WO1994018300A2 - Nettoyage - Google Patents

Nettoyage Download PDF

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Publication number
WO1994018300A2
WO1994018300A2 PCT/GB1994/000287 GB9400287W WO9418300A2 WO 1994018300 A2 WO1994018300 A2 WO 1994018300A2 GB 9400287 W GB9400287 W GB 9400287W WO 9418300 A2 WO9418300 A2 WO 9418300A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition
cleaning
acid
article
base
Prior art date
Application number
PCT/GB1994/000287
Other languages
English (en)
Other versions
WO1994018300A3 (fr
Inventor
Neil Rogers
Paul Withers
Original Assignee
Neil Rogers
Paul Withers
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Neil Rogers, Paul Withers filed Critical Neil Rogers
Priority to EP94906311A priority Critical patent/EP0683812A1/fr
Priority to AU60069/94A priority patent/AU6006994A/en
Priority to CA002155977A priority patent/CA2155977A1/fr
Publication of WO1994018300A2 publication Critical patent/WO1994018300A2/fr
Publication of WO1994018300A3 publication Critical patent/WO1994018300A3/fr

Links

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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof

Definitions

  • This invention relates to cleaning.
  • the invention provides a composition for use in cleaning, a process for the preparation of the composition and a method of cleaning.
  • Textile materials for example garments or curtains, are often cleaned using a well-known process of "dry cleaning".
  • dry cleaning an article to be cleaned is immersed in a cleaning fluid " and agitated to dislodge particles of dirt and grease.
  • the cleaning fluid aids removal of the dirt and grease from the article and subsequently aids dispersion and sequestration of the dirt and grease in the cleaning fluid.
  • Some problems with dry cleaning are associated with the cleaning fluids used.
  • the most widely used cleaning fluids are highly flammable hydrocarbons and chlorinated hydrocarbons, particularly tetrachloroethene.
  • highly inflammable solvents which also have low flash points, presents a significant fire risk and, accordingly, the solvents must be handled very carefully under strictly controlled conditions.
  • the use of the solvents presents an environmental hazard and a health risk to personnel, since they are often carcinogenic.
  • the solvents are highly volatile and may be absorbed through the skin or inhaled. Thus, it would be preferable to use a less problematic solvent in cleaning.
  • an aqueous based cleaning composition comprising, in addition to a major part of water, a surface active agent, a base and an organic acid, or a salt of a base and an organic acid, and a dispersed phase of a hydrocarbon.
  • a process for the preparation of the cleaning composition of the first aspect comprising admixing a major proportion of water with minor proportions of a surface active agent, a base and an organic acid, or a salt of a base and an organic acid, and a hydrocarbon.
  • the cleaning composition is effective for removing dirt and grease from many articles, for example, from textile materials.
  • the composition is particularly advantageous in comparison to the solvents used in dry cleaning described above since a major portion of the composition is water and only a minor portion is comprised by potentially flammable and/or toxic hydrocarbon. Thus, the composition may - be more environmentally and toxicologically acceptable compared to the known dry cleaning solvents.
  • the cleaning composition is also effective for cleaning non-textile materials, for example work surfaces made of wood or plastics material. Other uses of the cleaning composition are in metal degreasing and wool scouring.
  • the preferred hydrocarbons for use in the cleaning composition of the invention are terpenes which are built up of isoprene (C £ H 8 ) units. Terpenes are classified into open chain, monocyclic, bicyclic, sesqui and polyterpenes and any such form of terpene may be used in the composition of the invention. Most preferably the terpene is limonene which has the chemical name 4-isopropenyI-l- methylcyclohexene (C 10 H 16 ). Limonene may be provided by D'limonene which is of citrus origin. D'Limonene generally contains at least 95% 4-isopropenyl-l-methylcyclohexene. Another name for D'Limonene is stripper oil (see also Food Chemicals Codex, 1981). D'Limonene is mostly composed of mono Terpene Hydrocarbons.
