CA2136850A1 - Improvements relating to cleaning compositions - Google Patents
Improvements relating to cleaning compositionsInfo
- Publication number
- CA2136850A1 CA2136850A1 CA002136850A CA2136850A CA2136850A1 CA 2136850 A1 CA2136850 A1 CA 2136850A1 CA 002136850 A CA002136850 A CA 002136850A CA 2136850 A CA2136850 A CA 2136850A CA 2136850 A1 CA2136850 A1 CA 2136850A1
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- Canada
- Prior art keywords
- solvent
- solvent component
- composition according
- composition
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
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
2136850 9325654 PCTABScor01 The invention provides a homogeneous, aqueous, cleaning composition which comprises surfactant and solvent, and is characterized in that it forms a solvent-water emulsion on evaporation of at least a portion of the solvent. In such systems the solvent system is selected such that it comprises: a first solvent component in an amount such that it is present at a level above the miscibility limit of that component with water, and, a second solvent component which is sufficiently volatile that, in use, it evaporates from the composition to leave a mixture of the first solvent component and water, said second solvent component being present at a level such that first solvent component is solubilised in the composition. By using the second solvent to assist in the solution of the first solvent it is possible to obtain compositions which are clear, stable, isotropic compositions. In use, the second, volatile solvent component evaporates from the overall composition and the remaining first solvent component and water phase-separate, thus forming an emulsion, whereby the cleaning action of the first solvent component is potentiated. The emulsion formed generally has a coarse dispersed phase. This yields the advantages of a stable non-emulsion product as regards storage, dosing and manufacture, employs a relatively low level of solvent and provides the cleaning benefits of a free-solvent system.
Description
, IMPROVEMENTS RELATING TO CLF:ANING COMPOSITION5 Technical Field The present invention relates to improvements relating to cleaning compositions and in particular to improvements relating to cleaning compositions comprising surfactants and solvents.
Backaround of the Invention Many cleaning compositions for use in cleaning of household and industrial hard surfaces comprise solvent components, in addition to surfactants. These solvents are generally intended to improve cleaning performance by assisting in the removal of greasy or waxy soils. The advantages associated with the presence of solvents in such compositions are particularly marked at low surfactant levels, such as are found in compositions for use on highly reflective surfaces upon which high levels of surfactant residues cannot be tolerated.
Many of these solvent components are immiscible with water or have a relatively low level of miscibility above which they form emulsions and therefore those compositions which comprise levels of solvent above the miscibility limit either need to be shaken vigorously prior to use or the solvent needs to be present as a stable emulsion.
One such emulsion is disclosed in US 4689168 (The Drackett Company) which discloses anisotropic hard surface cleaning compositions containing volatile silicones, a non-volatile surfactant preferably selected from amongst anionic, nonionic surfactants and mixtures thereof and a polar organic solvent having a boiling point in the range 75-250C which is preferably ethyl, propyl or butyl alcohol and water.
ih - C3448 PCT ~6~5~
On shaking these compositions form semi-stable emulsions which break on contact with a hard surface to release the components.
Stable emulsions can be difficult to prepare and are prone to phase-separation. As consumers prefer stable, single phase systems and single phase systems are more readily formulated, processed, stored and dispensed than emulsions, the use of immiscible solvents in single phase compositions has been limited to relatively low levels.
Compositions comprising a binary solvent system of terpenes and polar solvents are described in EP 0040882 and EP 0080749.
Typical compositions for cleaning glass are described in EP 261874 (The Procter and Gamble Company: 1986/87). In that document are described cleaning compositions which comprise a specific isomer of n-butoxy propan-2-ol, available commercially as 'DOW~NOL PnB' (RTM, from the DOW Chemical Company). n butoxy propan-2-ol is miscible with water up to a level of around 6% dependent on temperature and levels of isomers. In that specification it is stated that the use of sprays to deliver the compositions to a surface is to be avoided due to odour problems.
A related later application EP 0428816 (P&G: 1989/90) discloses in general terms formulations comprising as a first solvent from 1-9% of ethanol, 0.5-3% of n-butoxy propan-2-ol, O.5-3% of n-propoxy propanol and, as a second solvent, 0.5-3%
of a primary or secondary monoalcohol having a five carbon alkyl chain.
Other systems have comprised emulsions. GB 2144763 (P&G: 1983) relates to hard-surface cleaners in the form of a so-called 'microemulsion~ of solvent, comprising at least 5% solvent and a magnesium salt. The use of microemulsions has been considered advantageous due to the improved cleaning 2~3~5~) ;- C3448 PCT
~erformance of free solvent as compared with solutions of solvent in water or other aqueous media. Microemulsions are described in that document as very fine emulsions which appear as homogeneous compositions.
Similar emulsion systems are disclosed in E~ 0347110 (Colgate: 1988): which relates to clear liquid detergents comprising anionics and nonionics, polar solvent consisting of Cl-C4 alkyl ethers of ethylene or diethylene glycol of mono, di or tripropylene glycol and 2.5-5% fragrance at pH 6-7. The last above-mentioned specification also discusses the detergency enhancing effect of magnesium in formulations containing anionic surfactants.
Backaround of the Invention Many cleaning compositions for use in cleaning of household and industrial hard surfaces comprise solvent components, in addition to surfactants. These solvents are generally intended to improve cleaning performance by assisting in the removal of greasy or waxy soils. The advantages associated with the presence of solvents in such compositions are particularly marked at low surfactant levels, such as are found in compositions for use on highly reflective surfaces upon which high levels of surfactant residues cannot be tolerated.
Many of these solvent components are immiscible with water or have a relatively low level of miscibility above which they form emulsions and therefore those compositions which comprise levels of solvent above the miscibility limit either need to be shaken vigorously prior to use or the solvent needs to be present as a stable emulsion.
One such emulsion is disclosed in US 4689168 (The Drackett Company) which discloses anisotropic hard surface cleaning compositions containing volatile silicones, a non-volatile surfactant preferably selected from amongst anionic, nonionic surfactants and mixtures thereof and a polar organic solvent having a boiling point in the range 75-250C which is preferably ethyl, propyl or butyl alcohol and water.
ih - C3448 PCT ~6~5~
On shaking these compositions form semi-stable emulsions which break on contact with a hard surface to release the components.
Stable emulsions can be difficult to prepare and are prone to phase-separation. As consumers prefer stable, single phase systems and single phase systems are more readily formulated, processed, stored and dispensed than emulsions, the use of immiscible solvents in single phase compositions has been limited to relatively low levels.
Compositions comprising a binary solvent system of terpenes and polar solvents are described in EP 0040882 and EP 0080749.
Typical compositions for cleaning glass are described in EP 261874 (The Procter and Gamble Company: 1986/87). In that document are described cleaning compositions which comprise a specific isomer of n-butoxy propan-2-ol, available commercially as 'DOW~NOL PnB' (RTM, from the DOW Chemical Company). n butoxy propan-2-ol is miscible with water up to a level of around 6% dependent on temperature and levels of isomers. In that specification it is stated that the use of sprays to deliver the compositions to a surface is to be avoided due to odour problems.
