (C14 C15 8.0 ethoxylate (E0 2.25) Dimethyl cocoamine oxide10.0 Water 52.0 Form: o/w microemulsion100.0 8- PEG 400 Distearate 5.6%
n-Dodecane 22.2 Alcohol (C14 C15) ethoxylate (E0 2.25) Dimethyl cocoamine oxide 7.4 Butyl carbitol 7.4 Water 50.0 Form: o/w microemulsion100.0 9- n-Dodecane 48.0%
Alkyl (Cg) phenol 30.0 (Igepal C0-630) ethoxylate (E0 9) Alcohol (C14 C15) 21.0 ethoxylate (E0 2.25) Water 1.0 Form: w/o solution 100.0 , -.
. . .
:
~83~ 62301-1434 WT. PERCENT
Butyl Carbitol (Union Carbide T~) 6.0 Alcohol (C14 C15 8.0 ethoxylate (E0 2.25) Dimethyl cocoamine oxide10.0 Water 52.0 Form: o/w microemulsion100.0 8- PEG 400 Distearate 5.6%
n-Dodecane 22.2 Alcohol (C14 C15) ethoxylate (E0 2.25) Dimethyl cocoamine oxide 7.4 Butyl carbitol 7.4 Water 50.0 Form: o/w microemulsion100.0 9- n-Dodecane 48.0%
Alkyl (Cg) phenol 30.0 (Igepal C0-630) ethoxylate (E0 9) Alcohol (C14 C15) 21.0 ethoxylate (E0 2.25) Water 1.0 Form: w/o solution 100.0 , -.
. . .
:
~83~ 62301-1434 WT. PERCENT
10- n-Dodecane 10.0%
Alkyl (Cg) phenol 5.0 ethoxylate (EO 9) Alcohol (C14 C15) ethoxylate (EO 2.25) Butyl carbitol 5.7 Water 74.3 Form: o/w microemulsion100.0 11- n-Dodecane 54.0%
Alkyl (Cg) phenol 30.0 ethoxylate (EO 9) Alcohol (C14 C15) 14.0 ethoxylate (EO 2.25) Water _ 2.0 Form: w/o microemulsion100.0 12- n Dodecane 17.0%
Alcohol (Cg-Cll) 9-7 ethoxylate (EO 6) Alcohol (C14 15) ethoxylate (EO 1) Water 68.8 Form: o/w microemulsion 100.0 , ~",1 ' - . ' ~:
~Z835~ ~
WT. PERCENT
Alkyl (Cg) phenol 5.0 ethoxylate (EO 9) Alcohol (C14 C15) ethoxylate (EO 2.25) Butyl carbitol 5.7 Water 74.3 Form: o/w microemulsion100.0 11- n-Dodecane 54.0%
Alkyl (Cg) phenol 30.0 ethoxylate (EO 9) Alcohol (C14 C15) 14.0 ethoxylate (EO 2.25) Water _ 2.0 Form: w/o microemulsion100.0 12- n Dodecane 17.0%
Alcohol (Cg-Cll) 9-7 ethoxylate (EO 6) Alcohol (C14 15) ethoxylate (EO 1) Water 68.8 Form: o/w microemulsion 100.0 , ~",1 ' - . ' ~:
~Z835~ ~
WT. PERCENT
13- n-Tridecane 15.4%
( 9 11) 9.5 ethoxylate (EO 6) Alcohol (C14 C15 4.8 ethoxylate (EO 1) Water 70.3 _ Form: o/w microemulsion100.0 14- n-Hexadecane 48.0 Alcohol (Cg-Cll) 31.8 ethoxylate (EO 6) Alcohol (C14 C15) 16.9 ethoxylate (EO 1) Water 3.3 Form: w/o solution 100.0 15- n-Dodecane 35.1 Alcohol (Cg-Cll) 51.3 ethoxylate (EO 6) Alcohl (C14 C15) 9.1 Water 4.5 -Form: w/o solution 100.0 ` ' '. ` ' ' ' .