  • D'Limonene Synonyms for D'Limonene include (+)-Carvene, Citrene, Limonene, 1,8-p-Menthadiene.
  • the preferred source of D'Limonene is Brazilian.
  • terpene hydrocarbons derived form the essential oils extracted from the leaves, blossoms, fruits and barks belonging to the family Coniferae and Myrtaceae and the genus Citrus may also be used in place of D'Limonene.
  • the essential oils comprise mixtures of Terpenes which have the empirical formula (C 5 H 8 ) n and oxidation products of these.
  • White spirit (C.A.S. No. 8052-41-3) includes a mixture of saturated and unsaturated hydrocarbons and, optionally, aromatic hydrocarbons and the invention covers the constituents of the mixture singularly or in combination.
  • the white spirit includes aromatic hydrocarbons, preferably it comprises 15-20% of aromatic hydrocarbons.
  • Aromatic hydrocarbons include C 6 -C 12 aromatics.
  • Preferred aromatic hydrocarbons include C 7 (toluene), C 8 and C g aromatic hydrocarbons.
  • Turpentine is also a mixture of hydrocarbons, for example cyclic terpene hydrocarbons, primarily ⁇ -pinene and the invention of the first aspect covers the constituents of the mixture singularly or in combination.
  • hydrocarbon' as used herein is also intended to cover substituted hydrocarbons, e.g. halogenated hydrocarbons such as chlorinated hydrocarbons.
  • the amount of hydrocarbon present in the composition is preferably less than 10%, more preferably less than 5% by weight of the total weight thereof. Even more preferably the amount of hydrocarbon is less than 3% and ideally less than 2% on the same weight basis.
  • the composition further comprises an organic acid and a base, or a salt of these two components.
  • the organic acid should be a weak acid. Most preferably the organic acid is a water soluble carboxylic acid, ideally one having 6 or less carbon atoms. It is also preferred that the organic acid is a monocarboxylic acid. Thus preferred acids include formic acid, propionic acid, butyric acid, valeric acid, and caproic acid.
  • the most preferred acid for use in the composition is glacial acetic acid although other commercial grades commonly known as ethanoic acid, technical grade, vinegar acid may also be used. It is however possible to use higher functionality acids, e.g. citric acid.
  • free acid is included in the composition then it is preferably incorporated therein in an amount of less than 10%, more preferably less than 5%, and most preferably less than 2%, by weight of the total weight of the composition.
  • the base is preferably ammonia used in the form of an aqueous solution (e.g. products known as ammonia solution, aqueous ammonia, ammonia liquor, and ammonium hydroxide.
  • aqueous solution e.g. products known as ammonia solution, aqueous ammonia, ammonia liquor, and ammonium hydroxide.
  • Preferred ammonia solutions are these known as '880 ammonia' having an ammonia content of 33- 34%.
  • the ammonia solution should be a clear, colourless solution free from suspended matter and residual deposits.
  • Bases other than ammonia may also be used, e.g. alkali metal hydroxides such as sodium or potassium hydroxide.
  • Other bases which may be used include alkanolamines.
  • the amount of base used is preferably less than 10%, more preferably less than 5% by weight of the composition, most preferably less than 2% by weight. Any amount of base relative to acid may be used.
  • salts of a base and an organic acid will generally be added instead of the free acid and base, but may be added as a supplement thereto.
  • Preferred salts are those derived from any of the aforementioned bases and organic acids. Most preferred are the ammonium salts of organic carboxylic acids, e.g. ammonium acetate.
  • the salt if used, is preferably added in an amount of less than 10%, more preferably less than 5%, e.g. less than 2%.
  • the actual acid/base combination or salt used in the composition may be governed by the end use thereof.
  • the acid is preferably acetic acid and the base is preferably ammonia.
  • ammonium acetate may be used as salt.
  • the acid is formic acid and the base is ammonia.
  • ammonium formate may be used as a salt.
  • Water from any source may be used in the composition. It is, however, preferred to use soft water or distilled water. The recommended water type is distilled, although this may be replaced with de-ionised or waters up to a Hardness of 30ppm calcium as calcium carbonate. Generally the amount of water present will not be less than 60%, more usually not less than 70% by weight.
