WO1997026020A1 - Novel fragrant resin for uniformly diffusing a complex fragrance composition - Google Patents

Novel fragrant resin for uniformly diffusing a complex fragrance composition Download PDF

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Publication number
WO1997026020A1
WO1997026020A1 PCT/FR1997/000076 FR9700076W WO9726020A1 WO 1997026020 A1 WO1997026020 A1 WO 1997026020A1 FR 9700076 W FR9700076 W FR 9700076W WO 9726020 A1 WO9726020 A1 WO 9726020A1
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WO
WIPO (PCT)
Prior art keywords
perfumed
resin
weight
complex
blocks
Prior art date
Application number
PCT/FR1997/000076
Other languages
French (fr)
Inventor
Marcel Jean
Yves Aubert
Roland Leroux
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Elf Atochem S.A.
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Publication date
Application filed by Elf Atochem S.A. filed Critical Elf Atochem S.A.
Priority to EP97900656A priority Critical patent/EP0876162A1/en
Publication of WO1997026020A1 publication Critical patent/WO1997026020A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • A61L9/042—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating with the help of a macromolecular compound as a carrier or diluent

Definitions

  • the present invention relates to a new perfumed resin allowing the regular diffusion in the form of vapor of complex volatile substances.
  • the present invention relates more particularly to a perfumed resin comprising a polymeric resin of the polyetheresteramide type containing the complex volatile substances to be released, the objects shaped from said resin, their preparation process and their use for ambient perfuming.
  • plastics such as polypropylene or ethyl vinyl acetate
  • EVA seems to be the most efficient but its capacity remains very limited, generally less than 10% of its weight, and in a very restrictive way because many usual raw materials of perfumery can only be incorporated in tiny amounts proportions.
  • the perfumer therefore has recourse to bases of perfumes of simple formulation and deodorants which are often closer to the field of household and maintenance products than to the world of perfumery.
  • FR-A-1176992 describes a process for manufacturing solid perfumes which consists in the massive incorporation of a perfume in a synthetic resin; no specific resin being mentioned.
  • US-P-3926655 describes a material essentially devoid of solvent consisting of a polyamide resin, in particular the resins sold under the name versamid®, containing a fragrance essence.
  • US-P-4184099 describes devices intended to contain volatile, scenting, insecticidal or bactericidal substances consisting of polyamide resins of a nature similar to that of the resins described in US-P-3926655 but of higher molecular weight.
  • Polyolefin matrix products suitable for use in a "master-batch" process characterized by a high content of volatile perfuming substances, such as Polyiff from Flavors & Fragrance Inc., have also been described.
  • the matrices used correspond to resins based on low density polyethylene, polypropylene and ethylene vinyl acetate.
  • EP-A-0167633 describes a material for controlling harmful insects allowing the slow release of an insecticidal formulation. This material is formed by mixing and molding chlorinated polyethylene, a thermoplastic elastomer and an insecticidal ingredient.
  • EP-A-0671123 describes a material for combating harmful insects, said material comprising an elastomer comprising polyamide blocks and polyether blocks, in combination with an insecticide, such as esbiotrine.
  • a device for combating insects comprising a thermoplastic elastomer, at least one chemical mediator acting on the behavior of insects and mites and chosen from pheromones, kairomones or allomones and optionally undecylenic acid or its derivatives has been described in EP-A-0680693.
  • This document discloses the use as elastomer of elastomers comprising polyamide blocks and polyether blocks. The only example provided describes a device allowing the constant diffusion over time of the corn sesame pheromone.
  • FR-A-2675387 describes a process for preparing a perfumed object capable of withstanding drastic temperature and hygrometry conditions. This process comprises a phase of impregnating a polymeric resin of the polyetheresteramide type with a perfume by kneading (until the perfume is saturated), followed by a rest phase and an injection phase, implemented at a temperature below 100 ° C.
  • the perfumer knows that to achieve a sophisticated perfuming of the environment he will have to use comparable raw materials and formulations similar to those of body perfumes. It also seems highly desirable that the formulation of a product intended to be breathed in fairly large amounts has a level of safety comparable to that of body perfumes in contact with the skin.
  • FR-A-2579983 neither describes nor suggests that a polymer resin of polyetheresteramide type can be used for the preparation of a perfumed resin suitable for the diffusion of complex perfumed compositions according to the present invention.
  • the Applicant has surprisingly demonstrated that a perfumed resin made up of a polymeric resin of the polyetheresteramide type containing a complex perfumed composition allows a regular diffusion of all the odorous constituent substances without causing the phenomenon of separation of the diffusion of the substances according to their volatility conventionally encountered in articles of dissemination of the prior art and therefore without significant degradation of its qualities over time.
  • Such a resin therefore makes it possible to obtain sophisticated ambient perfumes comparable to body perfumes.
  • the present invention is based on the surprising effect that such a resin does not behave like a chromatographic separation support leading to a separate diffusion of the various volatile components which it contains. Unexpectedly, all the volatile constituents are released in a constant manner without any phenomenon of separation and consequently without any notable degradation of the qualities of the perfumed composition.
  • the present invention therefore provides a perfumed resin comprising:
  • PA represents the polyamide segment and PE represents the polyether segment and n is an integer representing the distribution of the repeating units; and (b) a complex scent composition.
  • the perfumed resin according to the invention comprises, by weight relative to the weight of said perfumed resin, 99% to 5% by weight of polymer resin of polyetheresteramide type and 1 to 95% by weight of a complex perfumed composition, and preferably 90 to 5% by weight of polymeric resin of polyetheresteramide type and 10 to 95% by weight of a complex perfumed composition, respectively.
  • the perfumed resin according to one embodiment the perfumed resin according to one embodiment.
  • 1 invention comprises, by weight relative to the weight of said perfumed resin, 50 to 10% by weight of polymeric resin of the polyetheresteramide type and 50 to 90% by weight of a complex perfumed composition.
  • the perfumed resin according to the invention comprises, by weight relative to the weight of said perfumed resin, about 40% by weight of polymer resin of polyetheresteramide type and about 60% by weight of a complex perfumed composition.
  • the polymer resin of the PEEA type is obtained from PA-12 blocks and PTMG blocks, preferably with a Shore A hardness of 25.
  • the complex perfumed composition comprises at least 5 components, preferably at least 20 components.
  • the invention also provides a perfumed resin, further comprising ethyl alcohol, in a proportion of 5 to 30% of the final weight, preferably about 10%.
  • This alcohol is preferably the so-called "perfumery" alcohol.
  • the invention also relates to a process for the preparation of a perfumed resin as described above by mixing the polymeric resin of the PEEA type with the complex perfumed composition.
  • the mixture is used by coating according to the drageer technique.
  • the resin mixture is incorporated
  • PEEA / complex perfumed composition of ethyl alcohol in a proportion of 5 to 30% of the final weight, preferably about 10%.
  • the present invention also relates to articles shaped from a perfumed resin as described above as well as the masterbatches obtained from such a perfumed resin.
  • the present invention also relates to the use of perfumed resins, shaped articles and masterbatches as described above for the perfume of ambience and in particular for the perfume of ambience for automobile.
  • - Figure 1 is a curve giving, as a function of time, the quantity of volatile patchouli materials released, for various supports
  • - Figure 2 is a curve giving, as a function of time, the ratio between a component of patchouli and the galaxolide released, for various supports;
  • FIG. 3a, 3b and 3c are curves giving, as a function of time, the quantity of three volatile materials specific to patchouli released, for various supports.
  • the polyetheresteramide polymer (PEEA) consists of a linear chain of rigid polyamide segments and flexible polyether segments corresponding to the formula:
  • PA represents the polyamide segment and PE represents the polyether segment and n is an integer representing the distribution of the repeating units.
  • This PEEA polymer is obtained by any suitable process; in particular the PEEA resin is obtained by reaction in the molten state between a dicarboxylic polyamide with terminal carboxylic functions of an average molecular weight of between 300 and 15,000 and a linear or branched aliphatic polyoxyalkylene glycol with terminal hydroxyl functions and with a weight average molecular between 200 and 6000, under high vacuum at temperatures between 100 and 400 ° C, in the presence of a catalyst which is for example a tetraalkyl-orthotitanate of general formula Ti (OR) 4 or a tetraalkyl-orthostannate of general formula Zn (OR) 4; R being a linear or branched aliphatic hydrocarbon radical whose number of carbon atoms is between 1 and 24 and whose content by weight relative to the reaction mixture is between 0.001 and 5%.
  • a catalyst which is for example a tetraalkyl-orthotitanate of general formula Ti (OR
  • polymers containing polyamide blocks and polyether blocks result from the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia:
  • polyamide blocks with dicarboxylic ends with polyoxyalkylenated blocks with diamine ends obtained by cyanoethylation and hydrogenation of polyoxyalkylene alpha-omega dihydroxylated aliphatic sequences called polyetherdiols;
  • polyamide sequences with dicarboxylic ends originate, for example, from the condensation of alpha-omega aminocarboxylic acids, from lactams or from substantially stoichiometric combinations of dicarboxylic acids and diamines, in the presence of a chain-limiting dicarboxylic acid.
  • the polyamide blocks are PA6 or PA12.
  • the average molecular weight Mn of the polyamide blocks varies from 300 to 15,000 and preferably from 600 to 5,000.
  • the number-average molecular weight Mn of the polyether sequences is between 10 and 6000 and preferably between 200 and 3000.
  • polymers containing polyamide blocks and polyether blocks can also comprise units distributed randomly.
  • These polymers can be prepared by the simultaneous reaction of polyether and precursors of polyamide blocks. For example, polyetherdiol, a lactam (or a corresponding alpha-omega amino acid) and a chain-limiting diacid can be reacted in the presence of a little water.
  • a polymer is obtained which essentially has polyether blocks, polyamide blocks of very variable length, but also the various reactants which have reacted randomly which are distributed statistically along the polymer chain.
  • polyamide block and polyether block polymers whether they originate from the copolycondensation of polyamide and polyether blocks prepared beforehand or from a reaction in one step, exhibit, for example, Shore D hardnesses which may be between 20 and 75, and a intrinsic viscosity between 0.8 and 2.5 as measured in metacresol at 25 ° C for an initial concentration of 0.8 g / 100 ml.
  • polyether blocks are derived from polyethylene glycol, polyoxypropylene glycol or polyoxytetramethylene glycol, they are either used as such and copolycondenses with polyamide blocks having carboxylic ends, or they are aminated to be transformed into polyether diamines and condensed with blocks polyamide with carboxylic ends. They can also be mixed with polyamide precursors and a chain limiter to obtain polymers with polyamide blocks and polyether blocks having randomly distributed units.
  • the polyether can for example be a polyethylene glycol (PEG), a polypropylene glycol (PPG) or a polytetramethylene glycol (PTMG, also called poly tetrahydrofuran, PTHF).
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PTMG polytetramethylene glycol
  • PTHF poly tetrahydrofuran
  • the polyether blocks are in the polymer chain with polyamide blocks and polyether blocks in the form of diols or diamines, they are called for simplification PEG blocks or PPG blocks or PTMG blocks. It would not be departing from the scope of the present invention if the polyether blocks contained different units such as those derived from ethylene glycol, propylene glycol or tetramethylene glycol.
  • the polymer with polyamide blocks and polyether blocks comprises a single type of polyamide block and a single type of polyether block.
  • polymers with PA12 blocks and PEG blocks are used, polymers with PA12 blocks and PTMG blocks, polymers with PA6 blocks and PEG blocks, and polymers with PA6 and PTMG blocks.
  • the polymer with polyamide blocks and polyether blocks is such that the polyamide is the minor constituent by weight, that is to say that the amount of polyamide which is in the form of blocks and that which is optionally distributed statistically in the chain represents at most 50% by weight of the polymer with polyamide blocks and polyether blocks.
  • the amount of polyamide and the amount of polyether are in a weight ratio (polyamide / polyether) of between 1/1 and 1/5.
  • a polyetheresteramide advantageously used in the invention has a polyamide / polyether weight ratio of 0.3.
  • Such polymers containing polyamide blocks and polyether blocks are sold by the company Elf Atochem under the name Pebax®.
  • PEBAX any type of PEBAX can be used in the context of the present invention.
  • the flexible grades of PEBAX which have the particularity of absorbing a large quantity of volatile matter (ie 1.2 times their weight of complex volatile matter such as high-end perfumes) and then diffusing them in their entirety with great regularity over time and without causing their separation are particularly suitable in the context of the present invention.
  • PEBAX® of low hardness such as PEBAX® obtained from PA-12 and PTMG, will be used.
  • This PEEA polymer can be in the form of beads with a diameter of a few mm.
  • complex perfumed composition is understood to mean, in the context of the present invention, a composition containing at least 2 volatile aromatic components used in the composition of a perfume or a deodorant, said volatile components generally having different volatilities. Preferably, there are at least 5, advantageously at least 20 components. Perfumed compositions can contain 30 and up to 50 or even 80 components. Mention may be made, by way of example of complex compositions, of compositions of animal or vegetable origin.
  • aromatic component as used in the context of the present invention includes all volatile odorous components which can be used in the formulation of a perfume or a deodorant and includes in particular the compounds cited in the encyclopedia Kirk Othmer (vol 16, page 947-970) as well as the various known food flavors.
  • the ethyl alcohol used in the perfumed resins of the invention makes it possible to homogenize the perfume base and to promote the development of aromas and scents during desorption.
  • Ethyl alcohol, in particular perfume alcohol is very well absorbed by the polyetheresteramide and improves, by maceration or over time, the quality of a perfume or aroma extract.
  • the perfumed resin according to the present invention can be prepared by mixing the polyetheresteramide type polymer with the complex perfumed composition to be incorporated. Any mixing technique conventionally used in the prior art can be used for this purpose. The most suitable mixing operation is carried out by coating using the bezel technique, slowly rotating at 30/60 rpm, at an ambient temperature of 20 to 25 ° C, with continuous incorporation of the complex scented composition simply carried out by pouring the latter through a tap whose flow rate is regulated to prevent an excess of the perfumed composition does not interfere with the free movement of the granules in the rotating bezel.
  • the impregnation time will vary from 20 to 120 minutes to obtain granules which are dry to the touch, immediately or after a resting phase.
  • the rotation speed can be varied during impregnation, to take account of the variation in behavior of the granules, depending on whether they are either completely or partially immersed in a liquid or whether they have absorbed the liquid.
  • the speed of rotation is chosen so that the granules are preferably always in motion.
  • the temperature at which the impregnation is carried out can also be higher than ambient temperature, and preferably lower than 40-45 ° C.
  • the appearance of the impregnated granules is slightly translucent and offers interesting decorative possibilities.
  • a colorant, when added, can be added during the impregnation of the resin or preferably beforehand in the perfume base.
  • the invention also relates to a decorated object.
  • the impregnation process according to the invention also makes it possible to avoid the use of colloidal silica, such as aerosil®.
  • colloidal silica such as aerosil®.
  • ethyl alcohol denatured according to the norm of the country of consumption
  • perfume quality is the so-called "perfume quality" alcohol.
  • the perfumed resin according to the present invention can be used as it is, that is to say in the form of beads having a diameter of a few millimeters, or can be shaped into various shapes, functional or decorative. It can be easily shaped by extrusion or by molding according to the usual techniques used for the transformation of thermoplastic polymer materials.
  • the processing temperature is conventional, but can be as high as 160 ° C.
  • the perfumed resin according to the present invention can, moreover, be used for the preparation of concentrates which, for example, in the form of granules or extrudates, will be incorporated into other thermoplastic polymers according to the so-called "master-batch” method. ".
  • thermoplastic polymers can be, for example, (co) polyolefins, EVA, PVC and others.
  • the present invention relates to articles shaped from the present scented resin and masterbatches obtained from the latter.
  • a particular application of the present invention is the manufacture of room fragrance articles and more particularly of room fragrance articles for cars.
  • the perfumed resin according to the present invention allowing constant diffusion of complex perfumed compositions can therefore also be combined with systems which accelerate the diffusion of volatile substances such as ventilation, heat, or setting in motion. Furthermore, this diffusion is perfect, both with PEEAs in the form of industrial granules and thermoformed ones.
  • compositions and the articles resulting therefrom can contain any type of additive or adjuvant conventionally used by those skilled in the art.
  • Example 1 illustrate the invention without limiting it.
  • This example describes a comparative test of the absorption capacity of lavender essence by different products, namely: PEBAX®, cellulose wadding, ethylene vinyl acetate (EVA) and polyethylene (PE).
  • the essence of lavender is complex because it contains more than 20 different chemical compounds.
  • the Pebax® used is a PA12 / PTMG copolymer, having a PA12 / PTMG weight ratio of 600/2000, a melt flow index (MFI) of 10 (measured at 235 ° C., under 1 kg, with a 2mm die).
  • This example compares the diffusion capacity of Patchouli essence (more than 20 components) from different supports such as: PEBAX, cellulose wadding, EVA and PE. This test is implemented over a period of 4 months.
  • the diffusion capacity of a complex perfumed composition from different supports is compared.
  • the supports studied are: PEBAX® (identical to that of Example 1), cellulose wadding, EVA and PE.
  • the comparative test, implemented over a period of 4 months, makes it possible to study the diffusion of a composition containing essences of Patchouli and Galaxolide (one component, in solvent).
  • Example 4 The capacity of diffusion of a complex perfumed composition from different supports is compared.
  • the supports studied are: PEBAX® (identical to that of Example 1), cellulose wadding and EVA.
  • the comparative test implemented over a period of 25 days, makes it possible to study the diffusion of a composition containing Lavandin essences (more than 20 components).
  • Peak B is the broad peak between 13.10 and 13.75
  • peak C is the peak at 14.10
  • peak D is the peak at 15.20, data being obtained with pure lavandin at 125 ° C, and with an Innowax column (30m / 0.320mm / 0.5 ⁇ m).
  • FIGS. 3a, 3b and 3c The results are represented graphically in FIGS. 3a, 3b and 3c, which give the quantities of the substances corresponding to the peaks considered as a function of time, for Pebax®, EVA and cellulose wadding supports.

Abstract

A fragrant resin, including (a) a polymeric resin such as a polyether-esteramide and (b) a complex fragrance composition, is disclosed. A method for preparing said resin and the use thereof for providing an ambient fragrance are also disclosed.

Description

NOUVELLE RESINE PARFUMEE PERMETTANT LA DIFFUSION REGULIERE D'UNE COMPOSITION PARFUMEE COMPLEXE NOVEL SCENTED RESIN ALLOWING THE REGULAR DIFFUSION OF A COMPLEX SCENTED COMPOSITION
La présente invention a pour objet une nouvelle résine parfumée permettant la diffusion régulière sous forme de vapeur de substances volatiles complexes. La présente invention concerne plus particulièrement une résine parfumée comprenant une résine polymère de type polyétheresteramide renfermant les substances volatiles complexes devant être libérées, les objets façonnés à partir de ladite résine, leur procédé de préparation et leur utilisation pour le parfumage d'ambiance.The present invention relates to a new perfumed resin allowing the regular diffusion in the form of vapor of complex volatile substances. The present invention relates more particularly to a perfumed resin comprising a polymeric resin of the polyetheresteramide type containing the complex volatile substances to be released, the objects shaped from said resin, their preparation process and their use for ambient perfuming.
Un grand nombre d'articles décrits dans l'art antérieur pour le parfumage de l'environnement consistent en des produits obtenus par imprégnation de parfums dans des corps spongieux tels que le papier, la feutrine ou des matières d'origine minérale. Pour obtenir les meilleurs résultats, ces supports doivent être imprégnés de la plus grande quantité possible de bases parfumantes, avec ou sans solvant, au delà de leur propre poids.A large number of articles described in the prior art for perfuming the environment consist of products obtained by impregnating perfumes in spongy bodies such as paper, felt or materials of mineral origin. To obtain the best results, these supports must be impregnated with the greatest possible quantity of perfuming bases, with or without solvent, beyond their own weight.
Tous les produits obtenus par imprégnation de ces supports sont caractérisés par une diffusion du parfum forte au début et qui s'altère très rapidement dans le temps, ce qui limite leurs performances. Il s'en suit que cette performance, déjà limitée dans le cas d'un simple objet parfumé à poser ou à suspendre, devient tout à fait insuffisante si l'on souhaite associer ces produits à des systèmes qui en accéléreront la diffusion tels que la ventilation, la chaleur ou la mise en mouvement.All the products obtained by impregnating these supports are characterized by a strong diffusion of the perfume at the start and which deteriorates very quickly over time, which limits their performance. It follows that this performance, already limited in the case of a simple scented object to place or hang, becomes completely insufficient if one wishes to associate these products with systems which will accelerate their dissemination such as ventilation, heat or setting in motion.
Dans le cas des corps spongieux tels que le papier, le parfumeur créateur connaît parfaitement ce phénomène puisqu'il utilise lui même des touches à parfums sous forme de bandelettes de papier. Ces touches à parfums trempées dans un parfum complexe, pouvant contenir parfois 50 à 80 composants, favorisent 1 ' evaporation successive des composant selon leur volatilité, pour mettre en évidence successivement les notes de tête les plus volatiles, les notes de coeur, et enfin les notes de fond. Il est bien évident qu'un produit parfumant utilisant ce type de support spongieux pour accueillir une grande quantité de parfums complexes ne pourra pas diffuser ce parfum de façon régulière et prolongée sans que ne soit dissocié ses différents composants. Une telle dissociation conduit à une dégradation notable des qualités odorantes des parfums utilisés.In the case of spongy bodies such as paper, the creative perfumer is perfectly aware of this phenomenon since he himself uses perfume buttons in the form of strips of paper. These soaked perfume touches in a complex perfume, which can sometimes contain 50 to 80 components, favor the successive evaporation of the components according to their volatility, to successively highlight the most volatile top notes, the heart notes, and finally the base notes. It is obvious that a perfuming product using this type of spongy support to accommodate a large quantity of complex perfumes will not be able to diffuse this perfume in a regular and prolonged way without dissociating its different components. Such a dissociation leads to a notable degradation of the odorous qualities of the perfumes used.
L'emploi de différentes matières plastiques a été proposé pour la préparation d'articles de diffusion. Certaines matières plastiques, telles que le polypropylène ou 1 'éthyl vinyl acétate, peuvent être également imprégnées, mais avec des capacités d'accueil beaucoup plus réduites. L 'EVA parait être le plus performant mais sa capacité d'accueil reste fort limitée, généralement moins de 10% de son poids, et de façon très restrictive car de nombreuses matières premières habituelles de la parfumerie ne peuvent être incorporées que dans d'infimes proportions. Le parfumeur a donc recours à des bases de parfums de formulation simple et surodorantes qui sont souvent plus proches du domaine des produits ménagers et d'entretien que du monde de la parfumerie.The use of different plastics has been proposed for the preparation of dissemination articles. Certain plastics, such as polypropylene or ethyl vinyl acetate, can also be impregnated, but with much reduced capacity. EVA seems to be the most efficient but its capacity remains very limited, generally less than 10% of its weight, and in a very restrictive way because many usual raw materials of perfumery can only be incorporated in tiny amounts proportions. The perfumer therefore has recourse to bases of perfumes of simple formulation and deodorants which are often closer to the field of household and maintenance products than to the world of perfumery.
Différents documents de l'art antérieur décrivent ce type de produits.Various documents of the prior art describe this type of product.
FR-A-1176992 décrit un procédé de fabrication de parfums solides qui consiste en l'incorporation massive d'un parfum dans une résine synthétique; aucune résine spécifique n'étant mentionnée.FR-A-1176992 describes a process for manufacturing solid perfumes which consists in the massive incorporation of a perfume in a synthetic resin; no specific resin being mentioned.
US-P-3926655 décrit un matériau essentiellement dépourvu de solvant constitué par une résine polyamidique, notamment les résines vendues sous la dénomination versamid®, contenant une essence parfumante.US-P-3926655 describes a material essentially devoid of solvent consisting of a polyamide resin, in particular the resins sold under the name versamid®, containing a fragrance essence.
US-P-4184099 décrit des dispositifs destinés à contenir des substances volatiles, parfumantes, insecticides ou bactéricides constitués de résines polyamidiques d'une nature analogue à celle des résines décrites dans le brevet US-P-3926655 mais de poids moléculaire plus élevé.US-P-4184099 describes devices intended to contain volatile, scenting, insecticidal or bactericidal substances consisting of polyamide resins of a nature similar to that of the resins described in US-P-3926655 but of higher molecular weight.
Des produits à matrice polyoléfinique adaptés pour une utilisation dans un procédé "master-batch" (ou mélange- maître) , caractérisés par un contenu élevé en substances volatiles parfumantes, tels que le Polyiff de Flavors & Fragrance Inc., ont également été décrits. Les matrices utilisées correspondent à des résines à base de polyéthylène à basse densité, de polypropylène et d'éthylène vinyl acétate.Polyolefin matrix products suitable for use in a "master-batch" process, characterized by a high content of volatile perfuming substances, such as Polyiff from Flavors & Fragrance Inc., have also been described. The matrices used correspond to resins based on low density polyethylene, polypropylene and ethylene vinyl acetate.
EP-A-0167633 décrit un matériau pour lutter contre les insectes nuisibles permettant la libération lente d'une formulation insecticide. Ce matériau est formé par mélange et moulage de polyéthylène chloré, d'un élastomere thermoplastique et d'un ingrédient insecticide.EP-A-0167633 describes a material for controlling harmful insects allowing the slow release of an insecticidal formulation. This material is formed by mixing and molding chlorinated polyethylene, a thermoplastic elastomer and an insecticidal ingredient.
EP-A-0671123 décrit un matériau pour lutter contre les insectes nuisibles, ledit matériau comprenant un élastomere comprenant des blocs polyamides et des blocs polyéthers, en association avec un insecticide, tel que 1 'esbiotrine. Un dispositif pour lutter contre les insectes comprenant un élastomere thermoplastique, au moins un médiateur chimique agissant sur le comportement des insectes et acariens et choisi parmi les phéromones, les kairomones ou les allomones et éventuellement de l'acide undécylénique ou ses dérivés a été décrit dans EP-A-0680693. Ce document divulgue l'utilisation en tant qu'élastomère des élastomères comprenant des blocs polyamides et des blocs polyéthers. Le seul exemple fourni décrit un dispositif permettant la diffusion constante au cours du temps de la phéromone de la sésamie de maïs.EP-A-0671123 describes a material for combating harmful insects, said material comprising an elastomer comprising polyamide blocks and polyether blocks, in combination with an insecticide, such as esbiotrine. A device for combating insects comprising a thermoplastic elastomer, at least one chemical mediator acting on the behavior of insects and mites and chosen from pheromones, kairomones or allomones and optionally undecylenic acid or its derivatives has been described in EP-A-0680693. This document discloses the use as elastomer of elastomers comprising polyamide blocks and polyether blocks. The only example provided describes a device allowing the constant diffusion over time of the corn sesame pheromone.
D'autre part, un article pour la diffusion de vapeurs assainissantes consistant en une résine polymère de type polyétheresteramide contenant de 1 à 60% en poids, par rapport au poids de la résine, d'une substance volatile parfumante, odorante, insecticide, insectifuge, répulsive ou attirant les animaux a été décrit dans le brevet FR-A- 2579983. Il est décrit que l'article selon ce brevet permet une diffusion prolongée et uniforme des vapeurs d'une substance volatile (assainissante) . EP-A-0596772 décrit des compositions consistant en une résine polymère de type polyetheresteramide contenant de l'acide undécylénique, pour une action désodorisante; il n'y a pas d'utilisation d'un quelconque parfum ou autre et une seule substance imprégnée est décrite.On the other hand, an article for the diffusion of sanitizing vapors consisting of a polymeric resin of the polyetheresteramide type containing from 1 to 60% by weight, relative to the weight of the resin, of a volatile perfume, odorant, insecticide, insect repellant , repellent or attracting animals has been described in patent FR-A-2579983. It is described that the article according to this patent allows a prolonged and uniform diffusion of the vapors of a volatile (sanitizing) substance. EP-A-0596772 describes compositions consisting of a polymeric resin of the polyetheresteramide type containing undecylenic acid, for a deodorant action; there is no use of any perfume or the like and only one impregnated substance is described.
FR-A-2675387 décrit un procédé de préparation d'un objet parfumé susceptible de résister à des conditions de températures et d'hygrométrie drastiques. Ce procédé comporte une phase d'imprégnation d'une résine polymère de type polyetheresteramide par un parfum par malaxage (jusqu'à saturation de parfum) , suivie d'une phase de repos et d'une phase d'injection, mise en oeuvre à une température inférieure à 100°C.FR-A-2675387 describes a process for preparing a perfumed object capable of withstanding drastic temperature and hygrometry conditions. This process comprises a phase of impregnating a polymeric resin of the polyetheresteramide type with a perfume by kneading (until the perfume is saturated), followed by a rest phase and an injection phase, implemented at a temperature below 100 ° C.
Aucun des documents de l'art antérieur ne résout le problème du parfumage d'ambiance de qualité supérieure.None of the documents of the prior art solves the problem of high quality room perfuming.
En effet, le parfumeur sait que pour réaliser un parfumage sophistiqué de l'environnement il devra utiliser des matières premières comparables et des formulations similaires à celles des parfums corporels. Il parait également hautement souhaitable que la formulation d'un produit destiné à être respiré dans d'assez fortes quantités présente un niveau de sécurité comparable à celui des parfums corporels en contact avec la peau.Indeed, the perfumer knows that to achieve a sophisticated perfuming of the environment he will have to use comparable raw materials and formulations similar to those of body perfumes. It also seems highly desirable that the formulation of a product intended to be breathed in fairly large amounts has a level of safety comparable to that of body perfumes in contact with the skin.
D'autre part, l'attitude du consommateur montre clairement qu'il attend de son parfum d'ambiance un bénéfice comparable à ses habitudes en matière de parfum corporel, comparable aux senteurs de la nature que le parfumeur s'est ingénié à lui restituer aussi bien dans les parfums pour la toilette que dans les arômes alimentaires. II existe donc un besoin pour un article permettant de libérer des compositions parfumées complexes d'une façon régulière sans conduire à la séparation des différents constituants et par conséquent sans dégradation notable de leurs qualités au cours du temps. Aucun des documents de l'art antérieur ne décrit une résine parfumée permettant la diffusion de compositions parfumées complexes ni ne suggère comment obtenir une résine adaptée à cette fin. En particulier, le document FR-A- 2579983 ni ne décrit ni ne suggère qu'une résine polymère de type polyetheresteramide peut être utilisée pour la préparation d'une résine parfumée adaptée à la diffusion de compositions parfumées complexes selon la présente invention. La demanderesse a mis en évidence de façon surprenante qu'une résine parfumée constituée d'une résine polymère de type polyetheresteramide renfermant une composition parfumée complexe permet une diffusion régulière de l'ensemble des substances constitutives odorantes sans entraîner le phénomène de séparation de la diffusion des substances en fonction de leur volatilité classiquement rencontré dans les articles de diffusion de l'art antérieur et par conséquent sans dégradation notable de ses qualités dans le temps.On the other hand, the attitude of the consumer clearly shows that he expects from his room fragrance a benefit comparable to his habits in terms of body perfume, comparable to the scents of nature that the perfumer has tried to restore to him. both in toiletries and in food flavors. There is therefore a need for an article making it possible to release complex perfumed compositions in a regular manner without leading to the separation of the various constituents and therefore without significant degradation of their qualities over time. None of the documents of the prior art describes a perfumed resin allowing the diffusion of complex perfumed compositions nor does it suggest how to obtain a resin suitable for this purpose. In particular, the document FR-A-2579983 neither describes nor suggests that a polymer resin of polyetheresteramide type can be used for the preparation of a perfumed resin suitable for the diffusion of complex perfumed compositions according to the present invention. The Applicant has surprisingly demonstrated that a perfumed resin made up of a polymeric resin of the polyetheresteramide type containing a complex perfumed composition allows a regular diffusion of all the odorous constituent substances without causing the phenomenon of separation of the diffusion of the substances according to their volatility conventionally encountered in articles of dissemination of the prior art and therefore without significant degradation of its qualities over time.
Une telle résine permet donc l'obtention de parfums d'ambiance sophistiqués comparables aux parfums corporels.Such a resin therefore makes it possible to obtain sophisticated ambient perfumes comparable to body perfumes.
La présente invention repose sur l'effet surprenant qu'une telle résine ne se comporte pas comme un support de séparation chromatographique conduisant à une diffusion séparée des différents composants volatils qu'il renferme. De façon inattendue, tous les constituants volatils sont libérés d'une façon constante sans aucun phénomène de séparation et par conséquent sans aucune dégradation notable des qualités de la composition parfumée.The present invention is based on the surprising effect that such a resin does not behave like a chromatographic separation support leading to a separate diffusion of the various volatile components which it contains. Unexpectedly, all the volatile constituents are released in a constant manner without any phenomenon of separation and consequently without any notable degradation of the qualities of the perfumed composition.
La présente invention fournit donc une résine parfumée comprenant :The present invention therefore provides a perfumed resin comprising:
(a) une résine polymère de type polyether-esteramide répondant à la formule :(A) a polymeric resin of polyether-esteramide type corresponding to the formula:
Figure imgf000007_0001
Figure imgf000007_0001
dans laquelle PA représente le segment polyamide et PE représente le segment polyéther et n est un entier représentant la répartition des unités récurrentes; et (b) une composition parfumée complexe.wherein PA represents the polyamide segment and PE represents the polyether segment and n is an integer representing the distribution of the repeating units; and (b) a complex scent composition.
Selon un mode de réalisation, la résine parfumée selon l'invention comprend, en poids par rapport au poids de ladite résine parfumée, 99% à 5% en poids de résine polymère de type polyetheresteramide et 1 à 95% en poids d'une composition parfumée complexe, et de préférence respectivement 90 à 5% en poids de résine polymère de type polyetheresteramide et 10 à 95% en poids d'une composition parfumée complexe.According to one embodiment, the perfumed resin according to the invention comprises, by weight relative to the weight of said perfumed resin, 99% to 5% by weight of polymer resin of polyetheresteramide type and 1 to 95% by weight of a complex perfumed composition, and preferably 90 to 5% by weight of polymeric resin of polyetheresteramide type and 10 to 95% by weight of a complex perfumed composition, respectively.
Selon un mode de réalisation, la résine parfumée selonAccording to one embodiment, the perfumed resin according to
1 ' invention comprend, en poids par rapport au poids de ladite résine parfumée, 50 à 10% en poids de résine polymère de type polyetheresteramide et 50 à 90% en poids d'une composition parfumée complexe.1 invention comprises, by weight relative to the weight of said perfumed resin, 50 to 10% by weight of polymeric resin of the polyetheresteramide type and 50 to 90% by weight of a complex perfumed composition.
Selon un mode de réalisation, la résine parfumée selon l'invention comprend, en poids par rapport au poids de ladite résine parfumée, environ 40% en poids de résine polymère de type polyetheresteramide et environ 60% en poids d'une composition parfumée complexe.According to one embodiment, the perfumed resin according to the invention comprises, by weight relative to the weight of said perfumed resin, about 40% by weight of polymer resin of polyetheresteramide type and about 60% by weight of a complex perfumed composition.
Selon un autre mode de réalisation, dans la résine parfumée selon l'invention, la résine polymère de type PEEA est obtenue à partir de blocs PA-12 et de blocs PTMG, de préférence avec une dureté Shore A de 25. Selon un autre mode de réalisation, dans la résine parfumée selon l'invention, la composition parfumée complexe comprend au moins 5 composants, de préférence au moins 20 composants .According to another embodiment, in the perfumed resin according to the invention, the polymer resin of the PEEA type is obtained from PA-12 blocks and PTMG blocks, preferably with a Shore A hardness of 25. According to another mode embodiment, in the perfumed resin according to the invention, the complex perfumed composition comprises at least 5 components, preferably at least 20 components.
L'invention fournit encore une résine parfumée, comprenant de plus de l'alcool ethylique, en une proportion de 5 à 30% du poids final, de préférence environ 10%. Cet alcool est de préférence l'alcool dit "de parfumerie".The invention also provides a perfumed resin, further comprising ethyl alcohol, in a proportion of 5 to 30% of the final weight, preferably about 10%. This alcohol is preferably the so-called "perfumery" alcohol.
L'invention a aussi pour objet un procédé de préparation d'une résine parfumée telle que décrite ci- dessus par mélange de la résine polymère de type PEEA avec la composition parfumée complexe.The invention also relates to a process for the preparation of a perfumed resin as described above by mixing the polymeric resin of the PEEA type with the complex perfumed composition.
Selon un mode de réalisation particulier le mélange est mis en oeuvre par enrobage selon la technique du drageoir.According to a particular embodiment, the mixture is used by coating according to the drageer technique.
Selon un autre mode de réalisation du procédé selon la présente invention on incorpore au mélange résineAccording to another embodiment of the method according to the present invention, the resin mixture is incorporated
PEEA/composition parfumée complexe de l'alcool ethylique, en une proportion de 5 à 30% du poids final, de préférence environ 10%. La présente invention a également pour objet les articles façonnés à partir d'une résine parfumée telle que décrite ci-dessus ainsi que les mélanges-maîtres obtenus à partir d'une telle résine parfumée. La présente invention concerne également l'utilisation des résines parfumées, articles façonnés et mélanges-maîtres tels que décrits ci-dessus pour le parfumage d'ambiance et notamment pour le parfumage d'ambiance pour automobile.PEEA / complex perfumed composition of ethyl alcohol, in a proportion of 5 to 30% of the final weight, preferably about 10%. The present invention also relates to articles shaped from a perfumed resin as described above as well as the masterbatches obtained from such a perfumed resin. The present invention also relates to the use of perfumed resins, shaped articles and masterbatches as described above for the perfume of ambiance and in particular for the perfume of ambiance for automobile.
L'invention est maintenant décrite plus en détails dans la description qui suit, et en référence aux dessins annexés, dans lesquels :The invention is now described in more detail in the following description, and with reference to the accompanying drawings, in which:
- la figure 1 est une courbe donnant, en fonction du temps, la quantité de matières volatiles de patchouli libérées, pour divers supports; - la figure 2 est une courbe donnant, en fonction du temps, le rapport entre un composant du patchouli et le galaxolide libérés, pour divers supports;- Figure 1 is a curve giving, as a function of time, the quantity of volatile patchouli materials released, for various supports; - Figure 2 is a curve giving, as a function of time, the ratio between a component of patchouli and the galaxolide released, for various supports;
- les figures 3a, 3b et 3c sont des courbes donnant, en fonction du temps, la quantité de trois matières volatiles spécifiques du patchouli libérées, pour divers supports.- Figures 3a, 3b and 3c are curves giving, as a function of time, the quantity of three volatile materials specific to patchouli released, for various supports.
Le polymère polyetheresteramide (PEEA) est constitué d'un enchaînement linéaire de segments polyamides rigides et de segments polyéthers souples répondant à la formule :The polyetheresteramide polymer (PEEA) consists of a linear chain of rigid polyamide segments and flexible polyether segments corresponding to the formula:
Figure imgf000009_0001
Figure imgf000009_0001
dans laquelle PA représente le segment polyamide et PE représente le segment polyether et n est un entier représentant la répartition des unités récurrentes.in which PA represents the polyamide segment and PE represents the polyether segment and n is an integer representing the distribution of the repeating units.
Ce polymère PEEA est obtenu par tout procédé approprié; en particulier la résine PEEA est obtenue par réaction à l'état fondu entre un polyamide dicarboxylique à fonctions carboxyliques terminales d'un poids moléculaire moyen compris entre 300 et 15000 et un polyoxyalkylène glycol aliphatique linéaire ou ramifié à fonctions hydroxyles terminales et d'un poids moléculaire moyen compris entre 200 et 6000, sous vide poussé à des températures comprises entre 100 et 400°C, en présence d'un catalyseur qui est par exemple un tétraalkyl-orthotitanate de formule générale Ti(OR)4 ou un tétraalkyl-orthostannate de formule générale Zn(OR)4 ; R étant un radical hydrocarboné aliphatique linéaire ou ramifié dont le nombre d'atomes de carbone est compris entre 1 et 24 et dont la teneur en poids par rapport au mélange réactionnel est comprise entre 0,001 et 5%.This PEEA polymer is obtained by any suitable process; in particular the PEEA resin is obtained by reaction in the molten state between a dicarboxylic polyamide with terminal carboxylic functions of an average molecular weight of between 300 and 15,000 and a linear or branched aliphatic polyoxyalkylene glycol with terminal hydroxyl functions and with a weight average molecular between 200 and 6000, under high vacuum at temperatures between 100 and 400 ° C, in the presence of a catalyst which is for example a tetraalkyl-orthotitanate of general formula Ti (OR) 4 or a tetraalkyl-orthostannate of general formula Zn (OR) 4; R being a linear or branched aliphatic hydrocarbon radical whose number of carbon atoms is between 1 and 24 and whose content by weight relative to the reaction mixture is between 0.001 and 5%.
Ces polymères à blocs polyamide et blocs polyether résultent de la copolycondensation de séquences polyamide à extrémités réactives avec des séquences polyether à extrémités réactives, telles que, entre autres :These polymers containing polyamide blocks and polyether blocks result from the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia:
- séquences polyamide à extrémités diamines avec des séquences polyoxyalkylénés à extrémités dicarboxyliques;- polyamide blocks with diamine ends with polyoxyalkylenated blocks with dicarboxylic ends;
- séquences polyamide à extrémités dicarboxyliques avec des séquences polyoxyalkylénés à extrémités diamines obtenues par cyanoéthylation et hydrogénation de séquences polyoxyalkylène alpha-oméga dihydroxylées aliphatiques appelés polyetherdiols;- polyamide blocks with dicarboxylic ends with polyoxyalkylenated blocks with diamine ends obtained by cyanoethylation and hydrogenation of polyoxyalkylene alpha-omega dihydroxylated aliphatic sequences called polyetherdiols;
- - séquences polyamide à extrémités diamines avec des séquences polyetherdiols, les produits obtenus étant dans ce cas particulier, des polyétheresteramides;- - polyamide blocks with diamine ends with polyetherdiol blocks, the products obtained being in this particular case, polyetheresteramides;
Les séquences polyamide à extrémités dicarboxyliques proviennent, par exemple, de la condensation d'acides alpha- oméga aminocarboxyliques, de lactames ou de combinaisons sensiblement stoechiométriques de diacides carboxyliques et de diamines, en présence d'un diacide carboxylique limitateur de chaîne. Avantageusement, les blocs polyamide sont du PA6 ou du PA12.The polyamide sequences with dicarboxylic ends originate, for example, from the condensation of alpha-omega aminocarboxylic acids, from lactams or from substantially stoichiometric combinations of dicarboxylic acids and diamines, in the presence of a chain-limiting dicarboxylic acid. Advantageously, the polyamide blocks are PA6 or PA12.
Le poids moléculaire moyen Mn des séquences polyamide varie de 300 à 15 000 et de préférence de 600 à 5 000.The average molecular weight Mn of the polyamide blocks varies from 300 to 15,000 and preferably from 600 to 5,000.
Le poids moléculaire moyen en nombre Mn des séquences polyether est compris entre 10 et 6 000 et de préférence entre 200 et 3 000.The number-average molecular weight Mn of the polyether sequences is between 10 and 6000 and preferably between 200 and 3000.
Les polymères à blocs polyamide et blocs polyether peuvent aussi comprendre des motifs répartis de façon aléatoire. Ces polymères peuvent être préparés par la réaction simultanée du polyether et des précurseurs des blocs polyamide. Par exemple, on peut faire réagir du polyétherdiol , un lactame (ou un alpha-oméga aminoacide correspondant) et un diacide limiteur de chaîne en présence d'un peu d'eau. On obtient un polymère ayant essentiellement des blocs polyéthers, des blocs polyamide de longueur très variable, mais aussi les différents réactifs ayant réagi de façon aléatoire qui sont répartis de façon statistique le long de la chaîne polymère.The polymers containing polyamide blocks and polyether blocks can also comprise units distributed randomly. These polymers can be prepared by the simultaneous reaction of polyether and precursors of polyamide blocks. For example, polyetherdiol, a lactam (or a corresponding alpha-omega amino acid) and a chain-limiting diacid can be reacted in the presence of a little water. A polymer is obtained which essentially has polyether blocks, polyamide blocks of very variable length, but also the various reactants which have reacted randomly which are distributed statistically along the polymer chain.
Ces polymères à blocs polyamide et blocs polyether qu'ils proviennent de la copolycondensation de séquences polyamide et polyether préparées auparavant ou d'une réaction en une étape, présentent, par exemple, des duretés Shore D pouvant être comprise entre 20 et 75, et une viscosité intrinsèque comprise entre 0,8 et 2,5 telle que mesurée dans le métacrésol à 25°C pour une concentration initiale de 0,8 g/100 ml.These polyamide block and polyether block polymers, whether they originate from the copolycondensation of polyamide and polyether blocks prepared beforehand or from a reaction in one step, exhibit, for example, Shore D hardnesses which may be between 20 and 75, and a intrinsic viscosity between 0.8 and 2.5 as measured in metacresol at 25 ° C for an initial concentration of 0.8 g / 100 ml.
Que les blocs polyether dérivent du polyéthylène glycol, du polyoxypropylène glycol ou du polyoxy- tétraméthylène glycol, ils sont soit utilisés tels quels et copolycondenses avec des blocs polyamide à extrémités carboxyliques, soit ils sont aminés pour être transformés en polyether diamines et condensés avec des blocs polyamide à extrémités carboxyliques. Ils peuvent être aussi mélangés avec des précurseurs de polyamide et un limiteur de chaîne pour obtenir des polymères à blocs polyamide et blocs polyether ayant des motifs répartis de façon statistique.Whether polyether blocks are derived from polyethylene glycol, polyoxypropylene glycol or polyoxytetramethylene glycol, they are either used as such and copolycondenses with polyamide blocks having carboxylic ends, or they are aminated to be transformed into polyether diamines and condensed with blocks polyamide with carboxylic ends. They can also be mixed with polyamide precursors and a chain limiter to obtain polymers with polyamide blocks and polyether blocks having randomly distributed units.
De tels polymères à blocs polyamide et polyether sont décrits dans les brevets suivants, incorporés par référence à la présente demande : US-P-4331786, US-P-4115475, US-P- 4195015, US-P-4839441 , US-P-4864014 , US-P-4230838 et US-P- 4332920.Such polymers with polyamide and polyether blocks are described in the following patents, incorporated by reference into the present application: US-P-4331786, US-P-4115475, US-P- 4195015, US-P-4839441, US-P -4864014, US-P-4230838 and US-P- 4332920.
Le polyether peut être par exemple un polyéthylène glycol (PEG) , un polypropylène glycol (PPG) ou un polytétraméthylène glycol (PTMG, aussi appelé poly tétrahydrofurane, PTHF) .The polyether can for example be a polyethylene glycol (PEG), a polypropylene glycol (PPG) or a polytetramethylene glycol (PTMG, also called poly tetrahydrofuran, PTHF).
Que les blocs polyether soient dans la chaîne du polymère à blocs polyamide et blocs polyether sous forme de diols ou de diamines, on les appelle par simplification blocs PEG ou blocs PPG ou blocs PTMG. On ne sortirait pas du cadre de la présente invention si les blocs polyether contenaient des motifs différents tels que ceux dérivant de l'éthylène glycol, du propylène glycol ou du tétraméthylène glycol. De préférence, le polymère à blocs polyamide et blocs polyether comprend un seul type de bloc polyamide et un seul type de bloc polyether. On utilise avantageusement des polymères à blocs PA12 et blocs PEG, des polymères à blocs PA12 et blocs PTMG, des polymères à blocs PA6 et blocs PEG, et des polymères à blocs PA6 et PTMG.Whether the polyether blocks are in the polymer chain with polyamide blocks and polyether blocks in the form of diols or diamines, they are called for simplification PEG blocks or PPG blocks or PTMG blocks. It would not be departing from the scope of the present invention if the polyether blocks contained different units such as those derived from ethylene glycol, propylene glycol or tetramethylene glycol. Preferably, the polymer with polyamide blocks and polyether blocks comprises a single type of polyamide block and a single type of polyether block. Advantageously, polymers with PA12 blocks and PEG blocks are used, polymers with PA12 blocks and PTMG blocks, polymers with PA6 blocks and PEG blocks, and polymers with PA6 and PTMG blocks.
On peut aussi utiliser des mélanges de polymères à blocs polyamide et blocs polyether.It is also possible to use mixtures of polymers with polyamide blocks and polyether blocks.
Avantageusement, le polymère à blocs polyamide et blocs polyether est tel que le polyamide est le constituant minoritaire en poids, c'est-à-dire que la quantité de polyamide qui est sous forme de blocs et celle qui est éventuellement répartie de façon statistique dans la chaîne représente au plus 50% en poids du polymère à blocs polyamide et blocs polyether. Avantageusement, la quantité de polyamide et la quantité de polyether sont dans un rapport en poids (polyamide/polyéther) compris entre 1/1 et 1/5. Un polyetheresteramide employé avec avantage dans l'invention présente un ratio pondéral polyamide/polyéther de 0,3. De tels polymères à blocs polyamide et à blocs polyether sont commercialisés par la société Elf Atochem sous la dénomination Pebax®.Advantageously, the polymer with polyamide blocks and polyether blocks is such that the polyamide is the minor constituent by weight, that is to say that the amount of polyamide which is in the form of blocks and that which is optionally distributed statistically in the chain represents at most 50% by weight of the polymer with polyamide blocks and polyether blocks. Advantageously, the amount of polyamide and the amount of polyether are in a weight ratio (polyamide / polyether) of between 1/1 and 1/5. A polyetheresteramide advantageously used in the invention has a polyamide / polyether weight ratio of 0.3. Such polymers containing polyamide blocks and polyether blocks are sold by the company Elf Atochem under the name Pebax®.
Tout type de PEBAX peut être utilisé dans le cadre de la présente invention. Les grades souples de PEBAX qui possèdent comme particularité d'absorber en quantité importante des matières volatiles (i.e. 1,2 fois leur poids de matières volatiles complexes telles que les parfums de haut de gamme) puis de les diffuser dans leur intégralité avec une grande régularité dans le temps et sans entraîner leur séparation sont particulièrement appropriés dans le cadre de la présente invention. On utilisera de préférence les PEBAX® de faible dureté, tel que le PEBAX® obtenu à partir de PA-12 et de PTMG. Ce polymère PEEA peut se présenter sous la forme de billes d'un diamètre de quelques mm.Any type of PEBAX can be used in the context of the present invention. The flexible grades of PEBAX which have the particularity of absorbing a large quantity of volatile matter (ie 1.2 times their weight of complex volatile matter such as high-end perfumes) and then diffusing them in their entirety with great regularity over time and without causing their separation are particularly suitable in the context of the present invention. Preferably PEBAX® of low hardness, such as PEBAX® obtained from PA-12 and PTMG, will be used. This PEEA polymer can be in the form of beads with a diameter of a few mm.
On entend par composition parfumée complexe dans le cadre de la présente invention une composition contenant au moins 2 composants aromatiques volatils entrant dans la composition d'un parfum ou d'un déodorant, lesdits composants volatils présentant généralement des volatilités différentes. De préférence, il y a au moins 5, avantageusement au moins 20 composants. Des compositions parfumées peuvent contenir 30 et jusque 50, voire 80 composants. On peut citer à titre d'exemple de compositions complexes les compositions d'origine animale ou végétale. Le terme composant aromatique tel qu'il est utilisé dans le cadre de la présente invention englobe tous les composants odorants volatils pouvant être utilisés dans la formulation d'un parfum ou d'un déodorant et comprend notamment les composés cités dans l'encyclopédie Kirk Othmer (vol 16, page 947-970) ainsi que les différents arômes alimentaires connus . L'alcool ethylique utilisé dans les résines parfumées de l'invention, en particulier l'alcool de parfumerie, permet d'homogénéiser la base parfum et de favoriser le développement des arômes et senteurs lors de la désorption. L'alcool ethylique, en particulier l'alcool de parfumerie, est très bien absorbé par le polyetheresteramide et améliore, par macération ou dans le temps, les qualité d'un extrait de parfum ou d'arôme.The term “complex perfumed composition” is understood to mean, in the context of the present invention, a composition containing at least 2 volatile aromatic components used in the composition of a perfume or a deodorant, said volatile components generally having different volatilities. Preferably, there are at least 5, advantageously at least 20 components. Perfumed compositions can contain 30 and up to 50 or even 80 components. Mention may be made, by way of example of complex compositions, of compositions of animal or vegetable origin. The term aromatic component as used in the context of the present invention includes all volatile odorous components which can be used in the formulation of a perfume or a deodorant and includes in particular the compounds cited in the encyclopedia Kirk Othmer (vol 16, page 947-970) as well as the various known food flavors. The ethyl alcohol used in the perfumed resins of the invention, in particular perfume alcohol, makes it possible to homogenize the perfume base and to promote the development of aromas and scents during desorption. Ethyl alcohol, in particular perfume alcohol, is very well absorbed by the polyetheresteramide and improves, by maceration or over time, the quality of a perfume or aroma extract.
La résine parfumée selon la présente invention peut être préparée par mélange du polymère de type polyetheresteramide avec la composition parfumée complexe devant être incorporée. Toute technique de mélange classiquement utilisée dans l'art antérieur peut être utilisée à cette fin. L'opération de mélange la plus adaptée est réalisée par enrobage selon la technique du drageoir, mis en rotation lente à 30/60 tours/minutes, à une température ambiante de 20 à 25°C, avec une incorporation continue de la composition parfumée complexe réalisée simplement par déversement de cette dernière par un robinet dont le débit est réglé pour éviter qu'un excès de la composition parfumée ne vienne gêner le libre mouvement des granulés dans le drageoir en rotation. Selon la proportion composition parfumée/résine polymère de type polyetheresteramide recherchée, le temps d'imprégnation variera de 20 à 120 minutes pour obtenir des granules secs au toucher, immédiatement ou après une phase de repos. La vitesse de rotation peut être variée au cours de l'imprégnation, pour tenir compte de la variation de comportement des granulés, selon que ceux-ci sont soit complètement soit partiellement immergés dans un liquide ou que ceux-ci ont absorbé le liquide. La vitesse de rotation est choisie de sorte que les granulés soit de préférence toujours en mouvement. La température à laquelle est mise en oeuvre l'imprégnation peut être aussi supérieure à la température ambiante, et de préférence inférieure à 40-45°C.The perfumed resin according to the present invention can be prepared by mixing the polyetheresteramide type polymer with the complex perfumed composition to be incorporated. Any mixing technique conventionally used in the prior art can be used for this purpose. The most suitable mixing operation is carried out by coating using the bezel technique, slowly rotating at 30/60 rpm, at an ambient temperature of 20 to 25 ° C, with continuous incorporation of the complex scented composition simply carried out by pouring the latter through a tap whose flow rate is regulated to prevent an excess of the perfumed composition does not interfere with the free movement of the granules in the rotating bezel. Depending on the proportion of perfumed composition / polymer resin of polyetheresteramide type desired, the impregnation time will vary from 20 to 120 minutes to obtain granules which are dry to the touch, immediately or after a resting phase. The rotation speed can be varied during impregnation, to take account of the variation in behavior of the granules, depending on whether they are either completely or partially immersed in a liquid or whether they have absorbed the liquid. The speed of rotation is chosen so that the granules are preferably always in motion. The temperature at which the impregnation is carried out can also be higher than ambient temperature, and preferably lower than 40-45 ° C.
L'aspect des granules imprégnés est légèrement translucide et offre des possibilités décoratives intéressantes. Un colorant, lorsqu'il est ajouté, peut l'être lors de l'imprégnation de la résine ou de préférence au préalable dans la base parfum. L'invention a aussi pour objet un objet décoré.The appearance of the impregnated granules is slightly translucent and offers interesting decorative possibilities. A colorant, when added, can be added during the impregnation of the resin or preferably beforehand in the perfume base. The invention also relates to a decorated object.
Le procédé d'imprégnation selon l'invention permet par ailleurs d'éviter l'emploi de silice colloïdale, telle que aerosil®. Pour favoriser l'imprégnation mais également pour s'approcher du comportement des parfums corporels et améliorer la perception de ses qualités, on incorpore avantageusement de l'alcool ethylique (dénaturé selon la norme du pays de consommation) , avantageusement en une proportion de 10% du poids final. L'alcool préféré est l'alcool dit "de qualité parfumerie".The impregnation process according to the invention also makes it possible to avoid the use of colloidal silica, such as aerosil®. To favor the impregnation but also to approach the behavior of the body perfumes and improve the perception of its qualities, one advantageously incorporates ethyl alcohol (denatured according to the norm of the country of consumption), advantageously in a proportion of 10% of the final weight. The preferred alcohol is the so-called "perfume quality" alcohol.
La résine parfumée selon la présente invention peut être utilisée telle quelle c'est à dire sous la forme de billes présentant un diamètre de quelques millimètres, ou peut être façonnée en diverses formes, fonctionnelles ou décoratives. Elle peut être façonnée facilement par extrusion ou par moulage selon les techniques usuelles utilisées pour la transformation des matériaux polymères thermoplastiques. La température de transformation est classique, mais peut être aussi élevée que 160°C.The perfumed resin according to the present invention can be used as it is, that is to say in the form of beads having a diameter of a few millimeters, or can be shaped into various shapes, functional or decorative. It can be easily shaped by extrusion or by molding according to the usual techniques used for the transformation of thermoplastic polymer materials. The processing temperature is conventional, but can be as high as 160 ° C.
La résine parfumée selon la présente invention peut, par ailleurs, être utilisée pour la préparation de concentrés qui, par exemple, sous forme de granulés ou d'extrudats, seront incorporés dans d'autres polymères thermoplastiques selon la méthode dite du "master-batch" .The perfumed resin according to the present invention can, moreover, be used for the preparation of concentrates which, for example, in the form of granules or extrudates, will be incorporated into other thermoplastic polymers according to the so-called "master-batch" method. ".
Cette méthode dite du "master-batch" est décrite, par exemple, dans Rubber & Plastics, 423283 (1961) . Ces polymères thermoplastiques peuvent être, par exemple, des (co)polyoléfines, l'EVA, le PVC et autres.This so-called "master-batch" method is described, for example, in Rubber & Plastics, 423283 (1961). These thermoplastic polymers can be, for example, (co) polyolefins, EVA, PVC and others.
Ainsi, selon un mode de réalisation, la présente invention à pour objet des articles façonnés à partir de la présente résine parfumée et des mélanges-maîtres obtenus à partir de cette dernière.Thus, according to one embodiment, the present invention relates to articles shaped from the present scented resin and masterbatches obtained from the latter.
Une application particulière de la présente invention est la fabrication d'articles de parfum d'ambiance et plus particulièrement d'articles de parfum d'ambiance pour automobile. La résine parfumée selon la présente invention permettant une diffusion constante des compositions parfumées complexes peut donc être également associée à des systèmes qui accélèrent la diffusion des substances volatiles tels que la ventilation, la chaleur, ou la mise en mouvement. Par ailleurs, cette diffusion est parfaite, tant avec des PEEA sous forme de granules industriels que thermo formés .A particular application of the present invention is the manufacture of room fragrance articles and more particularly of room fragrance articles for cars. The perfumed resin according to the present invention allowing constant diffusion of complex perfumed compositions can therefore also be combined with systems which accelerate the diffusion of volatile substances such as ventilation, heat, or setting in motion. Furthermore, this diffusion is perfect, both with PEEAs in the form of industrial granules and thermoformed ones.
Bien entendu, la présente composition ainsi que les articles en résultant peuvent contenir tout type d'additif ou adjuvant classiquement utilisé par l'homme de l'art.Of course, the present composition and the articles resulting therefrom can contain any type of additive or adjuvant conventionally used by those skilled in the art.
Les exemples suivants illustrent l'invention sans la limiter. Exemple 1 :The following examples illustrate the invention without limiting it. Example 1:
Cet exemple décrit un test comparatif de la capacité d'absorption d'essence de lavande par différents produits à savoir: PEBAX®, ouate de cellulose, éthylène vinyl acétate (EVA) et polyéthylène (PE) .This example describes a comparative test of the absorption capacity of lavender essence by different products, namely: PEBAX®, cellulose wadding, ethylene vinyl acetate (EVA) and polyethylene (PE).
L'essence de lavande est complexe car contient plus de 20 différents composés chimiques. Le Pebax® utilisé est un copolymère PA12/PTMG, présentant un rapport pondéral PA12/PTMG de 600/2000, un indice d'écoulement à l'état fondu (MFI) de 10 (mesuré à 235°C, sous 1kg, avec une filière de 2mm) .The essence of lavender is complex because it contains more than 20 different chemical compounds. The Pebax® used is a PA12 / PTMG copolymer, having a PA12 / PTMG weight ratio of 600/2000, a melt flow index (MFI) of 10 (measured at 235 ° C., under 1 kg, with a 2mm die).
Les résultats obtenus après élimination de l'excès de parfum non absorbé sont donnés dans le tableau 1 ci-dessous. Tableau 1The results obtained after elimination of the excess of unabsorbed perfume are given in Table 1 below. Table 1
Figure imgf000016_0001
Figure imgf000016_0001
* Les variations de volume ne sont pas mesurables .* Changes in volume are not measurable.
Exemple 2Example 2
Cet exemple compare la capacité de diffusion de l'essence de Patchouli (plus de 20 composants) à partir de différents supports tels que: PEBAX, ouate de cellulose, EVA et PE. Ce test est mis en oeuvre sur une période de 4 mois.This example compares the diffusion capacity of Patchouli essence (more than 20 components) from different supports such as: PEBAX, cellulose wadding, EVA and PE. This test is implemented over a period of 4 months.
L'analyse chromatographique montre que la diffusion des matières volatiles à travers le PEBAX® demeure constante dans le temps. Les résultats sont représentés graphiquement à la figure 1. Exemple 3 :Chromatographic analysis shows that the diffusion of volatile matter through PEBAX® remains constant over time. The results are shown graphically in Figure 1. Example 3:
La capacité de diffusion d'une composition parfumée complexe à partir de différents supports est comparée. Les supports étudiés sont: PEBAX® (identique à celui de l'exemple 1), ouate de cellulose, EVA et PE. Le test comparatif, mis en oeuvre sur une période de 4 mois, permet d'étudier la diffusion d'une composition contenant des essences de Patchouli et Galaxolide (un composant, en solvant) .The diffusion capacity of a complex perfumed composition from different supports is compared. The supports studied are: PEBAX® (identical to that of Example 1), cellulose wadding, EVA and PE. The comparative test, implemented over a period of 4 months, makes it possible to study the diffusion of a composition containing essences of Patchouli and Galaxolide (one component, in solvent).
L'analyse par chromatographie en phase gazeuse des vapeurs diffusées montre que le PEBAX® permet une diffusion constante et dans leur intégralité de l'ensemble des substances volatiles présentes et ce sans qu'aucun phénomène de séparation ne soit observé. Les résultats sont représentés graphiquement à la figure 2, qui donne le rapport entre un composé du patchouli et le galaxolide. Exemple 4 : La capacité de diffusion d'une composition parfumée complexe à partir de différents supports est comparée. Les supports étudiés sont: PEBAX® (identique à celui de l'exemple 1), ouate de cellulose et EVA. Le test comparatif, mis en oeuvre sur une période de 25 jours, permet d'étudier la diffusion d'une composition contenant des essences de Lavandin (plus de 20 composants) .Analysis by gas chromatography of the vapors diffused shows that PEBAX® allows a constant and complete diffusion of all the volatile substances present without any phenomenon of separation being observed. The results are shown graphically in Figure 2, which gives the relationship between a patchouli compound and galaxolide. Example 4: The capacity of diffusion of a complex perfumed composition from different supports is compared. The supports studied are: PEBAX® (identical to that of Example 1), cellulose wadding and EVA. The comparative test, implemented over a period of 25 days, makes it possible to study the diffusion of a composition containing Lavandin essences (more than 20 components).
L'essence de lavandin étant constituée de très nombreux constituants, on a choisi de suivre l'évolution de deux pics intenses et d'un pic large. Le pic B est le pic large entre 13,10 et 13,75, le pic C est le pic à 14,10, et le pic D est le pic à 15,20, les données étant obtenues avec du lavandin pur à 125°C, et avec une colonne Innowax (30m/0,320mm/0,5μm) .The essence of lavandin being made up of very many constituents, we chose to follow the evolution of two intense peaks and a broad peak. Peak B is the broad peak between 13.10 and 13.75, peak C is the peak at 14.10, and peak D is the peak at 15.20, data being obtained with pure lavandin at 125 ° C, and with an Innowax column (30m / 0.320mm / 0.5μm).
Pour étudier la cinétique de désorption du lavandin, on prélève aux jours des mesures une quantité de composition de lOOmg, qui est désorbée complètement à 125°C pendant 35mn, puis en utilisant la technique ci-dessus on détermine les quantités respectives de chaque pic.To study the desorption kinetics of lavandin, a quantity of composition of 100 mg is taken from the measurement days, which is completely desorbed at 125 ° C for 35 minutes, then using the above technique, the respective amounts of each peak are determined.
Les résultats sont représentés graphiquement aux figures 3a, 3b et 3c, qui donnent les quantités des substances correspondant aux pics considérés en fonction du temps, pour des supports Pebax®, EVA et ouate de cellulose.The results are represented graphically in FIGS. 3a, 3b and 3c, which give the quantities of the substances corresponding to the peaks considered as a function of time, for Pebax®, EVA and cellulose wadding supports.
Par ailleurs, on a déterminé le pourcentage % en poids de matières volatiles présentes dans la composition, initialement et après 15 jours à l'air libre. Les résultats sont consignés dans le tableau 2 ci -dessous : Tableau 2Furthermore, the percentage by weight of volatile matter present in the composition was determined initially and after 15 days in the open air. The results are reported in Table 2 below: Table 2
Figure imgf000018_0001
Figure imgf000018_0001
Les résultats obtenus dans le présent exemple montrent que le PEBAX® permet, par rapport à l'EVA et à la ouate de cellulose, une diffusion constante et dans leur intégralité de l'ensemble des substances volatiles présentes.The results obtained in the present example show that PEBAX® allows, with respect to EVA and cellulose wadding, a constant diffusion and in their entirety of all the volatile substances present.
Bien entendu, l'invention n'est pas limitée aux modes de réalisation décrits mais est susceptible de nombreuses variantes aisément accessibles à l'homme de l'art. Of course, the invention is not limited to the embodiments described but is capable of numerous variants easily accessible to those skilled in the art.

Claims

REVENDICATIONS
1 . Résine parfumée comprenant :1. Scented resin comprising:
( a ) une résine polymère de type polyether- esteramide répondant à la formule :(a) a polymer resin of polyether-esteramide type corresponding to the formula:
Figure imgf000019_0001
Figure imgf000019_0001
dans laquelle PA représente le segment polyamide et PE représente le s egment polyether et n est un enti er représentant la répartition des unités récurrentes ; et (b) une composition parfumée complexe .in which PA represents the polyamide segment and PE represents the polyether segment and n is an integer representing the distribution of the recurring units; and (b) a complex scent composition.
2. Résine parfumée selon la revendication 1 comprenant, en poids par rapport au poids de ladite résine parfumée, 99% à 5% en poids, de préférence 90 à 5% en poids, de résine polymère de type polyetheresteramide et 1 à 95% en poids, de préférence 10 à 95% en poids.2. Perfumed resin according to claim 1 comprising, by weight relative to the weight of said perfumed resin, 99% to 5% by weight, preferably 90 to 5% by weight, of polymeric resin of polyetheresteramide type and 1 to 95% by weight. weight, preferably 10 to 95% by weight.
3. Résine parfumée selon la revendication 1 ou 2, comprenant, en poids par rapport au poids de ladite résine parfumée, 50 à 10% en poids de résine polymère de type polyetheresteramide et 50 à 90% en poids d'une composition parfumée complexe.3. Perfumed resin according to claim 1 or 2, comprising, by weight relative to the weight of said perfumed resin, 50 to 10% by weight of polymeric resin of the polyetheresteramide type and 50 to 90% by weight of a complex perfumed composition.
4. Résine parfumée selon l'une quelconque des revendications 1 à 3, comprenant, en poids par rapport au poids de ladite résine parfumée, environ 40% en poids de résine polymère de type polyetheresteramide et environ 60% en poids d'une composition parfumée complexe.4. Perfumed resin according to any one of claims 1 to 3, comprising, by weight relative to the weight of said perfumed resin, approximately 40% by weight of polyetheresteramide type polymer resin and approximately 60% by weight of a perfumed composition complex.
5. Résine parfumée selon l'une quelconque des revendications 1 à 4, dans laquelle la résine polymère de type PEEA est obtenue à partir de blocs PA-12 et de blocs PTMG, de préférence avec une dureté Shore A de 25. 5. Perfumed resin according to any one of claims 1 to 4, in which the polymer resin of the PEEA type is obtained from PA-12 blocks and PTMG blocks, preferably with a Shore A hardness of 25.
6 . Résine parfumée selon l ' une quelconque des revendications l à 5 , dans laquel le la compos i t ion parf umée compl exe comprend au moins 5 composant s , de préf érence au moins 20 composants .6. Perfumed resin according to any one of Claims 1 to 5, in which the complete perfumed composition comprises at least 5 components, preferably at least 20 components.
7 . Résine parfumée selon l ' une quelconque des revendications précédentes , comprenant de plus de l ' alcool ethylique , en une proportion de 5 à 30% du poids f inal , de préf érence environ 10% .7. Perfumed resin according to any one of the preceding claims, further comprising ethyl alcohol, in a proportion of 5 to 30% of the final weight, preferably about 10%.
8. Résine parfumée selon la revendication 7, dans laquelle l'alcool ethylique est l'alcool de parfumerie.8. Perfumed resin according to claim 7, in which the ethyl alcohol is perfume alcohol.
9. Procédé de préparation d'une résine parfumée selon l'une quelconque des revendications précédentes par mélange de la résine polymère de type PEEA avec la composition parfumée complexe.9. Process for the preparation of a perfumed resin according to any one of the preceding claims by mixing the polymeric resin of the PEEA type with the complex perfumed composition.
10. Procédé de préparation selon la revendication 9, dans lequel on incorpore au mélange de l'alcool ethylique, en une proportion de 5 à 30% du poids final, de préférence environ 10%.10. The preparation process according to claim 9, in which ethyl alcohol is incorporated in the mixture in a proportion of 5 to 30% of the final weight, preferably approximately 10%.
11. Procédé de préparation selon la revendication 9 ou 10, dans lequel le mélange est mis en oeuvre par enrobage selon la technique du drageoir.11. The preparation method according to claim 9 or 10, in which the mixture is used by coating according to the drageer technique.
12. Article façonné à partir d'une résine parfumée selon l'une quelconque des revendications 1 à 8.12. An article shaped from a perfumed resin according to any one of claims 1 to 8.
13. Article façonné selon la revendication 12, qui est décoré.13. The shaped article according to claim 12, which is decorated.
14. Mélange-maître obtenu à partir d'une résine parfumée selon l'une quelconque des revendications 1 à 8. 14. Masterbatch obtained from a perfumed resin according to any one of claims 1 to 8.
15. Utilisation d'une résine parfumée selon l'une quelconque des revendications 1 à 8 ou d'un article selon la revendication 12 ou 13 pour le parfumage d'ambiance.15. Use of a perfumed resin according to any one of claims 1 to 8 or of an article according to claim 12 or 13 for ambient perfuming.
16. Utilisation selon la revendication 15 pour le parfumage d'ambiance pour automobile. 16. Use according to claim 15 for the perfume of ambiance for automobile.
PCT/FR1997/000076 1996-01-16 1997-01-16 Novel fragrant resin for uniformly diffusing a complex fragrance composition WO1997026020A1 (en)

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EP0920987A1 (en) * 1997-12-05 1999-06-09 ERA BESCHICHTUNG GmbH & CO. KG Plastic covering material containing fragrance
WO2004014438A1 (en) 2003-06-12 2004-02-19 Firmenich Sa Gels for dispensing active volatile materials
US7708982B2 (en) 2003-06-12 2010-05-04 Firmenich Sa Gels for dispensing active volatile materials
CN100480308C (en) * 2003-11-14 2009-04-22 宝洁公司 Polymeric compositions for sustained release of volatile materials
WO2005049717A3 (en) * 2003-11-14 2005-07-21 Procter & Gamble Polymeric compositions for sustained release of volatile materials
WO2005049717A2 (en) * 2003-11-14 2005-06-02 The Procter & Gamble Company Polymeric compositions for sustained release of volatile materials
EP1531169A1 (en) * 2003-11-14 2005-05-18 The Procter & Gamble Company Polymeric compositions for sustained release of volatile materials
US7833515B2 (en) 2003-11-14 2010-11-16 Procter & Gamble Company Polymeric compositions for sustained release of volatile materials
US8043606B2 (en) 2005-12-07 2011-10-25 The Procter & Gamble Company Polymeric compositions for sustained release of volatile materials
US8916140B2 (en) 2005-12-07 2014-12-23 The Procter & Gamble Company Polymeric compositions for sustained release of volatile materials
FR2897354A1 (en) * 2006-02-16 2007-08-17 Arkema Sa Use of a copolymer e.g. as a breathable-water proof product, an additive conferring breathable-water proof properties on thermoplastic polymers to form a membrane with selective diffusion as a function of the type of gas
JP2009155649A (en) * 2009-02-20 2009-07-16 Firmenich Sa Gel for dispensing active volatile material
WO2011067732A1 (en) 2009-12-04 2011-06-09 Firmenich Sa Gel air freshener
US8679469B2 (en) 2009-12-04 2014-03-25 Firmenich Sa Gel air freshener

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FR2743566A1 (en) 1997-07-18
FR2743566B1 (en) 1998-05-07
EP0876162A1 (en) 1998-11-11

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