EP0609121B1 - Solid washing composition containing at least one biodegradable and non-hygroscopic polycarboxylic polymer - Google Patents

Solid washing composition containing at least one biodegradable and non-hygroscopic polycarboxylic polymer Download PDF

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Publication number
EP0609121B1
EP0609121B1 EP94400134A EP94400134A EP0609121B1 EP 0609121 B1 EP0609121 B1 EP 0609121B1 EP 94400134 A EP94400134 A EP 94400134A EP 94400134 A EP94400134 A EP 94400134A EP 0609121 B1 EP0609121 B1 EP 0609121B1
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Prior art keywords
detergent composition
water
composition according
polymer
soluble
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EP94400134A
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German (de)
French (fr)
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EP0609121A1 (en
Inventor
Arnaud Ponce
Florence Tournilhac
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • the subject of the present invention is a solid detergent composition containing at least one biodegradable polycarboxylic polymer in a form not water-soluble, compatible with prolonged storage.
  • a common detergent composition incorporates many reagents, each of them being assigned a very specific function.
  • these classic reagents we can more particularly mention the builder.
  • tripolyphosphates have been the most frequently used in detergent compositions and detergents. However, they are partly responsible for the eutrophication of the lakes and waters slow flow when not sufficiently eliminated by treatment plants waters ; so we try to replace them partially or completely.
  • Copolymers of acrylic acid and maleic anhydride (or their alkaline salts or ammonium) have been proposed (European Patent No. 25,551) as inhibitors inlay.
  • sodium polyaspartates and polyglutamates which are useful for their total biodegradability, testify to a good builder activity (US patent 4,428 749). It has been shown that it is the negatively charged form of these compounds which is the active form in the builder function.
  • water-soluble salts of these peptide polymers are found to be unsuitable for prolonged storage in solid detergent formulations. Quickly, they tend to hydrolyze and then degrade on contact with agents oxidants and bases also present in the detergent formula. After a months of storage, these compounds prove incapable of fulfilling their role as builder.
  • the object of the present invention is precisely to propose a solution to this problem of stability over time.
  • the object of the present invention is a particular formulation of carboxylic polymers in detergent compositions. Due to this formulation, their biodegradability and builder properties are preserved and stability chemical is theirs.
  • the present invention advantageously solves the aforementioned problem.
  • water-soluble function is meant a hydrolyzable function which has not not been salified with a non-water soluble inorganic salt.
  • the water-soluble function covers the acid form and the form salified with a water-soluble salt.
  • non-water-soluble salt is intended to denote, within the framework of the present invention, a hydrolyzable function salified with a non-water-soluble inorganic salt.
  • detergent composition denotes, according to the invention, washing machine detergents, dishwashing detergents or any other cleaning product for household use.
  • detergent bath or “detergent medium” means the aqueous detergent solution (detergent composition) present in the washing machine during the washing ; the quantity of detergent present is that recommended by the manufacturer; this one is generally less than 20g / liter; the pH of such a solution is greater than 9.
  • Polycarboxylic polymers as claimed, no longer have hygroscopic character within a formulation detergent powder.
  • a polycarboxylic polymer is considered according to the invention to have a "non-hygroscopic character" insofar as it can be stored effectively and for a long time, i.e. at least 1 month at 40 ° C at within a washing powder.
  • effective storage is meant to define storage at at the end of which the degradation, usually observed, is considerably reduced and in consequently the builder activity is preserved.
  • polycarboxylic polymer is intended to denote according to the invention any polymer having a structural brittleness due, for example, to the presence in the main chain of at least one hydrolyzable function.
  • the polycarboxylic polymer having a non- hygroscopic according to the invention can be derived from peptide polymers, polyesters carboxylic acids, polyethers of carboxylic acids, polyamines of acids carboxylic, polycarbamates and / or oxidized sugars or polysaccharides.
  • these are polymers peptide.
  • peptide polymers which can be used, it is possible to cite the polymers or copolymers of amino acids of the aspartic acid type or glutamic.
  • Said polypeptide polymers can have a weight-average molecular mass of the order of 2,000 to 10 7 and generally of the order of 3,500 to 60,000.
  • Aspartic, glutamic polymers and aspartic acid / glutamic acid copolymers are commercial products. They can for example be prepared according to the methods described in JACS 75, 6530 (1953), JACS 80, 3361 (1958), J. Med. Chem. 16 , 893 (1973), Polymer 23 , 1237 (1982).
  • polycarboxylic polymers are present in the compositions detergents in at least partial form of one of their non-water-soluble inorganic salt or a mixed salt, water-soluble salt / non-water-soluble salt.
  • non-water-soluble inorganic salt is intended to denote more particularly the calcium and magnesium.
  • the non-hygroscopic polycarboxylic polymer put preferably used according to the invention, is calcium polyaspartate.
  • the polymer polycarboxylic may be only partially in the form of one of its non-salts water-soluble, provided of course that the expected non-hygroscopic nature, be reached.
  • carboxylic functions can, where appropriate, remain present at the level of the structure of the carboxylic polymer either under their acid form or in a salified form with a water-soluble salt. In the latter case, it it is a mixed salt. Mention may in particular be made, as water-soluble salt, of sodium, potassium and ammonium. It can in particular be the Ca / Na pair.
  • the Na / Ca pair is preferably used.
  • This non-hygroscopy can also be obtained from an arrangement steric specific for carboxylic polymers.
  • the present invention extends in particular to formulations in which the corresponding polycarboxylic polymer that is to say not hygroscopic, is in the form of granules whose external surface is consisting of at least one polycarboxylic polymer of non-character hygroscopic and the core of at least one polycarboxylic polymer, of a nature identical or different chemical, water-soluble.
  • polycarboxylic polymer not water-soluble is meant a polymer of which the or the acid functions would be salified in the form of a water-insoluble inorganic salt and in a proportion such as corresponding carboxylic polymer has a character non-hygroscopic and therefore stable in detergent powders.
  • This capsule of non-hygroscopic polycarboxylic polymer does not degrade within the powder detergent and preserves the core, which consists of polycarboxylic polymer under a water-soluble form, ie acid or water-soluble salt.
  • the quantity of biodegradable polycarboxylic polymer with character non hygroscopic, entering the detergent composition, making the subject of the invention can vary widely depending on the activity to which it is intended within the detergent formulation. This quantity can in particular represent from 0.2 to 80% of the weight of the detergent composition. In the particular case where the polycarboxylic polymer according to the invention is used as co-builder this amount preferably varies between 2 and 15% of the weight of said detergent composition.
  • the detergent composition at least a surfactant, in an amount which can range from 2 to 50%, preferably from 6 to 30%, the weight of said detergent composition.
  • Various constituents may also be present in the detergent composition of the invention in order to obtain detergents or powdered cleaning products.
  • the detergent composition which is the subject of the invention has good efficacy, whether in primary detergency or in secondary detergency.
  • incorporation of a polycarboxylic polymer in a form as claimed that is to say which is only water-soluble in a detergent medium, guarantees the detergent composition a storage stability, clearly greater than that of a composition directly containing the biodegradable polypeptide, conventionally in a water-soluble form.
  • the present invention also extends to the uses of the claimed composition for washing in a washing machine or dishwasher, or for household washing.
  • control detergent a detergent of composition above but containing instead of calcium polyaspartate, sodium polyaspartate.
  • the mineral inlay is calculated from the ash rate (in% compared to to the total weight of the cotton) of the fabrics washed, dried and burnt at 950 ° C for 3 hours.
  • the purpose of this example is to measure the biodegradability of the polyaspartate of calcium.
  • the corresponding "ultimate" biodegradability is measured according to the standard AFNOR T90 -312 (in accordance with international standard ISO 7827)