.
- 21 - ~ ~3~
WT. PERCENT
( 9 11) 9.5 ethoxylate (EO 6) Alcohol (C14 C15 4.8 ethoxylate (EO 1) Water 70.3 _ Form: o/w microemulsion100.0 14- n-Hexadecane 48.0 Alcohol (Cg-Cll) 31.8 ethoxylate (EO 6) Alcohol (C14 C15) 16.9 ethoxylate (EO 1) Water 3.3 Form: w/o solution 100.0 15- n-Dodecane 35.1 Alcohol (Cg-Cll) 51.3 ethoxylate (EO 6) Alcohl (C14 C15) 9.1 Water 4.5 -Form: w/o solution 100.0 ` ' '. ` ' ' ' .
.
- 21 - ~ ~3~
WT. PERCENT
16- n-Dodecane 14.8%
Oxohexyl acetate 0.2 Alcohol (Cg-Cll) 22.0 ethoxylate (EO 6) (C14 C15) 3.0 Water 60.0 Form: o/w microemulsion 100.0 17- n-Dodecane 30.0 Alcohol (Cl2 C14) 20.0 ethoxylate (EO 5) Water 50,0 Form: gel 100.0 18- n-Dodecane 25.0 (Cg Cll) 37-3 ethoxylate (EO 6) Alcohol (C14 C15) 5~1 (Neodol 45) Oxyhexyl acetate 0.4 Water 32.2 Form: gel 100.0 ~ `
. - .
. . : ' ' ' :
- 22 ~ 3~
WT. PERCENT
Oxohexyl acetate 0.2 Alcohol (Cg-Cll) 22.0 ethoxylate (EO 6) (C14 C15) 3.0 Water 60.0 Form: o/w microemulsion 100.0 17- n-Dodecane 30.0 Alcohol (Cl2 C14) 20.0 ethoxylate (EO 5) Water 50,0 Form: gel 100.0 18- n-Dodecane 25.0 (Cg Cll) 37-3 ethoxylate (EO 6) Alcohol (C14 C15) 5~1 (Neodol 45) Oxyhexyl acetate 0.4 Water 32.2 Form: gel 100.0 ~ `
. - .
. . : ' ' ' :
- 22 ~ 3~
WT. PERCENT
19- n-Decane 40.9%
Alcohol (Cg-Cll) 23.6 ethoxylate (EO 6) Alcohol (C14 C15) 11.0 ethoxylate (EO 1) Water 24.5 Form: gel 100.0 20- n-Dodecane 10.0%
Alcohol (C12 C14 ) 10 . O
ethoxylate (EO 5) Water 80.0 Form: oil-in-water 100.0 microemulsion 21- n-Dodecane 45.0%
Alcohol (C12 C14) 45.0 ethoxylate (EO 5) Water 10.0 Form: water-in-oil microemulsion 100.0 . .
, . : . .
.
' .
- 23 ~ ~Z83~
Compositions 22-24 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.
WT. PERCENT
Alcohol (Cg-Cll) 23.6 ethoxylate (EO 6) Alcohol (C14 C15) 11.0 ethoxylate (EO 1) Water 24.5 Form: gel 100.0 20- n-Dodecane 10.0%
Alcohol (C12 C14 ) 10 . O
ethoxylate (EO 5) Water 80.0 Form: oil-in-water 100.0 microemulsion 21- n-Dodecane 45.0%
Alcohol (C12 C14) 45.0 ethoxylate (EO 5) Water 10.0 Form: water-in-oil microemulsion 100.0 . .
, . : . .
.
' .
- 23 ~ ~Z83~
Compositions 22-24 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.