A related later application EP 0428816 (P&G: 1989/90) discloses in general terms formulations comprising as a first solvent from 1-9% of ethanol, 0.5-3% of n-butoxy propan-2-ol, O.5-3% of n-propoxy propanol and, as a second solvent, 0.5-3%
of a primary or secondary monoalcohol having a five carbon alkyl chain.
Other systems have comprised emulsions. GB 2144763 (P&G: 1983) relates to hard-surface cleaners in the form of a so-called 'microemulsion~ of solvent, comprising at least 5% solvent and a magnesium salt. The use of microemulsions has been considered advantageous due to the improved cleaning 2~3~5~) ;- C3448 PCT
~erformance of free solvent as compared with solutions of solvent in water or other aqueous media. Microemulsions are described in that document as very fine emulsions which appear as homogeneous compositions.
Similar emulsion systems are disclosed in E~ 0347110 (Colgate: 1988): which relates to clear liquid detergents comprising anionics and nonionics, polar solvent consisting of Cl-C4 alkyl ethers of ethylene or diethylene glycol of mono, di or tripropylene glycol and 2.5-5% fragrance at pH 6-7. The last above-mentioned specification also discusses the detergency enhancing effect of magnesium in formulations containing anionic surfactants.
3 discloses compositions of ethyl acetate, glycerol and water with optional surfactant in mixtures which are normally two phase systems except in a narrow formulation band.
EP 105063 discloses cleaning compositions which comprise a principal solvent and, when necessa~y, an auxiliary solvent which is utilized to solubilise the principal`solvent. The examples of EP 105063 employ, as the water-miscible solvent, diethylene glycol mono-n-butyl ether (commercially available as 'BUTYL DIGOL' (TM)).
US-A-4212758 discloses a cleansing agent which comprises as water-soluble components isopropyl alcohol and 1,2-propandiol, together with oleic acid and water-insoluble ethyl acetate.
~-~ US-A-3764544 discloses the use of ethyl acetate or other related acetates as an ester solvent, in combination with a coupling agent such as a glycol ether solvent~
Despite the research which has been conducted in this field a number of technical problems remain.
- C3448 PCT ~36~
- .a -Where microemulsions are employed they are difficult to produce, but where they are not used insufficient solvent may be present for effective cleaning.
In addition, the use of certain surfactants may lead to a product which are unstable, or appear so, on even short term storage. These products may be discarded by consumers thereby pointlessly releasing surfactants and solvents into the environment.
Moreover, normal use of a surfactant~solvent cleaning composition will increase the environmental loading of solvent and surfactant.
It is therefore desirable to ensure that of the surfactants released into the environment some are readily biodegradable and consequently use of environmentally preferable surfactants in cleaning compositions is preferred.
Unfortunately, it has proved difficult to formulate homogeneous solvent-containing systems which comprise these surfactants.
- C3448 PCT ~3 Additionally, the use of lower rather than higner levels of solvent is preferred as this reduces both cost and environmental release of solvent. However, as mentioned above, the use of low levels of solvent can gi~e poor cleaning results.
From the above it can be seen that it is desirabIe to prepare stable, biodegradable, products which comprise relatively low levels of solvent and which provide the effective cleaning performance associated with higher levels of solvent.
Brief Descri~tion of the Invention ':
We have now devised homogeneneous solvent and surfactant-containing systems which, in use, decompose into emulsions.
Accordingly, the present invention provides a homogeneous, isotropic, aqueous, solvent-containing, cleaning composition wherein-the solvent system comprises:
~ a) a first solvent component in an amount such that it is -- present at a level above the miscibility limit of that solvent component with water, and, b) a second solvent component present at a level such that the first solvent component is solubilised in the composition, C~3RACTERISED IN THAT said first sol~ent component is selected from glycol ethers and said second solvent component is sufficiently volatile that, in use, said second solvent - 25 component evaporates from the composition ~o leave a solvent-water emulsion comprising the first solvent component and water.
AMENDED SHE~
~ - C3448 PCT 3~
. . , Detailed Descri~tion of the Invention By using the second, volatile solvent to assist in the solution of the first solvent it is possible to obtain compositions which are clear, stable, isotropic compositions and do not constitute microemulsions. In use of the product, ~he second solvent component evaporates from the overall composition and the remaining first solvent component and water phase~separate, thus forming an emulsion, whereby the cleaning action of the first solvent component is -10 potentiated. The emulsion thus formed generally has a coarse dispersed phase. This yields the advantages of a stable non-emulsion product as regards storage, dosing and manufacture, -employs a relatively low level of solvent and provides the cleaning benefits of a free-solvent system.
First Solvent The presence of a first solvent component in an amounc such that it is present at a level above the miscibility li~it of said solvent component with water is an essential feature of the invention.
Preferably, the first solvent component is selected from the group comprising propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, dipropylene glycol mono t-butyl ether, diethylene glycol hexyl ether, and mixtures thereof.
Most preferably, the first solvent component is propylene glycol mono n-butyl ether (n-butoxy propan-2-ol), preferably present at a level of 6%-12%.
Second Solven~
The presence of a second, volatile solvent component is an essential feature of the invention.
Preferably, the second solvent component is selected from volatile alcohols; water miscible, volatile glycol ethers, aldehydes, ketones, di-alkyl ethers and mixtures thereof.
More preferably, said second solvent component is selected from the group comprising: methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether and mixtures lG thereof.
Most preferably, the second solvent component comprises, ethanol, isopropanol or mixtures thereof. Ethanol in the form of industrial methylated spirits is suitable for the practice of the invention.
Surfactants Surfactants are optional components of formulations according to the present invention although it is desirable that compositions according to the invention further comprise one or more surfactant species.
The nature of the surfactant is not critical to the general function of the invention.
In embodiments of the invention the surfactant species are generally, anionic or nonionic, although it i9 envisaged that cationic, zwitterionic and amphoteric surfactants can be employed. Mixtures of both anionic and nonionic can be employed.
In particularly preferred embodiments of the present invention the cleaning composition further comprises an 5~
anionic surfactant. It is envisaged that a broad range of anionic surfactants can be used in the embodiments of the present invention, some of which are listed below. In each case the anionic surfactant will be present together with a 5 suitable counter-ion.
Preferably the compositions further comprise magnesium ions in an amount corresponding to at least 0.02 M where M is the molar amount of anionic surfactant in the composition.
