EP0403336B1 - Composition for the antifelting of wool and process of improvement - Google Patents
Composition for the antifelting of wool and process of improvement Download PDFInfo
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- EP0403336B1 EP0403336B1 EP90401561A EP90401561A EP0403336B1 EP 0403336 B1 EP0403336 B1 EP 0403336B1 EP 90401561 A EP90401561 A EP 90401561A EP 90401561 A EP90401561 A EP 90401561A EP 0403336 B1 EP0403336 B1 EP 0403336B1
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- microparticles
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- methacrylate
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/12—Processes in which the treating agent is incorporated in microcapsules
Definitions
- the subject of the invention is a composition for the anti-felting treatment of wool.
- Woolen articles can undergo irreversible shrinkage caused by felting during successive wet processes such as washing or dyeing, during use or during maintenance operations. This shrinkage is due to the very nature of the fibers that make up wool. These keratin-based fibers are in fact composed of a multitude of scales which, during repeated mechanical operations, are caused to overlap. A frictional force then appears between the scales of the fibers which has the effect of reducing the dimensions of the finished article.
- All industrial wool anti-felting treatment processes are based on means making it possible to reduce the friction forces. Some of these treatments are based on the degradation of the scales of the fibers constituting the wool, generally by the action of oxidizing means.
- oxidizing means are chlorine, in the form of gas or hypochloric acid, and the sodium salt of dichlorocyanuric acid.
- These polymers must have a certain number of qualities and in particular they must have a resistance to washing, to drying and a permanence when the simple use of the fiber on which they are applied (resistance to friction, to sweat, to light ). They must, moreover, not alter the intrinsic quality of the wool during their application.
- the main disadvantage of many commercial products is to make the wool on which they are applied rough: the fiber becomes hard and difficult to wear. This phenomenon is due to the high glass transition temperature of the polymer. In order to obtain a compromise between the anti-felting qualities and the softness of the wool, the polymer must have a relatively low glass transition temperature. The polymer must also be able to completely cover the fiber. Consequently, the surface of the fiber must be completely wetted by the composition containing the polymer.
- the composition containing the polymer must have a sufficiently low surface tension to achieve this aim.
- the composition used must have a flexibility of use allowing a continuous or discontinuous treatment to be carried out on combed wool ribbons, fabrics or even knitwear.
- it must be able to be used at a concentration of active product making it possible to limit the cost of the operation.
- the prior art wool anti-felting compositions do not simultaneously exhibit these different properties.
- the invention thus relates to a composition for the anti-felting treatment of wool comprising on the one hand between 5 and 20% by weight of microparticles constituted by a copolymer of acrylic and / or methacrylic monomer units, and on the other hand between 80 and 95% water with stabilizers added, in which the microparticles have a surface consisting of a copolymer containing a high proportion by weight of N-alkylazetidinyl acrylate units and / or N-alkylazetidinyl methacrylate units, the interior said microparticles consisting of a copolymer containing a small proportion by weight of N-alkylazetidinyl acrylate units and / or N-alkylazetidinyl methacrylate units.
- the surface of the microparticles is formed by a copolymer containing a high proportion by weight of N-cyclohexylazetidinyl methacrylate units (I), the interior of the microparticles consisting of a copolymer containing a small proportion by weight of N-cyclohexylazetidinyl methacrylate units.
- the microparticles consist of N-cyclohexylazetidine methacrylate units and acrylic or methacrylic monomer units chosen from the group consisting of methyl methacrylate, 2-ethylhexyl acrylate, butyl acrylate, butyl methacrylate, ethyl acrylate, acrylonitrile.
- An advantageous variant of the invention consists in using a composition in which the microparticles consist of a terpolymer of N-cyclohexylazetidinyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate.
- microparticles for the anti-felting treatment of wool according to the invention can be in different forms.
- the microparticles have a gradient structure: the concentration of N-cyclohexylazetidinyl methacrylate units in the copolymer constituting the microparticles decreases from the surface towards the center of the microparticles.
- the microparticles can also have a "core-shell” structure, a structure making it possible to distinguish at least two layers of copolymer having a different composition: a first layer located on the surface called “shell” and consisting of a copolymer containing a high proportion by weight of N-alkylazetidinyl methacrylate units and / or N-alkylazetidinyl acrylate units and at least one second layer called "core” consisting of a copolymer containing a low proportion by weight of methacrylate units of N-alkylazetidinyl and / or of N-alkylazetidinyl acrylate units.
- composition according to the invention having microparticles consisting of a shell containing between 50 and 95% by weight, preferably between 85 and 95% by weight N-alkylazetidinyl methacrylate and / or N-alkylazetidinyl acrylate units and a "core" containing between 5 and 50%, preferably between 10 and 20% of N-alkylazetidinyl methacrylate units and / or N acrylate -alkylazetidinyl, the percentage by overall weight of the microparticles in units of N-alkylazetidinyl being from 10 to 50%, preferably from 20 to 30%.
- the crosslinkable composition for the anti-felting treatment of wool according to the invention can be produced according to a synthetic route known from the state of the art such as emulsion polymerization or any other method allowing the formation of microparticles. It offers numerous technical advantages and makes it possible to carry out continuous and discontinuous treatment of the wool so as to make it non-shrink.
- This composition can be used so as to use a low concentration of active product (approximately 0.5% to 1% of dry product relative to the weight of wool treated against 1 to 2% for the products of the state of technical) and thus has a very interesting economic character for its industrial application. It preserves the intrinsic qualities of wool, which while acquiring qualities of infertility, retains its natural appearance.