WT. PERCENT
22- n-Dodecane 58.8%
Alcohol (C12 C14) 39.2 ethoxyla-te (EO 5) Water 2.0 Form: w/o solution 100.0 , 23 n-Tridecane (Norpar 13) 50.0 Alcohol (Cg-Cll) 22.2 ethoxylate (EO 6) Alcohol (C14 C15) 17.8 : ethoxylate (EO 2.25) Water 10.0 Form: w/o solution 100.0 24- n-Tridecane 40.0 Alcohol (Cg-Cll) 27.8 ethoxylate (EO 6) Alcohol ~Cg-Cll) 22.2 ethoxylate (EO 1) Water 10.0 Form: w/o solution 100.0 :`,'': ` ' ' - ' :
.: . .
- 24 - ~ 5 ~ ~
Shown below is Composition 25, similar to Compostions 23 and 24 but significantly different insofar as it is formulated to be infinitely dilutable and hence in accord with the invention.
WT. PERCENT
Alcohol (C12 C14) 39.2 ethoxyla-te (EO 5) Water 2.0 Form: w/o solution 100.0 , 23 n-Tridecane (Norpar 13) 50.0 Alcohol (Cg-Cll) 22.2 ethoxylate (EO 6) Alcohol (C14 C15) 17.8 : ethoxylate (EO 2.25) Water 10.0 Form: w/o solution 100.0 24- n-Tridecane 40.0 Alcohol (Cg-Cll) 27.8 ethoxylate (EO 6) Alcohol ~Cg-Cll) 22.2 ethoxylate (EO 1) Water 10.0 Form: w/o solution 100.0 :`,'': ` ' ' - ' :
.: . .
- 24 - ~ 5 ~ ~
Shown below is Composition 25, similar to Compostions 23 and 24 but significantly different insofar as it is formulated to be infinitely dilutable and hence in accord with the invention.
WT. PERCENT
25- n-Tridecane 45.0%
Alcohol (Cg-Cll) 25.0 ethoxylate (EO 6) Alcohol (C14 C15) 20.0 ethoxylate (EO 2.25) Water 10.0 Form: w/o solution 100.0 The following procedure was followed in evaluating the eficacy of pre spotting compositions in accordance with the invention relative to the performance of commercial liquid compositions intended for oily soil removal.
The stained swatches to be cleaned were 3" x 4" and consisted of the following:
1- Dirty motor oil on Dacron doubleknit (DMO);
2- Barbecue sauce on Dacron doubleknit (BB~);
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 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 'reated swatches were Trade-mark D
- 25 - ~Z83~
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 liter 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 li~uor, the swatches were washed for 12 minutes at 100F while agitated at 100 rpm. The wash liquor was then discarded and replaced with one liter of water at 100F containing 150 ppm of artificial hardness. The swatches were then rinsed 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 ollowing e~uation:
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), compositions in accordance with the invention, were formulated as shown below:
--- 26 - ~83~
COMPOSITION A
WT. PERCENT
n-Dodecane 15.0%
Alcohol (Cg-Cll) 15.0 ethoxylate ( EO 6) (C14 C15) 4.0 ethoxylate (EO 1) Water 66.0 Form: o/w micxoemulsion 100.0 COMPOSITION B
n-Dodecane 44.0%
( 9 11) 44.0 ethoxylate (EO 6) Alcohol (C14 C15)11.0 ethoxylate (EO 1) Water 1.0 -Form: w/o solution 100.0 Compositions A and B were evaluated for soil removal in accordance with the procedure described above as were the follow-ing four commercial formulations: a pre-spotter; a liquid laundry deterg~nt composition; a pine oil-based liquid cleaner containing about 30% pine oil; and a petroleum-based all purpose cleaner containing about 40% petroleum distillates. The results of the soil removal tests are shown below indicating the % SR
achieved for each composition. A difference of about 5% SR uni-ts . , ' :
.
Alcohol (Cg-Cll) 25.0 ethoxylate (EO 6) Alcohol (C14 C15) 20.0 ethoxylate (EO 2.25) Water 10.0 Form: w/o solution 100.0 The following procedure was followed in evaluating the eficacy of pre spotting compositions in accordance with the invention relative to the performance of commercial liquid compositions intended for oily soil removal.