The magnesium salt of the anionic synthetic detergent to be 10 used in the present invention can be a magnesium salt of the . well-known types of anionic detergent surfactants, such as s the C1O_C18 alkylbenzene sulphonates, ClO-C~8 alkanesulphonates, sulphonated C10-C22 fatty acids or esters thereof, C8-C:18 olefinsulphonates, di-(C6-Clo alkyl) sulphosuccinates, C10-C~8 alkylsulphates, C10-C18 alkylethersulphates containing from 1 to 10 moles of ethylene-oxide. Further examples can be found in Schwartz-Perry "Surface Active Agents and Detergentsll, Vol. I (1949) and Vol. II (1958).
li:
Particularly, preferred amongst the anionic detergents are ,.,~
the magnesium salts of primary alcohol sulphates. These are believed to be more readily biodegradable than other surfactants and are available in commercial quantities from renewable resources.
Primary alcohol sulphates are mixture of materials of the 2S general formulation:
, wherein R is a C9 to Cl8 primary alkyl group and X is a solubilising cation. Suitable cations include sodium, magnesium, potassium, ammonium and mixtures thereof.
In general, the final composition should comprise from 0.05 to 10% by weight of the magnesium salt of the anionic s5~
synthetic detergent, preferably from 0.1 to 7.5% by weight.
The magnesium salt of the anionic synthetic detergent may be incorporated as such in the final composition, or may be formed by in-situ neutralisation of the anionic synthetic detergent in acid from with a suitable neutralising magnesium compound such as magnesium-oxide, -hydroxide, -carbonate, etc. The magnesium salt of the anionic synthetic detergent may also be formed in situ by the addition of a magnesium salt such as magnesium sulphate to the alkali-metal ammonium or alkanolamine salt of the anionoic synthetic detergent in the composition.
In addition to, or as an alternative to, anionic surfactants, nonionic surfactants can be employed. The preferred nonionic surfactant is selected from the group comprising ethoxylated alcohols of the general formula:
Rl-(OCH2CH2)~--OH
wherein R~ is straight or branched, C3 to Cl8 alkyl and the ~ average degree of ethoxylation (i.e. the ethylene oxide chain -- 20 length) m is 1-14.
As is illustrated ~y reference to examples given below, we hzve dçtermined that particularly eîfective compositions are formed when the surfactant system consists solely of the magnesium salt of an anionic surfactant, particu~arly the magnesium salt of a primary alcohol sulphate.
Preferred compositions according to the present invention therefore comprise:
~;, a) the magnesium salt of an anionic surfactant, preferably the magnesium salt of primary alcohol sulphate, b) 6%-12% wt n-butoxy propanol, c) water, and, '_ C3448 PCT
g d) sufficient volatile alcohol to prevent phase separation between the water and the n-butoxy propanol.
Minors The compositions of the invention can further comprise other S components selected from the group comprising: further surfactant species, perfumes, electrolytes, colours and dyes, abrasives, hygiene agents, further solvent components, foam-control agents, viscosity modifying agents, hydrotropes and mixtures thereof. Provided that these components are present at sufficiently low levels they do not interfere with the function of the invention.
Process As~ects of the Invention It is preferable to spray the compositions directly onto a soiled surface rather than cleaning the surface with a cloth or sponge dampened with the compositions. It is believed that the evaporation of one of the components of the cleaning composition is critical to the use of the inventive compositions in practice and that evaporation proceeds more effectively during the spraying operation and from a surface than from a cloth.
Accordingly, a further aspect of the present invention comprises a process including the steps of:
a) directly treating a surface with a composition according to the present invention, b) permitting the second solvent component to at least partially evaporate, and, c) performing a mechanical cleaning operation.
- lC -A yet- further aspect of the present invention relates to a homogeneneous composition comprising solvent and surfactant which decomposes into a solvent-water emulsion as a portion of the solvent evaporates, packaged in a container adapted to produce a spray.
In order that the present invention may be further understood it will be described hereafter by way of example and with reference to the accompanying figures 1 and 2 wherein;
Figure 1 is a graph showing the cleaning efficiency of lQ commercial n-butoxy propan-2-ol (DOWANOL PnB) with i concentration, and, .
- Figure 2 illustrates the cleaning efficiency of the compositions prepared as examples in graphical form.
EX.~MPLES 1-4 , Cleaning compositions were 2rePared as in Table 1 below, all -~ figures being given in wt% on product and being made up to ~~ 100% with water. The following abbreviations are used to identify the components mentioned in Tables 1, 2 and 3:
PnB: Dowanol PnB [RTM]: n-butoxv propan-2-ol, P2L: Pentan-2-ol, IMS: Industrial methylated spirits: ethanol, BD: Butyl Digol [RTM]: di ethylene glycol butyl ether - DOB: Dobanol 91-8 [RTM]: nonionic surfactant NH3: Ammonia ~::? 25 LAS: Linear alkyl sulphonate: surfactant (as ammonium sal~).
PAS: Magnesium salt of Clo-Cl8 primary alcohol sulphate:
anionic surfactant.
NON: Dobanol 91-350FA [RTM]: nonionic surfactant.
~3~5~) - '1 From figure 1 it can be seen that the cleaning efficiency of PnB-based compositions is particularly dependent on PnB
concentration in the range between 5 and 7 wt% concentration on product. To obtain these results 1.0 ml of each neat i 5 sample was applied with a sponge on t,o soiled Decamel [RTM]
tiles (soiled with 80/20 fat/particulate soil at 0.25mg/cm.cm) and wiped using 10 reciprocal Sheen rubbing cycles (76 g/cm.cm applied load). The percentage cleaning efficiency was calculated from reflectance measurements.
The maximum miscibility of PnB with water is around 6%wt and consequently formulations comprising >6%wt are normally phase separated into an aqueous and an excess solvent phase. From Figure 1 it is clear that free solvent is far more effective in cleaning operations than solvent which is dissolved in an aqueous medium.
Single phase compositions were formed by simple mixing of the components according to the formulations given in Table 1, the balance of the formulation being water.
., .
, In order to determine'the effectiveness of the compositions, 0.6ml of each neat sample was sprayed on to soiled Decamel [RTM] tiles (soiled with 80/20 fat/particulate soil at 0.25mg/cm.cm) and left for one minute before wiping with a sponge cloth using 10 reciprocal Sheen rubbing cycles (76 g/cm.cm applied load). The percentage cleaning efficiency 25, was calculated from tile-surface reflectance measurements.
Comparative example,s are marked with an asterisk.
-.
, .
~ ~ C3~48 PCT ~3~
T~3~E 1 Exam~le ¦ DOB ¦ IMS ¦ BD ¦ PnB
_____ ~ ~
1*- ~ 09% - _ 5%
2* O . 09% 20% _ 596 _ _ 3 O . 0996 13% _ 7%
_ 4* O . 09% 13% 7%
_ ___ __ . ~ r Percentage cleaning efficiency results for the above mentioned formulations are shown in figure 2. In decreasing order, cleaning efficiency was 3>2>1>4.
Example 1 is a control experiment to illustrate the base-line cleaning effect of a single phase system containing PnB. The le~el of PnB in this example has been selected such that it lies below the maximum miscibility with water and consequently the system forms a homogeneous mixture. It can be seen from comparative exzmple 2 that the addition of IMS
improves the cleaning performance only slightly.
