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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/042—Acids
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/46—Esters of carboxylic acids with amino alcohols; Esters of amino carboxylic acids with alcohols
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
• • 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
• • 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
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces

Definitions

• the present invention relates to a composition for rinsing and drying vehicles, which makes it possible to rinse previously washed vehicles, enabling the fast and effective removal of the water and particles left on the surface of the vehicles during the washing process, as well as providing adequate shine.
• vehicle washing meaning by vehicle any means of transport for passengers or goods, including cars, vans, lorries, buses, motorcycles, three-wheeler vans, golf carts, train and/or underground carriages and engines, light aircraft and commercial and/or passenger aeroplanes, etc.
• vehicle washing is carried out in automatic installations (automated vehicle wash) or semi-automatic installations (using high pressure hoses) .
• EP-A-0264634 discloses an agent for drying and polishing cars that consists of 5-90% by weight, preferably between 8-80% by weight, of a compound with formula wherein R 1 and R 2 are a C 8 -C 20 alkyl or alkenyl group, R 3 is a C 1 -C 4 alkyl group, R is hydrogen, n is a number between 1 and 20, and A is a benzoate or propionate anion; and between 5-70%, preferably between 8-50% by weight, of a non-ionic emulsifier with formula or formula wherein a is 1 or 2, x is a number between 1 and 20, preferably between 3 and 5, y and z are each numbers between 2 and 20, preferably 2; and the rest, up to 100% by weight, is water or an organic solvent.
• EP-A-0703291 discloses an agent for drying and polishing cars that comprises between 1-30% by weight of a quaternary ammonium compound with formula wherein R 1 is independently a C 6 -C 20 alkyl or alkenyl group, m and n are independently of each other a number from 1 to 6, R 2 is a C 1 -C 4 alkyl group, R 4 is hydrogen or a C 1 -C 4 alkyl group, R 5 is hydrogen or a group with formula C(O)R 1 , R 3 is a C 1 -C 4 alkyl group or a group with formula wherein R 4 and R 5 are as defined above and p is a number between 1 and 6; and A (-) is an anion; and water, and optionally, additional additives selected from non-ionic emulsifiers, dihydric alcohols, C 1 -C 6 alkyl ethers of dihydric alcohols, C 8 -C 18 alcohols with a mean molecular weight (M
• quaternary ammonium compounds do not present an adequate biodegradability (those that do not present ester bonds).
• ester bonds the production of quaternary ammonium compounds (with or without ester bonds) requires highly toxic (carcinogenic) alkylating agents, such as methyl chloride, dimethyl sulphate, benzyl chloride, etc., which require very particular handling conditions.
• the present invention offers an efficient solution to the problems mentioned in the prior art, providing a composition for rinsing and drying vehicles that comprises at least one addition salt of an ester amine with formula (1) wherein
• Diluted aqueous compositions for rinsing and drying vehicles which can be produced by diluting in water a composition comprising at least one addition salt of an ester amine with formula (1) with at least one organic or inorganic acid, also forms part of the object of the invention.
• Another additional object of the present invention is the use of the aforementioned compositions comprising at least one addition salt of an ester amine with formula (1) with at least one organic or inorganic acid for rinsing and drying vehicles.
• a procedure for rinsing and drying vehicles that consists of applying an aqueous composition comprising at least one addition salt of an ester amine with formula (1) with at least one organic or inorganic acid to a vehicle after the process of washing said vehicle also forms part of the object of the invention.
• the ester amine with formula (1) is produced by condensing a fatty acid with general formula (2) R 5 -COOH (2) with an alkanol amine with general formula (3) in whose formulas
• fatty acids with general formula (2) that are condensed (esterified) with an alkanol amine with general formula (3) are those from oils and vegetable and animal fats, such as coconut, tallow, palm, sunflower, soy, olein, olive, pomace, rapeseed, tall oil, etc., possibly fully or partially hydrogenated, and purified or synthetic fatty acids such as capronic acid, caprylic acid, caprinic acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, 2-ethylhexanoic acid, oleic acid, elaidinic acid, petroselinic acid, linoleic acid, linolenic acid, arachinic acid, gadoleic acid, behenic acid and erucic acid, or mixtures thereof.