The stained swatches to be cleaned were 3" x 4" and consisted of the following:
1- Dirty motor oil on Dacron doubleknit (DMO);
2- Barbecue sauce on Dacron doubleknit (BB~);
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 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 'reated swatches were Trade-mark D
- 25 - ~Z83~
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 liter 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 li~uor, the swatches were washed for 12 minutes at 100F while agitated at 100 rpm. The wash liquor was then discarded and replaced with one liter of water at 100F containing 150 ppm of artificial hardness. The swatches were then rinsed 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 ollowing e~uation:
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), compositions in accordance with the invention, were formulated as shown below:
--- 26 - ~83~
COMPOSITION A
WT. PERCENT
n-Dodecane 15.0%
Alcohol (Cg-Cll) 15.0 ethoxylate ( EO 6) (C14 C15) 4.0 ethoxylate (EO 1) Water 66.0 Form: o/w micxoemulsion 100.0 COMPOSITION B
n-Dodecane 44.0%
( 9 11) 44.0 ethoxylate (EO 6) Alcohol (C14 C15)11.0 ethoxylate (EO 1) Water 1.0 -Form: w/o solution 100.0 Compositions A and B were evaluated for soil removal in accordance with the procedure described above as were the follow-ing four commercial formulations: a pre-spotter; a liquid laundry deterg~nt composition; a pine oil-based liquid cleaner containing about 30% pine oil; and a petroleum-based all purpose cleaner containing about 40% petroleum distillates. The results of the soil removal tests are shown below indicating the % SR
achieved for each composition. A difference of about 5% SR uni-ts . , ' :
.
- 27 - ~ ~ ~3~
is considered to be -the minimum that can be visually detected in a side-by-side comparison of two fabrics.
% SR
Pre-spotter D BBQ EMPA SEBUM_ Composition A
(o/w microemulsion) 8.2 55.9 30.1 73.4 Composition B
(w/o solution3 42.2 57.5 50.2 68.1 Pre-spotter 7.~ 39.6 49.0 63.5 Liquid laundry detergent 5.1 49.7 37.6 72.3 Pine oil-based cleaner9.8 63.6 55.3 66.5 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 (Composition B) was markedly superior in perEormance relative to all four of the commercial pre-spotting and cleaning compositions. This was most evident 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 laundr~ detergent but slightly inferior ove,rall to the pine oil-based cleaner and the petroleum-based cleaner. The latter cleaners however are more susceptible to problems of redeposition of the organic solvent, particularly at higher temperatures, such as above 100F.
The procedure of Example 4 was followed to evaluate Composition C, a water-in-oil solution in accordance with the invention, relative to a commercial liquid pre-spotting composition and a commercial liquid laundry deteryent. Tap water at 114F was ~.
:: ' . - . ' ' . .
is considered to be -the minimum that can be visually detected in a side-by-side comparison of two fabrics.
% SR
Pre-spotter D BBQ EMPA SEBUM_ Composition A
(o/w microemulsion) 8.2 55.9 30.1 73.4 Composition B
(w/o solution3 42.2 57.5 50.2 68.1 Pre-spotter 7.~ 39.6 49.0 63.5 Liquid laundry detergent 5.1 49.7 37.6 72.3 Pine oil-based cleaner9.8 63.6 55.3 66.5 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 (Composition B) was markedly superior in perEormance relative to all four of the commercial pre-spotting and cleaning compositions. This was most evident 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 laundr~ detergent but slightly inferior ove,rall to the pine oil-based cleaner and the petroleum-based cleaner. The latter cleaners however are more susceptible to problems of redeposition of the organic solvent, particularly at higher temperatures, such as above 100F.
The procedure of Example 4 was followed to evaluate Composition C, a water-in-oil solution in accordance with the invention, relative to a commercial liquid pre-spotting composition and a commercial liquid laundry deteryent. Tap water at 114F was ~.