A significant improvement is attained when the starting concentration of PnB is above the maximum miscibility level, as in example 3. The compositions of example 3 are clear, homogeneous systems which, in use, lose the alcoholic solvent to the ambient and reach a composition at which there is just sufficient alcohol present to solubilise all of the PnB
present. At this composition, further loss of volatile solvent results in phase separation of the PnB.
Comparative example 4 shows that when BD, is present below its maximum miscibility in the starting composition cleaning is less effective.
~ 3~
EX~MPLES 5-13 In order to further demonstrate the characteristic features or the present invention a number of known compositions as described in EP 0428816 were prepared with the formulations given below in Table 2 and their phase-behaviour on evaporation noted. The balance of each composition was water and the figures quoted are weight percentages on product.
Examples 5-12, as marked with an asterisk, are these comparative examples whereas example 13 is an embodiment of the invention, identical to example 3 given above.
__~
~xam~le hAS NH3 I~S PnB P2~ ¦ DO~
~______ 5* 0.1 _ 9.0 0.5 0.5 _ _ _ 6* 0.1 _ g.0 0.5 1.0 _ _ 1~ 7* 0.1 _ 9.0 0.5 1.5 _ . _ 8* _ 0.1 _ 9.0 _ 0.5 2.0 g*_ 0.1 _ 9.0 0.5 2.5_ _ 10* 0.1 _ 9.0 0.5 3.0 _ _ _ _ _ 11~ 0.1 0.2 9.0 1.5 1.5 _ _ 12* 0.1 _ 8.0 3.0 3.0 _ _ . .
13 _ _ 13 7.0 _ 0.0~
_ __ __ _ , I , I 1-:. !
'';' All samples were clear isotropic liquids at room temperature apart from sample 8 which was cloudy. This sample was therefore excluded from the following.
In separate experiments each sample was applied to a black ceramic tile and spread over the surface with a clean, dry 36~
~ C3~48 PCT
cloth to form a thin film which was allowed to evaporate to dryness. The film was observed closely by eye to determine the formation of any emulsion (indicated by a transformation from a transparent film to an opaque film). T~e only sample observed to form an emulsion was that of example 13, an embodiment of the invention.
Further examples are given in Table 3 below. Examples 14-27 illustrate the effect of the choice of surfactant on product performance.
To obtain the results listed in Table 3, 1.0 ml of each neat sample was applied with a sponge on to soiled ~ecamel ~RTM]
tiles (soiled with 80/20 fattparticulate soil at 0.25mg~cm.cm) and wiped by hand using reciprocal rubbing cycles. The cleaning efficiency was determined in relation to the effort required: 1 corresponds to little effort whereas 5 corresponds to some difficulty in removing the soil. Comparàtive examples are indicated by an asterisk.
As noted above, the maximum miscibility of PnB with water is around 6%wt and consequently formulations comprising >6%wt PnB are normally phase separated into an aqueous phase and an excess solvent phase. However, in the presence of the co-solvent the formulations of examples 16-19 exhibited a single phase. i i ~
a {~;
C34~8 PCT
, I . _~ __ ~ ; _ Com~one:~t Wt . % PAS NON PnB IPA ¦ I~S BD Score _ I _ _ Sa3~l~
I _ _ ~ __ _ __ _ _ .
14* _ 0.1 j5.0 _ _ _ 4.7 lS* 0.1 _ 5.0 _ _ _ 5 _ .
16 _ 0.1 7 1~ _ _ 2.3 _ 17 0 .1 _ 7 13 _ _ 1 .3 _ _ _ _ 18 _ 0.1 7 _ 13 _ 2.3 19 0.1 _ 7 _ 13 _ 2.3 _ 20* 0.1 _ _ 20 _ _ 5 21* _ 0.1 _ 2a - 5 _ 22* 0.1 _ _ _ 20 _ 5 _ _ 23* _ 0.1 _ _ 20 _ 5 _ _ 24* 0.1 _ _ _ _ 10 5 _ _ 25* 0.1 _ _ _ _ 5 5 _ _ ~ _ 26* 0.1 _ _ 5 _ 5 5 ,_ 27* 0.1 _ _ _ 5 S 5 Examples 14 and 15 are control experiments to illustrate the cleaning effect of a single phase system containing PnB, below the maximum miscibility. The cleaning performance of - 20 these compositions appears slightly better in the presence of the nonionic surfactant (comparative example 14) than the anionic surfactant (comparative example 15). This is in agreement with the results noted in respect of comparative example 1 mentioned above.
. C3448 PCT ~ 3~5~
It can be seen from embodiments 17 and 19 that the addition of IPA or IMS as co-solvents in the presence of a slightly increased level of PnB improves the cleaning performance grea~ly. This is in agreement wi~h the results discussed above comparing examples 1 and 3 as mentioned above.
Examples 16 and 18 are examples using a nonionic surfactant.
Although these compositions had a cleaning performance approaching that of embodiments 17 and 19, the compositions became cloudy on storage. It is to be noted that the anionic surfactant in compositions according to the preferred embodiment of the present invention exhibi~s better cleaning performance than the nonionic surfactant (compare examples 16 and 17).
Comparative examples 20-27 shows that combinations of solvent which fall outside of the scope of the present invention did not have @ffective cleaning performance. In these comparative compositions no emulsion was formed on the evaporation of the volatile solvent component.
- From the examples given above it can be seen that hcmogeneous, solvent systems which phase separate to form an emulsion on evaporation of a portion of the solvent give improved cleaning performance over homogeneous systems which comprise similar quantities of solvent but which do not exhibit the phase separation behaviour in use.
:
EP 105063 discloses cleaning compositions which comprise a principal solvent and, when necessa~y, an auxiliary solvent which is utilized to solubilise the principal`solvent. The examples of EP 105063 employ, as the water-miscible solvent, diethylene glycol mono-n-butyl ether (commercially available as 'BUTYL DIGOL' (TM)).
US-A-4212758 discloses a cleansing agent which comprises as water-soluble components isopropyl alcohol and 1,2-propandiol, together with oleic acid and water-insoluble ethyl acetate.
~-~ US-A-3764544 discloses the use of ethyl acetate or other related acetates as an ester solvent, in combination with a coupling agent such as a glycol ether solvent~
Despite the research which has been conducted in this field a number of technical problems remain.
- C3448 PCT ~36~
- .a -Where microemulsions are employed they are difficult to produce, but where they are not used insufficient solvent may be present for effective cleaning.
In addition, the use of certain surfactants may lead to a product which are unstable, or appear so, on even short term storage. These products may be discarded by consumers thereby pointlessly releasing surfactants and solvents into the environment.
Moreover, normal use of a surfactant~solvent cleaning composition will increase the environmental loading of solvent and surfactant.
It is therefore desirable to ensure that of the surfactants released into the environment some are readily biodegradable and consequently use of environmentally preferable surfactants in cleaning compositions is preferred.