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

The present invention relates to a solid detergent composition containing at least one biodegradable polycarboxylic (polycarboxyl) polymer, characterised in that the said polymer is present therein either: - partially or completely in the form of one of its non-water-soluble inorganic salts or - in the form of a mixed water-soluble/non-water-soluble salt, the said corresponding polycarboxylic polymer possessing a substantially non-hygroscopic nature compatible with prolonged storage in the said detergent formulation. The present invention also relates to the uses of the said composition.

Description

La présente invention a pour objet une composition détergente solide contenant au moins un polymère polycarboxylique biodégradable sous une forme non hydrosoluble, compatible avec un stockage prolongé.The subject of the present invention is a solid detergent composition containing at least one biodegradable polycarboxylic polymer in a form not water-soluble, compatible with prolonged storage.

Une composition détergente courante incorpore de nombreux réactifs, chacun d'entre eux étant affecté d'une fonction bien spécifique. Parmi ces réactifs classiques, on peut plus particulièrement mentionner le builder.A common detergent composition incorporates many reagents, each of them being assigned a very specific function. Among these classic reagents, we can more particularly mention the builder.

On entend par builder tout constituant qui améliore les performances des agents de surface d'une composition détergente. D'une manière générale, un builder possède de multiples fonctions.

  • il assure au sein d'un milieu lessiviel l'enlèvement des ions indésirables, notamment alcalino-terreux (calcium, magnésium), par séquestration, complexation ou précipitation pour prévenir la précipitation des tensio-actifs anioniques,
  • il apporte une réserve d'alcalinité et de force ionique,
  • il maintient en suspension les salissures extraites,
  • il empêche l'incrustation minérale du linge.
Builder is understood to mean any constituent which improves the performance of the surfactants of a detergent composition. Generally speaking, a builder has multiple functions.
  • it ensures, within a detergent medium, the removal of undesirable ions, in particular alkaline earth ions (calcium, magnesium), by sequestration, complexation or precipitation to prevent the precipitation of anionic surfactants,
  • it provides a reserve of alkalinity and ionic strength,
  • it keeps the extracted dirt in suspension,
  • it prevents mineral encrustation of the linen.

Pendant très longtemps, les tripolyphosphates ont été les "builders" les plus fréquemment utilisés dans les compositions détergentes et les produits de lavage. Cependant, ils sont en partie responsables de l'eutrophisation des lacs et des eaux à écoulement lent lorsqu'ils ne sont pas suffisamment éliminés par les stations d'épuration des eaux ; aussi cherche t-on à les remplacer partiellement ou totalement.For a very long time, tripolyphosphates have been the most frequently used in detergent compositions and detergents. However, they are partly responsible for the eutrophication of the lakes and waters slow flow when not sufficiently eliminated by treatment plants waters ; so we try to replace them partially or completely.

Les zéolithes seules ne peuvent remplacer les tripolyphosphates; elles doivent être renforcées dans leur action par d'autres additifs.Zeolites alone cannot replace tripolyphosphates; they must be reinforced in their action by other additives.

Des copolymères d'acide acrylique et d'anhydride maléique (ou leurs sels alcalins ou d'ammonium) ont été proposés (brevet européen n°25.551) comme inhibiteurs d'incrustation.Copolymers of acrylic acid and maleic anhydride (or their alkaline salts or ammonium) have been proposed (European Patent No. 25,551) as inhibitors inlay.

Toutefois, ces copolymères d'acide acrylique et d'anhydride maléique de même que les zéolithes sont incapables de se biodégrader en milieu naturel.However, these copolymers of acrylic acid and maleic anhydride likewise that zeolites are unable to biodegrade in a natural environment.

Dans le souci de satisfaire aux récentes exigences écologiques, des polymères peptidiques, de type polymères ou copolymères d'acides aminés ont également été proposés à titre de builder.In order to meet recent ecological requirements, polymers peptides, polymers or copolymers of amino acids have also been proposed as a builder.

En particulier, les polyaspartates et polyglutamates de sodium, intéressants pour leur totale biodégradabilité, témoignent d'une bonne activité builder ( brevet US 4 428 749). Il a été démontré que c'est la forme chargée négativement de ces composés qui est la forme active dans la fonction builder. In particular, sodium polyaspartates and polyglutamates, which are useful for their total biodegradability, testify to a good builder activity (US patent 4,428 749). It has been shown that it is the negatively charged form of these compounds which is the active form in the builder function.

Malheureusement, les sels hydrosolubles de ces polymères peptidiques s'avèrent inadaptés à un stockage prolongé au sein des formulations détergentes solides. Rapidement, ils ont tendance à s'hydrolyser puis à se dégrader au contact des agents oxydants et basiques également présents dans la formule lessivielle. Au terme d'un mois de stockage, ces composés s'avèrent inaptes à assurer leur rôle de builder.Unfortunately, the water-soluble salts of these peptide polymers are found to be unsuitable for prolonged storage in solid detergent formulations. Quickly, they tend to hydrolyze and then degrade on contact with agents oxidants and bases also present in the detergent formula. After a months of storage, these compounds prove incapable of fulfilling their role as builder.

L'objet de la présente invention est précisément de proposer une solution à ce problème de stabilité dans le temps.The object of the present invention is precisely to propose a solution to this problem of stability over time.

Plus précisément, la présente invention a pour but une formulation particulière des polymères carboxyliques dans les compositions détergentes. De part cette formulation, leurs propriétés de biodégradabilité et de "builder" sont préservées et une stabilité chimique leur est acquise.More specifically, the object of the present invention is a particular formulation of carboxylic polymers in detergent compositions. Due to this formulation, their biodegradability and builder properties are preserved and stability chemical is theirs.

La difficulté rencontrée, dans la mise au point de cette formulation particulière, se pose au niveau d'un compromis entre la stabilité chimique du composé et l'aptitude de ce composé à conduire, ultérieurement, au sein du bain lessiviel, à l'espèce active c'est à dire la forme chargée négativement. La stabilité chimique ne doit pas être acquise aux dépens de la génération subséquente de l'espèce active.The difficulty encountered in developing this particular formulation is poses at the level of a compromise between the chemical stability of the compound and the ability to this compound to lead, subsequently, in the detergent bath, to the active species to say the negatively charged form. Chemical stability should not be acquired at costs of the subsequent generation of the active species.

La présente invention permet avantageusement de résoudre le problème pré-cité.The present invention advantageously solves the aforementioned problem.

Plus particulièrement, la présente invention se rapporte à une composition détergente solide contenant au moins un polymère polycarboxylique biodégradable caractérisée en ce que ledit polymère y est présent soit,

  • partiellement ou complètement, sous la forme d'un de ses sels inorganiques non hydrosoluble soit
  • sous la forme d'un sel mixte hydrosoluble / non hydrosoluble,
ledit polymère polycarboxylique correspondant présentant un rapport molaire sel non hydrosoluble / fonction hydrosoluble et/ou un agencement stérique sel non hydrosoluble / fonction hydrosoluble tel(s) qu'il(s) lui confère(nt) un caractère non hygroscopique compatible avec un stockage prolongé au sein de ladite formulation détergente solide.More particularly, the present invention relates to a solid detergent composition containing at least one biodegradable polycarboxylic polymer characterized in that the said polymer is present therein,
  • partially or completely, in the form of one of its non-water-soluble inorganic salts, either
  • in the form of a mixed water-soluble / non-water-soluble salt,
said corresponding polycarboxylic polymer having a molar ratio of water-insoluble salt / water-soluble function and / or a steric arrangement of water-insoluble salt / water-soluble function such that it gives a non-hygroscopic character compatible with prolonged storage within said solid detergent formulation.

Par fonction hydrosoluble, on entend désigner une fonction hydrolysable qui n'a pas été salifiée par un sel inorganique non hydrosoluble. A titre illustratif, dans le cas d'une fonction carboxylique, la fonction hydrosoluble couvre la forme acide et la forme salifiée avec un sel hydrosoluble. By water-soluble function is meant a hydrolyzable function which has not not been salified with a non-water soluble inorganic salt. By way of illustration, in the case of a carboxylic function, the water-soluble function covers the acid form and the form salified with a water-soluble salt.

Par sel non hydrosoluble, on entend désigner, dans le cadre de la présente invention, une fonction hydrolysable salifiée par un sel inorganique non hydrosoluble.The term “non-water-soluble salt” is intended to denote, within the framework of the present invention, a hydrolyzable function salified with a non-water-soluble inorganic salt.

Par composition détergente, on désigne selon l'invention les lessives lave-linge, les lessives lave-vaisselle ou tout autre produit de lavage à usage ménager.The term “detergent composition” denotes, according to the invention, washing machine detergents, dishwashing detergents or any other cleaning product for household use.

On entend par "bain lessiviel" ou "milieu lessiviel" la solution aqueuse de lessive (composition détergente) présente dans la machine à laver au cours des cycles de lavage ; la quantité de lessive présente est celle préconisée par le fabriquant ; celle-ci est généralement inférieure à 20g/litre ; le pH d'une telle solution est supérieur à 9.The term "detergent bath" or "detergent medium" means the aqueous detergent solution (detergent composition) present in the washing machine during the washing ; the quantity of detergent present is that recommended by the manufacturer; this one is generally less than 20g / liter; the pH of such a solution is greater than 9.

De manière inattendue, la Demanderesse a constaté que la formulation de polymères polycarboxyliques sous la forme au moins partielle d'un de leurs sels inorganiques non hydrosolubles permettait de concilier à l'activité builder, une stabilité chimique accrue.Unexpectedly, the Applicant has found that the formulation of polycarboxylic polymers in at least partial form of one of their salts non-water-soluble inorganics made it possible to reconcile with builder activity, stability increased chemical.

Les polymères polycarboxyliques, tels que revendiqués, ne possèdent plus de caractère hygroscopique au sein d'une formulation détergente en poudre.Polycarboxylic polymers, as claimed, no longer have hygroscopic character within a formulation detergent powder.

Un polymère polycarboxylique est considéré selon l'invention comme présentant un "caractère non hygroscopique" dans la mesure où il peut être stocké efficacement et de manière prolongée c'est à dire au moins 1 mois à 40°C au sein d'une poudre lessivielle. Par stockage efficace, on entend définir un stockage au terme duquel la dégradation, usuellement observée, est considérablement réduite et en conséquence l'activite builder est préservée.A polycarboxylic polymer is considered according to the invention to have a "non-hygroscopic character" insofar as it can be stored effectively and for a long time, i.e. at least 1 month at 40 ° C at within a washing powder. By effective storage is meant to define storage at at the end of which the degradation, usually observed, is considerably reduced and in consequently the builder activity is preserved.

Ces conditions de stockages, soient 1 mois à 40°C, sont considérées dans la profession des lessiviers comme les conditions représentatives d'un stockage d'une formulation lessivielle sur des rayonnages commerciaux.These storage conditions, i.e. 1 month at 40 ° C, are considered in the profession of laundry workers as the conditions representative of a storage of a detergent formulation on commercial shelves.

De manière générale, par polymère polycarboxylique, on entend désigner selon l'invention tout polymère présentant une fragilité structurelle due, par exemple, à la présence dans la chaíne principale d'au moins une fonction hydrolysable.Generally, the term “polycarboxylic polymer” is intended to denote according to the invention any polymer having a structural brittleness due, for example, to the presence in the main chain of at least one hydrolyzable function.

A titre illustratif, le polymère polycarboxylique à caractère non hygroscopique selon l'invention, peut dériver de polymères peptidiques, polyesters d'acides carboxyliques, polyéthers d'acides carboxyliques, polyamines d'acides carboxyliques, polycarbamates et/ou de sucres ou polysaccharides oxydés.By way of illustration, the polycarboxylic polymer having a non- hygroscopic according to the invention, can be derived from peptide polymers, polyesters carboxylic acids, polyethers of carboxylic acids, polyamines of acids carboxylic, polycarbamates and / or oxidized sugars or polysaccharides.

Selon un mode de réalisation préféré de l'invention, il s'agit de polymères peptidiques.According to a preferred embodiment of the invention, these are polymers peptide.

A titre d'exemples de polymères peptidiques, pouvant être mis en oeuvre, on peut citer les polymères ou copolymères d'acides aminés du type acide aspartique ou glutamique. As examples of peptide polymers which can be used, it is possible to cite the polymers or copolymers of amino acids of the aspartic acid type or glutamic.

On peut citer tout particulièrement les polyacides aspartiques, les polyacides glutamiques, les copolymères acide aspartique/acide glutamique selon des proportions quelconques.Mention may very particularly be made of aspartic polyacids, polyacids glutamic, aspartic acid / glutamic acid copolymers in proportions any.

Lesdits polymères polypeptidiques peuvent présenter une masse moléculaire moyenne en poids de l'ordre de 2 000 à 107 et généralement de l'ordre de 3 500 à 60 000.Said polypeptide polymers can have a weight-average molecular mass of the order of 2,000 to 10 7 and generally of the order of 3,500 to 60,000.

Les polymères aspartiques, glutamiques et les copolymères acides aspartique/acide glutamique sont des produits du commerce. Ils peuvent par exemple être préparés selon les procédés décrits dans J.A.C.S. 75, 6530 (1953), J.A.C.S. 80, 3361 (1958), J.Med.Chem.16, 893 (1973), Polymer 23, 1237 (1982).Aspartic, glutamic polymers and aspartic acid / glutamic acid copolymers are commercial products. They can for example be prepared according to the methods described in JACS 75, 6530 (1953), JACS 80, 3361 (1958), J. Med. Chem. 16 , 893 (1973), Polymer 23 , 1237 (1982).

Ces polymères polycarboxyliques sont présents dans les compositions détergentes sous forme au moins partielle d'un de leur sel inorganique non hydrosoluble ou d'un sel mixte, sel hydrosoluble/sel non hydrosoluble.These polycarboxylic polymers are present in the compositions detergents in at least partial form of one of their non-water-soluble inorganic salt or a mixed salt, water-soluble salt / non-water-soluble salt.

Par sel inorganique non hydrosoluble, on entend désigner plus particulièrement le calcium et le magnésium.The term “non-water-soluble inorganic salt” is intended to denote more particularly the calcium and magnesium.

Il s'agit de préférence du sel de calcium.It is preferably the calcium salt.

Le polymère polycarboxylique, à caractère non hygroscopique, mis en oeuvre préférentiellement selon l'invention, est le polyaspartate de calcium.The non-hygroscopic polycarboxylic polymer, put preferably used according to the invention, is calcium polyaspartate.

Selon un mode de réalisation particulier de l'invention, le polymère polycarboxylique peut être que partiellement sous la forme d'un de ses sels non hydrosolubles, sous réserve bien entendu que le caractère non hygroscopique attendu, soit atteint.According to a particular embodiment of the invention, the polymer polycarboxylic may be only partially in the form of one of its non-salts water-soluble, provided of course that the expected non-hygroscopic nature, be reached.

Ceci signifie que certaines fonctions carboxyliques peuvent, le cas échéant, demeurer présentes au niveau de la structure du polymère carboxylique soit sous leur forme acide ou sous une forme salifiée avec un sel hydrosoluble. Dans ce dernier cas, il s'agit d'un sel mixte. A titre de sel hydrosoluble on peut notamment citer le sodium, potassium et ammonium. Il peut notamment s'agir du couple Ca/Na.This means that certain carboxylic functions can, where appropriate, remain present at the level of the structure of the carboxylic polymer either under their acid form or in a salified form with a water-soluble salt. In the latter case, it it is a mixed salt. Mention may in particular be made, as water-soluble salt, of sodium, potassium and ammonium. It can in particular be the Ca / Na pair.

Bien entendu, il est à la portée de l'homme de l'art de déterminer soit, la proportion de fondions acide à salifier selon l'invention ou, le rapport molaire sel inorganique non hydrosoluble/sel hydrosoluble à atteindre, pour conduire au caractère non hygroscopique recherché.Of course, it is within the capacity of those skilled in the art to determine either, the proportion of acidic foundations to be salified according to the invention or, the non-inorganic salt molar ratio water-soluble / water-soluble salt to be reached, to lead to the non- hygroscopic sought.

A titre de sel mixte, on utilise de préférence le couple Na/Ca.As a mixed salt, the Na / Ca pair is preferably used.

Cette non-hygroscopie peut également être obtenue à partir d'un agencement stérique spécifique de polymères carboxyliques.This non-hygroscopy can also be obtained from an arrangement steric specific for carboxylic polymers.

La présente invention s'étend en particulier à des formulations dans lesquelles le polymère polycarboxylique correspondant c'est à dire à caractère non hygroscopique, se présente sous la forme de granulés dont la surface externe est constituée d'au moins un polymère polycarboxylique à caractère non hygroscopique et le noyau d'au moins un polymère polycarboxylique, de nature chimique identique ou différente, hydrosoluble. Par polymère polycarboxylique non hydrosoluble, on entend un polymère dont des ou les fonctions acides seraient salifiées sous la forme d'un sel inorganique non hydrosoluble et dans une proportion telle que le polymère carboxylique correspondant présente un caractère non hygroscopique et soit donc stable dans les poudres détergentes. Cette capsule de polymère polycarboxylique non hygroscopique ne se dégrade pas au sein de la poudre détergente et préserve le noyau, lui constitué de polymère polycarboxylique sous une forme hydrosoluble c'est à dire acide ou sel hydrosoluble.The present invention extends in particular to formulations in which the corresponding polycarboxylic polymer that is to say not hygroscopic, is in the form of granules whose external surface is consisting of at least one polycarboxylic polymer of non-character hygroscopic and the core of at least one polycarboxylic polymer, of a nature identical or different chemical, water-soluble. By polycarboxylic polymer not water-soluble, is meant a polymer of which the or the acid functions would be salified in the form of a water-insoluble inorganic salt and in a proportion such as corresponding carboxylic polymer has a character non-hygroscopic and therefore stable in detergent powders. This capsule of non-hygroscopic polycarboxylic polymer does not degrade within the powder detergent and preserves the core, which consists of polycarboxylic polymer under a water-soluble form, ie acid or water-soluble salt.

La quantité de polymère polycarboxylique biodégradable et à caractère non hygroscopique, entrant dans la composition détergente, faisant l'objet de l'invention, peut varier largement en fonction de l'activité à laquelle il est destiné au sein de la formulation lessivielle. Cette quantité peut notamment représenter de 0,2 à 80 % du poids de la composition détergente. Dans le cas particulier où le polymère polycarboxylique selon l'invention est employé à titre de co-builder cette quantité varie de préférence entre 2 et 15% du poids de ladite composition détergente.The quantity of biodegradable polycarboxylic polymer with character non hygroscopic, entering the detergent composition, making the subject of the invention, can vary widely depending on the activity to which it is intended within the detergent formulation. This quantity can in particular represent from 0.2 to 80% of the weight of the detergent composition. In the particular case where the polycarboxylic polymer according to the invention is used as co-builder this amount preferably varies between 2 and 15% of the weight of said detergent composition.

A côté de ce biopolymère, est présent, dans la composition détergente, au moins un agent tensio-actif, en quantité pouvant aller de 2 à 50%, de préférence de 6 à 30%, du poids de ladite composition détergente.Next to this biopolymer, is present, in the detergent composition, at least a surfactant, in an amount which can range from 2 to 50%, preferably from 6 to 30%, the weight of said detergent composition.

Parmi les agents tensio-actifs entrant dans la composition détergente faisant l'objet de l'invention, on peut citer :

  • les agents tensio-actifs anioniques du type savons et métaux alcalins (sels alcalins d'acides gras en C8 - C24), sulfonates alcalins (alcoylbenzène sulfonates en C8 - 13, alcoylsulfonates en C12 - C16, alcools gras en C6 - C16 sulfatés, alkylphénols en C8 -C13 sulfatés), les sulfosuccinates alcalins (alcoylsulfosuccinates en C12 - C16),
  • les agents tensio-actifs non ioniques du type alcoylphénols en C6 - C12 polyoxyéthylénés, alcools aliphatiques en C8 - C22 oxyéthylénés, les copolymères bloc oxyde d'éthylène - oxyde de propylène, les amides carboxyliques éventuellement polyoxyéthylénées,
  • les agents tensio-actifs amphotères du type alcoyldiméthylbétaïnes,
  • les agents tensio-actifs cationiques du type chlorures ou bromures d'alkyltriméthylammonium, d'alkyldiméthylammonium.
Among the surfactants included in the detergent composition forming the subject of the invention, there may be mentioned:
  • anionic surfactants of the know type and alkali metals (alkali metal salts of fatty acids C 8 - C 24), alkali metal sulfonates (alkylbenzene sulfonates, C 8 - 13 alkyl sulfonates, C 12 - C 16 fatty alcohols, C 6 - C 16 sulfates, C 8 -C 13 alkylphenols sulfates), alkali sulfosuccinates (C 12 -C 16 alkyl sulfosuccinates),
  • nonionic surfactants of the polyoxyethylenated C 6 -C 12 alkylphenols type, oxyethylenated C 8 -C 22 aliphatic alcohols, ethylene oxide-propylene oxide block copolymers, optionally polyoxyethylenated carboxylic amides,
  • amphoteric surfactants of the alkyl dimethyl betaines type,
  • cationic surfactants of the chlorides or bromides of alkyltrimethylammonium, of alkyl dimethylammonium.

Divers constituants peuvent en outre être présents dans la composition détergente de l'invention afin d'obtenir des lessives ou des produits de nettoyage en poudre.Various constituents may also be present in the detergent composition of the invention in order to obtain detergents or powdered cleaning products.

Peuvent ainsi être en outre présents dans la composition détergente ci-dessus décrite :

  • des "builders" du type :
    • phosphates à raison de moins de 25% du poids total de la formulation,
    • zéolithes jusqu'à environ 40% du poids total de la formulation,
    • carbonate de sodium jusqu'à environ 80% du poids total de la formulation,
    • acide nitriloacétique jusqu'à environ 10% du poids total de la formulation,
    • acide citrique, acide tartrique jusqu'à environ 20% du poids total de la formulation,
    la quantité totale de "builder" correspondant à environ 0,2 à 80%, de préférence de 20 à 45% du poids total de ladite composition détergente,
  • des inhibiteurs de corrosion tels que les silicates jusqu'à environ 25% du poids total de ladite composition détergente,
  • des agents de blanchiment du type perborates, chloroisocyanates, N, N, N', N' - tétraacétyléthylènediamine (TAED) jusqu'à environ 30% du poids total de ladite composition détergente,
  • des agents anti-redéposition du type carboxyméthylcellulose, méthylcellulose en quantités pouvant aller jusqu'à environ 5% du poids total de ladite composition détergente,
  • des agents anti-incrustation du type copolymères d'acide acrylique et d'anhydride maléique en quantité pouvant aller jusqu'à 10% environ du poids total de ladite composition détergente,
  • des charges du type sulfate de sodium en quantité pouvant aller jusqu'à 50% du poids total de ladite composition détergente.
May also be present in the detergent composition described above:
  • "builders" like:
    • phosphates at a rate of less than 25% of the total weight of the formulation,
    • zeolites up to about 40% of the total weight of the formulation,
    • sodium carbonate up to about 80% of the total weight of the formulation,
    • nitriloacetic acid up to approximately 10% of the total weight of the formulation,
    • citric acid, tartaric acid up to about 20% of the total weight of the formulation,
    the total quantity of "builder" corresponding to approximately 0.2 to 80%, preferably from 20 to 45% of the total weight of said detergent composition,
  • corrosion inhibitors such as silicates up to approximately 25% of the total weight of said detergent composition,
  • bleaching agents of the perborate, chloroisocyanate, N, N, N ', N' - tetraacetylethylenediamine (TAED) type up to approximately 30% of the total weight of said detergent composition,
  • anti-redeposition agents of the carboxymethylcellulose, methylcellulose type in amounts which can range up to approximately 5% of the total weight of said detergent composition,
  • anti-scaling agents of the acrylic acid and maleic anhydride copolymer type in an amount which can range up to approximately 10% of the total weight of said detergent composition,
  • fillers of the sodium sulfate type in an amount which can range up to 50% of the total weight of said detergent composition.