:: ' . - . ' ' . .
- 28 ~ 3~
used in place of 100F water containing 150 ppm hardness. The stains tested were ~MO, BBQ and EMPA as previously described.
Composition C was comprised of the following:
COMPOSITION C
WT. PERCEMT
n-Dodecane 48.2%
Oxohexyl alcohol 0.8 Alcohol (C~-Cll~ 34.2 ethoxylate (EO 6) Alcohol (C14 C15) 14.8 ethoxylate (EO 1) Water _ 2.0 Form: w/o solution 100.0 The results of the cleaning tests are shown below:
% S.R
Pre-S~_tter DMO BBQ EMPA
Composition C 30.166.1 42.1 Commercial pre-spotter 6.441.5 37.5 Liquid laundry detergent 3.2 47.0 35.6 As shown in the Table above, Composition C was markedly superior as a pre-spotting composition relative to the commercial compositions.
I) :
- . .
.
, :' . . . .
. . .
used in place of 100F water containing 150 ppm hardness. The stains tested were ~MO, BBQ and EMPA as previously described.
Composition C was comprised of the following:
COMPOSITION C
WT. PERCEMT
n-Dodecane 48.2%
Oxohexyl alcohol 0.8 Alcohol (C~-Cll~ 34.2 ethoxylate (EO 6) Alcohol (C14 C15) 14.8 ethoxylate (EO 1) Water _ 2.0 Form: w/o solution 100.0 The results of the cleaning tests are shown below:
% S.R
Pre-S~_tter DMO BBQ EMPA
Composition C 30.166.1 42.1 Commercial pre-spotter 6.441.5 37.5 Liquid laundry detergent 3.2 47.0 35.6 As shown in the Table above, Composition C was markedly superior as a pre-spotting composition relative to the commercial compositions.
I) :
- . .
.
, :' . . . .
. . .
Claims (16)
1. 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 compris-ing 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 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 composition 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 characterized by being infinitely dilutable with water without concomitant phase separation such that the addition of water to said pre-spotting composition in an amount of one hundred parts water to one part of said composition results in a diluted composition which is entirely in a clear single phase; and (g) the balance optionally comprising a minor amount of adjuvants.
(a) from about 10 to 70% of an organic solvent compris-ing 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 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 composition 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 characterized by being infinitely dilutable with water without concomitant phase separation such that the addition of water to said pre-spotting composition in an amount of one hundred parts water to one part of said composition results in a diluted composition which is entirely in a clear single phase; and (g) the balance optionally comprising a minor amount of adjuvants.
2. A pre-spotting composition according to claim 1 wherein the amount of water is from about 1 to 15%, by weight of the composition.
3. A pre-spotting composition according to claim 1 wherein the organic solvent is n-dodecane.
4. A pre-spotting composition according to claim 1 wherein the nonionic surfactant is the condensation product of a primary alcohol having from 12 to 14 carbon atoms with five mole of ethylene oxide per mole of said alcohol, and wherein said pre-spotting composition is substantially free of said co-surfactant.
5. A pre-spotting composition according to claim 1 wherein the HLB value of the nonionic surfactant or surfactant mixture in the pre-spotting composition is from about 9 to 11.
6. A pre-spotting composition according to claim 1 which contains a supplementary nonionic surfactant comprised of an alkyl phenol ethoxylate.
7. A pre-spotting composition according to claim 1 which contains a supplementary nonionic surfactant comprised of an amine oxide.
8. A pre-spotting composition according to claim 1 in the form of a water-in-oil solution 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.
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 process of spotting and laundering fabrics containing an oily soil and/or stain comprising:
(1) contacting the soiled fabrics with an effective amount of a clear, single-phase, liquid microemulsion, solution, or gel laundry pre-spotting composition which comprises, by weight:
(a) from about 10 to 70% of an organic solvent compris-ing 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 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 composition being no greater than about 60%;
(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 percentage of each component of the composition being such as to form a clear, single-phase pre-spotting composition which is further characterized by being infinitely dilutable with water without concomitant phase separation such that the addition of water to said pre-spotting composition in an amount of one hundred parts water to one part of said composition results in a diluted composition which is entirely in a clear single phase; and (g) the balance optionally comprising a minor amount of adjuvants; and (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 substantially free of said oily soils and/or stains.