Unfortunately, it has proved difficult to formulate homogeneous solvent-containing systems which comprise these surfactants.
- C3448 PCT ~3 Additionally, the use of lower rather than higner levels of solvent is preferred as this reduces both cost and environmental release of solvent. However, as mentioned above, the use of low levels of solvent can gi~e poor cleaning results.
From the above it can be seen that it is desirabIe to prepare stable, biodegradable, products which comprise relatively low levels of solvent and which provide the effective cleaning performance associated with higher levels of solvent.
Brief Descri~tion of the Invention ':
We have now devised homogeneneous solvent and surfactant-containing systems which, in use, decompose into emulsions.
Accordingly, the present invention provides a homogeneous, isotropic, aqueous, solvent-containing, cleaning composition wherein-the solvent system comprises:
~ a) a first solvent component in an amount such that it is -- present at a level above the miscibility limit of that solvent component with water, and, b) a second solvent component present at a level such that the first solvent component is solubilised in the composition, C~3RACTERISED IN THAT said first sol~ent component is selected from glycol ethers and said second solvent component is sufficiently volatile that, in use, said second solvent - 25 component evaporates from the composition ~o leave a solvent-water emulsion comprising the first solvent component and water.
AMENDED SHE~
~ - C3448 PCT 3~
. . , Detailed Descri~tion of the Invention By using the second, volatile solvent to assist in the solution of the first solvent it is possible to obtain compositions which are clear, stable, isotropic compositions and do not constitute microemulsions. In use of the product, ~he second solvent component evaporates from the overall composition and the remaining first solvent component and water phase~separate, thus forming an emulsion, whereby the cleaning action of the first solvent component is -10 potentiated. The emulsion thus formed generally has a coarse dispersed phase. This yields the advantages of a stable non-emulsion product as regards storage, dosing and manufacture, -employs a relatively low level of solvent and provides the cleaning benefits of a free-solvent system.
First Solvent The presence of a first solvent component in an amounc such that it is present at a level above the miscibility li~it of said solvent component with water is an essential feature of the invention.
Preferably, the first solvent component is selected from the group comprising propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, dipropylene glycol mono t-butyl ether, diethylene glycol hexyl ether, and mixtures thereof.
Most preferably, the first solvent component is propylene glycol mono n-butyl ether (n-butoxy propan-2-ol), preferably present at a level of 6%-12%.
Second Solven~
The presence of a second, volatile solvent component is an essential feature of the invention.
Preferably, the second solvent component is selected from volatile alcohols; water miscible, volatile glycol ethers, aldehydes, ketones, di-alkyl ethers and mixtures thereof.
More preferably, said second solvent component is selected from the group comprising: methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether and mixtures lG thereof.
Most preferably, the second solvent component comprises, ethanol, isopropanol or mixtures thereof. Ethanol in the form of industrial methylated spirits is suitable for the practice of the invention.
Surfactants Surfactants are optional components of formulations according to the present invention although it is desirable that compositions according to the invention further comprise one or more surfactant species.
The nature of the surfactant is not critical to the general function of the invention.
In embodiments of the invention the surfactant species are generally, anionic or nonionic, although it i9 envisaged that cationic, zwitterionic and amphoteric surfactants can be employed. Mixtures of both anionic and nonionic can be employed.
In particularly preferred embodiments of the present invention the cleaning composition further comprises an 5~
anionic surfactant. It is envisaged that a broad range of anionic surfactants can be used in the embodiments of the present invention, some of which are listed below. In each case the anionic surfactant will be present together with a 5 suitable counter-ion.
Preferably the compositions further comprise magnesium ions in an amount corresponding to at least 0.02 M where M is the molar amount of anionic surfactant in the composition.
The magnesium salt of the anionic synthetic detergent to be 10 used in the present invention can be a magnesium salt of the . well-known types of anionic detergent surfactants, such as s the C1O_C18 alkylbenzene sulphonates, ClO-C~8 alkanesulphonates, sulphonated C10-C22 fatty acids or esters thereof, C8-C:18 olefinsulphonates, di-(C6-Clo alkyl) sulphosuccinates, C10-C~8 alkylsulphates, C10-C18 alkylethersulphates containing from 1 to 10 moles of ethylene-oxide. Further examples can be found in Schwartz-Perry "Surface Active Agents and Detergentsll, Vol. I (1949) and Vol. II (1958).
li:
Particularly, preferred amongst the anionic detergents are ,.,~
the magnesium salts of primary alcohol sulphates. These are believed to be more readily biodegradable than other surfactants and are available in commercial quantities from renewable resources.
Primary alcohol sulphates are mixture of materials of the 2S general formulation:
, wherein R is a C9 to Cl8 primary alkyl group and X is a solubilising cation. Suitable cations include sodium, magnesium, potassium, ammonium and mixtures thereof.
In general, the final composition should comprise from 0.05 to 10% by weight of the magnesium salt of the anionic s5~
synthetic detergent, preferably from 0.1 to 7.5% by weight.
The magnesium salt of the anionic synthetic detergent may be incorporated as such in the final composition, or may be formed by in-situ neutralisation of the anionic synthetic detergent in acid from with a suitable neutralising magnesium compound such as magnesium-oxide, -hydroxide, -carbonate, etc. The magnesium salt of the anionic synthetic detergent may also be formed in situ by the addition of a magnesium salt such as magnesium sulphate to the alkali-metal ammonium or alkanolamine salt of the anionoic synthetic detergent in the composition.
In addition to, or as an alternative to, anionic surfactants, nonionic surfactants can be employed. The preferred nonionic surfactant is selected from the group comprising ethoxylated alcohols of the general formula:
Rl-(OCH2CH2)~--OH
wherein R~ is straight or branched, C3 to Cl8 alkyl and the ~ average degree of ethoxylation (i.e. the ethylene oxide chain -- 20 length) m is 1-14.
As is illustrated ~y reference to examples given below, we hzve dçtermined that particularly eîfective compositions are formed when the surfactant system consists solely of the magnesium salt of an anionic surfactant, particu~arly the magnesium salt of a primary alcohol sulphate.
Preferred compositions according to the present invention therefore comprise:
~;, a) the magnesium salt of an anionic surfactant, preferably the magnesium salt of primary alcohol sulphate, b) 6%-12% wt n-butoxy propanol, c) water, and, '_ C3448 PCT
g d) sufficient volatile alcohol to prevent phase separation between the water and the n-butoxy propanol.
Minors The compositions of the invention can further comprise other S components selected from the group comprising: further surfactant species, perfumes, electrolytes, colours and dyes, abrasives, hygiene agents, further solvent components, foam-control agents, viscosity modifying agents, hydrotropes and mixtures thereof. Provided that these components are present at sufficiently low levels they do not interfere with the function of the invention.
Process As~ects of the Invention It is preferable to spray the compositions directly onto a soiled surface rather than cleaning the surface with a cloth or sponge dampened with the compositions. It is believed that the evaporation of one of the components of the cleaning composition is critical to the use of the inventive compositions in practice and that evaporation proceeds more effectively during the spraying operation and from a surface than from a cloth.