La composition détergente faisant l'objet de l'invention présente une bonne efficacité que ce soit en détergence primaire ou en détergence secondaire. En outre, l'incorporation d'un polymère polycarboxylique sous une forme telle que revendiquée c'est à dire qui n'est hydrosoluble qu'au sein d'un milieu lessiviel, garantie à la composition détergente une stabilité au stockage, nettement supérieure à celle d'une composition contenant directement le polypeptide biodégradable, classiquement sous une forme hydrosoluble.
La présente invention s'étend également aux utilisations de la composition revendiquée pour le lavage en lave-linge ou lave-vaisselle, ou pour le lavage ménager.The detergent composition which is the subject of the invention has good efficacy, whether in primary detergency or in secondary detergency. In addition, the incorporation of a polycarboxylic polymer in a form as claimed, that is to say which is only water-soluble in a detergent medium, guarantees the detergent composition a storage stability, clearly greater than that of a composition directly containing the biodegradable polypeptide, conventionally in a water-soluble form.
The present invention also extends to the uses of the claimed composition for washing in a washing machine or dishwasher, or for household washing.

Les exemples suivants sont donnés à titre indicatif et ne peuvent pas être considérés comme une limite du domaine et de l'esprit de l'invention.The following examples are given for information only and cannot be considered as limiting the field and the spirit of the invention.

EXEMPLE 1EXAMPLE 1 Formulation d'une composition détergente lave-linge à partir de polyaspartate de calcium.Formulation of a washing machine detergent composition from polyaspartate calcium.

Par mélange à sec des différents additifs, on obtient la composition détergente solide suivante : COMPOSITION DE LA LESSIVE % EN POIDS Alkylbenzène sulfonate linéaire 7,5 CEMUSOL LA 90 â (acide laurique polyoxyéthylénée commercialise par S.F.O.S) 4 Zéolithe 4 A 24 Silicate de Na (SiO2/Na2O = 2) 1,5 Carbonate de Na 10 TAED 2 Perborate de Na 15 Ethylénediamine tétracétique 0,1 Polyaspartate de calcium 3 Tiponal DMSXâ 0,1 Tiponal SOPâ (azurants commercialisés par CIBA-CEIGY) 0,1 Antimousse siliconé 0,2 Alcalase 0,15 Savinase (enzymes) 0,15 Sulfate de Na qsp 100% By dry mixing of the various additives, the following solid detergent composition is obtained: LAUNDRY COMPOSITION % IN WEIGHT Linear alkylbenzene sulfonate 7.5 CEMUSOL LA 90 â (polyoxyethylenated lauric acid sold by SFOS) 4 Zeolite 4 A 24 Na silicate (SiO 2 / Na 2 O = 2) 1.5 Na carbonate 10 TAED 2 Na perborate 15 Ethylenediamine tetracetic 0.1 Calcium polyaspartate 3 Tiponal DMSX â 0.1 Tiponal SOP â (brighteners marketed by CIBA-CEIGY) 0.1 Silicone defoamer 0.2 Alcalase 0.15 Savinase (enzymes) 0.15 Na sulfate qs 100%

On appellera "lessive témoin" une lessive de composition ci-dessus mais contenant à la place du polyaspartate de calcium, du polyaspartate de sodium.We will call "control detergent" a detergent of composition above but containing instead of calcium polyaspartate, sodium polyaspartate.

Chacune de ces formulations est stockée pendant un mois à 40°C.Each of these formulations is stored for one month at 40 ° C.

EXEMPLE 2EXAMPLE 2 Performance en détergence secondaire de la lessive lave-linge de l'exemple 1Secondary detergent performance of the washing machine in Example 1

Après un stockage prolongé, l'activité en détergence secondaire et plus particulièrement l'effet "incrustation" des précipités qui peuvent se produire durant le lavage, sur les tissus a été déterminée pour la lessive de l'exemple 1 et la lessive témoin.After prolonged storage, activity in secondary detergents and more particularly the "incrustation" effect of the precipitates which can occur during the washing, on the fabrics was determined for the laundry of Example 1 and the laundry witness.

Cet effet a été mesuré après 20 lavages réalisés en présence des éprouvettes de tissus suivantes:

  • textiles coton Testfabric 405 (1)
  • coton Krefeld 12A (2)
This effect was measured after 20 washes performed in the presence of the following tissue samples:
  • cotton textiles Testfabric 405 (1)
  • cotton Krefeld 12A (2)

L'incrustation minérale est calculée à partir du taux de cendres (en % par rapport au poids total du coton) des tissus lavés, séchés et brulés à 950°C pendant 3 heures.The mineral inlay is calculated from the ash rate (in% compared to to the total weight of the cotton) of the fabrics washed, dried and burnt at 950 ° C for 3 hours.

L'effet inhibiteur d'incrustation est apprécié par le rapport taux de cendres avec additifs/taux de cendres sans additifs qui figure sous la lettre T dans le tableau I ci-après. TISSU T LESSIVE TEMOIN T LESSIVE DE L'EXEMPLE 1 T LESSIVE SANS POLYMERE (1) 100 % 75 % 100 % (2) 100 % 60% 100 % The encrusting inhibiting effect is appreciated by the ratio of ash rate with additives / ash rate without additives which appears under the letter T in Table I below. TISSUE T LAUNDRY T LAUNDRY OF EXAMPLE 1 LAUNDRY WITHOUT POLYMER (1) 100% 75% 100% (2) 100% 60% 100%

On note que seule la lessive à base de polyaspartate de calcium présente une activité anti-incrustante après 1 mois de stockage.Note that only the detergent based on calcium polyaspartate has an activity anti-scaling after 1 month of storage.

EXEMPLE 3EXAMPLE 3

Cet exemple a pour but de mesurer la biodégradabilité du polyaspartate de calcium. La biodégradabilité "ultime" correspondante est mesurée selon la norme AFNOR T90 -312 (en conformité avec la norme internationale ISO 7827)The purpose of this example is to measure the biodegradability of the polyaspartate of calcium. The corresponding "ultimate" biodegradability is measured according to the standard AFNOR T90 -312 (in accordance with international standard ISO 7827)

Le test est réalisé à partir :

  • d'un inoculum obtenu par filtration d'eau d'entrée de la station d'épuration urbaine de Saint Germain au Mont d'Or (Rhône).
  • d'un milieu d'essai contenant 4 x 107 bactéries/ml.
  • d'une quantité de produit à tester telle que le milieu d'essai contienne une concentration en carbone organique de l'ordre de 40 mg/l. Le taux de biodégradabilité du produit testé en fonction du temps est de l'ordre de 60 % en 20 jours dans les conditions de rejet en eau de rivière.
The test is carried out from:
  • an inoculum obtained by filtration of inlet water from the urban wastewater treatment plant of Saint Germain to Mont d'Or (Rhône).
  • a test medium containing 4 × 10 7 bacteria / ml.
  • an amount of product to be tested such that the test medium contains a concentration of organic carbon of the order of 40 mg / l. The rate of biodegradability of the product tested as a function of time is around 60% in 20 days under the conditions of discharge into river water.

Claims (13)

  1. Solid detergent composition containing at least one biodegradable polycarboxylic polymer, characterized in that the said polymer is present therein either,
    partially or completely, in the form of one of its water-insoluble inorganic salts or
    in the form of a water-soluble/water-insoluble mixed salt,
    the said corresponding polycarboxylic polymer having a molar ratio water-insoluble salt/water-soluble functional group and/or a steric arrangement water-insoluble salt/water-soluble functional group such that it (they) confer(s) thereon a non-hygroscopic character, compatible with prolonged storage inside the said solid detergent formulation.
  2. Detergent composition according to Claim 1, characterized in that the polycarboxylic polymer of non-hygroscopic character is provided in the form of granules whose external surface consists of at least one polycarboxylic polymer of non-hygroscopic character and the core of at least one water-soluble polycarboxylic polymer of identical or different chemical nature.
  3. Detergent composition according to Claim 1 or 2, characterized in that the polycarboxylic polymer of non-hygroscopic character is derived from peptide polymers, from polyesters of carboxylic acids, from polyethers of carboxylic acids, polyamines of carboxylic acids, from polycarbamates and/or from oxidized sugars or polysaccharides.
  4. Detergent composition according to one of Claims 1 to 3, characterized in that the carboxylic polymer of non-hygroscopic character is preferably derived from peptide polymers.
  5. Detergent composition according to Claim 4, characterized in that it preferably involves polymers or copolymers of amino acids of the aspartic or glutamic acid type.
  6. Detergent composition according to one of Claims 1 to 5, characterized in that the water-insoluble inorganic salts are calcium or magnesium.
  7. Detergent composition according to one of the preceding claims, characterized in that the water-insoluble inorganic salt used is a calcium salt.
  8. Detergent composition according to one of Claims 1 to 7, characterized in that the mixed salt is a Na/Ca.
  9. Detergent composition according to one of Claims 1 to 7, characterized in that the polycarboxylic polymer of non-hygroscopic character is calcium polyaspartate.
  10. Detergent composition according to any one of Claims 1 to 9, characterized in that the said polymer represents from 0.2 to 80 % of the weight of the said detergent composition.
  11. Detergent composition according to Claim 10, characterized in that the said polymer preferably represents from 2 to 15 % of the weight of the said detergent composition.
  12. Detergent composition according to any one of Claims 1 to 11, characterized in that at least one surfactant is present in a quantity ranging from 2 to 50 % of the weight of the said composition.
  13. Use of a detergent composition according to one of Claims 1 to 12 for washing in washing machines or dishwashers, or for household washing.
EP94400134A 1993-01-27 1994-01-24 Solid washing composition containing at least one biodegradable and non-hygroscopic polycarboxylic polymer Expired - Lifetime EP0609121B1 (en)

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FR9300776A FR2700775B1 (en) 1993-01-27 1993-01-27 Solid detergent composition containing at least one biodegradable and non-hygroscopic polycarboxylic polymer.

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DE19526089A1 (en) * 1995-07-18 1997-01-23 Bayer Ag Washing process with polycarboxylic acid salts
FR2774311B1 (en) * 1998-02-02 2000-03-17 Rhodia Chimie Sa WATER-DISPERSABLE GRANULES COMPRISING A HYDROPHOBIC ACTIVE MATERIAL
KR100347752B1 (en) * 2000-01-25 2002-08-09 주식회사 하이닉스반도체 Apparatus and Method for objective speech quality measure in a Mobile Communication System
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JP2594882B2 (en) 1997-03-26
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FR2700775A1 (en) 1994-07-29
US5520842A (en) 1996-05-28
CA2114382A1 (en) 1994-07-28
DE69425915D1 (en) 2000-10-26
ES2152296T3 (en) 2001-02-01
BR9400369A (en) 1994-08-16
DE69425915T2 (en) 2001-04-19
ATE196499T1 (en) 2000-10-15
JPH0748596A (en) 1995-02-21
AU5399294A (en) 1994-08-04
PT609121E (en) 2001-03-30
NZ250756A (en) 1996-03-26
CA2114382C (en) 2001-07-03

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