EP3411464B1 - Detergent compositions for cleaning in the cosmetic and pharmaceutical industry - Google Patents

Detergent compositions for cleaning in the cosmetic and pharmaceutical industry Download PDF

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Publication number
EP3411464B1
EP3411464B1 EP17707631.2A EP17707631A EP3411464B1 EP 3411464 B1 EP3411464 B1 EP 3411464B1 EP 17707631 A EP17707631 A EP 17707631A EP 3411464 B1 EP3411464 B1 EP 3411464B1
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Prior art keywords
detergent composition
fatty alcohols
composition
use according
chosen
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EP17707631.2A
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German (de)
French (fr)
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EP3411464A1 (en
Inventor
Gaétan Rauwel
Jacques Criquelion
Stéphane TERRIER
Bertrand Letartre
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Ecolab USA Inc
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Ecolab USA Inc
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04Cleaning involving contact with liquid
    • B08B3/08Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04Cleaning involving contact with liquid
    • B08B3/10Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3409Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/722Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • C11D2111/20

Definitions

  • the present invention relates to the use of detergent compositions for cleaning manufacturing equipment, packaging or any other equipment used in the manufacture or packaging of hydrophobic cosmetic or pharmaceutical preparations.
  • the invention also relates to such detergent compositions as such.
  • Manufacturing and packaging equipment as well as any other equipment used in the manufacture and packaging of cosmetic and pharmaceutical products are generally cleaned using a dynamic system with turbulence.
  • dynamic systems include in particular "cleaning in place” (CIP, in English “clean in place” or CIP), soaking with strong agitation, washing in a closed circuit via washing balls, cleaning in washer and cleaning in washing cabin.
  • These cleaning systems require specific non-foaming detergents to prevent the formation of foam due to the turbulence created in the system.
  • These detergents are generally strongly alkaline and therefore contain significant amounts of alkali hydroxide as well as surfactants and sequestering and antiflocculation agents.
  • the European patent application EP 1,200,544 describes for example an alkaline detergent for the elimination of residues containing pigments appearing during the manufacture or packaging of pharmaceutical or cosmetic products.
  • This detergent contains surfactants, in particular nonionic such as alkoxylated fatty alcohols, alkylpolyglucosides and / or alkoxylated fatty amines, and a combination of polyaspartic acid and gluconic acid or of their salts as complexing agents.
  • this detergent does not allow the removal of highly hydrophobic residues from production and packaging facilities. which represents a major drawback today due to the fact that cosmetic products such as for example foundations, mascaras, lipsticks are more and more hydrophobic and rich in pigments, in particular in oxides such as for example in titanium oxide.
  • a detergent composition for removing stains of oxidized grease adhering to the surfaces of floors, walls and kitchen implements containing a nonionic surfactant based on an amine oxide.
  • a nonionic surfactant based on an amine oxide improves the detergent power and at the same time acts as a solubilizing agent for the water-insoluble organic solvent also contained in the detergent composition.
  • this document also teaches that when the content of the amine oxide surfactant is less than 20% by weight, the detergency is insufficient to remove stains of oxidized fat or persistent stains of denatured fat.
  • a detergent composition which is based on the combination of a non-ionic surfactant, a co-surfactant and a specifically chosen organic alkaline agent. for its ability to effectively remove a wide range of hydrophobic residues typically encountered in the manufacture and packaging of cosmetic and pharmaceutical preparations.
  • residues can for example be finished products, such as foundations, sunscreens, lipsticks, mascaras, toothpastes, etc., semi-finished products such as bases for foundation, creams, etc. or raw materials such as for example gels and silicones, volatile or not, containing modified clays such as hectorite and its derivatives.
  • This specific combination of a nonionic surfactant, a co-surfactant and an organic alkaline agent makes it possible to effectively remove even extremely hydrophobic residues, containing or not containing pigments, from manufacturing and packaging facilities. as well as any other material used in the manufacture or packaging of cosmetic or pharmaceutical preparations. These other materials include in particular stainless steel buckets, spatulas, transfer and suction pipes, transfer and suction pumps, dosing nozzles, filling nozzles for packaging lines.
  • a detergent based on this combination specific removes a wide range of different residues such as foundation, lipsticks, waterproof mascaras, toothpastes, extremely hydrophobic raw materials containing pigments such as for example modified clays such as hectorite and its derivatives, in particular bentones.
  • the alkoxylated nonionic surfactant chosen from alkoxylated fatty alcohols is a mixture of several alkoxylated fatty alcohols. Such a mixture contains ethoxylated, propoxylated, butoxylated and optionally pentoxylated fatty alcohols.
  • the alkoxylated fatty alcohol (s) are alkoxylated branched C5 to C11 fatty alcohols.
  • a preferred nonionic surfactant of the invention contains a mixture of ethoxylated, propoxylated, butoxylated and optionally pentoxylated branched C5 to C11 fatty alcohols.
  • the short branched chain confers a high critical micellar concentration (CMC), thus limiting the formation of micelles at low doses (availability of surfactants for detergency), the hydrophilic part, composed of d oxide units.
  • CMC critical micellar concentration
  • the hydrophilic part composed of d oxide units.
  • the steric hindrance resulting from the presence of butylene oxide contributes to stabilizing this surfactant in an acaline medium.
  • These surfactants combine a high wetting power with a very low foaming effect and are also biodegradable.
  • nonionic surfactants which are particularly suitable for the present invention are the alkoxylated fatty alcohols sold by the company BASF (Ludwigshafen, Germany) under the name Plurafac® LF, in particular Plurafac® LF 305, Plurafac® LF 120 and Plurafac® LF 711.
  • the alkoxylated nonionic surfactant is advantageously contained in the detergent composition in an amount of 3 to 20%, preferably 5 to 15%, more preferably 5 to 10% and more preferably still about 10% by weight relative to the total weight of the composition.
  • the non-aromatic co-surfactant is chosen from amine-oxides, alkylsulphates and alkylsulphonates.
  • the amine oxides include in particular C10 to C16 alkyl dimethyl amine oxides.
  • a preferred amine oxide is N, N-dimethyl decyl amine oxide, sold for example under the name Ammonyx® DO40 by the company Stepan (Stepan Europe, Voreppe, France).
  • For the alkylsulphates and alkylsulphonates they may in particular be sodium, potassium or ammonium, preferably sodium, sulphates and sulphonates.
  • Alkyl sulphates include in particular C 6 to C 10 alkyl sulphates.
  • alkylsulfate is 2-ethylhexylsulfate, sold under the name EMPICOL® 0585 / U (Huntsman).
  • Alkylsulfonates include in particular C6 to C8 alkylsulfonates.
  • An example of such a commercial alkylsulfonate is BIO-TERGE® PAS-7S marketed by the company Stepan (Stepan Europe, Voreppe, France).
  • the non-aromatic co-surfactant is contained in the detergent composition in an amount of 1 to 15%, preferably 3 to 10%, more preferably 3 to 6% and more preferably still about 6% by weight relative to the total weight of the composition.
  • an organic alkaline agent chosen from amino alcohols, excluding monoethanolamine, has the advantage of providing a reserve of alkalinity without damaging materials sensitive to corrosion or exhibiting a strong tendency to carbonation.
  • an organic alkaline agent chosen from amino alcohols, excluding monoethanolamine, has the advantage of providing a reserve of alkalinity without damaging materials sensitive to corrosion or exhibiting a strong tendency to carbonation.
  • chosen from triethanolamine and 2-amino-2-methyl-1-propanol more preferably the aminoalcohol is triethanolamine.
  • the organic alkaline agent chosen from amino alcohols is advantageously contained in the detergent composition in an amount of 5 to 50%, preferably 10 to 40% and more preferably still from 15 to 30% by weight relative to the total weight of the product. composition.
  • the detergent composition used in accordance with the invention may further comprise an aromatic hydrotrope.
  • This hydrotropic agent aromatic can for example be chosen from xylenesulphonates, toluenesulphonates and cumenesulphonates. They can in particular be sodium, potassium or ammonium sulphonates, preferably sodium. Xylenesulphonates being preferred since they make it possible to monitor the concentration of the detergent, in particular in the rinsing water, by HPLC. Those skilled in the art will know how to adapt the amount of aromatic hydrotrope as a function in particular of the amounts of organic alkaline agent and of alkoxylated nonionic surfactants employed.
  • the detergent composition used in accordance with the invention may further comprise an alkali hydroxide.
  • the detergent composition comprises less than 5%, more preferably less than 3% and more preferably still less than 2% by weight of alkali hydroxide relative to the total weight of the detergent composition.
  • the alkaline hydroxide can in particular be chosen from sodium hydroxide and potassium hydroxide.
  • the detergent composition used in accordance with the invention may further comprise other adjuvants such as, for example, third solvents, such as propylene glycol or ethylene glycol, and / or antiflocculant agents.
  • the antiflocculant agents can for example be phosphonic acids and their alkali metal salts (phosphonates), such as, for example, 1-hydroxy-ethane-1,1-diphosphonic acid, aminotrismethylene-phosphonic acid, ethylenediaminotetramethylene-phosphonic acid, phosphonobutanetricarboxylic acid, diethylenetriamine penta (methylene phosphonic acid; or homo-, co- or terpolymers based on acrylic acid or alkali metal salts thereof (polyacrylates).
  • phosphonic acids and their alkali metal salts phosphonates
  • phosphonates such as, for example, 1-hydroxy-ethane-1,1-diphosphonic acid, aminotrismethylene-phosphonic acid, ethylenediaminotetramethylene-phosphonic
  • the ready-to-use detergent composition generally has a pH of 7 to 13, preferably 8 to 12.
  • the detergent composition contains neither polyaspartic acid nor gluconic acid or one of their salts.
  • the detergent composition is advantageously used at a temperature of 40 to 85 ° C, preferably from 55 to 70 ° C, more preferably from 60 to 70 ° C and more preferably around 65 ° C.
  • the detergent composition is used in a dynamic cleaning system with turbulence.
  • the dynamic cleaning system with turbulence is chosen from cleaning in place, soaking with agitation, washing in a closed circuit via washing balls, cleaning in a washer and cleaning in the washing cabin.
  • the present invention also relates to the detergent composition used in the use according to the invention as described above.
  • This composition may be in the form of a concentrate to be diluted with water, preferably softened, demineralized or osmosed, before use or in the form of a ready-to-use solution.
  • Figure 4 Photos of whitening toothpaste residues before and after the performance test with KOPHANIOS CIP MAXI PP (Laboratoires Anios) and composition C7 according to the invention.
  • compositions with amine oxide A.1. Compositions with amine oxide
  • Table 1 gives the composition of nine of these compositions, the other two compositions were respectively KOPHANIOS CIP MAXI PP (Laboratoires Anios, Hellemmes, France) and the detergent of Example 3 of the patent application EP 1,200,544 .
  • compositions with alkylsulfate or alkylsulfonate are provided with alkylsulfate or alkylsulfonate
  • the detergency is quantified by visual assessment (remaining product, traces, shine, etc.).
  • composition C7 is clearly more efficient than the reference product KOPHANIOS CIP MAXI PP on all the residues tested and composition C9 shows performances of the same level as those of composition C7.