• oils and vegetable and animal fats such as coconut, tallow, palm, sunflower, soy, olein, olive, pomace
• the fatty acid is a C 16 -C 22 acid containing a degree of insaturation such that the Iodine Value falls within the 5-200 range, or more preferably 60-160. It is particularly preferable for the Iodine Value to fall between either the 70-95 range or the 95-130 range. It is also preferable for the fatty acid(s) used to have a cis-trans isomer ratio of 80:20 to 95:5. More preferably, the isomer trans content of said fatty acid(s) is lower than 10%. An optimum trans isomer content is between 0.5 and 5%.
• alkanol amines with general formula (3) that can be used: triethanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, propanol diethanolamine, ethanol diisopropanolamine and triisopropanolamine, possibly alkoxylated with ethylene oxide, or mixtures thereof, non-alkoxylated alkanol amines being preferred, especially triethanolamine and N-methyldiethanolamine.
• Esterification can be carried out using known methods, as has been disclosed for instance in patent application ES-A-2021900 .
• the esterification reaction is carried out by condensing the fatty acid using an alkanol amine or mixture of alkanol amines at a temperature of between 120°C and 220°C for a period of 2 to 10 hours, preferably at a low pressure of about 5 to 200 mbar and in the presence of some of the catalysts already known for esterification, e.g. hypophosphorous acid or paratoluene sulphonic acid, and also in the presence of some of the usual stabilisers and antioxidants, such as tocopherols, BHT, BHA, citric acid, etc.
• the catalysts already known for esterification e.g. hypophosphorous acid or paratoluene sulphonic acid
• stabilisers and antioxidants such as tocopherols, BHT, BHA, citric acid, etc.
• the molar ratio between the fatty acid and the alkanol amine ranges between 1.0:1.0 and 3.0:1.0.
• the result of the esterification reaction is a mixture of mono-, di- and triesters of fatty acids or mono- and diesters, depending on the number of hydroxyl groups of the alkanol amine that is made to react with the fatty acid.
• the reaction product is a mixture containing between 10-40% by weight, preferably between 19-35% by weight of monoester, between 40-60% by weight, preferably between 46-52% by weight of diester, and between 10-40% by weight, preferably between 16-35% by weight of triester.
• Suitable acids for producing addition salts of the ester amine with formula (1) can be organic or inorganic acids.
• Suitable inorganic acids are hydrochloric acid, phosphoric acid (orthophosphoric acid), nitric acid, sulphuric acid or a mixture thereof. Phosphoric acid is preferred.
• Suitable organic acids are C 1 -C 6 chain carboxylic acids, C 1 -C 6 chain ⁇ -hydroxy-carboxylic acids, C 6 -C 22 chain fatty acids, di- or tricarboxylic acids and C 6 -C 22 ether carboxylic acids, or a mixture thereof.
• suitable carboxylic acids or C 1 -C 6 chain ⁇ -hydroxycarboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, glycolic acid, or mixtures thereof.
• acetic acid and glycolic acid are preferred, formic acid being the most preferable.
• C 6 -C 22 chain fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid, arachinic acid, behenic acid, or a mixture thereof. Oleic acid and linoleic acid are preferred.
• Suitable di- or tricarboxylic acids are succinic acid, malic acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, suberic acid, maleic acid, and terephthalic acid and those produced by heat-induced oligomerisation of unsaturated fatty acids, citric acid (3-hydroxy-1,3,5-pentanotricarboxylic acid), or mixtures thereof.
• Adipic acid, maleic acid and citric acid are preferred.