(1) contacting the soiled fabrics with an effective amount of a clear, single-phase, liquid microemulsion, solution, or gel laundry pre-spotting composition which comprises, by weight:
(a) from about 10 to 70% of an organic solvent compris-ing 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 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 composition being no greater than about 60%;
(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 percentage of each component of the composition being such as to form a clear, single-phase pre-spotting composition which is further characterized by being infinitely dilutable with water without concomitant phase separation such that the addition of water to said pre-spotting composition in an amount of one hundred parts water to one part of said composition results in a diluted composition which is entirely in a clear single phase; and (g) the balance optionally comprising a minor amount of adjuvants; and (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 substantially free of said oily soils and/or stains.
10. A process according to claim 9 wherein said pre-spotting composition contains from about 1 to 15%, by weight, water.
11. A process according to claim 9 wherein the organic solvent in said pre-spotting composition is n-dodecane.
12. A process according to claim 9 wherein the nonionic surfactant in said pre-spotting composition is the condensation product of a primary alcohol having from 12 to 14 carbon atoms with five mole of ethylene oxide per mole of said alcohol, and wherein said pre-spotting composition is substantially free of said co-surfactant.
13. A process according to claim 9 wherein the HLB value of the nonionic surfactant or surfactant mixture in said pre-spotting composition is from about 9 to 11.
14. A process according to claim 9 wherein the pre-spotting composition contains a supplementary nonionic surfactant comprised of an alkyl phenol ethoxylate.
15. A process according to claim 9 wherein the pre-spotting composition contains a supplementary nonionic surfactant comprised of an amine oxide.
16. A process according to claim 9 wherein the pre-spotting composition is in the form of a water-in-oil solution 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 an 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90271686A | 1986-09-02 | 1986-09-02 | |
| US902,716 | 1986-09-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1283511C true CA1283511C (en) | 1991-04-30 |
Family
ID=25416291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000544828A Expired - Lifetime CA1283511C (en) | 1986-09-02 | 1987-08-19 | Laundry pre-spotter composition providing improved oily soil removal |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS6368700A (en) |
| AR (1) | AR243928A1 (en) |
| AU (1) | AU597414B2 (en) |
| BE (1) | BE1001724A4 (en) |
| BR (1) | BR8704494A (en) |
| CA (1) | CA1283511C (en) |
| DE (1) | DE3728547A1 (en) |
| DK (1) | DK449787A (en) |
| ES (1) | ES2005285A6 (en) |
| FR (1) | FR2603300B1 (en) |
| GB (1) | GB2194547B (en) |
| HK (1) | HK97893A (en) |
| IL (1) | IL83641A (en) |
| IT (1) | IT1211751B (en) |
| MY (1) | MY101656A (en) |
| NZ (1) | NZ221523A (en) |