- composition can be applied to wool according to gentle methods lowering the energy costs. It can be applied to many types of wool: raw, woven, knitted, finished or not, etc. It also has great application flexibility allowing it to be used at any stage of a finishing process after the classic chlorination stage. During the anti-felting treatment with the composition according to the invention, the use of a softener is no longer essential.
- the invention also relates to a process for finishing wool comprising an anti-felting treatment phase using the above compositions, which can be combined with great flexibility with the conventional dyeing and chlorination phases. It is possible to carry out the anti-felting treatment before, after or partially before and partially after the dyeing step provided that the conventional pre-chlorination step has already been performed.
- the invention will be more easily understood thanks to the nonlimiting exemplary embodiment which follows.
- the example describes the production of an anti-felt composition containing microparticles having a "core-shell" structure in several layers and consisting of a terpolymer "N-cyclohexylazetidinyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate” and shows a use of this composition during an anti-felting process.
- the composition has the great advantage of not being reactive at room temperature and of having a long pot life.
- Mixtures 1, 2 and 3 are prepared according to the following table:
- This synthesis makes it possible to obtain a latex of structured microparticles having a shell corresponding to the polymerization of mixture III and a core consisting of two layers: a first central layer obtained by polymerization of mixture I, a second layer obtained by polymerization of mixture II.
- the bark is polymerized in the same way using the mixture of monomers III. Throughout the polymerization, stirring is maintained at 25 revolutions per minute and a stream of nitrogen sweeps through the top of the reactor. At the end of the bark polymerization, the latex is slowly cooled to room temperature.
- a first part of the composition is used during a continuous process of anti-felting treatment of wool and a second part during a discontinuous process.
- the anti-felting treatment process used is a conventional continuous industrial process.
- the wool arrives in the form of a ribbon to a trowel composed of a succession of trays containing the different solutions necessary for the treatment.
- the wool ribbon is successively dipped into each of these trays.
- the first stage is a classic chlorination stage. This step makes it possible to increase the surface tension of the wool to improve the adhesion and the distribution of polymer on the fibers by incorporation of RSO3H and RCOOH groups.
- This pre-chlorination is carried out by soaking the wool in a bath of NaOCl, sulfuric acid and wetting agent at a pH of 1.5 to 2.0 and at a temperature of 15 to 20 ° C.
- the wool is then rinsed at a temperature of 20 to 30 ° C in order to remove the reaction products from the pre-chlorination step.
- the next step is to dechlorinate the wool.
- This dechlorination is carried out at a pH of 8.5 to 9.5 and at a temperature of 20 to 35 ° C using a solution of sodium bisulfite. This operation improves the anti-felting effect and lightens the wool.
- the wool is then rinsed at 20-35 ° C and then treated with the anti-felting composition obtained in paragraph 2, at a rate of 0.5 to 1% by weight of active material relative to the weight of the treated wool.
- the temperature is maintained between 20 and 30 ° C and the pH is brought to a value between 4 and 5 by addition of acid, for example acetic acid, to the composition.
- the wool is then dried at 60-80 ° C for about 10 minutes. It is during this last stage that the crosslinking of the azetidine groups on the fibers takes place.
- the discontinuous process used is a diving and exhaustion process.
- the wool is again rinsed for 10 minutes in the cold, then treated at room temperature with a solution containing 0.5 to 1% by weight of the composition obtained in paragraph A.2, the pH of the solution being fixed between 4 and 5 by addition of acetic acid, and finally dried as above at 60-80 ° C for about 10 minutes.
- the AFS Ana Felting Shrinkage shrinkage rate was measured, according to test method No. 31 extracted from the International Wool Standart, after several washes of the treated wool. The results obtained were compared with the results obtained with batches of wool treated according to an identical process using a polymer product of adipic acid-diethylenetriamine-epichlorohydrin of the state of the art, Hercosett ® 125 (Hercules). The results are given in the following table.
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- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
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- Treatment Of Sludge (AREA)
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Abstract
Description
L'invention a pour objet une composition pour le traitement antifeutrant de la laine.The subject of the invention is a composition for the anti-felting treatment of wool.
Les articles en laine peuvent subir lors de processus humides successifs tels que le lavage ou les teintures, à l'usage ou lors d'opérations d'entretien un rétrécissement irréversible provoqué par le feutrage. Ce rétrécissement est dû à la nature même des fibres qui constituent la laine. Ces fibres à base de kératine sont en effet composées d'une multitude d'écailles qui, lors d'opérations mécaniques répétées, sont amenées à se chevaucher. Il apparaît alors une force de friction entre les écailles des fibres qui a pour effet de diminuer les dimensions de l'article fini.Woolen articles can undergo irreversible shrinkage caused by felting during successive wet processes such as washing or dyeing, during use or during maintenance operations. This shrinkage is due to the very nature of the fibers that make up wool. These keratin-based fibers are in fact composed of a multitude of scales which, during repeated mechanical operations, are caused to overlap. A frictional force then appears between the scales of the fibers which has the effect of reducing the dimensions of the finished article.