Accordingly, a further aspect of the present invention comprises a process including the steps of:
a) directly treating a surface with a composition according to the present invention, b) permitting the second solvent component to at least partially evaporate, and, c) performing a mechanical cleaning operation.
- lC -A yet- further aspect of the present invention relates to a homogeneneous composition comprising solvent and surfactant which decomposes into a solvent-water emulsion as a portion of the solvent evaporates, packaged in a container adapted to produce a spray.
In order that the present invention may be further understood it will be described hereafter by way of example and with reference to the accompanying figures 1 and 2 wherein;
Figure 1 is a graph showing the cleaning efficiency of lQ commercial n-butoxy propan-2-ol (DOWANOL PnB) with i concentration, and, .
- Figure 2 illustrates the cleaning efficiency of the compositions prepared as examples in graphical form.
EX.~MPLES 1-4 , Cleaning compositions were 2rePared as in Table 1 below, all -~ figures being given in wt% on product and being made up to ~~ 100% with water. The following abbreviations are used to identify the components mentioned in Tables 1, 2 and 3:
PnB: Dowanol PnB [RTM]: n-butoxv propan-2-ol, P2L: Pentan-2-ol, IMS: Industrial methylated spirits: ethanol, BD: Butyl Digol [RTM]: di ethylene glycol butyl ether - DOB: Dobanol 91-8 [RTM]: nonionic surfactant NH3: Ammonia ~::? 25 LAS: Linear alkyl sulphonate: surfactant (as ammonium sal~).
PAS: Magnesium salt of Clo-Cl8 primary alcohol sulphate:
anionic surfactant.
NON: Dobanol 91-350FA [RTM]: nonionic surfactant.
~3~5~) - '1 From figure 1 it can be seen that the cleaning efficiency of PnB-based compositions is particularly dependent on PnB
concentration in the range between 5 and 7 wt% concentration on product. To obtain these results 1.0 ml of each neat i 5 sample was applied with a sponge on t,o soiled Decamel [RTM]
tiles (soiled with 80/20 fat/particulate soil at 0.25mg/cm.cm) and wiped using 10 reciprocal Sheen rubbing cycles (76 g/cm.cm applied load). The percentage cleaning efficiency was calculated from reflectance measurements.
The maximum miscibility of PnB with water is around 6%wt and consequently formulations comprising >6%wt are normally phase separated into an aqueous and an excess solvent phase. From Figure 1 it is clear that free solvent is far more effective in cleaning operations than solvent which is dissolved in an aqueous medium.
Single phase compositions were formed by simple mixing of the components according to the formulations given in Table 1, the balance of the formulation being water.
., .
, In order to determine'the effectiveness of the compositions, 0.6ml of each neat sample was sprayed on to soiled Decamel [RTM] tiles (soiled with 80/20 fat/particulate soil at 0.25mg/cm.cm) and left for one minute before wiping with a sponge cloth using 10 reciprocal Sheen rubbing cycles (76 g/cm.cm applied load). The percentage cleaning efficiency 25, was calculated from tile-surface reflectance measurements.
Comparative example,s are marked with an asterisk.
-.
, .
~ ~ C3~48 PCT ~3~
T~3~E 1 Exam~le ¦ DOB ¦ IMS ¦ BD ¦ PnB
_____ ~ ~
1*- ~ 09% - _ 5%
2* O . 09% 20% _ 596 _ _ 3 O . 0996 13% _ 7%
_ 4* O . 09% 13% 7%
_ ___ __ . ~ r Percentage cleaning efficiency results for the above mentioned formulations are shown in figure 2. In decreasing order, cleaning efficiency was 3>2>1>4.
Example 1 is a control experiment to illustrate the base-line cleaning effect of a single phase system containing PnB. The le~el of PnB in this example has been selected such that it lies below the maximum miscibility with water and consequently the system forms a homogeneous mixture. It can be seen from comparative exzmple 2 that the addition of IMS
improves the cleaning performance only slightly.
A significant improvement is attained when the starting concentration of PnB is above the maximum miscibility level, as in example 3. The compositions of example 3 are clear, homogeneous systems which, in use, lose the alcoholic solvent to the ambient and reach a composition at which there is just sufficient alcohol present to solubilise all of the PnB
present. At this composition, further loss of volatile solvent results in phase separation of the PnB.
Comparative example 4 shows that when BD, is present below its maximum miscibility in the starting composition cleaning is less effective.
~ 3~
EX~MPLES 5-13 In order to further demonstrate the characteristic features or the present invention a number of known compositions as described in EP 0428816 were prepared with the formulations given below in Table 2 and their phase-behaviour on evaporation noted. The balance of each composition was water and the figures quoted are weight percentages on product.
Examples 5-12, as marked with an asterisk, are these comparative examples whereas example 13 is an embodiment of the invention, identical to example 3 given above.
__~
~xam~le hAS NH3 I~S PnB P2~ ¦ DO~
~______ 5* 0.1 _ 9.0 0.5 0.5 _ _ _ 6* 0.1 _ g.0 0.5 1.0 _ _ 1~ 7* 0.1 _ 9.0 0.5 1.5 _ . _ 8* _ 0.1 _ 9.0 _ 0.5 2.0 g*_ 0.1 _ 9.0 0.5 2.5_ _ 10* 0.1 _ 9.0 0.5 3.0 _ _ _ _ _ 11~ 0.1 0.2 9.0 1.5 1.5 _ _ 12* 0.1 _ 8.0 3.0 3.0 _ _ . .
13 _ _ 13 7.0 _ 0.0~
_ __ __ _ , I , I 1-:. !
'';' All samples were clear isotropic liquids at room temperature apart from sample 8 which was cloudy. This sample was therefore excluded from the following.
In separate experiments each sample was applied to a black ceramic tile and spread over the surface with a clean, dry 36~
~ C3~48 PCT
cloth to form a thin film which was allowed to evaporate to dryness. The film was observed closely by eye to determine the formation of any emulsion (indicated by a transformation from a transparent film to an opaque film). T~e only sample observed to form an emulsion was that of example 13, an embodiment of the invention.
Further examples are given in Table 3 below. Examples 14-27 illustrate the effect of the choice of surfactant on product performance.
To obtain the results listed in Table 3, 1.0 ml of each neat sample was applied with a sponge on to soiled ~ecamel ~RTM]
tiles (soiled with 80/20 fattparticulate soil at 0.25mg~cm.cm) and wiped by hand using reciprocal rubbing cycles. The cleaning efficiency was determined in relation to the effort required: 1 corresponds to little effort whereas 5 corresponds to some difficulty in removing the soil. Comparàtive examples are indicated by an asterisk.