| PH (1) | PH24177A (en) |
| TR (1) | TR24203A (en) |
| ZA (1) | ZA876158B (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3636085A1 (en) * | 1986-10-23 | 1988-04-28 | Henkel Kgaa | LOW-WATER, PASTE-SHAPED PREPARATION |
| US4954286A (en) * | 1988-04-14 | 1990-09-04 | Lever Brothers Company | Fabric pretreatment cleaning compositions |
| GB8913881D0 (en) * | 1989-06-16 | 1989-08-02 | Unilever Plc | Detergent compositions |
| ES2100884T3 (en) * | 1989-06-29 | 1997-07-01 | Buckeye Int | PERFECTED COMPOSITIONS OF AQUEOUS MICROEMULSIONS FOR CLEANING / DEGREASING CONTAINING AN ADJUVANT. |
| US5035826A (en) * | 1989-09-22 | 1991-07-30 | Colgate-Palmolive Company | Liquid crystal detergent composition |
| US5585034A (en) * | 1991-11-21 | 1996-12-17 | Colgate-Palmolive Co. | Gelled near tricritical point compositions |
| GB9225540D0 (en) * | 1992-12-07 | 1993-01-27 | Ici Plc | Cleaning compositions |
| US5750487A (en) * | 1993-04-12 | 1998-05-12 | Colgate-Palmolive Co. | Tricritical point compositions |
| AU671895B2 (en) * | 1993-04-12 | 1996-09-12 | Colgate-Palmolive Company, The | Tricritical point composition |
| US5665268A (en) * | 1994-02-04 | 1997-09-09 | Deguertechin; Louis Oldenhove | Near tricritical point compositions |
| US5527485A (en) * | 1994-02-04 | 1996-06-18 | Colgate-Palmolive Co. | Near tricritical point compositions |
| US5643861A (en) * | 1994-02-04 | 1997-07-01 | Colgate-Palmolive Co. | Near tricritical point compositions containing a bleach and/or a disinfecting agent |
| US5527486A (en) * | 1994-02-04 | 1996-06-18 | Colgate-Palmolive Co. | Near tricritical point compositions |
| ES2119405T3 (en) * | 1994-03-31 | 1998-10-01 | Unilever Nv | DETERGENT COMPOSITIONS. |
| CA2173136A1 (en) * | 1994-03-31 | 1995-10-12 | Peter Robert Garrett | Detergent compositions |
| GB9413612D0 (en) * | 1994-07-06 | 1994-08-24 | Unilever Plc | Surfactant-oil microemulsion concentrates |
| WO1996019555A1 (en) * | 1994-12-21 | 1996-06-27 | Kao Corporation | Liquid detergent composition |
| EP1010749B1 (en) * | 1995-03-27 | 2006-02-22 | The Procter & Gamble Company | Activated liquid bleaching compositions |
| DE19517815A1 (en) * | 1995-05-18 | 1996-11-21 | Henkel Ecolab Gmbh & Co Ohg | Liquid water-based agent for cleaning textile surfaces |
| WO1997020098A1 (en) * | 1995-11-27 | 1997-06-05 | The Procter & Gamble Company | Cleaning method for textile fabrics |
| ES2182864T3 (en) * | 1995-12-02 | 2003-03-16 | Procter & Gamble | LIQUID COMPOSITIONS OF WHITENERS PACKED IN A SPRAYER TYPE DISPENSER, AND A PROCEDURE FOR PRE-TREATING FABRICS WITH THEM. |
| DE19612811A1 (en) * | 1996-03-30 | 1996-11-21 | Astrid Grose | Pretreatment liq. for cleaning textile heavily soiled with oil and grease |
| US5851976A (en) * | 1997-12-08 | 1998-12-22 | Colgate Palmolive Company | Microemulsion all purpose liquid cleaning compositions |
| DE10205134A1 (en) * | 2002-02-07 | 2003-08-21 | Henkel Kgaa | cleaning paste |
| US20040266643A1 (en) * | 2003-06-27 | 2004-12-30 | The Procter & Gamble Company | Fabric article treatment composition for use in a lipophilic fluid system |
| TWI400330B (en) | 2005-12-28 | 2013-07-01 | Kao Corp | Liquid detergent |