Description

La présente invention concerne l'utilisation de compositions détergentes pour le nettoyage d'équipements de fabrication, de conditionnement ou de tout autre matériel servant à la fabrication ou au conditionnement de préparations cosmétiques ou pharmaceutiques hydrophobes. L'invention concerne également de telles compositions détergentes en tant que telles.The present invention relates to the use of detergent compositions for cleaning manufacturing equipment, packaging or any other equipment used in the manufacture or packaging of hydrophobic cosmetic or pharmaceutical preparations. The invention also relates to such detergent compositions as such.

Les équipements de fabrication et de conditionnement ainsi que tout autre matériel servant à la fabrication et au conditionnement de produits cosmétiques et pharmaceutiques sont généralement nettoyés à l'aide de système dynamique avec turbulence. Ces systèmes dynamiques comprennent notamment le « nettoyage en place » (NEP, en anglais « clean in place » ou CIP), le trempage avec forte agitation, le lavage en circuit fermé via des boules de lavage, le nettoyage en laveur et le nettoyage en cabine de lavage.Manufacturing and packaging equipment as well as any other equipment used in the manufacture and packaging of cosmetic and pharmaceutical products are generally cleaned using a dynamic system with turbulence. These dynamic systems include in particular "cleaning in place" (CIP, in English "clean in place" or CIP), soaking with strong agitation, washing in a closed circuit via washing balls, cleaning in washer and cleaning in washing cabin.

Ces systèmes de nettoyage nécessitent des détergents spécifiques non moussant pour éviter la formation de mousse en raison des turbulences créées dans le système. Ces détergents sont en général fortement alcalins et contiennent de ce fait d'importantes quantités d'hydroxyde alcalin ainsi que des tensioactifs et agents de séquestration et d'antifloculation.These cleaning systems require specific non-foaming detergents to prevent the formation of foam due to the turbulence created in the system. These detergents are generally strongly alkaline and therefore contain significant amounts of alkali hydroxide as well as surfactants and sequestering and antiflocculation agents.

La demande de brevet européen EP 1 200 544 décrit par exemple un détergent alcalin pour l'élimination de résidus contenant des pigments apparaissant lors de la fabrication ou du conditionnement de produits pharmaceutiques ou cosmétiques. Ce détergent contient des tensioactifs, notamment non ioniques comme des alcools gras alcoxylés, des alkylpolyglucosides et/ou des amines grasses alcoxylés, et une combinaison d'acide polyaspartique et d'acide gluconique ou de leurs sels comme agents complexant. Toutefois, ce détergent ne permet pas l'élimination de résidus fortement hydrophobes des installations de production et de conditionnement ce qui représente un inconvénient majeur aujourd'hui du fait que les produits cosmétiques tels que par exemple fonds de teints, mascaras, rouges à lèvre sont de plus en plus hydrophobes et riches en pigments, notamment en oxydes tel que par exemple en oxyde de titane.The European patent application EP 1,200,544 describes for example an alkaline detergent for the elimination of residues containing pigments appearing during the manufacture or packaging of pharmaceutical or cosmetic products. This detergent contains surfactants, in particular nonionic such as alkoxylated fatty alcohols, alkylpolyglucosides and / or alkoxylated fatty amines, and a combination of polyaspartic acid and gluconic acid or of their salts as complexing agents. However, this detergent does not allow the removal of highly hydrophobic residues from production and packaging facilities. which represents a major drawback today due to the fact that cosmetic products such as for example foundations, mascaras, lipsticks are more and more hydrophobic and rich in pigments, in particular in oxides such as for example in titanium oxide.

Du document WO 99/53003 A1 , on connaît une composition détergente pour enlever des tâches de graisse oxydée adhérant aux surfaces de sol, murs et d'instruments de cuisine contenant un tensioactif non ionique à base d' amine-oxyde. Ce document enseigne que l'amine-oxyde améliore le pouvoir détergent et agit en même temps comme agent solubilisant pour le solvant organique insoluble dans l'eau également contenu dans la composition détergente. Toutefois, ce document enseigne également que lorsque la teneur en tensioactif à base d'amine-oxyde est inférieure à 20% en poids, le pouvoir détergent est insuffisant pour enlever des tâches de graisse oxydée ou des tâches persistentes de graisse dénaturée.Of the document WO 99/53003 A1 , a detergent composition is known for removing stains of oxidized grease adhering to the surfaces of floors, walls and kitchen implements containing a nonionic surfactant based on an amine oxide. This document teaches that the amine oxide improves the detergent power and at the same time acts as a solubilizing agent for the water-insoluble organic solvent also contained in the detergent composition. However, this document also teaches that when the content of the amine oxide surfactant is less than 20% by weight, the detergency is insufficient to remove stains of oxidized fat or persistent stains of denatured fat.

Il existe donc un besoin de nouveaux détergents permettant de nettoyer efficacement des résidus très hydrophobes, contenant des pigments ou non, rencontrés lors de la fabrication de produits cosmétiques et pharmaceutiques.There is therefore a need for new detergents making it possible to effectively clean very hydrophobic residues, containing or not containing pigments, encountered during the manufacture of cosmetic and pharmaceutical products.

Il est du mérite de la Demanderesse d'avoir mis au point au fruit de nombreuses recherches une nouvelle composition détergente répondant à ces exigences.The Applicant deserves credit for having developed, as a result of a great deal of research, a new detergent composition meeting these requirements.

Il est du mérite de la Demanderesse d'avoir trouvé que ces inconvénients pouvaient être palliés en utilisant une composition détergente qui repose sur la combinaison d'un tensioactif non-ioniqiue, d'un co-tensioactif et d'un agent alcalin organique spécifiquement choisie pour sa capacité à éliminer efficacement une large gamme de résidus hydrophobes typiquement rencontrés lors de la fabrication et du conditionnement de préparations cosmétiques et pharmaceutiques. Ces résidus peuvent par exemple être des produits finis, comme des fonds de teints, des crèmes solaires, rouges à lèvre, mascaras, dentifrices etc., des produits semi finis comme des bases pour fond de teint, crèmes, etc. ou des matières premières comme par exemple des gels et silicones, volatiles ou non, contenant des argiles modifiées telles que l'hectorite et ses dérivés.It is to the Applicant's merit to have found that these drawbacks could be overcome by using a detergent composition which is based on the combination of a non-ionic surfactant, a co-surfactant and a specifically chosen organic alkaline agent. for its ability to effectively remove a wide range of hydrophobic residues typically encountered in the manufacture and packaging of cosmetic and pharmaceutical preparations. These residues can for example be finished products, such as foundations, sunscreens, lipsticks, mascaras, toothpastes, etc., semi-finished products such as bases for foundation, creams, etc. or raw materials such as for example gels and silicones, volatile or not, containing modified clays such as hectorite and its derivatives.

L'invention concerne donc l'utilisation d'une composition détergente pour l'élimination de résidus hydrophobes, contenant des pigments ou non, des surfaces d'équipements de fabrication, de conditionnement ou de tout autre matériel servant à la fabrication ou au conditionnement de préparations cosmétiques ou pharmaceutiques, ladite composition détergente comprenant :

  • un tensioactif non ionique choisi parmi les alcools gras alcoxylés,
  • un co-tensioactif non aromatique choisi parmi les amine-oxydes, les alkylsulfates et les alkylsulfonates, et
  • un agent alcalin organique choisi parmi les aminoalcools, à l'exclusion de la monoéthanolamine,
le tensioactif non-ionique étant un mélange d'alcools gras alcoxylés contenant des alcools gras éthoxylés, propoxylés et butoxylés, et la teneur en co-tensioactif non aromatique étant contenu dans la composition détergente dans une quantité de 1 à 15 % en poids par rapport au poids total de la composition.The invention therefore relates to the use of a detergent composition for the removal of hydrophobic residues, whether or not containing pigments, from the surfaces of manufacturing equipment, packaging or any other material used in the manufacture or packaging of cosmetic or pharmaceutical preparations, said detergent composition comprising:
  • a nonionic surfactant chosen from alkoxylated fatty alcohols,
  • a non-aromatic co-surfactant chosen from amine-oxides, alkylsulphates and alkylsulphonates, and
  • an organic alkaline agent chosen from aminoalcohols, excluding monoethanolamine,
the nonionic surfactant being a mixture of alkoxylated fatty alcohols containing ethoxylated, propoxylated and butoxylated fatty alcohols, and the content of non-aromatic co-surfactant being contained in the detergent composition in an amount of 1 to 15% by weight relative to the total weight of the composition.

Cette combinaison spécifique d'un tensioactif non-ionique, d'un co-tensioactif et d'un agent alcalin organique permet en effet d'enlever efficacement les résidus même extrêmement hydrophobes, contenant des pigments ou non, des installations de fabrication et de conditionnement ainsi que de tout autre matériel servant à la fabrication ou au conditionnement de préparations cosmétiques ou pharmaceutiques. Ces autres matériels comprennent notamment les seaux en acier inoxydable, spatules, tuyaux de transfert et d'aspiration, pompes de transfert et d'aspiration, becs de dosage, becs de remplissage des lignes de conditionnement.This specific combination of a nonionic surfactant, a co-surfactant and an organic alkaline agent makes it possible to effectively remove even extremely hydrophobic residues, containing or not containing pigments, from manufacturing and packaging facilities. as well as any other material used in the manufacture or packaging of cosmetic or pharmaceutical preparations. These other materials include in particular stainless steel buckets, spatulas, transfer and suction pipes, transfer and suction pumps, dosing nozzles, filling nozzles for packaging lines.

Contrairement aux détergents utilisés dans l'état de la technique, l'utilisation selon l'invention d'un détergent reposant sur cette combinaison spécifique permet d'enlever une large gamme de résidus différents tels que fond de teints, rouges à lèvre, mascaras waterproof, dentifrices, matières premières extrêmement hydrophobes contenant des pigments comme par exemple des argiles modifiées telles que l'hectorite et ses dérivés, notamment les bentones.Unlike the detergents used in the state of the art, the use according to the invention of a detergent based on this combination specific removes a wide range of different residues such as foundation, lipsticks, waterproof mascaras, toothpastes, extremely hydrophobic raw materials containing pigments such as for example modified clays such as hectorite and its derivatives, in particular bentones.

Le tensioactif non ionique alcoxylé choisi parmi les alcools gras alcoxylés est un mélange de plusieurs alcools gras alcoxylés. Un tel mélange contient des alcools gras éthoxylés, propoxylés, butoxylés et éventuellement pentoxylés. De préférence, le ou les alcools gras alcoxylés sont des alcools gras ramifiés en C5 à C11 alcoxylés. Ainsi, un tensioactif non ionique préféré de l'invention contient un mélange d'alcools gras ramifiés en C5 à C11 éthoxylés, propoxylés, butoxylés et éventuellement pentoxylés. Dans ce type de tensioactif, la courte chaine ramifiée confère une concentration micellaire critique (CMC) élevée, limitant ainsi la formation de micelles à faible dose (disponibilité des tensioactifs à la détergence), la partie hydrophile, composée d'unités d'oxyde d'éthylène, d'oxyde de propyèlene et notamment d'oxyde de butylène, et éventuellement d'oxyde de pentylène, confère au tensioactif un effet antimoussant très prononcé. De plus, l'encombrement stérique conséquence de la présence d'oxyde de butylène participe à stabiliser ce tensioactif en milieu acalin. Ces tensioactifs allient un fort pouvoir mouillant avec un très faible effet moussant et sont en plus biodégradables. Des exemples de tensioactifs non ioniques particulièrement adaptés pour la présente invention sont les alcools gras alcoxylés commercialisés par la société BASF (Ludwigshafen, Allemagne) sous la dénomination Plurafac® LF, notamment Plurafac® LF 305, Plurafac® LF 120 et Plurafac® LF 711.The alkoxylated nonionic surfactant chosen from alkoxylated fatty alcohols is a mixture of several alkoxylated fatty alcohols. Such a mixture contains ethoxylated, propoxylated, butoxylated and optionally pentoxylated fatty alcohols. Preferably, the alkoxylated fatty alcohol (s) are alkoxylated branched C5 to C11 fatty alcohols. Thus, a preferred nonionic surfactant of the invention contains a mixture of ethoxylated, propoxylated, butoxylated and optionally pentoxylated branched C5 to C11 fatty alcohols. In this type of surfactant, the short branched chain confers a high critical micellar concentration (CMC), thus limiting the formation of micelles at low doses (availability of surfactants for detergency), the hydrophilic part, composed of d oxide units. ethylene, propyelene oxide and in particular butylene oxide, and optionally pentylene oxide, gives the surfactant a very pronounced antifoaming effect. In addition, the steric hindrance resulting from the presence of butylene oxide contributes to stabilizing this surfactant in an acaline medium. These surfactants combine a high wetting power with a very low foaming effect and are also biodegradable. Examples of nonionic surfactants which are particularly suitable for the present invention are the alkoxylated fatty alcohols sold by the company BASF (Ludwigshafen, Germany) under the name Plurafac® LF, in particular Plurafac® LF 305, Plurafac® LF 120 and Plurafac® LF 711.

Le tensioactif non ionique alcoxylé est avantageusement contenu dans la composition détergente dans une quantité de 3 à 20 %, de préférence de 5 à 15 %, plus préférentiellement de 5 à 10 % et plus préférentiellement encore d'environ 10 % en poids par rapport au poids total de la composition.The alkoxylated nonionic surfactant is advantageously contained in the detergent composition in an amount of 3 to 20%, preferably 5 to 15%, more preferably 5 to 10% and more preferably still about 10% by weight relative to the total weight of the composition.

Le co-tensioactif non aromatique est choisi parmi les amine-oxydes, les alkylsulfates et les alkylsulfonates. Les amine-oxydes comprennent notamment les alkyles en C10 à C16 diméthyl amine-oxydes. Un amine-oxyde préféré est le N,N-diméthyl décyl amine-oxyde, commercialisé par exemple sous la dénomination Ammonyx® DO40 par la société Stepan (Stepan Europe, Voreppe, France). Pour les alkylsulfates et alkylsulfonates, il peut notamment s'agir des sulfates et sulfonates de sodium, de potassium ou d'ammonium, de préférence de sodium. Les alkylsulfates comprennent notamment les alkylsulfates en C6 à C10. Un alkylsulfate préféré est le 2-éthylhexylsulfate, commercialisé sous la dénomination EMPICOL® 0585 / U (Huntsman). Les alkylsulfonates comprennent notamment les alkylsulfonates en C6 à C8. Un exemple d'un tel alkylsulfonate commercial est le BIO-TERGE® PAS-7S commercialisé par la société Stepan (Stepan Europe, Voreppe, France).The non-aromatic co-surfactant is chosen from amine-oxides, alkylsulphates and alkylsulphonates. The amine oxides include in particular C10 to C16 alkyl dimethyl amine oxides. A preferred amine oxide is N, N-dimethyl decyl amine oxide, sold for example under the name Ammonyx® DO40 by the company Stepan (Stepan Europe, Voreppe, France). For the alkylsulphates and alkylsulphonates, they may in particular be sodium, potassium or ammonium, preferably sodium, sulphates and sulphonates. Alkyl sulphates include in particular C 6 to C 10 alkyl sulphates. A preferred alkylsulfate is 2-ethylhexylsulfate, sold under the name EMPICOL® 0585 / U (Huntsman). Alkylsulfonates include in particular C6 to C8 alkylsulfonates. An example of such a commercial alkylsulfonate is BIO-TERGE® PAS-7S marketed by the company Stepan (Stepan Europe, Voreppe, France).

Le co-tensioactif non aromatique est contenu dans la composition détergente dans une quantité de 1 à 15 %, de préférence de 3 à 10 %, plus préférentiellement de 3 à 6 % et plus préférentiellement encore d'environ 6 % en poids par rapport au poids total de la composition.The non-aromatic co-surfactant is contained in the detergent composition in an amount of 1 to 15%, preferably 3 to 10%, more preferably 3 to 6% and more preferably still about 6% by weight relative to the total weight of the composition.

L'utilisation d'un agent alcalin organique choisi parmi les aminoalcools, à l'exclusion de la monoéthanolamine, présente l'avantage d'apporter une réserve d'alcalinité sans détériorer les matériaux sensibles à la corrosion ni présenter une forte tendance à la carbonatation. De préférence, choisi parmi la triéthanolamine et le 2-amino-2-methyl-1-propanol, plus préférentiellement l'aminoalcool est la triéthanolamine.The use of an organic alkaline agent chosen from amino alcohols, excluding monoethanolamine, has the advantage of providing a reserve of alkalinity without damaging materials sensitive to corrosion or exhibiting a strong tendency to carbonation. . Preferably, chosen from triethanolamine and 2-amino-2-methyl-1-propanol, more preferably the aminoalcohol is triethanolamine.

L'agent alcalin organique choisi parmi les aminoalcools est avantageusement contenu dans la composition détergente dans une quantité de 5 à 50 %, de préférence de 10 à 40 % et plus préférentiellement encore de 15 à 30 % en poids par rapport au poids total de la composition.The organic alkaline agent chosen from amino alcohols is advantageously contained in the detergent composition in an amount of 5 to 50%, preferably 10 to 40% and more preferably still from 15 to 30% by weight relative to the total weight of the product. composition.

La composition détergente utilisée conformément à l'invention peut en outre comprendre un hydrotrope aromatique. Cet agent hydrotrope aromatique peut par exemple être choisi parmi les xylènesulfonates, les toluènesulfonates et les cumènes sulfonates. Il peut notamment s'agir des sulfonates de sodium, de potassium ou d'ammonium, de préférence de sodium. Les xylènesulfonates étant préférés puisqu'ils permettent de suivre la concentration du détergent, notamment dans les eaux de rinçage, par HPLC. L'homme du métier saura adapter la quantité d'hydrotrope aromatique en fonction notamment des quantités d'agent alcalin organique et de tensioactifs non ionique alcoxylés employées.The detergent composition used in accordance with the invention may further comprise an aromatic hydrotrope. This hydrotropic agent aromatic can for example be chosen from xylenesulphonates, toluenesulphonates and cumenesulphonates. They can in particular be sodium, potassium or ammonium sulphonates, preferably sodium. Xylenesulphonates being preferred since they make it possible to monitor the concentration of the detergent, in particular in the rinsing water, by HPLC. Those skilled in the art will know how to adapt the amount of aromatic hydrotrope as a function in particular of the amounts of organic alkaline agent and of alkoxylated nonionic surfactants employed.

La composition détergente utilisée conformément à l'invention peut en outre comprendre un hydroxyde alcalin. De préférence, composition détergente comprend moins de 5%, plus préférentiellement moins de 3% et plus préférentiellement encore moins de 2% en poids d'hydroxyde alcalin par rapport au poids total de la composition détergente. L'hydroxyde alcalin peut notamment être choisi parmi l'hydroxyde de sodium et l'hydroxyde de potassium.The detergent composition used in accordance with the invention may further comprise an alkali hydroxide. Preferably, the detergent composition comprises less than 5%, more preferably less than 3% and more preferably still less than 2% by weight of alkali hydroxide relative to the total weight of the detergent composition. The alkaline hydroxide can in particular be chosen from sodium hydroxide and potassium hydroxide.

La composition détergente utilisée conformément à l'invention peut en outre comprendre d'autres adjuvants tels que par exemple des tiers solvants, tels que le propylène glycol ou l'éthylène glycol, et/ou des agents antifloculants. Les agents antifloculants peuvent par exemple être des acides phosphoniques et leurs sels alcalins (phosphonates), comme par exemple l'acide 1-hydroxy-éthane-1,1-diphosphonique, l'acide aminotrisméthylène-phosphonique, l'acide éthylènediaminotétraméthylène-phosphonique, l'acide phosphonobutanetricarboxylique, l'acide diethylènetriamine penta(méthylène phosphonique ; ou des homo-, co- ou terpolymères à base d'acide acrylique ou des sels de métaux alcalins de ceux-ci (polyacrylates).The detergent composition used in accordance with the invention may further comprise other adjuvants such as, for example, third solvents, such as propylene glycol or ethylene glycol, and / or antiflocculant agents. The antiflocculant agents can for example be phosphonic acids and their alkali metal salts (phosphonates), such as, for example, 1-hydroxy-ethane-1,1-diphosphonic acid, aminotrismethylene-phosphonic acid, ethylenediaminotetramethylene-phosphonic acid, phosphonobutanetricarboxylic acid, diethylenetriamine penta (methylene phosphonic acid; or homo-, co- or terpolymers based on acrylic acid or alkali metal salts thereof (polyacrylates).

La composition détergente prête à l'emploi présente généralement un pH de 7 à 13, de préférence de 8 à 12.The ready-to-use detergent composition generally has a pH of 7 to 13, preferably 8 to 12.

Dans un mode de réalisation particulier, la composition détergente ne contient ni acide polyaspartique ni acide gluconique ou l'un de leurs sels.In a particular embodiment, the detergent composition contains neither polyaspartic acid nor gluconic acid or one of their salts.

Dans l'utilisation selon l'invention, la composition détergente est avantageusement mise en œuvre à une température de 40 à 85 °C, de préférence de 55 à 70 °C, plus préférentiellement de 60 à 70°C et plus préférentiellement d'environ 65°C.In the use according to the invention, the detergent composition is advantageously used at a temperature of 40 to 85 ° C, preferably from 55 to 70 ° C, more preferably from 60 to 70 ° C and more preferably around 65 ° C.

Selon un mode de réalisation préféré de l'utilisation selon l'invention, la composition détergente est mise en œuvre dans un système de nettoyage dynamique avec turbulence. Avantageusement, le système de nettoyage dynamique avec turbulence est choisi parmi le nettoyage en place, le trempage avec agitation, le lavage en circuit fermé via des boules de lavage, le nettoyage en laveur et le nettoyage en cabine de lavage.According to a preferred embodiment of the use according to the invention, the detergent composition is used in a dynamic cleaning system with turbulence. Advantageously, the dynamic cleaning system with turbulence is chosen from cleaning in place, soaking with agitation, washing in a closed circuit via washing balls, cleaning in a washer and cleaning in the washing cabin.

La présente invention porte également sur la composition détergente mise en œuvre dans l'utilisation selon l'invention telle que décrite ci-dessus. Cette composition peut se présenter sous forme d'un concentré à diluer avec de l'eau, préférentiellement adoucie, déminéralisée ou osmosée, avant emploi ou sous forme d'une solution prête à l'emploi.The present invention also relates to the detergent composition used in the use according to the invention as described above. This composition may be in the form of a concentrate to be diluted with water, preferably softened, demineralized or osmosed, before use or in the form of a ready-to-use solution.

L'invention sera maintenant décrite à l'aide d'exemples non limitatifs de réalisation de l'invention.The invention will now be described with the aid of non-limiting examples of embodiment of the invention.

FIGURESFIGURES

  • Figure 1 : Photos de résidus de crème hydratante teintée - peau sèche avant et après le test de performance avec le KOPHANIOS CIP MAXI PP (Laboratoires Anios) et la composition C7 selon l'invention. Figure 1 : Photos of tinted moisturizer residue - dry skin before and after the performance test with KOPHANIOS CIP MAXI PP (Laboratoires Anios) and composition C7 according to the invention.
  • Figure 2 : Photos de résidus de rouge à lèvre avant et après le test de performance avec le KOPHANIOS CIP MAXI PP (Laboratoires Anios) et la composition C7 selon l'invention. Figure 2 : Photos of lipstick residues before and after the performance test with KOPHANIOS CIP MAXI PP (Laboratoires Anios) and composition C7 according to the invention.
  • Figure 3 : Photos de résidus de mascara waterproof noir avant et après le test de performance avec le KOPHANIOS CIP MAXI PP (Laboratoires Anios) et la composition C7 selon l'invention. Figure 3 : Photos of black waterproof mascara residue before and after the performance test with the KOPHANIOS CIP MAXI PP (Laboratoires Anios) and the composition C7 according to the invention.

Figure 4 : Photos de résidus de dentifrice blancheur avant et après le test de performance avec le KOPHANIOS CIP MAXI PP (Laboratoires Anios) et la composition C7 selon l'invention. Figure 4 : Photos of whitening toothpaste residues before and after the performance test with KOPHANIOS CIP MAXI PP (Laboratoires Anios) and composition C7 according to the invention.

EXEMPLESEXAMPLES

Plusieurs compositions détergentes ont été évaluées pour leur capacité à éliminer différents résidus rencontrés typiquement dans la fabrication de produits cosmétiques.Several detergent compositions have been evaluated for their ability to remove various residues typically encountered in the manufacture of cosmetic products.

A. Compositions détergentes testéesA. Detergent compositions tested A.1. Compositions avec amine-oxydeA.1. Compositions with amine oxide

Neuf compositions détergentes dont six selon l'invention (C4 à C9) ont été préparées et testées. Deux compositions de l'état de la technique ont également été testées.Nine detergent compositions, six of which according to the invention (C4 to C9) were prepared and tested. Two compositions of the state of the art were also tested.

Le tableau 1 donne la composition de neuf de ces compositions, les deux autres compositions étaient respectivement KOPHANIOS CIP MAXI PP (Laboratoires Anios, Hellemmes, France) et le détergent de l'exemple 3 de la demande de brevet EP 1 200 544 . Composition (% en poids/poids total) C1 C2 C3 C4 C5 C6 C7 C8 C9 Eau déminéralisée qsp Plurafac LF 305 (alcool gras alcoxylé) 0 10 10 5 10 10 10 10 10 Ammonyx® DO 40 (co-tensiactif) 6 0 6 6 3 6 6 1 15 Triéthanolamine 30 30 0 30 30 15 30 30 30 NaOH 1,5 Xylènesulfonate de sodium 6 Diproplylèneglycolbutoxyéther 10 Dequest 2066 (DTPMP) 0,125 Table 1 gives the composition of nine of these compositions, the other two compositions were respectively KOPHANIOS CIP MAXI PP (Laboratoires Anios, Hellemmes, France) and the detergent of Example 3 of the patent application EP 1,200,544 . Composition (% by weight / total weight) C1 C2 C3 C4 C5 C6 C7 C8 C9 Demineralized Water qsp Plurafac LF 305 (alkoxylated fatty alcohol) 0 10 10 5 10 10 10 10 10 Ammonyx® DO 40 (co-surfactant) 6 0 6 6 3 6 6 1 15 Triethanolamine 30 30 0 30 30 15 30 30 30 NaOH 1.5 Sodium xylenesulfonate 6 Diproplyleneglycolbutoxyether 10 Dequest 2066 (DTPMP) 0.125

A.2. Compositions avec alkylsulfate ou alkylsulfonateA.2. Compositions with alkylsulfate or alkylsulfonate

Neuf compositions détergentes (C10 à C18) dont six selon l'invention (C14 à C18) dans lesquels le co-tensioactif est un alkylsufate ou un alkylsulfonate ont été préparées. Le tableau 2 donne la composition de chacune de ces compositions. Tableau 2 Composition (% en poids/poids total) C10 C11 C12 C13 C14 C15 C16 C17 C18 Eau déminéralisée Qsp Plurafac LF 305 (alcool gras alcoxylé) 0 0 10 10 5 10 10 10 10 2-éthylhexylsulfate 6 6 3 6 Sodium Alkane Sulfonate 6 6 6 3 6 Triéthanolamine 30 30 0 0 30 30 30 30 30 NaOH 1,5 Xylènesulfonate de sodium 6 Diproplylèneglycol butoxyéther 10 Dequest 2066 (DTPMP) 0,125 Nine detergent compositions (C10 to C18) including six according to the invention (C14 to C18) in which the co-surfactant is an alkylsulfate or an alkylsulfonate were prepared. Table 2 gives the composition of each of these compositions. <b> Table 2 </b> Composition (% by weight / total weight) C10 C11 C12 C13 C14 C15 C16 C17 C18 Demineralized Water Qsp Plurafac LF 305 (alkoxylated fatty alcohol) 0 0 10 10 5 10 10 10 10 2-ethylhexylsulfate 6 6 3 6 Sodium Alkane Sulfonate 6 6 6 3 6 Triethanolamine 30 30 0 0 30 30 30 30 30 NaOH 1.5 Sodium xylenesulfonate 6 Diproplylene glycol butoxyether 10 Dequest 2066 (DTPMP) 0.125

B. Essais de performanceB. Performance tests 1) Protocole d'essai1) Test protocol

Ces essais de performances ont été effectués selon le protocole d'essai suivant avec les compositions C1 à C19, Kophanios CIP MAXI PP (KCMPP) et le détergent de l'exemple 3 de la demande de brevet EP 1 200 544 , dilués à 5% v/v dans de l'eau adoucie.These performance tests were carried out according to the following test protocol with compositions C1 to C19, Kophanios CIP MAXI PP (KCMPP) and the detergent of Example 3 of the patent application EP 1,200,544 , diluted to 5% v / v in softened water.

Support: béchers en acier inoxydable de qualité 316 L d'un volume de 200 mL.

  1. 1) Dépôt d'une couche uniforme du produit à éliminer sur les parois interne du bécher.
  2. 2) Séchage à air ambiant pendant 10 minutes.
  3. 3) Remplissage au trois quart du bécher avec la solution détergente à tester.
  4. 4) Mise sous agitation de la solution à l'aide d'un barreau aimanté sur agitateur magnétique à une température de 65 ± 5°C pendant 30 min.
Support: 316 L grade stainless steel beakers with a volume of 200 mL.
  1. 1) Deposit of a uniform layer of the product to be eliminated on the internal walls of the beaker.
  2. 2) Dry in ambient air for 10 minutes.
  3. 3) Three quarters full of the beaker with the detergent solution to be tested.
  4. 4) Stirring of the solution using a bar magnet on a magnetic stirrer at a temperature of 65 ± 5 ° C for 30 min.

La quantification de la détergence se fait par appréciation visuelle (produit restant, traces, brillance, ...).The detergency is quantified by visual assessment (remaining product, traces, shine, etc.).

2) Résultats des essais2) Test results

Les essais de performance ont clairement démontré que seul les compositions détergentes contenant la combinaison spécifique d'un tensioactif non-ionique, d'un co-tensioactif et d'un agent alcalin organique permettent d'éliminer tous les résidus testés de façon satisfaisante. Les tableaux 3 et 4 ci-après résument les résultats. Tableau 3 Produit cosmétique C1 C2 C3 C4 C5 C6 C7 C8 C9 KOPHANIOS CIP MAXI PP EP1200544 - Ex. 3 Crème hydratante teintée - peau sèche - - + + + ++ ++ + ++ - + Rouge à lèvre - - + + + ++ ++ + ++ -- - Fond de teint -- - + + + ++ ++ + ++ -- n.e. Mascara waterproof noir -- - + + ++ ++ ++ + ++ - n.e. Dentifrice blancheur - - + + + ++ ++ ++ ++ + n.e. Bentone Gel VS-5V -- + - + ++ + ++ ++ ++ - - Tableau 4 Produit cosmétique C10 C11 C12 C13 C14 C15 C16 C17 C18 Crème hydratante teintée - peau sèche -- -- + + + - - ++ ++ Rouge à lèvre -- -- + + + + + + ++ Fond de teint -- -- + + + + + ++ ++ Mascara waterproof noir -- -- - - + + + + + Dentifrice blancheur - - + + + + + ++ ++ Bentone Gel VS-5V -- -- -- -- + ++ + ++ + -- : absence d'efficacité, pratiquement tout le résidu reste
- : légère détergence, sans effet significatif
+ : détergence correcte mais présence de quelques traces ou d'un léger voile terne sur la surface des inox,
++ : bon effet détersif, absence de voile terne et surface des inox brillante
n.e. : non évalué
The performance tests have clearly demonstrated that only detergent compositions containing the specific combination of a nonionic surfactant, a co-surfactant and an organic alkaline agent make it possible to remove all the residues tested in a satisfactory manner. Tables 3 and 4 below summarize the results. <b> Table 3 </b> Cosmetic product C1 C2 C3 C4 C5 C6 C7 C8 C9 KOPHANIOS CIP MAXI PP EP1200544 - Ex. 3 Tinted moisturizer - dry skin - - + + + ++ ++ + ++ - + Lipstick - - + + + ++ ++ + ++ - - Face powder - - + + + ++ ++ + ++ - born Black waterproof mascara - - + + ++ ++ ++ + ++ - born Whitening toothpaste - - + + + ++ ++ ++ ++ + born Bentone Gel VS-5V - + - + ++ + ++ ++ ++ - - Cosmetic product C10 C11 C12 C13 C14 C15 C16 C17 C18 Tinted moisturizer - dry skin - - + + + - - ++ ++ Lipstick - - + + + + + + ++ Face powder - - + + + + + ++ ++ Black waterproof mascara - - - - + + + + + Whitening toothpaste - - + + + + + ++ ++ Bentone Gel VS-5V - - - - + ++ + ++ + -: lack of efficacy, practically all the residue remains
-: slight detergency, no significant effect
+: correct detergency but presence of some traces or a slight dull veil on the stainless steel surface,
++: good detergent effect, no dull haze and shiny stainless steel surface
ne: not evaluated

Les photos reproduites aux figures 1 à 4 montrent la supériorité de la performance de nettoyage de la composition C7 par rapport au KOPHANIOS CIP MAXI PP. La composition C7 est nettement plus performante que le produit de référence KOPHANIOS CIP MAXI PP sur tous les résidus testés et la composition C9 montre des performances du même niveau que celles de la composition C7.The photos reproduced in figures 1 to 4 show the superior cleaning performance of composition C7 compared to KOPHANIOS CIP MAXI PP. Composition C7 is clearly more efficient than the reference product KOPHANIOS CIP MAXI PP on all the residues tested and composition C9 shows performances of the same level as those of composition C7.

Claims (15)

  1. Use of a detergent composition for eliminating hydrophobic residues, optionally containing pigments, from manufacturing equipment, packaging or any other material used for manufacturing or packaging cosmetic or pharmaceutical preparations, said detergent composition comprising
    alcohols
    - a non-aromatic cosurfactant chosen from amine oxides, alkyl sulfates and alkyl sulfonates, and
    - an organic alkaline agent chosen from amino alcohols, excluding monoethanolamine,
    the nonionic surfactant being a mixture of alkoxylated fatty alcohols containing ethoxylated, propoxylated and butoxylated fatty alcohols, and the non-aromatic cosurfactant content being contained in the detergent composition in a quantity of from 1% to 15% by weight with respect to the total weight of the composition.
  2. Use according to claim 1, characterised in that the nonionic surfactant is a mixture of alkoxylated fatty alcohols containing ethoxylated, propoxylated, butoxylated and pentoxylated fatty alcohols.
  3. Use according to claim 1 or 2, characterised in that the non-aromatic cosurfactant is an amine oxide, preferably a C10 to C16 N,N-dimethylalkylamine oxide, more preferentially N,N-dimethyldecylamine oxide.
  4. Use according to any one of claims 1 to 3, characterised in that the organic alkaline agent chosen from amino alcohols is triethanolamine.
  5. Use according to any one of claims 1 to 4, characterised in that the detergent composition further comprises an aromatic hydrotrope.
  6. Use according to any one of claims 1 to 5, characterised in that the detergent composition comprises less than 5% by weight alkaline hydroxide with respect to the total weight of the detergent composition.
  7. Use according to any one of claims 1 to 6, characterised in that the detergent composition is used at a temperature of 40° to 85°C.
  8. Use according to any one of claims 1 to 7, wherein the detergent composition is used in a dynamic cleaning system with turbulence.
  9. Use according to claim 8, wherein the dynamic cleaning system with turbulence is chosen from cleaning in place, soaking with stirring, washing in closed circuit via washing balls, cleaning in a washer and cleaning in a washing booth.
  10. Detergent composition comprising:
    - a nonionic surfactant chosen from alkoxylated fatty alcohols,
    - a non-aromatic cosurfactant chosen from amine oxides, alkyl sulfates and alkyl sulfonates, and
    - an organic alkaline agent chosen from amino alcohols, excluding monoethanolamine,
    the nonionic surfactant being a mixture of alkoxylated fatty alcohols containing ethoxylated, propoxylated and butoxylated fatty alcohols, and the non-aromatic cosurfactant content being contained in the detergent composition in a quantity of from 1% to 15% by weight with respect to the total weight of the composition.
  11. Detergent composition according to claim 10, characterised in that the nonionic surfactant is a mixture of alkoxylated fatty alcohols containing ethoxylated, propoxylated, butoxylated and pentoxylated fatty alcohols.
  12. Composition according to claim 10, characterised in that the non-aromatic cosurfactant is an amino oxide, preferably a C10 to C16 N,N-dimethylalkylamine oxide, more preferentially N,N-dimethyldecylamine oxide.
  13. Composition according to any one of claims 10 to 12, characterised in that the organic alkaline agent chosen from amino alcohols is triethanolamine.
  14. Composition according to any one of claims 10 to 13, characterised in that the detergent composition further comprises an aromatic hydrotrope.
  15. Composition according to any one of claims 10 to 14, characterised in that the detergent composition comprises less than 5% by weight alkaline hydroxide with respect to the total weight of the detergent composition.
EP17707631.2A 2016-02-05 2017-02-03 Detergent compositions for cleaning in the cosmetic and pharmaceutical industry Active EP3411464B1 (en)

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PL17707631T PL3411464T3 (en) 2016-02-05 2017-02-03 Detergent compositions for cleaning in the cosmetic and pharmaceutical industry

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0561103A1 (en) * 1992-03-17 1993-09-22 The Procter & Gamble Company Dilutable compositions and method for cleaning of hard surfaces

Family Cites Families (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8810188D0 (en) * 1988-04-29 1988-06-02 Unilever Plc Detergent composition
JPH0320212A (en) * 1989-06-17 1991-01-29 Nippon Oil & Fats Co Ltd Liquid detergent composition for body
EP0616027A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Concentrated cleaning compositions
US5567444A (en) 1993-08-30 1996-10-22 Ecolab Inc. Potentiated aqueous ozone cleaning and sanitizing composition for removal of a contaminating soil from a surface
US5582650A (en) * 1995-01-13 1996-12-10 International Paper Company Process for cleaning parts soiled or encrusted with polyester resin
US5770555A (en) 1995-11-20 1998-06-23 Rohm And Haas Company High alkali-containing cleaning concentrates
JP3085986B2 (en) * 1995-11-27 2000-09-11 ザ、プロクター、エンド、ギャンブル、カンパニー Laundry stain treatment composition and treatment method
AU3574297A (en) 1996-06-28 1998-01-21 Procter & Gamble Company, The Detergent composition
WO1998028392A1 (en) * 1996-12-20 1998-07-02 The Procter & Gamble Company Dishwashing detergent compositions containing alkanolamine
JPH10195489A (en) * 1996-12-28 1998-07-28 Lion Corp Liquid cleaner composition
JPH11302693A (en) * 1998-04-16 1999-11-02 Minnesota Mining & Mfg Co <3M> Concentrated detergent composition
DE19936179A1 (en) * 1999-07-31 2001-02-08 Henkel Ecolab Gmbh & Co Ohg Removal of pigment-containing residues in the pharmaceutical or cosmetic industry
US20050164902A1 (en) 2003-10-24 2005-07-28 Ecolab Inc. Stable compositions of spores, bacteria, and/or fungi
DE10038198A1 (en) * 2000-08-04 2002-02-21 Goldschmidt Ag Th Aqueous cleaning agent concentrates for rough, especially profiled tiles
JP2002060791A (en) * 2000-08-23 2002-02-26 Kao Corp Liquid detergent composition
JP2003238999A (en) * 2002-02-14 2003-08-27 Lion Corp Method for producing high concentration liquid detergent
US20040149311A1 (en) * 2002-11-15 2004-08-05 The Procter & Gamble Company Method for cleaning cookware and tableware with film-forming liquid dishwashing compositions, and compositions therefore
WO2004048363A1 (en) * 2002-11-22 2004-06-10 Takeda Pharmaceutical Company Limited Imidazole derivative, process for producing the same, and use
JP2005008703A (en) * 2003-06-17 2005-01-13 Lion Corp Mildewproofing method for hard surface
CA2640642C (en) * 2006-02-22 2014-06-10 Basf Se Surfactant mixture comprising short-chain and long-chain components
DE102006035013A1 (en) * 2006-07-28 2008-01-31 Schülke & Mayr GmbH System Cleaner Concentrate
US7691800B2 (en) * 2006-08-30 2010-04-06 B-Tech Ip Holdings, Llc Water-based cleaning agent and method for cleaning a spray gun
US7838485B2 (en) 2007-03-08 2010-11-23 American Sterilizer Company Biodegradable alkaline disinfectant cleaner with analyzable surfactant
GB0711992D0 (en) * 2007-06-21 2007-08-01 Reckitt Benckiser Inc Alkaline hard surface cleaning composition
US8247362B2 (en) * 2008-06-17 2012-08-21 Colgate-Palmolive Company Light duty liquid cleaning compositions and methods of manufacture and use thereof
EP2318495A1 (en) * 2008-06-17 2011-05-11 Colgate-Palmolive Company Light duty liquid cleaning compositions and methods of manufacture and use thereof
WO2010003934A1 (en) 2008-07-07 2010-01-14 Basf Se Enzyme composition comprising enzyme containing polymer particles
WO2010009305A2 (en) * 2008-07-17 2010-01-21 Delaval Holding Ab Method of cleaning food and beverage manufacturing and handling equipmemt
AU2009307047A1 (en) 2008-10-24 2010-04-29 Ixom Operations Pty Ltd Cleaning method
ES2840875T3 (en) * 2008-12-24 2021-07-07 Ecolab Usa Inc Cleaning composition
US8119588B2 (en) * 2009-01-21 2012-02-21 Stepan Company Hard surface cleaner compositions of sulfonated estolides and other derivatives of fatty acids and uses thereof
ES2472391T3 (en) * 2009-07-08 2014-07-01 The Procter & Gamble Company Hard surface cleaning composition
US20110150817A1 (en) * 2009-12-17 2011-06-23 Ricky Ah-Man Woo Freshening compositions comprising malodor binding polymers and malodor control components
JP5400601B2 (en) 2009-12-22 2014-01-29 花王株式会社 Detergent composition around rolling mill
CN102127491B (en) 2010-01-15 2013-02-27 谭钢 Bactericidal cleaning agent and preparation method thereof
JP5401359B2 (en) * 2010-02-16 2014-01-29 花王株式会社 Alkali detergent composition for hard surface
CA3111244C (en) 2011-01-05 2023-01-24 Ecolab Usa Inc. Aqueous acid cleaning, corrosion and stain inhibiting compositions in the vapor phase comprising a blend of nitric and sulfuric acid
US20120258903A1 (en) * 2011-04-07 2012-10-11 The Dial Corporation Sprayable liquid abrasive cleanser with polyethylene glycol
US8653015B2 (en) 2011-04-13 2014-02-18 American Sterilizer Company Environmentally friendly, multi-purpose refluxing cleaner
JP6306504B2 (en) 2011-07-01 2018-04-04 ノボザイムス アクティーゼルスカブ Liquid detergent composition
US20130150276A1 (en) * 2011-12-09 2013-06-13 The Procter & Gamble Company Method of providing fast drying and/or delivering shine on hard surfaces
JP2013133458A (en) * 2011-12-27 2013-07-08 Idemitsu Kosan Co Ltd Aqueous detergent
CA2861433C (en) * 2012-01-30 2019-09-03 Reckitt Benckiser Llc Stable, viscous, peroxide containing lavatory treatment compositions
US10093911B2 (en) 2012-02-17 2018-10-09 Novozymes A/S Subtilisin variants and polynucleotides encoding same
WO2014058462A1 (en) 2012-10-12 2014-04-17 The Research Foundation For The State University Of New York Electrophoresis controllers and methods for controlling electrophoresis process
CN103849498A (en) 2012-11-29 2014-06-11 埃科莱布美国股份有限公司 Cleaning additive and cleaning method adopting the cleaning additive
US9534190B2 (en) * 2012-12-20 2017-01-03 Ecolab Usa Inc. Citrate salt bathroom cleaners
CN103343060B (en) * 2013-07-17 2014-06-04 常熟奥首光电材料有限公司 Sapphire substrate wafer cleaning solution as well as preparation method, application and cleaning method thereof
EP3492571A1 (en) * 2014-05-02 2019-06-05 Novozymes A/S Detergent composition
US9677031B2 (en) 2014-06-20 2017-06-13 Ecolab Usa Inc. Catalyzed non-staining high alkaline CIP cleaner
JP2016011356A (en) 2014-06-27 2016-01-21 新日本理化株式会社 Acidic detergent composition for foam cleaning
WO2016046334A1 (en) 2014-09-25 2016-03-31 Novozymes A/S Use of enzyme for cleaning
US9957467B2 (en) * 2014-10-29 2018-05-01 The Procter & Gamble Company Hard surface cleaners comprising ethoxylated alkoxylated nonionic surfactants
WO2017079959A1 (en) * 2015-11-13 2017-05-18 The Procter & Gamble Company Detergent compositions
WO2017079958A1 (en) * 2015-11-13 2017-05-18 The Procter & Gamble Company Cleaning compositions containing a branched alkyl sulfate surfactant and a short-chain nonionic surfactant
FR3047488B1 (en) * 2016-02-05 2020-02-28 Laboratoires Anios DETERGENT COMPOSITIONS FOR CLEANING IN THE COSMETIC AND PHARMACEUTICAL INDUSTRY.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0561103A1 (en) * 1992-03-17 1993-09-22 The Procter & Gamble Company Dilutable compositions and method for cleaning of hard surfaces

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US20180334638A1 (en) 2018-11-22
US20220290070A1 (en) 2022-09-15
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US20240002749A1 (en) 2024-01-04
US11685878B2 (en) 2023-06-27
EP3411464A1 (en) 2018-12-12
JP2019504917A (en) 2019-02-21
WO2017134404A1 (en) 2017-08-10
JP2020125498A (en) 2020-08-20
JP6883134B2 (en) 2021-06-09
US11746305B2 (en) 2023-09-05
FR3047488B1 (en) 2020-02-28
CN109477036A (en) 2019-03-15
FR3047488A1 (en) 2017-08-11
CN109477036B (en) 2021-10-08
MX2018009450A (en) 2019-02-21

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