  • the detergent is adapted to disperse the hydrocarbon-containing solvent in the water. Any anionic and/or a non-ionic surfactant may be used.
  • the detergent is preferably biodegradable.
  • the detergent suitably comprises a long chain (e.g. C 8 -C 1 6 ) sulphonic acid (or salt thereof), for example a long chain alkyl benzene sulphonate such as dodecyl benzene sulphonate which may be in combination with a fatty alkylamide.
  • Other surfactants include olefin sulphonates and paraffin sulphonates.
  • the amount of surface active agent in the composition is preferably less than 10%, more preferably, less than 5%, e.g. less than 2%.
  • the surfactant may be added as formulation which contains components other than the surfactants e.g. water and terpene.
  • the surfactant formulation may for example contain at least one surface active agent together with a monoethanolamine, a glycol ether, D'limonene, and/or water.
  • One such formulation (referred to in Example 1 below as surfactant Formulation A) comprises the following components.
  • the D'limonene may exist as an emulsion in the water, the emulsified phase having a droplet size of 1 micron or less.
  • the D'Limonene present in this 'surfactant formulation' may provide part of the total D'limonene for the composition of the invention.
  • the monoethanolamine in the above formulation is preferred but may be replaced by any alkanolamine.
  • the butyl diglycol ether may be replaced with any suitably commercially available glycol ether such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and ethylene glycol monoethyl ether.
  • the 'surfactant formulation' may contain any one or combinations of the following components either in addition to or as at least a partial replacement for the MEA, DBSA and/or BGE, namely lauryl-myristyl ethoxylates, cetyl-stearyl ethoxylates, cetyl-oleyl alcohol ethoxylates, fatty alcohol ethoxylates, oxo alcohol ethoxylates, branched oxo alcohol ethoxylates, isotridecyl alcohol ethoxylates, 2- ethylehaxanol ethoxylates, nonylphenol ethoxylates, octylphenol ethoxylates, low foaming, biodegradable alkoxylates, amine oxides, alkylolamides, alcohol ethoxy sulphates, or castor oil ethoxylates or propoxylates.
  • Formulations in accordance with the invention may contain a perfume or a reodourant, particularly if it is desired to suppress the aroma of the hydrocarbon.
  • a reodourant will be particularly desirable in the case where the hydrocarbon is D'Limonene.
  • the preferred reodourant is a complex blend of essential oils and aromatic plant extract compounded with synthetic aroma chemicals.
  • the pH of a cleaning composition for use in cleaning textile articles is 5.5-6.5. It is however possible to use pH values outside this range, and this may be desirable for other cleaning applications. Thus for example the pH may be greater than 7. The pH may for example be greater than 9, e.g. in the range 9 to 12.
  • a preferred composition in accordance with the invention comprises
  • Carboxylic Acid e.g. acetic 1-2% by weight or formic
  • Base e.g. ammonia 1-2% by weight
  • the formulations may be mixed together in any suitable apparatus for producing the emulsified phase of the hydrocarbon, which will typically have a droplet size of 10-30 microns. It is preferred, but not essential, that the components are added to the water in the following order, namely acid, base, hydrocarbon, surface active agent, reodourant.
  • Formulations of the type exemplified above may be supplied to the end use. It is however also possible for the end user to be supplied with various component of the formulation and to effect the final mixing/dilution as required. Thus, for example, it is possible to produce a formulation comprising.
  • Such a formulation may be diluted, by the end user, with 80% of water and then 1% by weight of hydrocarbon and re-odourant. Dispersion of the hydrocarbon may take place in the apparatus in which the cleaning composition is used, e.g. laundry apparatus.
  • composition may include further components selected from the following.