| JP4996970B2 (en) * | 2006-05-18 | 2012-08-08 | 花王株式会社 | Liquid bleach detergent composition |
| GB201021822D0 (en) * | 2010-12-23 | 2011-02-02 | Reckitt & Colman Overseas | Cleaning composition and method |
| DE102014202990A1 (en) * | 2014-02-19 | 2015-08-20 | Henkel Ag & Co. Kgaa | concentrates |
| EP3115447A1 (en) * | 2015-07-09 | 2017-01-11 | The Procter and Gamble Company | Method of pretreating fabrics |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL179362A (en) * | 1952-06-30 | 1953-06-24 | Metallgesellschaft Ag | PROCESS FOR PREPARING A CLEANING EMULSION |
| JPS5139250B2 (en) * | 1972-04-20 | 1976-10-27 | ||
| FR2262692B1 (en) * | 1974-02-28 | 1977-03-04 | Raffinage Cie Francaise | |
| NL8000452A (en) * | 1979-02-07 | 1980-08-11 | Unilever Nv | PREPARATION FOR LAUNDRY. |
| GB2049722A (en) * | 1979-05-05 | 1980-12-31 | Barnes R I | A Cleansing Material |
| US4438009A (en) * | 1981-08-14 | 1984-03-20 | S. C. Johnson & Son, Inc. | Low solvent laundry pre-spotting composition |
-
1987
- 1987-08-19 CA CA000544828A patent/CA1283511C/en not_active Expired - Lifetime
- 1987-08-19 ZA ZA876158A patent/ZA876158B/en unknown
- 1987-08-19 MY MYPI87001376A patent/MY101656A/en unknown
- 1987-08-20 NZ NZ221523A patent/NZ221523A/en unknown
- 1987-08-21 AU AU77335/87A patent/AU597414B2/en not_active Ceased
- 1987-08-23 IL IL83641A patent/IL83641A/en not_active IP Right Cessation
- 1987-08-25 PH PH35734A patent/PH24177A/en unknown
- 1987-08-27 DK DK449787A patent/DK449787A/en not_active Application Discontinuation
- 1987-08-27 DE DE19873728547 patent/DE3728547A1/en not_active Withdrawn
- 1987-08-31 TR TR87/0601A patent/TR24203A/en unknown
- 1987-09-01 GB GB8720556A patent/GB2194547B/en not_active Expired - Lifetime
- 1987-09-01 BR BR8704494A patent/BR8704494A/en not_active Application Discontinuation
- 1987-09-01 ES ES8702539A patent/ES2005285A6/en not_active Expired
- 1987-09-01 IT IT8748342A patent/IT1211751B/en active
- 1987-09-02 JP JP62220073A patent/JPS6368700A/en active Pending
- 1987-09-02 AR AR87308597A patent/AR243928A1/en active
- 1987-09-02 FR FR8712215A patent/FR2603300B1/en not_active Expired - Fee Related
- 1987-09-02 BE BE8700978A patent/BE1001724A4/en not_active IP Right Cessation
-
1993
- 1993-09-23 HK HK978/93A patent/HK97893A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB2194547A (en) | 1988-03-09 |
| ZA876158B (en) | 1989-04-26 |
| HK97893A (en) | 1993-09-30 |
| NZ221523A (en) | 1990-07-26 |
| MY101656A (en) | 1991-12-31 |
| AR243928A1 (en) | 1993-09-30 |
| DE3728547A1 (en) | 1988-03-03 |
| AU7733587A (en) | 1988-03-10 |
| BR8704494A (en) | 1988-04-19 |
| IT1211751B (en) | 1989-11-03 |
| JPS6368700A (en) | 1988-03-28 |
| FR2603300A1 (en) | 1988-03-04 |
| GB8720556D0 (en) | 1987-10-07 |
| DK449787D0 (en) | 1987-08-27 |
| IL83641A0 (en) | 1988-01-31 |
| IL83641A (en) | 1990-11-05 |
| IT8748342A0 (en) | 1987-09-01 |
| AU597414B2 (en) | 1990-05-31 |
| FR2603300B1 (en) | 1993-05-28 |
| ES2005285A6 (en) | 1989-03-01 |
| GB2194547B (en) | 1990-07-11 |
| PH24177A (en) | 1990-03-22 |
| BE1001724A4 (en) | 1990-02-20 |
| TR24203A (en) | 1991-07-01 |
| DK449787A (en) | 1988-03-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |