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EP3189127B1 - Washing additive - Google Patents

Washing additive Download PDF

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Publication number
EP3189127B1
EP3189127B1 EP15756917.9A EP15756917A EP3189127B1 EP 3189127 B1 EP3189127 B1 EP 3189127B1 EP 15756917 A EP15756917 A EP 15756917A EP 3189127 B1 EP3189127 B1 EP 3189127B1
Authority
EP
European Patent Office
Prior art keywords
washing
additive
washing additive
detergent composition
tetramethylene phosphonate
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.)
Active
Application number
EP15756917.9A
Other languages
German (de)
French (fr)
Other versions
EP3189127A1 (en
Inventor
François BOUGARD
Pierre Stachura
Armelle LOGHMANIAN
Hélène LONCIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sopura SA
Original Assignee
Sopura SA
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 Sopura SA filed Critical Sopura SA
Priority to RS20190140A priority Critical patent/RS58460B1/en
Priority to SI201530590T priority patent/SI3189127T1/en
Priority to HRP20190207TT priority patent/HRP20190207T1/en
Publication of EP3189127A1 publication Critical patent/EP3189127A1/en
Application granted granted Critical
Publication of EP3189127B1 publication Critical patent/EP3189127B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
    • C11C1/04—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis
    • 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
    • C11D3/2086—Hydroxy 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
    • 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
    • C11D3/16—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
    • C11D3/36—Organic compounds containing phosphorus
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/365—Organic compounds containing phosphorus containing carboxyl groups
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • 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
    • C11D2111/18—Glass; Plastics

Definitions

  • the present invention relates to a washing additive suitable for cleaning reusable glass bottles.
  • the present invention also relates to a method for cleaning reusable glass bottles using said additive, as well as to a detergent composition comprising said additive.
  • This invention relates in particular to the food industry, preferably the beverage industry, and more particularly to the brewing industry for cleaning glass bottles.
  • glass bottles for the packaging of liquids dates back to ancient times. Although plastic bottles have since made their appearance and compete to a large extent with glass bottles, they are still used today, especially for the packaging of common food liquids, such as water, milk, water wine, fruit juices, sodas, and beers, since glass offers the advantage over plastic of being more inert. In addition, some glass bottles have the added advantage of being reusable.
  • Marketed glass bottles are generally labeled to inform the consumer of their contents. These labels are generally disposed at least on the body of the bottle, preferably on the front, where they are fixed using an adhesive.
  • these bottles When reusable, these bottles once used are collected and transported to factories where they are subjected, within special equipment called “washers”, to one or more automated cycles of cleaning / soaking / rinsing. In particular, the bottles are returned for greater cleaning efficiency.
  • the final quality control is done by mirage (visual control in transparency).
  • bottles are cleaned in an alkaline medium using a caustic soda solution and at temperatures of the order of 80 ° C.
  • a caustic soda solution In order to facilitate cleaning and promote detachment of the bottle label while preventing foaming in the equipment, it is generally expected to add one or more additives to the solution to form an effective detergent composition.
  • additives it has for example been proposed to use sequestering agents such as EDTA and / or dispersing agents such as phosphonates and polyacrylates.
  • sequestering agents such as EDTA
  • dispersing agents such as phosphonates and polyacrylates.
  • polyol derivatives in particular modified polysaccharide polymers, alkoxylated derivatives of alcohols, esters, amines or amides has also been proposed.
  • an effective detergent composition should allow not only internal but also satisfactory outdoor detergency of the containers, particularly bottles.
  • a detergent composition must allow the elimination of liquid residues (beer, wine, fruit juice, milk, soda, etc.) on the external and internal surfaces of the containers or bottles.
  • a detergent composition must also allow the level of the outer surface of the containers, in particular bottles, detachment of the label and other marking elements fixed on the surface of the containers, as well as the elimination of glues and / or adhesives, while avoiding the pollution of washing baths, especially due to the dissolution of the label, and in particular ink codes in these baths.
  • An effective detergent composition must also be able to be rinsed easily, that is to say, it must avoid leaving traces, especially caustic soda, on the surface of the containers including glass containers such as bottles.
  • an effective detergent composition must provide some protection for the integrity of the inner and outer surfaces of the containers, especially glass bottles, avoiding any degradation of the glass.
  • corrosion including any degradation of the elements etched on the surface of containers especially a bottle, such as marks obtained by pyrography.
  • the foam height formed during the cleaning cycles must be controllable.
  • an effective detergent composition must prevent the formation of mineral deposits, especially calcium carbonate deposits, generally called "tartar”.
  • Detergent compositions are currently available on the market. While these detergent compositions separately meet some of the above-mentioned technical criteria, none of them fill them all at the same time. Therefore, the present invention aims to provide such a composition that meets the aforementioned needs, which may possibly include elements derived from renewable biological materials and that can reduce its environmental impact, particularly by a lower use of caustic soda in obtaining an effective detergent composition.
  • WO 2013/053390 A1 discloses a detergent composition comprising a surfactant and lysine tetramethylene phosphonate. It does not describe a composition comprising a gluconic acid.
  • WO 2012/028203 A1 discloses a detergent composition comprising phosphonocarboxylic acid, gluconic acid and mixtures thereof. It does not describe a composition comprising lysine tetramethylene phosphonate.
  • DE 13 02 882 B discloses a bottle washing process comprising a bath comprising a chelant such as gluconic acid and / or aminoalkyldiphosphonic acid. It does not describe a composition comprising lysine tetramethylene phosphonate.
  • DE 43 38 626 A1 discloses a washing additive for the bath addition for cleaning glass bottles comprising an acid such as gluconic acid and a diphosphonic acid. It does not describe a composition comprising lysine tetramethylene phosphonate.
  • the present invention relates to a washing additive comprising (or consisting of) a lysine tetramethylene phosphonate (abbreviation: LTMP) and a carboxylic acid consisting of / corresponding to gluconic acid.
  • LTMP lysine tetramethylene phosphonate
  • the present invention also relates to a washing additive consisting of lysine tetramethylene phosphonate (abbreviation: LTMP) and a carboxylic acid corresponding to gluconic acid.
  • LTMP lysine tetramethylene phosphonate
  • lysine tetramethylene phosphonate and gluconic acid are present in a ratio by weight of lysine tetramethylene phosphonate: gluconic acid of between (approximately) 1: 1 and (approximately) 5: 1.
  • the weight ratio of lysine tetramethylene phosphonate to gluconic acid is from (about) 1.5: 1 to (about) 3: 1
  • the lysine tetramethylene phosphonate is present (in the additive) at a concentration of between (about) 2% and (about) 50% by weight, preferably between (about) 2% and (about 30% by weight, preferably between (about) 2% and (about) 10% by weight.
  • the additive according to the invention further comprises a dispersing agent, preferably a natural dispersing agent (that is to say a dispersing agent obtained from renewable biological materials).
  • a dispersing agent preferably a natural dispersing agent (that is to say a dispersing agent obtained from renewable biological materials).
  • said dispersing agent is a polycarboxylic dispersing agent.
  • the dispersing agent is selected from the group consisting of carboxymethyl cellulose, carboxymethyl inulin, inulin, polyaspartic acid, polyepoxy succinic acid, and mixtures thereof.
  • the dispersing agent is present in the additive according to the invention in a weight ratio of lysine tetramethylene phosphonate: dispersing agent of between (approximately) 10: 1 and (approximately) 3: 1.
  • the dispersing agent is present in the additive at a concentration of (about) 0.5 to (about) 10% by weight.
  • the dispersing agent is carboxymethyl inulin.
  • the washing additive according to the present invention further comprises a surfactant with low foaming power, but capable of facilitating the penetration and solubilization of the washing additive of the invention.
  • said surfactant is selected from the group consisting of ethyl propylene oxide copolymers, ethoxylated fatty acids and mixtures thereof.
  • said surfactant is present in a lysine tetramethylene phosphonate: surfactant ratio of between (approximately) 5: 1 and (approximately) 1: 2.
  • said surfactant is present in the additive at a concentration of between (about) 0.5% and (about) 20% by weight.
  • the washing additive consists of lysine tetramethylene phosphonate, gluconic acid and a low foaming surfactant, wherein the weight ratio of tetramethylene phosphonate: gluconic acid is between about 1.5: 1 and (about) 3: 1, and the concentration of low foaming surfactant is from (about) 0.5% to (about) 20%.
  • the present invention also relates to a detergent composition
  • a detergent composition comprising the washing additive of the invention and caustic soda (or other suitable solvent), said caustic soda (or other suitable solvent) being present at a concentration of between about 0.5% and (about) 3%, preferably between (about) 0.5% and (about) 1.5%.
  • said detergent composition is such that the wash additive is present at a concentration of between (about) 0.05% and (about) 0.5%, and preferably between (about) 0.1% and (about) 0.2%.
  • Another subject of the invention relates to an industrial process for cleaning mold-contaminated containers, preferably glass containers, and even more preferably to glass bottles, comprising the step of washing said containers with an additive of washing or detergent composition of the invention.
  • the washing is carried out by immersion in a bath containing the detergent composition of the invention at a temperature of between (about) 60 ° C and (about) 80 ° C, preferably between (about) 60 ° C and (about) 70 ° C, and / or by spraying said detergent composition.
  • the present invention also relates to the use of the washing additive and / or the detergent composition, and / or the process of the invention in the food industry, preferably in the beverage industry, and even more preferably in the brewing industry.
  • Another subject of the invention relates to the use of lysine tetramethylene phosphonate and at least gluconic acid, preferably applied simultaneously in a washing additive, to remove mold from the surface of containers, preferably glass bottles.
  • the invention also relates to the use of lysine tetramethylene phosphonate and at least gluconic acid, preferably applied simultaneously, as a washing solution without "scuffing", without corrosion of the surface of containers, preference of glass bottles.
  • Lysine tetramethylene phosphonate or LTMP is a molecule corresponding to the chemical formula 1 as shown in FIG. figure 1 and belongs to the family of phosphonic acids, whose salts are called phosphonates, generally known to be chelating agents, also called “sequestering agents” or “sequestering agents”, that is to say that they are molecules, and more specifically surfactants (see below) capable of acting as ligands by forming chemical complexes with metal ions such as copper, iron, nickel, which they thus limit the availability.
  • Lysine tetramethylene phosphonate is derived from lysine, a naturally occurring amino acid whose chemical formula is also included in the figure 1 (chemical formula 2).
  • surfactant refers to a natural or synthetic molecule capable of modifying the surface tension between two surfaces.
  • a surfactant is an amphiphilic molecule having a hydrophobic and apolar part and a hydrophilic and polar part. This dual property gives it a particular affinity for the oil / water or water / oil interfaces and is the basis for the stabilization of the dispersed systems.
  • the surfactants may be ionic or nonionic.
  • the surfactants can be anionic, cationic, or zwitterionic or amphoteric when the hydrophilic part has a positive charge and a negative charge which, from an electrical point of view , compensate each other.
  • surfactant is a term equivalent to the term "surfactant”.
  • the terms "detergent”, “foaming agent”, “little or no foaming agent”, “low foaming agents”, “dispersing agent” all refer to surfactants; these terms are descriptive terms of the function provided by the surfactant in the composition.
  • a “detergent” more specifically denotes a surfactant capable of removing organic and / or inorganic soil, including deposits of bacteria or bacteria or other microorganisms (molds, fungi, yeasts or even animals (such as molluscs)) on a surface of a solid by solubilizing said soils.
  • a “foaming agent” is a surfactant capable of adsorbing at the gas / liquid interface, in particular at the water / air interface and leading to the formation of foam by dispersing a large volume of gas (in particular air) in a small volume of liquid (especially water). According to its propensity to form foam, one will speak of agent with more or less great foaming power. It is known to those skilled in the art that the foaming power can be measured according to the so-called Ross-Miles method which makes it possible to evaluate an initial volume of foam and its stability over time. This method is based on a static measurement and is commonly used in industry. However, other measurement methods exist based in particular on dynamic principles.
  • Nonionic surfactants or surfactants in particular alkoxylated surfactants such as copolymerized EO / POs, alcohol alkoxylates, in particular block copolymer EO / POs such as Pluronic surfactants, dehypon LS-54 (R- (EO) 5 (PO 4 ), Dehypon LS-36 (R- (EO) 3 (PO) 6 ), Plurafac LF 221 (BASF), Tegoten EC11, LUTENOL (alcohol ethoxylates) or a mixture of them.
  • alkoxylated surfactants such as copolymerized EO / POs, alcohol alkoxylates, in particular block copolymer EO / POs
  • Pluronic surfactants dehypon LS-54 (R- (EO) 5 (PO 4 ), Dehypon LS-36 (R- (EO) 3 (PO) 6 ), Plurafac LF 221 (BASF), Tegoten EC11
  • Low foaming surfactants preferably include low foaming nonionic polymers, used for the purpose of increasing detergency while limiting foam generation.
  • low foaming nonionic polymers used for the purpose of increasing detergency while limiting foam generation.
  • Non-foaming surfactants or also known as "defoamer” are characterized by lower aqueous solubilities related to a lower proportion of hydrophilic element and have the primary function of destabilizing the structure of the foam.
  • the preferred surfactants are: Pluriol 1000, 2000 or 4000, as well as Pluronic L101; L61 or L81.
  • a “dispersing agent” or “dispersant” is a surfactant capable of fixing hydrophobic particles contained in a hydrophilic solution, avoiding their aggregation and promoting their dispersion in said solution.
  • percent (%) by weight refer to the concentration of an ingredient of a described composition, the weight of that ingredient divided by the total weight of the composition and multiplied by 100.
  • the terms "about” refer to variations in numerical quantities that may exist in the applications of the claimed products and may vary according to the purity or the source of obtaining the products, as well as the method of application of the claimed products. Preferably, these variations are of the order of 10% or 5%.
  • sensing or “corrosion” refers to any degradation of the glass at the level of containers, in particular bottles, including any degradation of the elements engraved on the surface of said containers, such as marks or drawings obtained by pyrography.
  • the figure 1 discloses the chemical formula of lysine tetra (methylene) phosphonate as used in the present invention (chemical formula 1), as well as that of lysine (chemical formula 2) from which it derives.
  • the figure 2 presents the results of soil cleaning tests present on glass plates which have been washed with different compositions, and in particular a detergent composition according to the invention.
  • the figure 3 presents the results of "scuffing" tests carried out on glass bottles treated with different detergent compositions, and in particular detergent compositions according to the invention.
  • the figure 4 presents the results of three series of measurement tests (tests Nos . 1 to 3) of the detergency performance of various detergent compositions, and in particular of detergent compositions according to the invention, as obtained on glass bottles treated with water. using said compositions.
  • the washing additive according to the present invention offers the advantage of satisfying all the technical criteria mentioned above. It is particularly suitable for the automatic cleaning of reusable glass bottles, although other applications may also be considered.
  • the additive according to the present invention has the advantage of using less caustic soda.
  • caustic soda is known to increase the pH of streams (rivers, rivers), thus posing a potential threat to aquatic fauna and flora.
  • Caustic soda can also infiltrate the earth, and thus harm agriculture and the environment of plants, minerals and animals directly or more distantly, or even contaminate the groundwater.
  • the composition according to the present invention has the additional advantage that it can be used in the cleaning phase over a lower temperature range compared to the compositions available on the market.
  • the washing additive according to the invention makes cleaning more energy efficient and less polluting.
  • the additive according to the present invention comprises a compound, LTMP, which is advantageously obtained from biological materials renewable, that is to say which derive from natural molecules, making it an additive a priori more ecological than many other additives proposed in the trade.
  • Comparative tests were performed by immersing previously soiled glass bottles with molds (fungi / yeasts). A label is stuck on the outside of bottles. The bottles are then immersed in baths comprising different detergent compositions containing different wash additives and 1% caustic soda at a temperature of 70 ° C. The effectiveness of the various wash additives is evaluated both in terms of visual cleaning-evaluation-and in terms of label peeling time.
  • Sample 2 Stained glass bottles subjected to immersion at 70 ° C in a detergent composition comprising 1% NaOH and 0.2% of a second additive (which we will call additive B) available commercially.
  • additive B a second additive
  • Sample 3 Stained glass bottles subjected to immersion at 70 ° C in a detergent composition according to the invention comprising 1% NaOH and 0.2% of an additive according to the invention.
  • This test involves immersing at 70 ° C a clean and dry glass bottle, previously weighed, seven hours in a detergent composition comprising 1% by weight of caustic soda and 0.2% of a washing additive. After which the bottle is dried and weighed again. The difference in weight corresponds to the dissolution of glass in the solution commonly known as "chemical scuffing" or chemical corrosion. To better simulate actual bottle cleaning conditions, 50 ppm calcium phosphate was added to the solutions. The difference in weight is expressed in grams, a significant loss being synonymous with high scuffing.
  • Sample 1 corresponds to a sample subjected to the same detergent composition with the same commercial washing additive as sample 1 in Example 1.
  • Sample 2 corresponds to a sample subjected to a detergent composition using a commercial washing additive known for its "anti-scuffing" properties.
  • Sample 3 corresponds to a sample subjected to the same detergent composition with the same washing additive according to the invention as sample 3 in Example 1.
  • sample subjected to a detergent composition according to the invention comprising a washing additive according to the invention (sample 3) has particularly low scuffing levels, comparable to those obtained with the washing additive known for its properties "Anti-scuffing".
  • washing additives according to the invention and thus the detergent compositions according to the invention derived therefrom, have experimentally shown antifoam behavior sufficient for the targeted application.
  • These additives according to the invention were not very aggressive with respect to the labels, limiting the losses of ink polluting the washing baths, but also limiting the degradation of the paper.
  • the test series no.1 (% performance 1), the detergency performance of the washing composition (detergent composition) corresponds to the percentage of perfectly clean bottles after a laboratory wash.
  • dirty bottles were immersed for 10 minutes in a bath at 80 ° C comprising a detergent composition comprising 2% by weight of NaOH and 0.2% by weight of the washing additive tested.
  • the bottles were then rinsed with tap water and filled with a solution of methylene blue.
  • the bottles were rinsed again and analyzed optically.
  • test series No. 2 (% performance 2)
  • the detergency performance corresponds to the percentage of perfectly clean plates after washing in the laboratory.
  • plates soiled with rice starch (provided by the test center on CFT materials bv) were immersed with stirring for 10 minutes in a bath at 80 ° C comprising a detergent composition comprising 2% by weight of NaOH and 0.2% by weight of the wash additive tested.
  • the plates were then rinsed with tap water and analyzed optically.
  • the percentage of clean plates corresponds to the ratio between the surface of the plates perfectly clean and the total surface of the plates.
  • test series no.3 (% performance 3)
  • the detergency performance corresponds to the percentage of perfectly clean bottles after washing in industrial washers.
  • dirty bottles were immersed for 10 minutes in a bath at 80 ° C comprising a detergent composition comprising 2% by weight of NaOH and 0.2% by weight of the washing additive tested.
  • the bottles were then rinsed with water and filled with a solution of methylene blue and analyzed optically.
  • the various washing additives were also tested in the laboratory for their anti-scuffing property.
  • the weight loss of bottles previously immersed for 7 hours at 80 ° C. was evaluated in a bath comprising a detergent composition comprising 2% by weight of NaOH and 0.2% by weight of the washing additive tested.
  • the result is expressed on a scale from 0 to 10, the value 0 corresponding to the result obtained with a standard anti-scuffing additive based on phosphonate, and the value corresponding to the result obtained with an EDTA additive which does not has no anti-scuffing properties.
  • Additive Composition 1 LTMP + phosphoric acid 2 LTMP + gluconic acid (invention) 3 HEDP + phosphoric acid 4 HEDP + gluconic acid 5 LTMP + phosphoric acid + surfactant 6 LTMP + gluconic acid + surfactant 7 HEDP + phosphoric acid + surfactant 8 HEDP + gluconic acid + surfactant 9
  • Commercial standard using a low-corrosion phosphonate 10 Commercial standard with high detergency using phosphoric acid 11

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Description

Objet de l'inventionObject of the invention

La présente invention se rapporte à un additif de lavage adapté au nettoyage de bouteilles de verre réutilisables. La présente invention se rapporte également à un procédé de nettoyage de bouteilles en verre réutilisables utilisant ledit additif, ainsi qu'à une composition détergente comprenant ledit additif. Cette invention concerne en particulier l'industrie alimentaire de préférence l'industrie des boissons, et encore plus particulièrement l'industrie brassicole pour le nettoyage des bouteilles en verre.The present invention relates to a washing additive suitable for cleaning reusable glass bottles. The present invention also relates to a method for cleaning reusable glass bottles using said additive, as well as to a detergent composition comprising said additive. This invention relates in particular to the food industry, preferably the beverage industry, and more particularly to the brewing industry for cleaning glass bottles.