Tous les procédés industriels de traitement antifeutrage de la laine sont basés sur des moyens permettant de diminuer les forces de friction. Certains de ces traitements sont basés sur la dégradation des écailles des fibres constituant la laine généralement par action de moyens oxydants. Les moyens oxydants les plus fréquemment utilisés sont le chlore, sous forme de gaz ou d'acide hypochlorique, et le sel de sodium de l'acide dichlorocyanurique. Ces traitements oxydants présentent l'inconvénient majeur d'altérer la fibre et donc son aspect et de diminuer les qualités de la laine.All industrial wool anti-felting treatment processes are based on means making it possible to reduce the friction forces. Some of these treatments are based on the degradation of the scales of the fibers constituting the wool, generally by the action of oxidizing means. The most frequently used oxidizing means are chlorine, in the form of gas or hypochloric acid, and the sodium salt of dichlorocyanuric acid. These oxidizing treatments have the major drawback of altering the fiber and therefore its appearance and of reducing the qualities of the wool.
Les autres traitements antifeutrants de la laine consistent à appliquer sur les fibres un polymère. En effet, lorsqu'un film de résine est déposé sur les fibres de laine, la structure en écaille de celle-ci est masquée. Ainsi, de très nombreux polymères ont été appliqués au traitement antifeutrant de la laine dans le but d'améliorer la résistance de celle-ci au rétrécissement. Certaines méthodes ont consisté à former directement le polymère sur la surface de la fibre. Ces méthodes présentent l'inconvénient de provoquer un grand nombre de liaisons entre les différentes fibres. Le plus, la quantité de polymère utilisé est importante et augmente le coût de l'opération.Other anti-felting treatments for wool consist in applying a polymer to the fibers. In fact, when a resin film is deposited on the wool fibers, the shell structure of the latter is masked. Thus, a large number of polymers have been applied to the anti-felting treatment of wool in order to improve the resistance of the latter to shrinkage. Some methods have involved directly forming the polymer on the surface of the fiber. These methods have the disadvantage of causing a large number of bonds between the different fibers. In addition, the quantity of polymer used is important and increases the cost of the operation.
Des techniques plus récentes ont consisté à appliquer sur le laine des polymères préformés. Dans le but de maintenir le polymère sur la fibre, on a utilisé, entre autres, des polymères comportant des groupements réactifs. Ainsi, le brevet allemand DE-A-2342083 déposé par BASF, décrit l'utilisation dans les compositions antifeutrantes de dispersion de polymères acryliques et de méthylolurées. Le brevet GB-A-2017179 déposé par Hercules décrit l'utilisation d'un produit de condensation acide adipique-diéthylène-triamine-épichlorhydrine (par exemple, Hercosett 57®).More recent techniques have consisted of applying preformed polymers to wool. In order to maintain the polymer on the fiber, use has been made, inter alia, of polymers comprising reactive groups. Thus, the German patent DE-A-2342083 filed by BASF, describes the use in anti-felting compositions for dispersing acrylic polymers and methylolureas. Patent GB-A-2017,179 filed by Hercules describes the use of an adipic acid-diethylene-triamine-epichlorohydrin condensation product (for example, Hercosett 57®).
Ces polymères doivent posséder un certain nombre de qualités et en particulier il doivent présenter une résistance au lavage, au séchage et un permanence lors de la simple utilisation de la fibre sur laquelle ils sont appliqués (solidité au frottement, à la sueur, à la lumière). Ils doivent, en outre, ne pas altérer la qualité intrinsèque de la laine lors de leur application. Le principal inconvénient de nombreux produits commerciaux est de rendre rêches les laines sur lesquelles ils sont appliqués: la fibre devient dure et difficile à porter. Ce phénomène est dû à la température de transition vitreuse élevée du polymère. Afin d'obtenir un compromis entre les qualités antifeutrantes et la douceur de la laine, le polymère devra posséder une température de transition vitreuse relativement basse. Le polymère doit également être capable de recouvrir complètement la fibre. En conséquence, la surface de la fibre doit être complètement mouillée par la composition contenant le polymère. Bien que l'on puisse augmenter la mouillabilité de la laine par différents procédés, la composition contenant le polymère devra posséder une tension superficielle suffisamment basse pour arriver à ce but. Par ailleurs, la composition utilisée devra posséder une souplesse d'utilisation permettant d'effectuer un traitement en continu ou en discontinu sur des rubans de laine peignés, des tissus ou bien des tricots. Elle doit enfin pouvoir être employée à une concentration en produit actif permettant de limiter le coût de l'opération. Les compositions antifeutrantes de la laine de l'état de la technique ne présentent pas simultanément ces différentes propriétés.These polymers must have a certain number of qualities and in particular they must have a resistance to washing, to drying and a permanence when the simple use of the fiber on which they are applied (resistance to friction, to sweat, to light ). They must, moreover, not alter the intrinsic quality of the wool during their application. The main disadvantage of many commercial products is to make the wool on which they are applied rough: the fiber becomes hard and difficult to wear. This phenomenon is due to the high glass transition temperature of the polymer. In order to obtain a compromise between the anti-felting qualities and the softness of the wool, the polymer must have a relatively low glass transition temperature. The polymer must also be able to completely cover the fiber. Consequently, the surface of the fiber must be completely wetted by the composition containing the polymer. Although the wettability of the wool can be increased by various methods, the composition containing the polymer must have a sufficiently low surface tension to achieve this aim. Furthermore, the composition used must have a flexibility of use allowing a continuous or discontinuous treatment to be carried out on combed wool ribbons, fabrics or even knitwear. Finally, it must be able to be used at a concentration of active product making it possible to limit the cost of the operation. The prior art wool anti-felting compositions do not simultaneously exhibit these different properties.