• C 6 -C 22 ether carboxylic acids are those that follow formula (4) R' -O- (CH 2 CH 2 O) n -COOM (4) wherein R' is an alkyl or alkenyl residue having 6 to 22 carbon atoms, n has a value that falls within the 1 to 15 range, most preferably from 2 to 10, and M is hydrogen or a suitable cation, preferably an alkaline metal cation such as sodium or potassium.
• R is an alkyl or alkenyl residue having 12 to 22 carbon atoms.
• the aliphatic hydrocarbon chain containing 6 to 22 carbon atoms, preferably 12 to 22 carbon atoms, is preferably derived from fats and oils of natural origin, as well as from synthetic triglycerides.
• Preferred fats and oils include palm oil, coconut oil, sunflower oil, rapeseed oil, castor oil, olive oil, soy oil and animal fats and oils such as beef tallow, bone oil, fish fats and oils, fully and partially hydrogenated oils thereof, and mixtures thereof.
• C 6 -C 22 ether carboxylic acids with general formula (4) can be produced using methods known by a person skilled in the art.
• the production process consists of two steps, the first being the reaction of an alcohol with a hydrocarbon chain of the desired length with ethylene oxide in normal reaction conditions, known by a person skilled in the art. It is also possible to use a previously ethoxylated alcohol.
• the ethoxylated alcohol is then made to react with a strong base, e.g. sodium or potassium hydroxide in the presence of a reducing agent such as sodium borohydride, to form the corresponding sodium or potassium alkoxylate.
• This product is made to react with sodium monochloroacetate to form the corresponding ethercarboxylate in salt form. Said salt is converted into the corresponding acid by washing with sulphuric acid.
• C 6 -C 22 ether carboxylic acids are AKYPO ® RO 10 VG (oleic type ether carboxylic acid with an average degree of ethoxylation of 1), AKYPO ® RO 20 VG (oleic type ether carboxylic acid with an average degree of ethoxylation of 2), AKYPO ® RO 50 VG (oleic type ether carboxylic acid with an average degree of ethoxylation of 5) and AKYPO ® RO 50 VG (oleic type ether carboxylic acid with an average degree of ethoxylation of 9) marketed by KAO Chemicals Europe.
• compositions for rinsing and drying vehicles are provided.
• compositions for rinsing and drying vehicles comprising, expressed as a weight percentage
• organic or inorganic acid(s) component b
• the organic or inorganic acid(s) component b
• the organic or inorganic acid(s) component b
• the organic or inorganic acid content (component b) in the composition of the present invention is also particularly preferable for the organic or inorganic acid content (component b) in the composition of the present invention to be between 0.1-10% by weight in relation to the total weight of the composition.
• the organic or inorganic acid(s) (component b) is therefore above the stoichiometric quantity needed to neutralise the ester amine to form its addition salt.
• fatty acid esters with a monohydric alcohol examples include cetyl 2-ethylhexanoate, methyl coconoate, methyl laurate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, methyl stearate, butyl stearate, 2-ethylhexyl stearate, isotridecyl stearate, methyl oleate, myristyl myristate, stearyl stearate, isobutyl oleate, or mixtures thereof. Cetyl 2-ethylhexanoate and 2-ethylhexyl palmitate are preferred.
• fatty acid esters with monohydric alcohols are those marketed under the name EXCEPARL ® by KAO Corporation.
• Suitable emulsifiers are non-ionic surfactants from at least one of the following groups:
• the emulsifier (component d) is selected from C 8 -C 22 alkoxylated fatty alcohols, C 12 -C 22 alkoxylated fatty acids, C 8 -C 15 alkoxylated alkylphenols and C 12 -C 22 alkoxylated alkylamines containing 2 to 15 moles of ethylene oxide; alkylpolyglucosides with 8 to 22, preferably with 10 to 18 carbon atoms in the carbon chain and 1 to 20, preferably 1.1 to 5, units of glucoside; alkoxylated glycerides or mixtures of alkoxylated glycerides and alkoxylated glycerine; and alkylglyceryl ethers, or mixtures thereof.
• C 8 -C 22 alkoxylated fatty alcohols, C 12 -C 22 alkoxylated fatty acids and C 12 -C 22 alkoxylated alkylamines containing 2 to 15 moles of ethylene oxide are preferred.
• the hydrotrope (component e) is selected from sodium cumenesulphonate, ammonium cumenesulphonate, ammonium xylenesulphonate, potassium toluenesulphonate, sodium toluenesulphonate, sodium xylenesulphonate, toluenesulphonic acid, xylenesulphonic acid, sodium polynaphthalenesulphonate, sodium polystyrene sulphonate, sodium methylnaphthalenesulphonate, disodium succinate, or mixtures thereof.
• Sodium cumenesulphonate and ammonium cumenesulphonate are preferred.
• the content of polyhydric alcohol or the ether thereof (component f) in the composition according to the invention ranges between 0.1-25% by weight.
• the polyhydric alcohol or the ether thereof is selected from ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol with a mean molecular weight (M w ) between 100 and 1000 by weight, glycerol, polyglycerol, methyl glycol, ethyl glycol, propyl glycol, butyl glycol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol, ethyl triglycol, butyl triglycol, or mixtures thereof.
• M w mean molecular weight
• Dihydric alcohols or their ethers are preferred. Particularly preferred are dihydric alcohol ethers such as methyl glycol, ethyl glycol, propyl glycol, butyl glycol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol.
• dihydric alcohol ethers such as methyl glycol, ethyl glycol, propyl glycol, butyl glycol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol.
• an aqueous composition for rinsing and drying vehicles comprising, expressed as a weight percentage
• the active substance of the aqueous compositions for rinsing and drying vehicles according to the present invention is preferably up to 60% by weight, more preferably up to 45% by weight, even more preferably up to 30% by weight, the active substance substantially comprising addition salts of the ester amine with formula (1) (component a) and, optionally, also components (b), (c), (d), (e) and (f). It is thus considered that said aqueous compositions are concentrated.
• the pH of said concentrated aqueous compositions for rinsing and drying vehicles preferably falls between 2.0 and 6.5, more preferably between 2.0 and 4.5.
• the viscosity of the concentrated aqueous compositions for rinsing and drying vehicles of the present invention ranges between 1 and 5000 mPa . s at 20°C, more preferably between 1 and 1000 mPa ⁇ s at 20°C.
• Aqueous compositions for rinsing and drying vehicles are usually applied in a very diluted form, so that the active concentration that is applied to the vehicles is between 0.001 and 1% by weight, more preferably between 0.005 and 0.5% by weight, the active substance substantially comprising addition salts of the ester amine with formula (1) (component a) and, optionally, also components (b), (c), (d), (e) and (f).
• Concentrated aqueous compositions for rinsing and drying vehicles to produce diluted aqueous compositions can be diluted with hard water, semi-hard water or soft water (demineralised water).
• concentrated aqueous compositions are diluted with demineralised water.
• the viscosity of the diluted aqueous compositions for rinsing and drying vehicles of the present invention ranges between 1 and 100 mPa ⁇ s at 20°C, more preferably between 1 and 50 mPa ⁇ s at 20°C.
• Aqueous compositions for rinsing and drying vehicles that can be produced by diluting a concentrated aqueous composition in water also form part of the object of the present invention.
• Said aqueous compositions for rinsing and drying vehicles are produced by diluting a concentrated composition as described above in water by a factor of between 2 and 2000 by volume, preferably between 5 and 1000, more preferably between 10 and 500, even more preferably between 150 and 400.
• Another additional object of the present invention is the use of aqueous compositions comprising at least one addition salt of an ester amine with formula (1) with at least one organic or inorganic acid wherein
• Suitable acids for producing addition salts of the ester amine with formula (1) can be organic or inorganic acids.
• Suitable inorganic acids are hydrochloric acid, phosphoric acid (orthophosphoric acid), nitric acid, sulphuric acid or a mixture thereof. Phosphoric acid is preferred.
• Suitable organic acids are C 1 -C 6 chain carboxylic acids, C 1 -C 6 chain ⁇ -hydroxy-carboxylic acids, C 6 -C 22 chain fatty acids, di- or tricarboxylic acids and C 6 -C 22 ether carboxylic acids, or a mixture thereof.
• suitable carboxylic acids or C 1 -C 6 chain ⁇ -hydroxycarboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, glycolic acid (hydroxyacetic acid), or mixtures thereof.
• acetic acid and glycolic acid are preferred, formic acid being the most preferable.
• C 6 -C 22 chain fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid, arachinic acid, behenic acid, or a mixture thereof. Oleic acid and linoleic acid are preferred.
• Suitable di- or tricarboxylic acids are succinic acid, malic acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, suberic acid, maleic acid, and terephthalic acid and those produced by heat-induced oligomerisation of unsaturated fatty acids, citric acid (3-hydroxy-1,3,5-pentanotricarboxylic acid), or mixtures thereof.
• Adipic acid, maleic acid and citric acid are preferred.
• C 6 -C 22 ether carboxylic acids are those that follow formula (4) R' -O- (CH 2 CH 2 O) n -COOM (4) wherein R' is an alkyl or alkenyl residue having 6 to 22 carbon atoms, n has a value that falls within the 1 to 15 range, most preferably from 2 to 10, and M is hydrogen or a suitable cation, preferably an alkaline metal cation such as sodium or potassium.
• R is an alkyl or alkenyl residue having 12 to 22 carbon atoms.
• a procedure for rinsing and drying vehicles which consists of applying a diluted aqueous composition comprising at least one addition salt of an ester amine with formula (1) with at least one organic or inorganic acid, which can be produced as described above, to a vehicle after the process of washing said vehicle, also forms part of the object of the invention.
• the washing process consists of a step of washing with a detergent, and a step of rinsing with water, generally demineralised.
• the aqueous composition of the present invention is applied to the vehicles, which is generally done by spraying or sprinkling.
• Example 1 Compositions for rinsing and drying vehicles
• compositions in Table 1 are prepared for rinsing and drying vehicles.
• Composition A is prepared according to the present invention, whilst C1 (Market product) and C2 (composition based on Esterquat) are comparative examples.
• Table 1.- Compositions for rinsing and drying vehicles weight percentages representing 100% of the active substance for each component
• A C1 C2 Butyl glycol 8.0% 10.0% 8.0% Butyl diglycol 4.0% --- 4.0% 1 Oleic type ester quat --- 4.0% 12.0% 2 Oleic type ester amine 12.0% --- 3 Fatty ester 4.0% 2.0% 4.0% 4 Aliphatic hydrocarbon --- 2.0% --- 5 Emulsifier 4.0% 3.0% 2.0% Sodium cumenesulphonate 3.5% --- --- Acetic acid --- 1.0% 1.0% Orthophosphoric acid 3.5% --- --- Demineralised water Up to 100% Up to 100% Up to 100% 1 Ester quat derived from triethanolamine and oleic acid (Tetranyl ® AO
• compositions in Table 1 were evaluated in an automated vehicle wash, using a dark blue Renault Megane vehicle.
• the car was previously washed with a standard shampoo, it was rinsed with demineralised water by osmosis and, finally, the compositions in Table 1 were applied, diluted with water in a proportion of 1/300 by volume.
• composition A presents a better overall behaviour than that of the formula prepared with ester quat and that of the formula prepared with a standard market product.

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• 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)
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• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (12)

Citations (4)

• 2006
  • 2006-03-31 ES ES200600853A patent/ES2294923B1/es not_active Withdrawn - After Issue
• 2007
  • 2007-02-08 EP EP07101949A patent/EP1840197A1/fr not_active Withdrawn

Patent Citations (4)

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