  • Thickening agents such as a xanthan polysaccharide compounded singly or with synthetic or natural thickeners such as cellulose ethers, locust bean gum, starches, sodium alginate etc. Such thickening agents would serve as an acid to reduce the effect of mechanical damage during use of the composition for washing textile articles.
  • a cationic surfactant for providing softening fabric conditioning 3.
  • a method of cleaning an article comprising treating the article with a cleaning composition according to the first aspect of the invention.
  • the method may comprise immersing the article, for example, a textile article, in the cleaning composition.
  • the method of the third aspect of the invention as applied to the cleaning of textile article has the significant advantage over conventional washing processes using water (e.g. in conjunction with detergent) in that it is found that the textile articles dry considerably more rapidly.
  • agitation means is provided for aiding cleaning.
  • a method of cleaning a textile article comprising arranging the textile article in a container which contains a cleaning composition in accordance with the first aspect of the invention and using ultrasonic waves to clean said article in said container.
  • ultrasonic waves are directed at the article in the container.
  • the direction of travel of the ultrasonic waves is varied during said method of cleaning.
  • the method of the fourth aspect of the invention may provide a method of cleaning which is improved over other known methods, in particular the dry cleaning method described above.
  • cleaning is achieved without physically agitating the textile articles.
  • Such physical agitation may reduce detrimental effects on the shape and/or texture of the articles.
  • the time that the article must spend in said container may be significantly less than in the dry cleaning method and, furthermore, the time that must be spent finishing the cleaned article may also be reduced.
  • the method suitably uses a cleaning apparatus (which provides s fifth aspect of the invention) which comprising a treatment fluid container in which a textile article to be cleaned may be immersed and ultrasonic cleaning means arranged to direct ultrasonic waves suitably at said textile article when in said container, so as to clean said textile article.
  • the cleaning apparatus may include holding means for a textile article. Movement means may be provided for moving a textile article held by said holding means from a first position in which it is not arranged within said container to a second position in which it is arranged with said container. Said holding means and/or said movement means are preferably integral components of said apparatus.
  • the apparatus may include a plurality of said holding means and/or said movement means. Said plurality are preferably arranged to be selectively positioned adjacent said container so that a selected article to be cleaned may be arranged in said container. Said plurality of holding means and/or movement means may be provided on a conveyor system.
  • the conveyor system preferably comprises an endless conveyor.
  • the apparatus may include a plurality of containers each containing a cleaning-composition.
  • the method may include arranging the article to be cleaned in each container during said method of cleaning.
  • One of said containers may include a composition arranged to rinse the textile article.
  • said holding means and/or said movement means are preferably adapted to arrange selectively the article to be cleaned in each container.
  • Filtration means may be provided for filtering the cleaning composition in one or each container.
  • the apparatus may include heating means for heating the cleaning composition in said bath.
  • the method includes heating the cleaning composition above ambient temperature but preferably to less than 100°C.
  • Example 1 The invention is illustrated by the following non-limiting examples.
  • Example 1 The invention is illustrated by the following non-limiting examples.
  • a cleaning composition was formulated by admixing the following component.
  • the composition was used in a converted Spencer dry-cleaning (Model 113) with overnight distillation (not used).
  • the cage diameter was 0.91 metres (3 feet). The following conditions were employed.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Valve Device For Special Equipments (AREA)
  • Control Of Throttle Valves Provided In The Intake System Or In The Exhaust System (AREA)

Abstract

Une composition de nettoyage à base aqueuse pour les textiles, par exemple, se compose, outre d'eau en majeure partie, d'un agent tensioactif, d'une base et d'un acide organique ou d'un sel d'une base et d'un acide organique, ainsi que d'une phase dispersée d'hydrocarbure, de préférence un terpène, et idéalement du limonène. Cette composition peut être utilisée pour nettoyer des articles textiles dans un procédé qui consiste à envoyer des ondes ultrasonores sur les articles à nettoyer.
PCT/GB1994/000287 1993-02-12 1994-02-11 Nettoyage WO1994018300A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94906311A EP0683812A1 (fr) 1993-02-12 1994-02-11 Nettoyage
AU60069/94A AU6006994A (en) 1993-02-12 1994-02-11 Cleaning
CA002155977A CA2155977A1 (fr) 1993-02-12 1994-02-11 Composition de nettoyage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9302869.4 1993-02-12
GB939302869A GB9302869D0 (en) 1993-02-12 1993-02-12 Cleaning

Publications (2)

Publication Number Publication Date
WO1994018300A2 true WO1994018300A2 (fr) 1994-08-18
WO1994018300A3 WO1994018300A3 (fr) 1994-11-24

Family

ID=10730362

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1994/000287 WO1994018300A2 (fr) 1993-02-12 1994-02-11 Nettoyage

Country Status (5)

Country Link
EP (1) EP0683812A1 (fr)
AU (1) AU6006994A (fr)
CA (1) CA2155977A1 (fr)
GB (1) GB9302869D0 (fr)
WO (1) WO1994018300A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999016955A1 (fr) * 1997-09-29 1999-04-08 Custom Cleaner, Inc. Necessaires de nettoyage a sec comprenant des compositions a base d'acide polysulfonique
WO1999042553A1 (fr) * 1998-02-20 1999-08-26 The Procter & Gamble Company Produit eliminant les taches sur les tapis via l'emission d'ondes sonores ou ultrasonores
EP1099791A1 (fr) * 1999-11-12 2001-05-16 Uwe Ollert Composition et procédé pour nettoyer le cuir
WO2008068488A1 (fr) * 2006-12-08 2008-06-12 Reckitt Benckiser (Uk) Limited Améliorations de compositions de nettoyage acides pour surfaces dures
US12110477B2 (en) 2018-09-20 2024-10-08 Mix 14 Ltd. Ink and stain removal

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0040882A1 (fr) * 1980-05-27 1981-12-02 THE PROCTER & GAMBLE COMPANY Compositions détergentes liquides
WO1993011213A1 (fr) * 1991-12-03 1993-06-10 E.I. Du Pont De Nemours And Company Composition de nettoyage

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0040882A1 (fr) * 1980-05-27 1981-12-02 THE PROCTER & GAMBLE COMPANY Compositions détergentes liquides
WO1993011213A1 (fr) * 1991-12-03 1993-06-10 E.I. Du Pont De Nemours And Company Composition de nettoyage

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999016955A1 (fr) * 1997-09-29 1999-04-08 Custom Cleaner, Inc. Necessaires de nettoyage a sec comprenant des compositions a base d'acide polysulfonique
WO1999042553A1 (fr) * 1998-02-20 1999-08-26 The Procter & Gamble Company Produit eliminant les taches sur les tapis via l'emission d'ondes sonores ou ultrasonores
AU743829B2 (en) * 1998-02-20 2002-02-07 Procter & Gamble Company, The Carpet stain removal product which uses sonic or ultrasonic waves
EP1099791A1 (fr) * 1999-11-12 2001-05-16 Uwe Ollert Composition et procédé pour nettoyer le cuir
WO2008068488A1 (fr) * 2006-12-08 2008-06-12 Reckitt Benckiser (Uk) Limited Améliorations de compositions de nettoyage acides pour surfaces dures
US8173585B2 (en) 2006-12-08 2012-05-08 Reckitt Benckiser (Uk) Limited Acidic hard surface cleaning compositions
US12110477B2 (en) 2018-09-20 2024-10-08 Mix 14 Ltd. Ink and stain removal

Also Published As

Publication number Publication date
AU6006994A (en) 1994-08-29
CA2155977A1 (fr) 1994-08-18
WO1994018300A3 (fr) 1994-11-24
EP0683812A1 (fr) 1995-11-29
GB9302869D0 (en) 1993-03-31

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