As noted above, the maximum miscibility of PnB with water is around 6%wt and consequently formulations comprising >6%wt PnB are normally phase separated into an aqueous phase and an excess solvent phase. However, in the presence of the co-solvent the formulations of examples 16-19 exhibited a single phase. i i ~
a {~;
C34~8 PCT
, I . _~ __ ~ ; _ Com~one:~t Wt . % PAS NON PnB IPA ¦ I~S BD Score _ I _ _ Sa3~l~
I _ _ ~ __ _ __ _ _ .
14* _ 0.1 j5.0 _ _ _ 4.7 lS* 0.1 _ 5.0 _ _ _ 5 _ .
16 _ 0.1 7 1~ _ _ 2.3 _ 17 0 .1 _ 7 13 _ _ 1 .3 _ _ _ _ 18 _ 0.1 7 _ 13 _ 2.3 19 0.1 _ 7 _ 13 _ 2.3 _ 20* 0.1 _ _ 20 _ _ 5 21* _ 0.1 _ 2a - 5 _ 22* 0.1 _ _ _ 20 _ 5 _ _ 23* _ 0.1 _ _ 20 _ 5 _ _ 24* 0.1 _ _ _ _ 10 5 _ _ 25* 0.1 _ _ _ _ 5 5 _ _ ~ _ 26* 0.1 _ _ 5 _ 5 5 ,_ 27* 0.1 _ _ _ 5 S 5 Examples 14 and 15 are control experiments to illustrate the cleaning effect of a single phase system containing PnB, below the maximum miscibility. The cleaning performance of - 20 these compositions appears slightly better in the presence of the nonionic surfactant (comparative example 14) than the anionic surfactant (comparative example 15). This is in agreement with the results noted in respect of comparative example 1 mentioned above.
. C3448 PCT ~ 3~5~
It can be seen from embodiments 17 and 19 that the addition of IPA or IMS as co-solvents in the presence of a slightly increased level of PnB improves the cleaning performance grea~ly. This is in agreement wi~h the results discussed above comparing examples 1 and 3 as mentioned above.
Examples 16 and 18 are examples using a nonionic surfactant.
Although these compositions had a cleaning performance approaching that of embodiments 17 and 19, the compositions became cloudy on storage. It is to be noted that the anionic surfactant in compositions according to the preferred embodiment of the present invention exhibi~s better cleaning performance than the nonionic surfactant (compare examples 16 and 17).
Comparative examples 20-27 shows that combinations of solvent which fall outside of the scope of the present invention did not have @ffective cleaning performance. In these comparative compositions no emulsion was formed on the evaporation of the volatile solvent component.
- From the examples given above it can be seen that hcmogeneous, solvent systems which phase separate to form an emulsion on evaporation of a portion of the solvent give improved cleaning performance over homogeneous systems which comprise similar quantities of solvent but which do not exhibit the phase separation behaviour in use.
:
Claims (14)
1. Homogeneous, isotropic, aqueous, solvent-containing, cleaning composition wherein the solvent system comprises:
a) a first solvent component in an amount such that it is present at a level above the miscibility limit of that solvent component with water, and, b) a second solvent component present at a level such that the first solvent component is solubilised in the composition, CHARACTERISED IN THAT said first solvent component is selected from glycol ethers and said second solvent component is sufficiently volatile that, in use, said second solvent component evaporates from the composition to leave a solvent water emulsion comprising the first solvent component and water.
a) a first solvent component in an amount such that it is present at a level above the miscibility limit of that solvent component with water, and, b) a second solvent component present at a level such that the first solvent component is solubilised in the composition, CHARACTERISED IN THAT said first solvent component is selected from glycol ethers and said second solvent component is sufficiently volatile that, in use, said second solvent component evaporates from the composition to leave a solvent water emulsion comprising the first solvent component and water.
2. Composition according to claim 1 wherein the first solvent component is selected from the group comprising propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, dipropylene glycol mono t-butyl ether, diethylene glycol hexyl ether, and mixtures thereof.
3. Composition according to claim 1 wherein the second solvent component is selected from volatile alcohols;
water miscible, volatile glycol ethers, aldehydes, ketones, di-alkyl ethers and mixtures thereof.
water miscible, volatile glycol ethers, aldehydes, ketones, di-alkyl ethers and mixtures thereof.
4. Composition according to claim 3 wherein the second component is selected from the group comprising:
methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether and mixtures thereof.
methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether and mixtures thereof.
5. Composition according to claim 1 further comprising a surfactant.
6. Composition according to claim 5 comprising an anionic surfactant.
7. Composition according to claim 6 wherein the anionic surfactant is the salt of primary alkyl sulphate of materials of the general formulation:
(ROSO3).X
wherein R is a C8 to C18 primary alkyl group and X is a suitable counterion.
(ROSO3).X
wherein R is a C8 to C18 primary alkyl group and X is a suitable counterion.
8. Composition according to claim 7 further comprising magnesium ions in an amount corresponding to at least 0.02 M where M is the molar amount of anionic surfactant in the composition.
9. Composition according to claim 5 comprising a nonionic surfactant.
10. Composition according to claim 9 comprising a nonionic surfactant selected from the group comprising ethoxylated alcohols of the general formula:
R1-(OCH2CH2)m-OH
wherein R1 is straight or branched, C8 to C18 alkyl and the average degree of ethoxylation (i.e. the ethylene oxide chain length) m is 1-14.
R1-(OCH2CH2)m-OH
wherein R1 is straight or branched, C8 to C18 alkyl and the average degree of ethoxylation (i.e. the ethylene oxide chain length) m is 1-14.
11. Cleaning composition according to claim 1 comprising:
a) 6%-12% wt n-butoxy propanol, b) water, c) sufficient volatile alcohol to prevent phase separation between the water and the n-butoxy propanol.
a) 6%-12% wt n-butoxy propanol, b) water, c) sufficient volatile alcohol to prevent phase separation between the water and the n-butoxy propanol.
12. Composition according to claim 11 further comprising:
a) the magnesium salt of an anionic surfactant
a) the magnesium salt of an anionic surfactant
13. Cleaning process including the steps of:
a) directly treating a surface with a composition according to any one of claims 1-12, b) permitting the second solvent component to at least partially evaporate, and, c) performing a mechanical cleaning operation.
a) directly treating a surface with a composition according to any one of claims 1-12, b) permitting the second solvent component to at least partially evaporate, and, c) performing a mechanical cleaning operation.