On a montré plus récemment l'intérêt potentiel que présentaient pour le traitement antifeutrant de la laine les polyacrylates de N-alkylazétidine (voir Goethals et coll., Polymer preparation, Am. Chem. Soc, Div.Polym.Chem., 22(1), pp. 126-127, 1981). On a maintenant trouvé que pour que le traitement soit efficace, il fallait utiliser des copolymères de (méth)acrylates de N-alkylazétidine sous forme de latex dont les microparticules offraient une structure particulière. L'invention concerne ainsi une composition pour le traitement antifeutrant de la laine comprenant d'une part entre 5 et 20 % en poids de microparticules constituées par un copolymère d'unités monomériques acryliques et/ou méthacryliques, et d'autre part entre 80 et 95 % d'eau additionnée de stabilisants, dans laquelle les microparticules possèdent une surface constituée d'un copolymère contenant une forte proportion en poids d'unités acrylate de N-alkylazétidinyle et/ou d'unités méthacrylate de N-alkylazétidinyle, l'intérieur desdites microparticules étant constitué d'un copolymère contenant une faible proportion en poids d'unités acrylate de N-alkylazétidinyle et/ou d'unités méthacrylate de N-alkylazétidinyle.More recently, the potential interest in the anti-felting treatment of wool has been shown for N-alkylazetidine polyacrylates (see Goethals et al., Polymer preparation, Am. Chem. Soc, Div.Polym.Chem., 22 (1 ), pp. 126-127, 1981). It has now been found that for the treatment to be effective, it is necessary to use copolymers of (meth) acrylates of N-alkylazetidine in the form of latex, the microparticles of which have a particular structure. The invention thus relates to a composition for the anti-felting treatment of wool comprising on the one hand between 5 and 20% by weight of microparticles constituted by a copolymer of acrylic and / or methacrylic monomer units, and on the other hand between 80 and 95% water with stabilizers added, in which the microparticles have a surface consisting of a copolymer containing a high proportion by weight of N-alkylazetidinyl acrylate units and / or N-alkylazetidinyl methacrylate units, the interior said microparticles consisting of a copolymer containing a small proportion by weight of N-alkylazetidinyl acrylate units and / or N-alkylazetidinyl methacrylate units.
Préférentiellement, la surface des microparticules est constituée par un copolymère contenant une forte proportion en poids d'unités méthacrylate de N-cyclohexylazétidinyle (I),
l'intérieur des microparticules étant constitué d'un copolymère contenant une faible proportion en poids d'unités méthacrylate de N-cyclohexylazétidinyle.Preferably, the surface of the microparticles is formed by a copolymer containing a high proportion by weight of N-cyclohexylazetidinyl methacrylate units (I),
the interior of the microparticles consisting of a copolymer containing a small proportion by weight of N-cyclohexylazetidinyl methacrylate units.
Egalement préférentiellement, les microparticules sont constituées d'unités méthacrylate de N-cyclohexylazétidine et d'unités monomériques acryliques ou méthacryliques choisies dans le groupe constitué par le méthacrylate de méthyle, l'acrylate de 2-éthylhexyle, l'acrylate de butyle, le méthacrylate de butyle, l'acrylate d'éthyle, l'acrylonitrile. Une variante avantageuse de l'invention consiste à utiliser une composition dans laquelle les microparticules sont constituées d'un terpolymère de méthacrylate de N-cyclohexylazétidinyle, de méthacrylate de méthyle et d'acrylate de 2-éthylhexyle.Also preferably, the microparticles consist of N-cyclohexylazetidine methacrylate units and acrylic or methacrylic monomer units chosen from the group consisting of methyl methacrylate, 2-ethylhexyl acrylate, butyl acrylate, butyl methacrylate, ethyl acrylate, acrylonitrile. An advantageous variant of the invention consists in using a composition in which the microparticles consist of a terpolymer of N-cyclohexylazetidinyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate.
Les microparticules pour le traitement antifeutrant de la laine selon l'invention peuvent se présenter sous différentes formes.The microparticles for the anti-felting treatment of wool according to the invention can be in different forms.
Selon une variante, les microparticules présentent une structure en gradient: la concentration en unités méthacrylate de N-cyclohexylazétidinyle dans le copolymère constituant les microparticules décroît de la surface vers le centre des microparticules.According to a variant, the microparticles have a gradient structure: the concentration of N-cyclohexylazetidinyl methacrylate units in the copolymer constituting the microparticles decreases from the surface towards the center of the microparticles.
Selon une approche particulièrement intéressante, les microparticules peuvent également présenter une structure "coeur-écorce", structure permettant de distinguer au moins deux couches de copolymère ayant une composition différente: une première couche située en surface appelée "écorce" et constituée d'un copolymère contenant une forte proportion en poids d'unités méthacrylate de N-alkylazétidinyle et/ou d'unités acrylate de N-alkylazétidinyle et au moins une seconde couche appelée "coeur" constituée d'un copolymère contenant une faible proportion en poids d'unités méthacrylate de N-alkylazétidinyle et/ou d'unités acrylate de N-alkylazétidinyle.According to a particularly advantageous approach, the microparticles can also have a "core-shell" structure, a structure making it possible to distinguish at least two layers of copolymer having a different composition: a first layer located on the surface called "shell" and consisting of a copolymer containing a high proportion by weight of N-alkylazetidinyl methacrylate units and / or N-alkylazetidinyl acrylate units and at least one second layer called "core" consisting of a copolymer containing a low proportion by weight of methacrylate units of N-alkylazetidinyl and / or of N-alkylazetidinyl acrylate units.
Ainsi selon cette seconde structure "coeur-écorce", il est particulièrement intéressant de mettre en oeuvre une composition selon l'invention possédant des microparticules constituées d'une écorce contenant entre 50 et 95 % en poids, préférentiellement entre 85 et 95 % en poids d'unités méthacrylate de N-alkylazétidinyle et/ou acrylate de N-alkylazétidinyle et d'un "coeur" contenant entre 5 et 50 % , préférentiellement entre 10 et 20 % d'unités méthacrylate de N-alkylazétidinyle et/ou acrylate de N-alkylazétidinyle, le pourcentage en poids global des microparticules en unités de N-alkylazétidinyle étant de 10 à 50 % , préférentiellement de 20 à 30 % .Thus according to this second "core-shell" structure, it is particularly advantageous to use a composition according to the invention having microparticles consisting of a shell containing between 50 and 95% by weight, preferably between 85 and 95% by weight N-alkylazetidinyl methacrylate and / or N-alkylazetidinyl acrylate units and a "core" containing between 5 and 50%, preferably between 10 and 20% of N-alkylazetidinyl methacrylate units and / or N acrylate -alkylazetidinyl, the percentage by overall weight of the microparticles in units of N-alkylazetidinyl being from 10 to 50%, preferably from 20 to 30%.
La composition réticulable pour le traitement antifeutrant de la laine selon l'invention peut être réalisée selon une voie de synthèse connue de l'état de la technique telle que la polymérisation en émulsion ou toute autre méthode permettant la formation des microparticules. Elle propose de nombreux avantages techniques et permet de réaliser en continu et en discontinu le traitement de la laine de façon à la rendre irrétrécissable.The crosslinkable composition for the anti-felting treatment of wool according to the invention can be produced according to a synthetic route known from the state of the art such as emulsion polymerization or any other method allowing the formation of microparticles. It offers numerous technical advantages and makes it possible to carry out continuous and discontinuous treatment of the wool so as to make it non-shrink.
Cette composition peut être utilisée de façon à mettre en oeuvre une concentration faible de produit actif (environ 0,5 % à 1 % de produit sec par rapport au poids de laine traité contre 1 à 2 % pour les produits de l'état de la technique) et présente ainsi un caractère économique très intéressant pour son application industrielle. Elle préserve les qualités intrinsèques de la laine, laquelle tout en acquérant des qualités d'infeutrabilité, conserve son aspect naturel.This composition can be used so as to use a low concentration of active product (approximately 0.5% to 1% of dry product relative to the weight of wool treated against 1 to 2% for the products of the state of technical) and thus has a very interesting economic character for its industrial application. It preserves the intrinsic qualities of wool, which while acquiring qualities of infertility, retains its natural appearance.
Un autre avantage consiste dans le fait que la composition peut être appliquée sur la laine selon des méthodes douces abaissant les coûts énergétiques. Elle peut être appliquée à de nombreux types de laine: brute, tissée, tricotée, produits finis ou non, etc... Elle présente par ailleurs une grande flexibilité d'application permettant de l'utiliser à n'importe quelle étape d'un procédé d'ennoblissement après l'étape classique de chlorage. Lors du traitement antifeutrant avec la composition selon l'invention, l'utilisation d'un adoucissant n'est plus indispensable.Another advantage consists in the fact that the composition can be applied to wool according to gentle methods lowering the energy costs. It can be applied to many types of wool: raw, woven, knitted, finished or not, etc. It also has great application flexibility allowing it to be used at any stage of a finishing process after the classic chlorination stage. During the anti-felting treatment with the composition according to the invention, the use of a softener is no longer essential.
L'invention concerne également un procédé d'ennoblissement de la laine comportant une phase de traitement antifeutrant à l'aide des compositions ci-dessus, qui peut être combinée avec une grande flexibilité avec les phases de teinture et de chlorage classiques. Il est possible d'effectuer le traitement antifeutrant avant, après ou partiellement avant et partiellement après l'étape de teinture pour peu que l'étape de préchlorage classique ait déjà été effectuée.The invention also relates to a process for finishing wool comprising an anti-felting treatment phase using the above compositions, which can be combined with great flexibility with the conventional dyeing and chlorination phases. It is possible to carry out the anti-felting treatment before, after or partially before and partially after the dyeing step provided that the conventional pre-chlorination step has already been performed.
Ainsi, on pourra employer quatre séquences:
- 1. préchlorage, teinture, traitement antifeutrant;
- 2. préchlorage, traitement antifeutrant partiel, teinture, traitement antifeutrant partiel;
- 3. préchlorage, traitement antifeutrant, teinture;
- 4. teinture, préchlorage, traitement antifeutrant, la composition selon l'invention, une fois appliquée sur la laine devant être portée à une température supérieure à 50°C pour permettre l'ouverture des cycles azétidines et leur réticulation. La mise en oeuvre peut en être effectuée selon tout procédé de traitement continu ou discontinu.
- 1. pre-chlorination, dyeing, anti-felting treatment;
- 2. pre-chlorination, partial anti-felting treatment, dyeing, partial anti-felting treatment;
- 3. pre-chlorination, anti-felting treatment, dyeing;
- 4. dyeing, pre-chlorination, anti-felting treatment, the composition according to the invention, once applied to the wool to be brought to a temperature above 50 ° C. to allow the opening of the azetidine cycles and their crosslinking. The implementation can be carried out according to any continuous or discontinuous treatment process.
L'invention sera plus facilement comprise grâce à l'exemple non limitatif de réalisation qui suit. L'exemple décrit la réalisation d'une composition antifeutrante contenant des microparticules présentant une structure "coeur-écorce" en plusieurs couches et constituées d'un terpolymère "méthacrylate de N-cyclohexylazétidinyle, méthacrylate de méthyle, acrylate de 2-éthylhexyle" et montre une utilisation de cette composition au cours d'un procédé antifeutrant. La composition présente le grand avantage de ne pas être réactive à température ambiante et de posséder une durée de vie en pot importante.The invention will be more easily understood thanks to the nonlimiting exemplary embodiment which follows. The example describes the production of an anti-felt composition containing microparticles having a "core-shell" structure in several layers and consisting of a terpolymer "N-cyclohexylazetidinyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate" and shows a use of this composition during an anti-felting process. The composition has the great advantage of not being reactive at room temperature and of having a long pot life.
On prépare les mélanges 1, 2 et 3 selon le tableau suivant:
Cette synthèse permet d'obtenir un latex de microparticules structurées ayant une écorce correspondant à la polymérisation du mélange III et un coeur constitué de deux couches: une première couche centrale obtenue par polymérisation du mélange I, une seconde couche obtenue par polymérisation du mélange II.This synthesis makes it possible to obtain a latex of structured microparticles having a shell corresponding to the polymerization of mixture III and a core consisting of two layers: a first central layer obtained by polymerization of mixture I, a second layer obtained by polymerization of mixture II.
Dans un réacteur à double enveloppe de 6 litres muni d'un agitateur, d'un condenseur et d'un système d'injection d'azote, on introduit 5 litres d'eau déminéralisée, puis 19 grammes de tétraborate de sodium. La température est maintenue à 50°C et un barbotage d'azote a lieu pendant une heure. On introduit ensuite dans le réacteur 50 grammes d'un émulsifiant non ionique (Tween 60 ®Atlas).5 liters of demineralized water are introduced into a 6-liter jacketed reactor fitted with an agitator, a condenser and a nitrogen injection system, followed by 19 grams of sodium tetraborate. The temperature is maintained at 50 ° C. and a sparging of nitrogen takes place for one hour. Then introduced into the reactor 50 grams of a nonionic emulsifier (Tween 60 ®Atlas).
Formation du "coeur". On introduit dans le réacteur 560 grammes du mélange I de monomères. En agitant à 250 tours par minute, une émulsion stable est obtenue. Une solution d'amorceur de 507 grammes de persulfate d'ammonium dissous dans 5 ml d'eau est introduite dans le réacteur. La polymérisation dure deux heures.Formation of the "heart". 560 grams of the mixture I of monomers are introduced into the reactor. By stirring at 250 revolutions per minute, a stable emulsion is obtained. An initiator solution of 507 grams of ammonium persulfate dissolved in 5 ml of water is introduced into the reactor. The polymerization lasts two hours.
Formation de la couche intermédiaire. On additionne ensuite 350 grammes du mélange II de monomères à l'aide d'une pompe doseuse pendant une heure. A la fin de l'addition, une solution de 5 grammes de persulfate d'ammonium dans 5 ml amorce la polymérisation. Celle-ci dure deux heures.Formation of the intermediate layer. 350 grams of the monomer mixture II are then added using a metering pump for one hour. At the end of the addition, a solution of 5 grams of ammonium persulfate in 5 ml initiates the polymerization. This lasts two hours.
Formation de la couche extérieure de l'écorce. L'écorce est polymérisée de la même manière à l'aide du mélange de monomères III. Pendant toute la polymérisation, l'agitation est maintenue à 25 tours par minute et un courant d'azote balaie le haut du réacteur. A la fin de la polymérisation de l'écorce, le latex est refroidi lentement jusqu'à la température ambiante.Formation of the outer layer of the bark. The bark is polymerized in the same way using the mixture of monomers III. Throughout the polymerization, stirring is maintained at 25 revolutions per minute and a stream of nitrogen sweeps through the top of the reactor. At the end of the bark polymerization, the latex is slowly cooled to room temperature.
Une première partie de la composition est mise en oeuvre au cours d'un procédé continu de traitement antifeutrant de la laine et une seconde partie au cours d'un procédé discontinu.A first part of the composition is used during a continuous process of anti-felting treatment of wool and a second part during a discontinuous process.
Le procédé de traitement antifeutrant utilisé est un procédé industriel continu classique. La laine arrive sous forme d'un ruban à une lisseuse composée d'une succession de bacs contenant les différentes solutions nécessaires au traitement. Par un système de rouleaux, le ruban de laine est successivement plongé dans chacun de ces bacs.The anti-felting treatment process used is a conventional continuous industrial process. The wool arrives in the form of a ribbon to a trowel composed of a succession of trays containing the different solutions necessary for the treatment. By a system of rollers, the wool ribbon is successively dipped into each of these trays.
La première étape est une étape classique de chlorage. Cette étape permet d'augmenter la tension de surface de la laine pour améliorer l'adhésion et la répartition de polymère sur les fibres par incorporation de groupements RSO₃H et RCOOH. Ce préchlorage est effectué en trempant la laine dans un bain de NaOCl, d'acide sulfurique et d'agent mouillant à un pH de 1,5 à 2,0 et à une température de 15 à 20 °C.The first stage is a classic chlorination stage. This step makes it possible to increase the surface tension of the wool to improve the adhesion and the distribution of polymer on the fibers by incorporation of RSO₃H and RCOOH groups. This pre-chlorination is carried out by soaking the wool in a bath of NaOCl, sulfuric acid and wetting agent at a pH of 1.5 to 2.0 and at a temperature of 15 to 20 ° C.
La laine est ensuite rincée à une température de 20 à 30°C afin d'éliminer les produits de réaction de l'étape de préchlorage.The wool is then rinsed at a temperature of 20 to 30 ° C in order to remove the reaction products from the pre-chlorination step.
L'étape suivante consiste à déchlorer la laine. Ce déchlorage est effectué à un pH de 8,5 à 9,5 et à une température de 20 à 35 °C grâce à une solution de bisulfite de sodium. Cette opération améliore l'effet antifeutrant et éclaircit la laine. La laine est ensuite rincée à 20-35°C puis traitée avec la composition antifeutrante obtenue au paragraphe 2, à raison de 0,5 à 1 % en poids de matière active par rapport au poids de la laine traitée. La température est maintenue entre 20 et 30°C et le pH est amené à une valeur comprise entre 4 et 5 par addition d'acide, par exemple d'acide acétique, à la composition.The next step is to dechlorinate the wool. This dechlorination is carried out at a pH of 8.5 to 9.5 and at a temperature of 20 to 35 ° C using a solution of sodium bisulfite. This operation improves the anti-felting effect and lightens the wool. The wool is then rinsed at 20-35 ° C and then treated with the anti-felting composition obtained in paragraph 2, at a rate of 0.5 to 1% by weight of active material relative to the weight of the treated wool. The temperature is maintained between 20 and 30 ° C and the pH is brought to a value between 4 and 5 by addition of acid, for example acetic acid, to the composition.
La laine est ensuite séchée à 60-80°C pendant 10 minutes environ. C'est durant cette dernière étape qu'a lieu la réticulation des groupements azétidines sur les fibres.The wool is then dried at 60-80 ° C for about 10 minutes. It is during this last stage that the crosslinking of the azetidine groups on the fibers takes place.
Le procédé discontinu utilisé est un procédé au plongé et par épuisement du bain.The discontinuous process used is a diving and exhaustion process.
La première étape consiste en une étape classique de chlorage effectuée en trempant la laine pendant 30 à 35 minutes à froid dans une solution aqueuse contenant 1g/l d'agent mouillant et 2 à 3 % en poids de chloroisocyanurate de sodium (par exemple le Basolan DC ® commercialisé par BASF), par rapport au poids de laine traitée (pH = 3,5 - 4).The first stage consists of a conventional chlorination stage carried out by soaking the wool for 30 to 35 minutes in cold in an aqueous solution containing 1 g / l of wetting agent and 2 to 3% by weight of sodium chloroisocyanurate (for example Basolan DC ® marketed by BASF), relative to the weight of treated wool (pH = 3.5 - 4).
La laine est ensuite rincée 10 minutes à l'eau froide, puis déchlorée dans le même bain avec 2 % en poids de bisulfite pendant 10 à 15 minutes à froid (pH = 3,5 - 4).The wool is then rinsed for 10 minutes with cold water, then dechlorinated in the same bath with 2% by weight of bisulfite for 10 to 15 minutes in the cold (pH = 3.5 - 4).
La laine est de nouveau rincée 10 minutes à froid, puis traitée à température ambiante par une solution contenant 0,5 à 1 % en poids de la composition obtenue au paragraphe A.2, le pH de la solution étant fixé entre 4 et 5 par addition d'acide acétique, et enfin séchée comme précédemment à 60-80°C pendant 10 minutes environ.The wool is again rinsed for 10 minutes in the cold, then treated at room temperature with a solution containing 0.5 to 1% by weight of the composition obtained in paragraph A.2, the pH of the solution being fixed between 4 and 5 by addition of acetic acid, and finally dried as above at 60-80 ° C for about 10 minutes.
Afin d'évaluer l'efficacité de la composition, on a mesuré le taux de rétrécissement AFS (Aera Felting Shrinkage), selon la méthode d'essai N° 31 extraite de l'International Wool Standart, après plusieurs lavages de la laine traitée. Les résultats obtenus ont été comparés aux résultats obtenus avec des lots de laine traités selon un procédé identique mettant en oeuvre un produit polymère d'acide adipique-diéthylènetriamine-épichlorhydrine de l'état de la technique, le Hercosett ® 125 (Hercules). Les résultats sont donnés dans le tableau suivant.
On constate qu'en présence d'une quantité minime de matière active (0,5 % en poids par rapport au poids de laine traitée), les résultats obtenus sont comparables à ceux obtenus avec un pourcentage plus élevé de produit de l'état de la technique. Le pouvoir antifeutrant de la composition selon l'invention est quatre fois plus élevé que celui de l'état de la technique.It is found that in the presence of a minimal amount of active material (0.5% by weight relative to the weight of treated wool), the results obtained are comparable to those obtained with a higher percentage of product in the state of the technique. The anti-felting power of the composition according to the invention is four times higher than that of the state of the art.
Claims (9)
- Crosslinkable composition for the antifelting treatment of wool comprising, on the one hand, between 5 and 20 % by weight of microparticles consisting of a copolymer of acrylic and/or methacrylic monomer units and, on the other hand, between 80 and 95 % of water to which stabilizing agents have been added, characterized in that the said microparticles have a surface consisting of a copolymer containing a high proportion by weight of N-alkylazetidinyl acrylate units and/or N-alkylazetidinyl methacrylate units, the interior of the said microparticles consisting of a copolymer containing a small proportion by weight of N-alkylazetidinyl acrylate units and/or N-alkylazetidinyl methacrylate units.
- Composition according to Claim 1, characterized in that the surface of the microparticles consists of a copolymer containing a high proportion of N-cyclohexylazetidinyl methacrylate units, the remainder of the said microparticles consisting of a copolymer containing a small proportion of N-cyclohexylazetidinyl methacrylate units.
- Composition according to Claims 1 and 2, characterized in that the microparticles consist of N-cyclohexylazetidinyl methacrylate units and of acrylic or methacrylic monomer units chosen from the group consisting of methyl methacrylate, 2-ethylhexyl acrylate, butyl acrylate, butyl methacrylate, ethyl acrylate and acrylonitrile.
- Composition according to Claim 3, characterized in that the microparticles consist of a terpolymer of N-cyclohexylazetidinyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate.
- Composition according to any one of the preceding claime, characterized in that the microparticles have a core/rind structure consisting of distinct polymer layers.
- Composition according to any one of the preceding claims, characterized in that the microparticles have a gradient structure.
- Composition according to Claim 5, characterized in that the microparticles consist of a rind containing between 50 and 95 % by weight of N-cyclohexylazetidinyl methacrylate units and/or N-cyclohexylazetidinyl acrylate units, the overall percentage by weight of N-cyclohexylazetidinyl units being from 10 to 50 %.
- Composition according to Claim 7, characterized in that the microparticles consist of a rind comprising 85 to 95 % by weight of N-alkylazetidinyl methacrylate monomer unite and of a core consisting of a copolymer comprising from 10 to 20 % by weight of N-alkylazetidinyl methacrylate units, the overall percentage by weight of N-alkylazetidinyl units being from 20 to 30 %.
- Process for improving the quality of wool comprising, in an unspecified order, the prechlorinating, dyeing and antifelting-treatment stages, characterized in that the antifelting treatment comprises the immersion of the wool in a composition according to any one of Claims 1 to 8 and its drying at a temperature of 60 to 80°C, the antifelting composition being used at a concentration of 0.5 to 1 % by weight of microparticles with respect to the wool.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8907971A FR2648486B1 (en) | 1989-06-16 | 1989-06-16 | COMPOSITION FOR ANTI-EUTRANT TREATMENT OF WOOL |
| FR8907971 | 1989-06-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0403336A1 EP0403336A1 (en) | 1990-12-19 |
| EP0403336B1 true EP0403336B1 (en) | 1994-01-19 |
Family
ID=9382775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90401561A Expired - Lifetime EP0403336B1 (en) | 1989-06-16 | 1990-06-08 | Composition for the antifelting of wool and process of improvement |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0403336B1 (en) |
| AT (1) | ATE100507T1 (en) |
| AU (1) | AU626122B2 (en) |
| DE (1) | DE69006109T2 (en) |
| DK (1) | DK0403336T3 (en) |
| ES (1) | ES2062441T3 (en) |
| FR (1) | FR2648486B1 (en) |
| NZ (1) | NZ234114A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3043430B2 (en) | 1995-09-08 | 2000-05-22 | ノボ ノルディスク アクティーゼルスカブ | 2-alkylpyrrolidines |
| GB0201165D0 (en) * | 2002-01-18 | 2002-03-06 | Unilever Plc | Azetidinium modidfied poymers and fabric treatment composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE234083C (en) * | ||||
| DE2342083A1 (en) * | 1973-08-21 | 1975-04-24 | Basf Ag | Anti-shrinkage and felting treatment of keratin fibres - by impregnation with soln. contg. sulphite, poly-N-methylol cpd. and reactive polymer |
| FR2395141A1 (en) * | 1977-06-21 | 1979-01-19 | Centre Tech Ind Papier | Slip resistant sheet comprising support - coated with paper coating compsn. contg. hollow microspheres of polyvinylidene chloride and opt. polyacrylonitrile |
-
1989
- 1989-06-16 FR FR8907971A patent/FR2648486B1/en not_active Expired - Fee Related
-
1990
- 1990-06-08 EP EP90401561A patent/EP0403336B1/en not_active Expired - Lifetime
- 1990-06-08 DK DK90401561.7T patent/DK0403336T3/en active
- 1990-06-08 DE DE69006109T patent/DE69006109T2/en not_active Expired - Fee Related
- 1990-06-08 AT AT90401561T patent/ATE100507T1/en not_active IP Right Cessation
- 1990-06-08 ES ES90401561T patent/ES2062441T3/en not_active Expired - Lifetime
- 1990-06-15 AU AU57191/90A patent/AU626122B2/en not_active Ceased
- 1990-06-18 NZ NZ234114A patent/NZ234114A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU5719190A (en) | 1990-12-20 |
| FR2648486A1 (en) | 1990-12-21 |
| DE69006109D1 (en) | 1994-03-03 |
| DE69006109T2 (en) | 1994-07-14 |
| DK0403336T3 (en) | 1994-02-28 |
| ATE100507T1 (en) | 1994-02-15 |
| EP0403336A1 (en) | 1990-12-19 |
| AU626122B2 (en) | 1992-07-23 |
| ES2062441T3 (en) | 1994-12-16 |
| FR2648486B1 (en) | 1991-08-30 |
| NZ234114A (en) | 1992-12-23 |
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