Etat de la techniqueState of the art

L'utilisation de bouteilles en verre pour le conditionnement de liquides remonte à l'Antiquité. Si les bouteilles en plastique ont depuis fait leur apparition et concurrencent dans une large mesure les bouteilles de verre, celles-ci sont encore utilisées de nos jours, notamment pour le conditionnement de liquides alimentaires courants, tels que l'eau, le lait, le vin, les jus de fruits, les sodas, et les bières, dans la mesure où le verre offre l'avantage par rapport au plastique d'être plus inerte. En outre, certaines bouteilles en verre présentent l'avantage supplémentaire d'être réutilisables.The use of glass bottles for the packaging of liquids dates back to ancient times. Although plastic bottles have since made their appearance and compete to a large extent with glass bottles, they are still used today, especially for the packaging of common food liquids, such as water, milk, water wine, fruit juices, sodas, and beers, since glass offers the advantage over plastic of being more inert. In addition, some glass bottles have the added advantage of being reusable.

Les bouteilles en verre commercialisées sont généralement étiquetées de manière à informer le consommateur de leur contenu. Ces étiquettes sont généralement disposées au moins sur le corps de la bouteille, de préférence sur le devant, où elles sont fixées à l'aide d'un adhésif.Marketed glass bottles are generally labeled to inform the consumer of their contents. These labels are generally disposed at least on the body of the bottle, preferably on the front, where they are fixed using an adhesive.

Lorsqu'elles sont réutilisables, ces bouteilles une fois utilisées sont collectées et acheminées vers des usines où elles sont soumises, au sein d'équipements particuliers appelés « laveuses », à un ou plusieurs cycles automatisés de nettoyages/trempages/rinçages. Les bouteilles y sont notamment retournées pour une plus grande efficacité de nettoyage. Le contrôle qualité final est réalisé par mirage (contrôle visuel en transparence).When reusable, these bottles once used are collected and transported to factories where they are subjected, within special equipment called "washers", to one or more automated cycles of cleaning / soaking / rinsing. In particular, the bottles are returned for greater cleaning efficiency. The final quality control is done by mirage (visual control in transparency).

Traditionnellement, le nettoyage des bouteilles s'effectue en milieu alcalin, à l'aide d'une solution de soude caustique, et à des températures de l'ordre de 80°C. Afin de faciliter le nettoyage et favoriser le décollement de l'étiquette des bouteilles tout en prévenant la formation de mousse dans l'équipement, on prévoit généralement d'ajouter un ou plusieurs additifs à la solution pour former une composition détergente efficace.Traditionally, bottles are cleaned in an alkaline medium using a caustic soda solution and at temperatures of the order of 80 ° C. In order to facilitate cleaning and promote detachment of the bottle label while preventing foaming in the equipment, it is generally expected to add one or more additives to the solution to form an effective detergent composition.

Parmi ces additifs, on a par exemple proposé d'utiliser des agents séquestrant tels que l'EDTA et/ou des agents dispersants tels que des phosphonates et des polyacrylates. L'utilisation de dérivés de polyols, en particulier des polymères de polysaccharides modifiés, des dérivés alkoxylés d'alcools, d'esters, d'amines ou d'amides ont également été proposés.Among these additives, it has for example been proposed to use sequestering agents such as EDTA and / or dispersing agents such as phosphonates and polyacrylates. The use of polyol derivatives, in particular modified polysaccharide polymers, alkoxylated derivatives of alcohols, esters, amines or amides has also been proposed.

Le choix de l'additif en vue de préparer la composition détergente efficace pose un certain nombre de difficultés techniques pour l'homme de l'art. En effet, pour assurer un maximum d'efficacité, une composition détergente efficace doit remplir un certain nombre de critères techniques, souvent difficilement conciliables.The choice of the additive to prepare the effective detergent composition poses a number of technical difficulties for those skilled in the art. Indeed, to ensure maximum efficiency, an effective detergent composition must meet a number of technical criteria, often difficult to reconcile.

Ainsi, une composition détergente efficace doit permettre une détergence non seulement intérieure mais aussi extérieure satisfaisante des récipients, en particulier des bouteilles. En d'autres termes, une composition détergente doit permettre l'élimination, sur les surfaces externes et internes des récipients ou des bouteilles, des résidus de liquides (bière, vin, jus de fruits, lait, sodas,...), mais aussi l'élimination des dépôts d'éléments biologiques ou issus desdits éléments biologiques tels que des bactéries ou des moisissures, c'est-à-dire des champignons et des levures, ainsi que des résidus et traces organiques et/ou minéraux de ces éléments biologiques.. De plus, pour être efficace, une composition détergente doit également permettre au niveau de la surface extérieure des récipients, en particulier des bouteilles, un décollement de l'étiquette et autre éléments de marquage fixés sur la surface des récipients, ainsi que l'élimination des colles et/ou adhésifs, tout en évitant la pollution des bains de lavage, notamment due à la dissolution de l'étiquette , et en particulier des codes à encre dans ces bains.Thus, an effective detergent composition should allow not only internal but also satisfactory outdoor detergency of the containers, particularly bottles. In other words, a detergent composition must allow the elimination of liquid residues (beer, wine, fruit juice, milk, soda, etc.) on the external and internal surfaces of the containers or bottles. also the removal of deposits of biological elements or from said biological elements such as bacteria or molds, that is to say, fungi and yeasts, as well as residues and traces organic and / or inorganic elements thereof In addition, to be effective, a detergent composition must also allow the level of the outer surface of the containers, in particular bottles, detachment of the label and other marking elements fixed on the surface of the containers, as well as the elimination of glues and / or adhesives, while avoiding the pollution of washing baths, especially due to the dissolution of the label, and in particular ink codes in these baths.

Une composition détergente efficace doit en outre pouvoir être rincée aisément, c'est-à-dire qu'elle doit éviter de laisser des traces, notamment de soude caustique, sur la surface des récipients notamment des récipients en verre comme des bouteilles.An effective detergent composition must also be able to be rinsed easily, that is to say, it must avoid leaving traces, especially caustic soda, on the surface of the containers including glass containers such as bottles.

Simultanément, une composition détergente efficace doit garantir une certaine protection de l'intégrité de la surface interne et externe des récipients, en particulier des bouteilles en verre, en évitant tout phénomène de dégradation du verre connu de l'homme de l'art sous le nom de « scuffing » ou « corrosion », y compris toute dégradation des éléments gravés sur la surface des récipients en particulier d'une bouteille, telles que des marques obtenues par pyrogravure. Or, en pratique, lorsqu'on utilise un additif visant à augmenter la détergence, on observe également malheureusement souvent une augmentation de la corrosion (scuffing).At the same time, an effective detergent composition must provide some protection for the integrity of the inner and outer surfaces of the containers, especially glass bottles, avoiding any degradation of the glass. known to those skilled in the art under the name of "scuffing" or "corrosion", including any degradation of the elements etched on the surface of containers especially a bottle, such as marks obtained by pyrography. However, in practice, when using an additive to increase the detergency, it is unfortunately also often observed an increase in corrosion (scuffing).

En outre, la hauteur de mousse formée lors des cycles de nettoyage doit pouvoir être contrôlée.In addition, the foam height formed during the cleaning cycles must be controllable.

Enfin, une composition détergente efficace doit prévenir la formation de dépôts minéraux, notamment les dépôts de carbonate de calcium, généralement dénommés « tartres ».Finally, an effective detergent composition must prevent the formation of mineral deposits, especially calcium carbonate deposits, generally called "tartar".

Des compositions détergentes sont actuellement disponibles sur le marché. Si ces compositions détergentes répondent séparément à certains des critères techniques évoqués ci-dessus, aucune d'entre elles ne les remplit tous en même temps. Par conséquent, la présente invention vise à fournir une telle composition qui réponde aux besoins susmentionnés, qui puisse éventuellement comprendre des éléments issus de matières biologiques renouvelables et qui puisse réduire son impact environnemental, en particulier par une utilisation moindre de soude caustique dans l'obtention d'une composition détergente efficace.Detergent compositions are currently available on the market. While these detergent compositions separately meet some of the above-mentioned technical criteria, none of them fill them all at the same time. Therefore, the present invention aims to provide such a composition that meets the aforementioned needs, which may possibly include elements derived from renewable biological materials and that can reduce its environmental impact, particularly by a lower use of caustic soda in obtaining an effective detergent composition.

WO 2013/053390 A1 décrit une composition détergente comprenant un tensioactif et lysine tétraméthylène phosphonate. Il ne décrit pas une composition comprenant un acide gluconique. WO 2013/053390 A1 discloses a detergent composition comprising a surfactant and lysine tetramethylene phosphonate. It does not describe a composition comprising a gluconic acid.

WO 2012/028203 A1 décrit une composition détergente comprenant l'acide de phosphonocarboxylique, l'acide gluconique et leurs mélanges. Il ne décrit pas une composition comprenant de lysine tétraméthylène phosphonate. WO 2012/028203 A1 discloses a detergent composition comprising phosphonocarboxylic acid, gluconic acid and mixtures thereof. It does not describe a composition comprising lysine tetramethylene phosphonate.

DE 13 02 882 B décrit un procédé de lavage des bouteilles comprenant un bain comprenant un chélatant comme l'acide gluconique et/ou l'acide d'aminoalkyldiphosphonique. Il ne décrit pas une composition comprenant de lysine tétraméthylène phosphonate. DE 13 02 882 B discloses a bottle washing process comprising a bath comprising a chelant such as gluconic acid and / or aminoalkyldiphosphonic acid. It does not describe a composition comprising lysine tetramethylene phosphonate.

DE 43 38 626 A1 décrit un additif de lavage pour l'addition en bain pour nettoyage de bouteilles en verre comprenant un acide comme l'acide gluconique et un acide diphosphonique. Il ne décrit pas une composition comprenant de lysine tétraméthylène phosphonate. DE 43 38 626 A1 discloses a washing additive for the bath addition for cleaning glass bottles comprising an acid such as gluconic acid and a diphosphonic acid. It does not describe a composition comprising lysine tetramethylene phosphonate.

Résumé de l'inventionSummary of the invention

La présente invention concerne un additif de lavage comprenant (ou consistant en) une lysine tétraméthylène phosphonate (abréviation : LTMP) et un acide carboxylique constitué par/correspondant à l'acide gluconique.The present invention relates to a washing additive comprising (or consisting of) a lysine tetramethylene phosphonate (abbreviation: LTMP) and a carboxylic acid consisting of / corresponding to gluconic acid.

La présente invention concerne également un additif de lavage consistant en de la lysine tétraméthylène phosphonate (abréviation : LTMP) et un acide carboxylique correspondant à l'acide gluconique.The present invention also relates to a washing additive consisting of lysine tetramethylene phosphonate (abbreviation: LTMP) and a carboxylic acid corresponding to gluconic acid.

De préférence, dans l'additif de lavage selon l'invention, la lysine tétraméthylène phosphonate et l'acide gluconique sont présents dans un rapport en poids lysine tétraméthylène phosphonate : acide gluconique compris entre (environ) 1:1 et (environ) 5:1.Preferably, in the washing additive according to the invention, lysine tetramethylene phosphonate and gluconic acid are present in a ratio by weight of lysine tetramethylene phosphonate: gluconic acid of between (approximately) 1: 1 and (approximately) 5: 1.

De préférence le rapport en poids entre la lysine tétraméthylène phosphonate et l'acide gluconique est compris entre (environ) 1,5 :1 et (environ) 3 :1Preferably the weight ratio of lysine tetramethylene phosphonate to gluconic acid is from (about) 1.5: 1 to (about) 3: 1

De préférence, selon la présente invention, la lysine tétraméthylène phosphonate est présente (dans l'additif) à une concentration comprise entre (environ) 2% et (environ) 50% en poids, de préférence entre (environ) 2 % et (environ) 30% en poids, de préférence entre (environ) 2 % et (environ) 10% en poids.Preferably, according to the present invention, the lysine tetramethylene phosphonate is present (in the additive) at a concentration of between (about) 2% and (about) 50% by weight, preferably between (about) 2% and (about 30% by weight, preferably between (about) 2% and (about) 10% by weight.

Avantageusement, l'additif selon l'invention comprend en outre un agent dispersant, de préférence un agent dispersant naturel (c'est-à-dire un agent dispersant obtenu à partir de matières biologiques renouvelables).Advantageously, the additive according to the invention further comprises a dispersing agent, preferably a natural dispersing agent (that is to say a dispersing agent obtained from renewable biological materials).

De préférence, ledit agent dispersant est un agent dispersant polycarboxylique.Preferably, said dispersing agent is a polycarboxylic dispersing agent.

De préférence, l'agent dispersant est choisi parmi le groupe constitué par la carboxyméthyl cellulose, la carboxyméthyl inuline, l'inuline, l'acide polyaspartique, l'acide polyépoxy succinique, et les mélanges de ceux-ci.Preferably, the dispersing agent is selected from the group consisting of carboxymethyl cellulose, carboxymethyl inulin, inulin, polyaspartic acid, polyepoxy succinic acid, and mixtures thereof.

Avantageusement, l'agent dispersant est présent dans l'additif selon l'invention dans un rapport en poids lysine tétraméthylène phosphonate : agent dispersant compris entre (environ) 10:1 et (environ) 3:1.Advantageously, the dispersing agent is present in the additive according to the invention in a weight ratio of lysine tetramethylene phosphonate: dispersing agent of between (approximately) 10: 1 and (approximately) 3: 1.

De préférence, l'agent dispersant est présent dans l'additif à une concentration comprise entre (environ) 0.5 et (environ) 10% en poids.Preferably, the dispersing agent is present in the additive at a concentration of (about) 0.5 to (about) 10% by weight.

De manière particulièrement avantageuse, l'agent dispersant est la carboxyméthyl inuline.In a particularly advantageous manner, the dispersing agent is carboxymethyl inulin.

De préférence, l'additif de lavage selon la présente invention comprend en outre un tensioactif à faible pouvoir moussant, mais apte à faciliter la pénétration et la solubilisation de l'additif de lavage de l'invention.Preferably, the washing additive according to the present invention further comprises a surfactant with low foaming power, but capable of facilitating the penetration and solubilization of the washing additive of the invention.

De préférence, ledit tensioactif est choisi parmi le groupe constitué par les copolymères d'éthyle propylène oxydes, les acides gras éthoxylés et les mélanges de ceux-ci.Preferably, said surfactant is selected from the group consisting of ethyl propylene oxide copolymers, ethoxylated fatty acids and mixtures thereof.

De préférence, ledit tensioactif est présent dans un rapport lysine tétraméthylène phosphonate : tensioactif compris entre (environ) 5:1 et (environ) 1:2.Preferably, said surfactant is present in a lysine tetramethylene phosphonate: surfactant ratio of between (approximately) 5: 1 and (approximately) 1: 2.

De préférence, ledit tensioactif est présent dans l'additif à une concentration comprise entre (environ) 0.5 % et (environ) 20% en poids.Preferably, said surfactant is present in the additive at a concentration of between (about) 0.5% and (about) 20% by weight.

Selon une forme préférée de l'invention, l'additif de lavage consiste en de la lysine tétraméthylène phosphonate, de l'acide gluconique et un tensioactif à faible pouvoir moussant, dans lequel le rapport pondéral tétraméthylène phosphonate : acide gluconique est compris entre (environ) 1,5:1 et (environ) 3:1, et la concentration en tensioactif à faible pouvoir moussant est comprise entre (environ) 0.5% et (environ) 20%.According to a preferred form of the invention, the washing additive consists of lysine tetramethylene phosphonate, gluconic acid and a low foaming surfactant, wherein the weight ratio of tetramethylene phosphonate: gluconic acid is between about 1.5: 1 and (about) 3: 1, and the concentration of low foaming surfactant is from (about) 0.5% to (about) 20%.

La présente invention se rapporte également à une composition détergente comprenant l'additif de lavage de l'invention et de la soude caustique (ou autre solvant adéquat), ladite soude caustique (ou autre solvant adéquat) étant présente à une concentration comprise entre (environ) 0.5 % et (environ) 3%, de préférence entre (environ) 0.5% et (environ) 1.5%.The present invention also relates to a detergent composition comprising the washing additive of the invention and caustic soda (or other suitable solvent), said caustic soda (or other suitable solvent) being present at a concentration of between about 0.5% and (about) 3%, preferably between (about) 0.5% and (about) 1.5%.

De préférence, ladite composition détergente est telle que l'additif de lavage est présent à une concentration comprise entre (environ) 0.05 % et (environ) 0.5%, et de préférence entre (environ) 0.1 % et (environ) 0.2%.Preferably, said detergent composition is such that the wash additive is present at a concentration of between (about) 0.05% and (about) 0.5%, and preferably between (about) 0.1% and (about) 0.2%.

Un autre objet de l'invention concerne un procédé industriel de nettoyage de récipients souillés par des moisissures, de préférence de récipients en verre, et de manière encore plus préférée de bouteilles en verre, comprenant l'étape de lavage desdits récipients avec un additif de lavage ou une composition détergente de l'invention.Another subject of the invention relates to an industrial process for cleaning mold-contaminated containers, preferably glass containers, and even more preferably to glass bottles, comprising the step of washing said containers with an additive of washing or detergent composition of the invention.

De préférence, dans ledit procédé industriel de l'invention, le lavage est effectué par immersion dans un bain contenant la composition détergente de l'invention à une température comprise entre (environ) 60°C et (environ) 80°C, de préférence entre (environ) 60°C et (environ) 70°C, et/ou par aspersion de ladite composition détergente.Preferably, in said industrial process of the invention, the washing is carried out by immersion in a bath containing the detergent composition of the invention at a temperature of between (about) 60 ° C and (about) 80 ° C, preferably between (about) 60 ° C and (about) 70 ° C, and / or by spraying said detergent composition.

La présente invention se rapporte également à l'utilisation de l'additif de lavage et/ou de la composition détergente, et/ou du procédé de l'invention dans l'industrie agro-alimentaire, de préférence dans l'industrie des boissons, et de manière encore plus préférée dans l'industrie brassicole.The present invention also relates to the use of the washing additive and / or the detergent composition, and / or the process of the invention in the food industry, preferably in the beverage industry, and even more preferably in the brewing industry.

Un autre objet de l'invention concerne l'utilisation de la lysine tétraméthylène phosphonate et d'au moins l'acide gluconique, appliqués de préférence de manière simultanée dans un additif de lavage, pour éliminer les moisissures de la surface de récipients, de préférence de bouteilles en verre.Another subject of the invention relates to the use of lysine tetramethylene phosphonate and at least gluconic acid, preferably applied simultaneously in a washing additive, to remove mold from the surface of containers, preferably glass bottles.

L'invention se rapporte aussi à l'utilisation de la lysine tétraméthylène phosphonate et d'au moins l'acide gluconique, appliqués de préférence de manière simultanée, comme solution de lavage sans « scuffing », sans corrosion de la surface de récipients, de préférence de bouteilles en verre.The invention also relates to the use of lysine tetramethylene phosphonate and at least gluconic acid, preferably applied simultaneously, as a washing solution without "scuffing", without corrosion of the surface of containers, preference of glass bottles.

Définitions : Definitions :

Dans la présente description, les termes utilisés et non définis ci-dessous sont ceux ayant la même signification et habituellement compris par la personne du métier.In the present description, the terms used and not defined below are those having the same meaning and usually understood by those skilled in the art.

La lysine tétraméthylène phosphonate ou LTMP est une molécule répondant à la formule chimique 1 telle que représentée à la figure 1 et appartient à la famille des acides phosphoniques, dont les sels sont appelés phosphonates, généralement connus pour être des agents chélatants, encore appelés « agents séquestrants » ou « séquestrants », c'est-à-dire que ce sont des molécules, et plus précisément des tensioactifs (voir ci-dessous) capables d'agir comme ligands en formant des complexes chimiques avec des ions métalliques tels que le cuivre, le fer, le nickel dont ils limitent ainsi la disponibilité.Lysine tetramethylene phosphonate or LTMP is a molecule corresponding to the chemical formula 1 as shown in FIG. figure 1 and belongs to the family of phosphonic acids, whose salts are called phosphonates, generally known to be chelating agents, also called "sequestering agents" or "sequestering agents", that is to say that they are molecules, and more specifically surfactants (see below) capable of acting as ligands by forming chemical complexes with metal ions such as copper, iron, nickel, which they thus limit the availability.

La lysine tétraméthylène phosphonate dérive de la lysine, un acide aminé naturel dont la formule chimique est également reprise dans la figure 1 (formule chimique 2).Lysine tetramethylene phosphonate is derived from lysine, a naturally occurring amino acid whose chemical formula is also included in the figure 1 (chemical formula 2).

Dans la présente description, le mot « tensioactif » ou surfactant se réfère à une molécule naturelle ou de synthèse capable de modifier la tension superficielle entre deux surfaces. D'un point de vue chimique, un tensioactif est une molécule amphiphile présentant une partie hydrophobe et apolaire et une partie hydrophile et polaire. Cette double propriété lui confère une affinité particulière pour les interfaces huile/eau ou eau/huile et est à la base de la stabilisation des systèmes dispersés.In the present description, the word "surfactant" or surfactant refers to a natural or synthetic molecule capable of modifying the surface tension between two surfaces. From a chemical point of view, a surfactant is an amphiphilic molecule having a hydrophobic and apolar part and a hydrophilic and polar part. This dual property gives it a particular affinity for the oil / water or water / oil interfaces and is the basis for the stabilization of the dispersed systems.

Les tensioactifs peuvent être ioniques ou non ioniques. Lorsqu'ils sont ioniques, selon la nature de la charge sur la partie hydrophile, les tensioactifs peuvent être anioniques, cationiques, ou zwittérioniques ou amphotères lorsque la partie hydrophile présente une charge positive et une charge négative qui, d'un point de vue électrique, se compensent mutuellement.The surfactants may be ionic or nonionic. When ionic, depending on the nature of the charge on the hydrophilic part, the surfactants can be anionic, cationic, or zwitterionic or amphoteric when the hydrophilic part has a positive charge and a negative charge which, from an electrical point of view , compensate each other.

Dans la présente description, le terme « surfactant » est un terme équivalent au terme « tensioactif ».In the present description, the term "surfactant" is a term equivalent to the term "surfactant".

Dans la présente description, les termes « détergent », « agent moussant », « agent peu ou pas moussant », « agents à faible pouvoir moussant », « agent dispersant », se rapportent tous à des tensioactifs ; ces termes sont des termes descriptifs de la fonction assurée par le tensioactif dans la composition.In the present description, the terms "detergent", "foaming agent", "little or no foaming agent", "low foaming agents", "dispersing agent" all refer to surfactants; these terms are descriptive terms of the function provided by the surfactant in the composition.

Ainsi, un « détergent » désigne plus spécifiquement un tensioactif capable d'enlever les salissures d'origine organiques et/ou minérales y compris des dépôts de bactéries ou issu de bactéries ou d'autres microorganismes (moisissures, champignons, levures, voire animaux (tels que des mollusques)) sur une surface d'un solide par solubilisation desdites salissures.Thus, a "detergent" more specifically denotes a surfactant capable of removing organic and / or inorganic soil, including deposits of bacteria or bacteria or other microorganisms (molds, fungi, yeasts or even animals ( such as molluscs)) on a surface of a solid by solubilizing said soils.

Un « agent moussant » est un tensioactif capable de s'adsorber à l'interface gaz/liquide, en particulier à l'interface eau/air et de conduire à la formation de mousse par dispersion d'un volume important de gaz (en particulier d'air) dans un faible volume de liquide (en particulier d'eau). Selon sa propension à former de la mousse, on parlera d'agent à plus ou moins grand pouvoir moussant. Il est connu de l'homme de l'art que le pouvoir moussant peut être mesuré selon la méthode dite de Ross-Miles qui permet d'évaluer un volume de mousse initial et sa stabilité dans le temps. Cette méthode repose sur une mesure statique et est couramment utilisée dans l'industrie. Toutefois, d'autres méthodes de mesure existent reposant notamment sur des principes dynamiques.A "foaming agent" is a surfactant capable of adsorbing at the gas / liquid interface, in particular at the water / air interface and leading to the formation of foam by dispersing a large volume of gas (in particular air) in a small volume of liquid (especially water). According to its propensity to form foam, one will speak of agent with more or less great foaming power. It is known to those skilled in the art that the foaming power can be measured according to the so-called Ross-Miles method which makes it possible to evaluate an initial volume of foam and its stability over time. This method is based on a static measurement and is commonly used in industry. However, other measurement methods exist based in particular on dynamic principles.

Les tensioactifs ou surfactants non ioniques notamment des tensioactifs alkoxylés tels que les EO/PO copolymères, les alkoxylates d'alcool notamment les EO/PO copolymères blocs tels que les tensioactifs Pluronic, le dehypon LS-54 (R-(EO)5(PO)4), le Dehypon LS-36 (R-(EO)3(PO)6), le Plurafac LF 221 (BASF), le Tegoten EC11, le LUTENOL (éthoxylates d'alcool) ou un mélange d'entre eux.Nonionic surfactants or surfactants, in particular alkoxylated surfactants such as copolymerized EO / POs, alcohol alkoxylates, in particular block copolymer EO / POs such as Pluronic surfactants, dehypon LS-54 (R- (EO) 5 (PO 4 ), Dehypon LS-36 (R- (EO) 3 (PO) 6 ), Plurafac LF 221 (BASF), Tegoten EC11, LUTENOL (alcohol ethoxylates) or a mixture of them.

Les tensioactifs peu moussants comprennent de préférence des polymères non ioniques peu moussants, utilisés dans le but d'augmenter la détergence tout en limitant la génération de mousse. A titre d'exemple, on peut citer : le Plurafac S 305 LF, le Plurafac S 405 LF, le Plurafac S 505 LF, le Plurafac SLF 18B, le Plurafac LF 303, le Plurafac LF-305, le Plurafac LF-4030 ou le Plurafac SLF-18B45 (BASF) ou un mélange d'entre eux.Low foaming surfactants preferably include low foaming nonionic polymers, used for the purpose of increasing detergency while limiting foam generation. By way of example, mention may be made of: Plurafac S 305 LF, Plurafac S 405 LF, Plurafac S 505 LF, Plurafac SLF 18B, Plurafac LF 303, Plurafac LF-305, Plurafac LF-4030 or Plurafac SLF-18B45 (BASF) or a mixture of them.

Les tensioactifs non moussants ou également appelés « defoamer » se caractérisent par des solubilités aqueuses plus faibles liées à une plus faible proportion d'élément hydrophile et ont pour fonction première de déstabiliser la structure de la mousse. Les tensioactifs préférés sont : le Pluriol 1000, 2000 ou 4000, ainsi que le Pluronic L101 ; L61 ou L81.Non-foaming surfactants or also known as "defoamer" are characterized by lower aqueous solubilities related to a lower proportion of hydrophilic element and have the primary function of destabilizing the structure of the foam. The preferred surfactants are: Pluriol 1000, 2000 or 4000, as well as Pluronic L101; L61 or L81.

Un « agent dispersant » ou « dispersant » est un tensioactif capable de fixer des particules hydrophobes contenues dans une solution hydrophile en évitant leur agrégation et en favorisant leur dispersion dans ladite solution.A "dispersing agent" or "dispersant" is a surfactant capable of fixing hydrophobic particles contained in a hydrophilic solution, avoiding their aggregation and promoting their dispersion in said solution.

Les termes pourcentage (%) en poids se réfèrent à la concentration d'un ingrédient d'une composition décrite, par le poids de cet ingrédient divisé par le total en poids de la composition et multiplié par 100. les termes « environ » se réfèrent à des variations de quantités numériques qui peuvent exister dans les applications des produits revendiqués et peuvent varier en fonction de la pureté ou de la source d'obtention des produits, ainsi que de la méthode d'application des produits revendiqués. De préférence, ces variations sont de l'ordre de 10 % ou de 5%. La présente invention sera décrite en détails dans les exemples suivants en référence aux figures annexées et présentés à titre d'illustrations non limitatives des différents aspects de la présente invention.The terms percent (%) by weight refer to the concentration of an ingredient of a described composition, the weight of that ingredient divided by the total weight of the composition and multiplied by 100. The terms "about" refer to variations in numerical quantities that may exist in the applications of the claimed products and may vary according to the purity or the source of obtaining the products, as well as the method of application of the claimed products. Preferably, these variations are of the order of 10% or 5%. The present invention will be described in detail in the following examples with reference to the appended figures and presented as non-limiting illustrations of the various aspects of the present invention.

On appelle « scuffing » ou « corrosion » toute dégradation du verre au niveau de récipients, en particulier de bouteilles, y compris toute dégradation des éléments gravés sur la surface desdits récipients, telles que des marques ou dessins obtenus par pyrogravure.The term "scuffing" or "corrosion" refers to any degradation of the glass at the level of containers, in particular bottles, including any degradation of the elements engraved on the surface of said containers, such as marks or drawings obtained by pyrography.

Brève description des figures et tablesBrief description of figures and tables

La figure 1 présente la formule chimique de la lysine tétra(méthylène) phosphonate telle qu'utilisée dans la présente invention (formule chimique 1), ainsi que celle de la lysine (formule chimique 2) dont elle dérive.The figure 1 discloses the chemical formula of lysine tetra (methylene) phosphonate as used in the present invention (chemical formula 1), as well as that of lysine (chemical formula 2) from which it derives.

La figure 2 présente les résultats de tests de nettoyage de salissures présentes sur des plaques en verre qui ont été lavées avec différentes compositions, et notamment une composition détergente selon l'invention.The figure 2 presents the results of soil cleaning tests present on glass plates which have been washed with different compositions, and in particular a detergent composition according to the invention.

La figure 3 présente les résultats de tests de « scuffing » réalisés sur des bouteilles de verre traités à l'aide de différentes compositions détergentes, et notamment des compositions détergentes selon l'invention.The figure 3 presents the results of "scuffing" tests carried out on glass bottles treated with different detergent compositions, and in particular detergent compositions according to the invention.

La figure 4 présente les résultats de trois séries de tests de mesure (tests nos 1 à 3) de la performance en détergence de différentes compositions détergentes, et notamment de compositions détergentes selon l'invention, tels qu'obtenus sur des bouteilles en verre traitées à l'aide desdites compositions.The figure 4 presents the results of three series of measurement tests (tests Nos . 1 to 3) of the detergency performance of various detergent compositions, and in particular of detergent compositions according to the invention, as obtained on glass bottles treated with water. using said compositions.

Description détaillée de l'inventionDetailed description of the invention

L'additif de lavage selon la présente invention offre l'intérêt de satisfaire l'ensemble des critères techniques évoqués ci-dessus. Il est particulièrement bien adapté au nettoyage automatique des bouteilles en verre réutilisables, même si d'autres applications peuvent également être envisagées.The washing additive according to the present invention offers the advantage of satisfying all the technical criteria mentioned above. It is particularly suitable for the automatic cleaning of reusable glass bottles, although other applications may also be considered.

En outre, l'additif selon la présente invention offre l'avantage d'utiliser moins de soude caustique. Or la soude caustique est connue pour augmenter le pH des cours d'eau (rivières, fleuves), représentant ainsi une menace potentielle pour la faune et la flore aquatiques. La soude caustique peut également s'infiltrer dans la terre, et ainsi nuire à l'agriculture comme à l'environnement des végétaux, des minéraux et des animaux directement proches ou plus lointains, voire contaminer les nappes phréatiques.In addition, the additive according to the present invention has the advantage of using less caustic soda. However, caustic soda is known to increase the pH of streams (rivers, rivers), thus posing a potential threat to aquatic fauna and flora. Caustic soda can also infiltrate the earth, and thus harm agriculture and the environment of plants, minerals and animals directly or more distantly, or even contaminate the groundwater.

La composition selon la présente invention présente l'avantage supplémentaire de pouvoir être utilisée en phase de nettoyage sur une plage de températures plus faibles par rapport aux compositions disponibles sur le marché. En d'autres termes, l'additif de lavage selon l'invention permet un nettoyage moins énergivore et moins polluant.The composition according to the present invention has the additional advantage that it can be used in the cleaning phase over a lower temperature range compared to the compositions available on the market. In other words, the washing additive according to the invention makes cleaning more energy efficient and less polluting.

D'autant plus que l'additif selon la présente invention comprend un composé, le LTMP, qui est avantageusement obtenu à partir de matières biologiques renouvelables, c'est-à-dire qui dérivent de molécules naturelles, ce qui en fait un additif a priori plus écologique que bien d'autres additifs proposés dans le commerce.Especially since the additive according to the present invention comprises a compound, LTMP, which is advantageously obtained from biological materials renewable, that is to say which derive from natural molecules, making it an additive a priori more ecological than many other additives proposed in the trade.

Exemple 1: Tests de détergence de bouteillesExample 1: Bottle detergency tests

Des tests comparatifs ont été réalisés par immersion de bouteilles en verre préalablement salies à l'aide de moisissures (champignons/levures). Une étiquette est collée sur l'extérieur de bouteilles. Les bouteilles sont ensuite immergées dans des bains comprenant différentes compositions détergentes contenant différents additifs de lavage et 1% de soude caustique à une température de 70°C. L'efficacité des différents additifs de lavage est évaluée à la fois en termes de nettoyage-évaluation visuelle- et en termes de temps de décollement de l'étiquette.Comparative tests were performed by immersing previously soiled glass bottles with molds (fungi / yeasts). A label is stuck on the outside of bottles. The bottles are then immersed in baths comprising different detergent compositions containing different wash additives and 1% caustic soda at a temperature of 70 ° C. The effectiveness of the various wash additives is evaluated both in terms of visual cleaning-evaluation-and in terms of label peeling time.

Les résultats obtenus pour une composition détergente selon l'invention et pour deux additifs A et B correspondant à deux formules commerciales différentes sont présentés dans le tableau 1 ci-dessous : Tableau 1 Echantillon Résultats de nettoyage Temps de décollement des étiquettes 1 +++- 1'12 (avant) 1'34 (arrière) 2 +++- 1'23 (avant) 2'25 (arrière) 3 ++++ 1'15 (avant) 1'26 (arrière) The results obtained for a detergent composition according to the invention and for two additives A and B corresponding to two different commercial formulas are presented in Table 1 below: <b> Table 1 </ b> Sample Cleaning results Label peeling time 1 +++ - 1'12 (before) 1'34 (back) 2 +++ - 1'23 (before) 2'25 (back) 3 ++++ 1'15 (before) 1'26 (back)

Dans le tableau 1, les produits testés sont les suivants : Echantillon 1 : bouteilles en verre souillées soumises à une immersion à 70°C dans une composition détergente comprenant 1% NaOH et 0.2% d'un premier additif (que nous appellerons additif A) disponible dans le commerce.In Table 1, the products tested are as follows: Sample 1: stained glass bottles subjected to immersion at 70 ° C in a detergent composition comprising 1% NaOH and 0.2% of a first additive (which we will call additive A) commercially available.

Echantillon 2 : bouteilles en verre souillées soumises à une immersion à 70°C dans une composition détergente comprenant 1% NaOH et 0.2% d'un deuxième additif (que nous appellerons additif B) disponible dans le commerce.Sample 2: Stained glass bottles subjected to immersion at 70 ° C in a detergent composition comprising 1% NaOH and 0.2% of a second additive (which we will call additive B) available commercially.

Echantillon 3 : bouteilles en verre souillées soumises à une immersion à 70°C dans une composition détergente selon l'invention comprenant 1% NaOH et 0.2% d'un additif selon l'invention.Sample 3: Stained glass bottles subjected to immersion at 70 ° C in a detergent composition according to the invention comprising 1% NaOH and 0.2% of an additive according to the invention.

La composition de l'additif pour l'échantillon 3 est la suivante:

  • 38g eau de ville
  • 9g acide gluconique 60%
  • 27g cumène sulfonate
  • 10g surfactant peu moussant (Fatty alcohol alkoxylates, Plurafac LF303© BASF)
  • 2g carboxymethylinuline
  • 14g LTMP
The composition of the additive for sample 3 is as follows:
  • 38g city water
  • 9g gluconic acid 60%
  • 27g cumene sulfonate
  • 10g low foaming surfactant (Fatty alcohol alkoxylates, Plurafac LF303 © BASF)
  • 2g carboxymethylinulin
  • 14g LTMP

Exemple 2: Test de détergence sur plaquesExample 2: Plate detergency test

Des tests comparatifs sur plaques de salissures standardisées constituées d'amidon appliqué sur du verre ont été réalisés. Pour cela, les plaques de salissure ont été immergées à 70°C ou 80°C dans un bain comprenant une composition détergente pendant un temps déterminé et sous agitation. Ladite composition détergente comprenait de 1 à 2% de soude caustique et soit l'additif de lavage selon l'invention (échantillon 3), soit un additif de lavage disponible dans le commerce (échantillons 1 et 2). La lecture des plaques ainsi traitées est visuelle.Comparative tests on standardized dirt plates made of starch applied on glass were carried out. For this, the dirt plates were immersed at 70 ° C or 80 ° C in a bath comprising a detergent composition for a determined time and with stirring. Said detergent composition comprised from 1 to 2% of caustic soda and either the washing additive according to the invention (sample 3) or a commercially available washing additive (samples 1 and 2). The reading of the plates thus treated is visual.

Les résultats obtenus sont présentés à la figure 2 et montrent les performances particulièrement intéressantes en termes de détergence de la composition détergente selon l'invention.The results obtained are presented at figure 2 and show the particularly advantageous performance in terms of detergency of the detergent composition according to the invention.

Exemple 3 : Test de «scuffing»Example 3: Scuffing Test

Ce test consiste à immerger à 70°C une bouteille de verre propre et sèche, préalablement pesée, sept heures dans une composition détergente comprenant de 1% en poids de soude caustique et 0.2% d'un additif de lavage. Après quoi la bouteille est séchée et pesée à nouveau. La différence de poids correspond à la dissolution du verre dans la solution dénommé couramment « scuffing chimique » ou corrosion chimique. Afin de mieux simuler les conditions réelles de nettoyage de bouteilles, 50 ppm de phosphate de calcium ont été ajoutés aux solutions. La différence de pesée est exprimée en gramme, une perte importante étant synonyme d'un « scuffing » élevé.This test involves immersing at 70 ° C a clean and dry glass bottle, previously weighed, seven hours in a detergent composition comprising 1% by weight of caustic soda and 0.2% of a washing additive. After which the bottle is dried and weighed again. The difference in weight corresponds to the dissolution of glass in the solution commonly known as "chemical scuffing" or chemical corrosion. To better simulate actual bottle cleaning conditions, 50 ppm calcium phosphate was added to the solutions. The difference in weight is expressed in grams, a significant loss being synonymous with high scuffing.

Trois échantillons, numérotés de 1 à 3, ont été testés et les résultats sont présentés à la figure 3.Three samples, numbered from 1 to 3, were tested and the results are presented at figure 3 .

L'échantillon 1 correspond à un échantillon soumis à la même composition détergente avec le même additif de lavage commercial que l'échantillon 1 dans l'exemple 1.Sample 1 corresponds to a sample subjected to the same detergent composition with the same commercial washing additive as sample 1 in Example 1.

L'échantillon 2 correspond à un échantillon soumis à une composition détergente utilisant un additif de lavage commercial connu pour ses propriétés « anti-scuffing ».Sample 2 corresponds to a sample subjected to a detergent composition using a commercial washing additive known for its "anti-scuffing" properties.

L'échantillon 3 correspond à un échantillon soumis à la même composition détergente avec le même additif de lavage selon l'invention que l'échantillon 3 dans l'exemple 1.Sample 3 corresponds to a sample subjected to the same detergent composition with the same washing additive according to the invention as sample 3 in Example 1.

Il apparait clairement de la figure 3 que l'échantillon soumis à une composition détergente selon l'invention comprenant un additif de lavage selon l'invention (échantillon 3) présente des niveaux de « scuffing » particulièrement bas, comparables à ceux obtenus avec l'additif de lavage connu pour ses propriétés « anti-scuffing ».It is clear from the figure 3 that the sample subjected to a detergent composition according to the invention comprising a washing additive according to the invention (sample 3) has particularly low scuffing levels, comparable to those obtained with the washing additive known for its properties "Anti-scuffing".

Exemple 4 : Autres tests Example 4 : Other tests

Les additifs de lavage selon l'invention, et donc les compositions détergentes selon l'invention en dérivant, ont montré expérimentalement un comportement antimousse suffisant pour l'application ciblée. Ces additifs selon l'invention se sont montrés peu agressifs vis-à-vis des étiquettes, limitant les pertes en encre polluant les bains de lavage, mais limitant également la dégradation du papier.The washing additives according to the invention, and thus the detergent compositions according to the invention derived therefrom, have experimentally shown antifoam behavior sufficient for the targeted application. These additives according to the invention were not very aggressive with respect to the labels, limiting the losses of ink polluting the washing baths, but also limiting the degradation of the paper.

Les essais de détergence effectués en laboratoire ont été confirmés par des tests en laveuses de bouteilles industrielles.The laboratory tests of detergency were confirmed by tests on industrial bottle washers.

Exemple 5 : Nature du phosphonate et de l'acide carboxyliqueExample 5 Nature of Phosphonate and Carboxylic Acid

Trois séries de tests ont été effectuées sur différents additifs de lavage afin de comparer l'effet de la nature du phosphonate et de la nature de l'acide carboxylique utilisés dans la composition détergente sur ses performances en termes de détergence. Les résultats obtenus sont présentés dans la figure 4 et résumés dans le tableau 2. De même, l'effet de la nature du phosphonate et celle de l'acide carboxylique sur les pouvoirs de corrosion (scuffing) de la composition détergente ont été testés et les résultats y sont également présentés.Three series of tests were performed on various wash additives to compare the effect of the nature of the phosphonate and the nature of the carboxylic acid used in the detergent composition on its detergency performance. The results obtained are presented in the figure 4 and summarized in Table 2. Similarly, the effect of the nature of the phosphonate and that of the carboxylic acid on the corrosion (scuffing) powers of the detergent composition were tested and the results are also presented.

Principe des différents tests :Principle of the different tests:

Dans une première série de tests, la série de tests no.1 (% performance 1), la performance en termes de détergence de la composition de lavage (composition détergente) correspond au pourcentage de bouteilles parfaitement propres après un lavage en laboratoire. Pour cela, des bouteilles sales ont été immergées pendant 10 minutes dans un bain à 80°C comprenant une composition détergente comprenant 2% en poids de NaOH et 0.2% en poids de l'additif de lavage testé. Les bouteilles ont été ensuite rincées à l'eau de ville et remplies avec une solution de bleu de méthylène. Les bouteilles ont été rincées à nouveau et analysées optiquement.In a first series of tests, the test series no.1 (% performance 1), the detergency performance of the washing composition (detergent composition) corresponds to the percentage of perfectly clean bottles after a laboratory wash. For this, dirty bottles were immersed for 10 minutes in a bath at 80 ° C comprising a detergent composition comprising 2% by weight of NaOH and 0.2% by weight of the washing additive tested. The bottles were then rinsed with tap water and filled with a solution of methylene blue. The bottles were rinsed again and analyzed optically.

Dans une deuxième série de tests, la série de tests no.2 (% performance 2), la performance en détergence correspond au pourcentage de plaques parfaitement propres après un lavage en laboratoire. Pour cela des plaques salies par de l'amidon de riz (fournies par le centre de tests sur les matériaux C.F.T. b.v.) ont été immergées sous agitation pendant 10 minutes dans un bain à 80°C comprenant une composition détergente comprenant 2% en poids de NaOH et 0.2% en poids de l'additif de lavage testé. Les plaques ont été ensuite rincées à l'eau de ville et analysées optiquement. Le pourcentage de plaques propres correspond au rapport entre la surface des plaques parfaitement propre et la surface totale des plaques.In a second series of tests, test series No. 2 (% performance 2), the detergency performance corresponds to the percentage of perfectly clean plates after washing in the laboratory. For this, plates soiled with rice starch (provided by the test center on CFT materials bv) were immersed with stirring for 10 minutes in a bath at 80 ° C comprising a detergent composition comprising 2% by weight of NaOH and 0.2% by weight of the wash additive tested. The plates were then rinsed with tap water and analyzed optically. The percentage of clean plates corresponds to the ratio between the surface of the plates perfectly clean and the total surface of the plates.

Dans la troisième série de tests, la série de tests no.3 (% performance 3), la performance en détergence correspond au pourcentage de bouteilles parfaitement propres après un lavage en laveuses industrielles. Pour cela des bouteilles sales ont été immergées pendant 10 minutes dans un bain à 80°C comprenant une composition détergente comprenant 2% en poids de NaOH et 0.2% en poids de l'additif de lavage testé. Les bouteilles ont été ensuite rincées à l'eau et remplies avec une solution de bleu de méthylène, puis analysées optiquement.In the third series of tests, test series no.3 (% performance 3), the detergency performance corresponds to the percentage of perfectly clean bottles after washing in industrial washers. For this, dirty bottles were immersed for 10 minutes in a bath at 80 ° C comprising a detergent composition comprising 2% by weight of NaOH and 0.2% by weight of the washing additive tested. The bottles were then rinsed with water and filled with a solution of methylene blue and analyzed optically.

Parallèlement, les différents additifs de lavage (additifs de 1 à 11) ont aussi été testés en laboratoire pour leur propriété anti-scuffing. Pour cela on a évalué la perte en poids de bouteilles préalablement immergées pendant 7h à 80°C dans un bain comprenant une composition détergente comprenant 2% en poids de NaOH et 0.2% en poids de l'additif de lavage testé. Le résultat est exprimé sur une échelle allant de 0 à 10, la valeur 0 correspondant au résultat obtenu avec un additif anti-scuffing standard à base de phosphonate, et la valeur 10 correspondant au résultat obtenu avec une additif à base d'EDTA qui ne présente pas de propriétés anti-scuffing.In parallel, the various washing additives (additives from 1 to 11) were also tested in the laboratory for their anti-scuffing property. For this, the weight loss of bottles previously immersed for 7 hours at 80 ° C. was evaluated in a bath comprising a detergent composition comprising 2% by weight of NaOH and 0.2% by weight of the washing additive tested. The result is expressed on a scale from 0 to 10, the value 0 corresponding to the result obtained with a standard anti-scuffing additive based on phosphonate, and the value corresponding to the result obtained with an EDTA additive which does not has no anti-scuffing properties.

Descriptif des produits testésDescription of the tested products

AdditifAdditive CompositionComposition 11 LTMP + acide phosphoriqueLTMP + phosphoric acid 22 LTMP + acide gluconique (invention)LTMP + gluconic acid (invention) 33 HEDP + acide phosphoriqueHEDP + phosphoric acid 44 HEDP + acide gluconiqueHEDP + gluconic acid 55 LTMP + acide phosphorique + surfactantLTMP + phosphoric acid + surfactant 66 LTMP + acide gluconique + surfactantLTMP + gluconic acid + surfactant 77 HEDP + acide phosphorique + surfactantHEDP + phosphoric acid + surfactant 88 HEDP + acide gluconique + surfactantHEDP + gluconic acid + surfactant 99 Standard commercial utilisant un phosphonate à faible pouvoir de corrosionCommercial standard using a low-corrosion phosphonate 1010 Standard commercial à haut pouvoir détergent utilisant l'acide phosphoriqueCommercial standard with high detergency using phosphoric acid 1111 Standard commercial à haut pouvoir détergent utilisant l'EDTACommercial standard with high detergency power using EDTA

Détails des compositions des différents additifs testés :Details of the compositions of the various additives tested:

  • Additif 1: 40% LTMP lysine tétraméthylène phosphonate (SPE 1001© : Italmach), 15% acide phosphorique acid (75%wt)Additive 1: 40% LTMP lysine tetramethylene phosphonate (SPE 1001 ©: Italmach), 15% phosphoric acid acid (75% wt)
  • Additif 2: 40% LTMP lysine tétraméthylène phosphonate (SPE 1001© : Italmach), 15% acide gluconique (60%wt)Additive 2: 40% LTMP lysine tetramethylene phosphonate (SPE 1001 ©: Italmach), 15% gluconic acid (60% wt)
  • Additif 3:40% 1-Hydroxyethylidène -1,1,-diphosphonic acid (HEDP, Dequest 2010© : Italmach), 15% phosphoric acid (75%wt)Additive 3: 40% 1-Hydroxyethylidene -1,1, -diphosphonic acid (HEDP, Dequest 2010 ©: Italmach), 15% phosphoric acid (75% wt)
  • Additif 4: 40% acide 1-Hydroxyethylidène -1,1,-diphosphonic acid (HEDP, Dequest 2010© : Italmach), 15% acide gluconique (60%wt)Additive 4: 40% 1-Hydroxyethylidene-1,1,1-diphosphonic acid (HEDP, Dequest 2010 ©: Italmach), 15% gluconic acid (60% wt)
  • Additif 5: 12% LTMP lysine tétraméthylène phosphonate (SPE 1001©: Italmach) 10% acide phosphorique (50%wt), 10% surfactant peu moussant (Fatty alcohol alkoxylates, Plurafac LF303© BASF), 2% agent dispersant (carboxymethyl inuline, CMI, Dequest PB© : Italmach)Additive 5: 12% LTMP lysine tetramethylene phosphonate (SPE 1001 ©: Italmach) 10% phosphoric acid (50% wt), 10% low foaming surfactant (Fatty alcohol alkoxylates, Plurafac LF303 © BASF), 2% dispersing agent (carboxymethyl inulin, CMI, Dequest PB ©: Italmach)
  • Additif 6: 12% LTMP lysine tétraméthylène phosphonate (SPE 1001©: Italmach) 10% acide gluconique (60%wt), 10% surfactant peu moussant (Fatty alcohol alkoxylates, Plurafac LF303© BASF), 2% agent dispersant (carboxymethyl inuline, CMI, Dequest PB©: Italmach)Additive 6: 12% LTMP lysine tetramethylene phosphonate (SPE 1001 ©: Italmach) 10% gluconic acid (60% wt), 10% low foaming surfactant (Fatty alcohol alkoxylates, Plurafac LF303 © BASF), 2% dispersing agent (carboxymethyl inulin, CMI, Dequest PB ©: Italmach)
  • Additif 7: 12% 1-Hydroxyethylidène -1,1,-diphosphonic acid (HEDP, Dequest 2010© : Italmach), 10% acide phosphorique (75%wt), 10% surfactant peu moussant (Fatty alcohol alkoxylates, Plurafac LF303© BASF), 2% agent dispersant (carboxymethyl inuline, CMI, Dequest PB© : Italmach)Additive 7: 12% 1-Hydroxyethylidene -1,1, -diphosphonic acid (HEDP, Dequest 2010 ©: Italmach), 10% phosphoric acid (75% wt), 10% low foaming surfactant (Fatty alcohol alkoxylates, Plurafac LF303 © BASF ), 2% dispersing agent (carboxymethyl inulin, CMI, Dequest PB ©: Italmach)
  • Additif 8: 12% 1-Hydroxyethylidène -1,1,-diphosphonic acid (HEDP, Dequest 2010© : Italmach), 10% gluconic acid (60%wt), 10% surfactant peu moussant (Fatty alcohol alkoxylates, Plurafac LF303© BASF), 2% agent dispersant (carboxyméthyl inuline, CMI, Dequest PB© : Italmach)Additive 8: 12% 1-Hydroxyethylidene -1,1, -diphosphonic acid (HEDP, Dequest 2010 ©: Italmach), 10% gluconic acid (60% wt), 10% low foaming surfactant (Fatty alcohol alkoxylates, Plurafac LF303 © BASF ), 2% dispersing agent (carboxymethyl inulin, CMI, Dequest PB ©: Italmach)
  • Additif 9: mélange de phosphonates (connu pour leur performance « antiscuffing »), d'agent dispersant et surfactant peu moussant. Il s'agit d'un additif commercial standard pour le lavage de bouteilles à base de phosphonates et à faible pouvoir de scuffing (de corrosion) connu sous le nom de Mix100BNA© : SopuraAdditive 9: mixture of phosphonates (known for their performance "antiscuffing"), dispersant and surfactant low foaming. It is a standard commercial additive for washing phosphonate-based bottles with low scuffing (corrosion) properties known as Mix100BNA ©: Sopura
  • Additif 10: acide phosphorique, acide phosphonique et surfactant peu moussant (Fatty alcohol alkoxylates). Il s'agit d'un additif commercial standard pour le lavage de bouteilles à base d'acide phosphorique à haut pouvoir de détergence, connu sous le nom de MIX100BPRD43© : SopuraAdditive 10: phosphoric acid, phosphonic acid and low foaming surfactant (Fatty alcohol alkoxylates). It is a standard commercial additive for the washing of phosphoric acid bottles with high detergency, known as MIX100BPRD43 ©: Sopura
  • Additif 11: acide éthylène diamine tetraacétique (EDTA) et surfactant peu moussant. Il s'agit additif commercial standard pour le lavage de bouteilles à base d'EDTA à haut pouvoir de détergence, connu sous le nom de MIX LEG© : SopuraAdditive 11: ethylene diamine tetraacetic acid (EDTA) and low foaming surfactant. It is a standard commercial additive for the washing of EDTA bottles with high detergency, known as MIX LEG ©: Sopura
Résultats des différents tests :Results of the different tests:

Tableau 2 Table 2 AdditifAdditive StabilitéStability Performance en détergence test no. 1Performance in detergency test no. 1 Performance en détergence test no. 2Performance in detergency test no. 2 Performance en détergence test no. 3Performance in detergency test no. 3 Pouvoir de corrosion (scuffing)Power of corrosion (scuffing) 11 StableStable 8080 6060 NDND 33 22 StableStable 9090 100100 9090 88 33 StableStable 6060 NDND NDND 22 44 StableStable 5050 NDND NDND 66 55 InstableUnstable InstableUnstable InstableUnstable InstableUnstable InstableUnstable 66 StableStable 8080 7070 8080 88 77 StableStable 5050 NDND NDND 22 88 StableStable 3030 NDND NDND 66 99 StableStable 1010 NDND 2020 1010 1010 StableStable 7070 8080 8080 22 1111 StableStable 9090 6060 100100 00

Les résultats présentés ci-dessus montrent que seule la combinaison de la LTMP comme phosphonate et de l'acide gluconique comme acide carboxylique permet d'obtenir une composition détergente présentant à la fois un haut pouvoir détergent et de bonnes propriétés anti-corrosion (« anti-scuffing »).The results presented above show that only the combination of LTMP as phosphonate and gluconic acid as carboxylic acid makes it possible to obtain a detergent composition having both a high detergency and good anti-corrosion properties ("anti-corrosion"). -scuffing ").

Claims (15)

  1. Washing additive comprising lysine tetramethylene phosphonate (LTMP) and gluconic acid.
  2. Washing additive according to claim 1, characterized in that lysine tetramethylene phosphonate and gluconic acid are present in a weight ratio of lysine tetramethylene phosphonate: gluconic acid between 1:1 and 5:1.
  3. Washing additive according to claim 1 or 2, characterized in that the lysine tetramethylene phosphonate is present in the additive at a concentration of between 2% and 50% by weight.
  4. Washing additive according to one of the preceding claims, characterized in that it comprises a dispersing agent, preferably a natural dispersing agent, such as a polycarboxylic dispersing agent, preferably selected from the group consisting of carboxymethyl cellulose, carboxymethyl inulin, inulin, polyaspartic acid, polyepoxy succinic acid, and mixtures thereof.
  5. Washing additive according to claim 4, characterized in that the dispersing agent is present in a weight ratio of lysine tetramethylene phosphonate: dispersing agent of between 10:1 and 3:1.
  6. Washing additive according to claim 4, characterized in that the dispersing agent is present in the additive at a concentration of between 0.5 and 10% by weight.
  7. Washing additive according to one of the preceding claims, characterized in that it comprises a low foaming surfactant, preferably selected from the group consisting of copolymers of ethyl propylene oxides, ethoxylated fatty acids and mixtures thereof.
  8. Washing additive according to claim 7, characterized in that the surfactant is present in a lysine tetramethylene phosphonate: surfactant ratio of between 5:1 and 1:2.
  9. Washing additive according to claim 7, characterized in that the surfactant is present in the additive at a concentration of between 0.5% and 20% by weight.
  10. Washing additive consisting of lysine tetramethylene phosphonate, gluconic acid and a low foaming surfactant, wherein the tetramethylene phosphonate : gluconic acid weight ratio is between 1.5:1 and 3:1, while the low foaming surfactant concentration is between 0.5% and 20%.
  11. Detergent composition comprising a washing additive according to any one of the preceding claims and caustic soda, wherein the caustic soda is present at a concentration between 0.5% and 3%, preferably between 0.5% and 1.5%, and wherein the washing additive is preferably present at a concentration of between 0.05% and 0.5%.
  12. Industrial process for cleaning mold-contaminated containers, preferably glass containers, and even more preferably glass bottles, comprising the step of washing the containers with a washing additive according to one of the claims 1 to 10 or the detergent composition according to claim 11, and wherein the washing is preferably carried out by immersion in a bath containing the detergent composition according to claim 11 at a temperature of between 60°C and 80°C and/or by spraying the detergent composition.
  13. Use of the washing additive according to one of the claims 1 to 10 and/or the detergent composition according to claim 11, and/or the method according to claim 12 in the food industry, preferably in the beverage industry, and even more so in the brewing industry.
  14. Use of lysine tetramethylene phosphonate and gluconic acid to remove mold from the surface of containers, preferably glass bottles.
  15. Use of lysine tetramethylene phosphonate and gluconic acid as a washing solution without scuffing.
EP15756917.9A 2014-09-01 2015-09-01 Washing additive Active EP3189127B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
RS20190140A RS58460B1 (en) 2014-09-01 2015-09-01 Washing additive
SI201530590T SI3189127T1 (en) 2014-09-01 2015-09-01 Washing additive
HRP20190207TT HRP20190207T1 (en) 2014-09-01 2015-09-01 WASHING SUPPLEMENT

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE2014/0659A BE1021365B1 (en) 2014-09-01 2014-09-01 ADDITIVE WASH
PCT/EP2015/069904 WO2016034562A1 (en) 2014-09-01 2015-09-01 Washing additive

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EP3189127A1 EP3189127A1 (en) 2017-07-12
EP3189127B1 true EP3189127B1 (en) 2018-10-31

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EP15756917.9A Active EP3189127B1 (en) 2014-09-01 2015-09-01 Washing additive

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EP (1) EP3189127B1 (en)
BE (1) BE1021365B1 (en)
ES (1) ES2709389T3 (en)
HR (1) HRP20190207T1 (en)
MX (1) MX374709B (en)
PT (1) PT3189127T (en)
RS (1) RS58460B1 (en)
RU (1) RU2666891C1 (en)
SI (1) SI3189127T1 (en)
WO (1) WO2016034562A1 (en)
ZA (1) ZA201701295B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106434034A (en) * 2016-07-11 2017-02-22 成都嘉鹏科技有限公司 Glass cleaning agent suitable for spray cleaning and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1302882B (en) * 1967-01-07 1971-01-07 Henkel & Cie Gmbh Process to supplement cleaning baths for the continuous cleaning of rigid material
DE4338626A1 (en) * 1993-11-12 1995-05-18 Henkel Kgaa Additive for glass bottle cleaning and its use to reduce glass corrosion
PL2611896T3 (en) * 2010-09-03 2017-10-31 Ecolab Usa Inc Composition for cleaning with enhanced activity
WO2013053390A1 (en) * 2011-10-12 2013-04-18 Dequest Ag Cleaning composition with improved stain removal
PL2850167T3 (en) * 2012-05-14 2019-04-30 Ecolab Usa Inc Label removal solution for returnable beverage bottles
RU2016123111A (en) * 2016-06-10 2017-12-14 Олег Савельевич Кочетов METHOD FOR CLEANING TANKS CONTAMINATED WITH OIL PRODUCTS

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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MX374709B (en) 2025-03-04
WO2016034562A1 (en) 2016-03-10
RS58460B1 (en) 2019-04-30
EP3189127A1 (en) 2017-07-12
ZA201701295B (en) 2018-05-30
BE1021365B1 (en) 2015-11-06
ES2709389T3 (en) 2019-04-16
PT3189127T (en) 2019-02-04
HRP20190207T1 (en) 2019-04-05
MX2017002666A (en) 2017-09-19
SI3189127T1 (en) 2019-04-30
RU2666891C1 (en) 2018-09-13

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