14. Composition according to any one of claims 1-12, packaged in a container adapted to produce a spray of said composition.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB929213073A GB9213073D0 (en) | 1992-06-18 | 1992-06-18 | Improvements relating to cleaning composition |
| GB9213073.1 | 1992-06-18 | ||
| GB929215902A GB9215902D0 (en) | 1992-07-27 | 1992-07-27 | Improvements relating to cleaning compositions |
| GB9215902.9 | 1992-07-27 | ||
| GB929218080A GB9218080D0 (en) | 1992-08-25 | 1992-08-25 | Improvements relating to cleaning compositions |
| GB9218080.1 | 1992-11-05 | ||
| PCT/EP1993/001330 WO1993025654A1 (en) | 1992-06-18 | 1993-05-27 | Improvements relating to cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2136850A1 true CA2136850A1 (en) | 1993-12-23 |
Family
ID=27266255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136850A Abandoned CA2136850A1 (en) | 1992-06-18 | 1993-05-27 | Improvements relating to cleaning compositions |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0647264B1 (en) |
| JP (1) | JPH07507584A (en) |
| AU (1) | AU678360B2 (en) |
| BR (1) | BR9306574A (en) |
| CA (1) | CA2136850A1 (en) |
| CZ (1) | CZ319594A3 (en) |
| DE (1) | DE69302384T2 (en) |
| ES (1) | ES2087743T3 (en) |
| HU (1) | HUT70082A (en) |
| IN (1) | IN176902B (en) |
| MY (1) | MY109133A (en) |
| SK (1) | SK154894A3 (en) |
| WO (1) | WO1993025654A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9319125D0 (en) * | 1993-09-15 | 1993-11-03 | Dow Europ Sa | Cleaning composition |
| AU675833B2 (en) * | 1994-03-23 | 1997-02-20 | Amway Corporation | Concentrated all-purpose light duty liquid cleaning composition and method of use |
| US5531939A (en) * | 1994-03-23 | 1996-07-02 | Amway Corporation | Concentrated glass and window cleaning composition and method of use |
| US5942484A (en) * | 1995-03-30 | 1999-08-24 | The Procter & Gamble Company | Phase-stable liquid fabric refreshment composition |
| US5681355A (en) * | 1995-08-11 | 1997-10-28 | The Procter & Gamble Company | Heat resistant dry cleaning bag |
| US5789368A (en) * | 1996-01-26 | 1998-08-04 | The Procter & Gamble Company | Fabric care bag |
| US6233771B1 (en) | 1996-01-26 | 2001-05-22 | The Procter & Gamble Company | Stain removal device |
| US5840675A (en) * | 1996-02-28 | 1998-11-24 | The Procter And Gamble Company | Controlled released fabric care article |
| US5891197A (en) * | 1996-08-02 | 1999-04-06 | The Proctor & Gamble Company | Stain receiver for dry cleaning process |
| US5872090A (en) * | 1996-10-25 | 1999-02-16 | The Procter & Gamble Company | Stain removal with bleach |
| US5849039A (en) * | 1997-01-17 | 1998-12-15 | The Procter & Gamble Company | Spot removal process |
| US5762648A (en) * | 1997-01-17 | 1998-06-09 | The Procter & Gamble Company | Fabric treatment in venting bag |
| US7008458B2 (en) | 1997-04-04 | 2006-03-07 | Hayday William A | Biodegradable ether dry cleaning solvent |
| US6273919B1 (en) | 1997-04-04 | 2001-08-14 | Rynex Holdings Ltd. | Biodegradable ether dry cleaning solvent |
| US5888250A (en) * | 1997-04-04 | 1999-03-30 | Rynex Holdings Ltd. | Biodegradable dry cleaning solvent |
| PL339081A1 (en) * | 1997-09-03 | 2000-12-04 | Johnson & Son Inc S C | Method of disinfecting non-porous hard surfaces and inhibiting mildew growth on them |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3764544A (en) * | 1971-08-06 | 1973-10-09 | L Haworth | Spot remover for wearing apparel |
| EP0005309A1 (en) * | 1978-02-14 | 1979-11-14 | Dawley Brook Papers Limited | Cleaning composition and method of removing printing ink from surfaces |
| US4212758A (en) * | 1978-10-20 | 1980-07-15 | Belkevich Petr I | Cleansing agents containing oleic acid, isopropanol and ethylacetate |
| SE438162B (en) * | 1979-05-29 | 1985-04-01 | Tepab Tek Prod Ab | PROCEDURE FOR CLEANING A SURFACE, IN PARTICULAR REMOVAL OF COATING LAYERS AND LAYOUTS FROM A SURFACE |
| CA1178160A (en) * | 1981-09-10 | 1984-11-20 | Donald B. Compton | Liquid hard-surface cleaner |
| GB2144763B (en) * | 1983-08-11 | 1987-10-28 | Procter & Gamble | Liquid detergent compositions with magnesium salts |
| US4689168A (en) * | 1984-06-08 | 1987-08-25 | The Drackett Company | Hard surface cleaning composition |
| US5075026A (en) * | 1986-05-21 | 1991-12-24 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition |
| US4921629A (en) * | 1988-04-13 | 1990-05-01 | Colgate-Palmolive Company | Heavy duty hard surface liquid detergent |
| EP0428816A1 (en) * | 1989-11-23 | 1991-05-29 | The Procter & Gamble Company | Hard-surface cleaning compositions |
| ZA925727B (en) * | 1991-08-09 | 1993-03-10 | Bristol Myers Squibb Co | Glass cleaning composition. |
-
1993
- 1993-05-27 ES ES93912803T patent/ES2087743T3/en not_active Expired - Lifetime
- 1993-05-27 BR BR9306574A patent/BR9306574A/en not_active Application Discontinuation
- 1993-05-27 EP EP93912803A patent/EP0647264B1/en not_active Expired - Lifetime
- 1993-05-27 JP JP6501062A patent/JPH07507584A/en active Pending
- 1993-05-27 SK SK1548-94A patent/SK154894A3/en unknown
- 1993-05-27 HU HU9403634A patent/HUT70082A/en unknown
- 1993-05-27 WO PCT/EP1993/001330 patent/WO1993025654A1/en not_active Application Discontinuation
- 1993-05-27 DE DE69302384T patent/DE69302384T2/en not_active Expired - Fee Related
- 1993-05-27 CA CA002136850A patent/CA2136850A1/en not_active Abandoned
- 1993-05-27 AU AU43184/93A patent/AU678360B2/en not_active Expired - Fee Related
- 1993-05-27 CZ CZ943195A patent/CZ319594A3/en unknown
- 1993-06-16 MY MYPI93001174A patent/MY109133A/en unknown
- 1993-06-17 IN IN194BO1993 patent/IN176902B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUT70082A (en) | 1995-09-28 |
| ES2087743T3 (en) | 1996-07-16 |
| BR9306574A (en) | 1998-12-08 |
| SK154894A3 (en) | 1995-07-11 |
| JPH07507584A (en) | 1995-08-24 |
| AU678360B2 (en) | 1997-05-29 |
| DE69302384T2 (en) | 1996-09-26 |
| EP0647264A1 (en) | 1995-04-12 |
| MY109133A (en) | 1996-12-31 |
| IN176902B (en) | 1996-10-05 |
| DE69302384D1 (en) | 1996-05-30 |
| AU4318493A (en) | 1994-01-04 |
| CZ319594A3 (en) | 1995-05-17 |
| WO1993025654A1 (en) | 1993-12-23 |
| EP0647264B1 (en) | 1996-04-24 |
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Legal Events
| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |