EP0390616B1 - Process for the antiseptic treatment of non-keratinous textile materials - Google Patents
Process for the antiseptic treatment of non-keratinous textile materials Download PDFInfo
- Publication number
- EP0390616B1 EP0390616B1 EP19900400245 EP90400245A EP0390616B1 EP 0390616 B1 EP0390616 B1 EP 0390616B1 EP 19900400245 EP19900400245 EP 19900400245 EP 90400245 A EP90400245 A EP 90400245A EP 0390616 B1 EP0390616 B1 EP 0390616B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- derivative
- mercurobutol
- polymeric
- polyhydroxylated
- antiseptic properties
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
Definitions
- the present invention relates to the treatment of certain polymeric materials, in particular of textile materials such as cotton, in particular with a view to giving them lasting antiseptic properties. These are precisely polyhydroxylated non-keratin materials, having little or no thiol functions or bisulphide bridges in their polymer structure; among textile materials, wool is therefore excluded.
- the invention also relates to the materials obtained by the treatment and having lasting antiseptic properties.
- Patent FR-A-83.00442 has already described a treatment intended to give a material antiseptic properties in which said polymeric material is subjected to a grafting reaction in which also intervenes a derivative of mercurobutol, having a functional group, bound to the phenolic nucleus of mercurobutol, and capable of intervening in a polymerization or polyaddition reaction.
- the mercurobutol derivative is placed in the graft, generally at the end of the chain, and provides the material thus grafted with antiseptic properties.
- it is the functional group, linked to the phenolic nucleus of mercurobutol, which intervenes.
- Patent GB-A-1,178,307 discloses a process for making an article containing keratin autosterile. This process known consists firstly in treating the article with solutions such as ammonium thioglycolate in order to break the bisulphide or cystenic bridges of keratin in order to produce sulphydryl groups, then in a second stage in treating the article with a solution a metal salt in order to replace the hydrogen ions of the sulphydryl group with the corresponding metal ions.
- the metal ions are chosen for their antiseptic action (silver, bismuth, copper or mercury).
- This process is specific for keratin polymeric materials, having thiol functions or disulphide bridges in their structure.
- the process of the invention consists, the polyhydroxylated material having in its polymeric structure no or few thiol functions and / or bisulphide bridges, in treating said material so as to fix in its polymeric structure thiol functions by causing the ethylene sulfide and then putting said material thus treated in the presence of a solution containing a heavy metal atom.
- a solution containing a heavy metal atom This will be in particular a solution containing mercury or a mercurial derivative having an antiseptic activity.
- the heavy metallic atom in the ionic state, for example mercury, silver, bismuth, copper either as such or in the form of a derivative, binds to the thiol functions which have been created in the polymer structure of the material during the first step in the process.
- the polyhydroxylated polymeric material is in particular cotton and fibranne.
- the mercurial derivative in solution is a derivative having antiseptic properties. It may in particular be mercurobutol or a derivative of mercurobutol, in particular bromomercuri-2 tertio-butyl-4 phenol allyl ether. It can be another mercurial derivative such as mercury phenyl borate or mercurescein, or another mercurial derivative recognized by the pharmacopoeia.
- a polyhydroxylated non-keratin polymeric material having lasting antiseptic properties obtained according to the above-mentioned process, and which comprises in its polymeric structure thiol functions linked to a heavy metal atom, alone or in the form of a derivative, having an antiseptic activity.
- a heavy metal atom alone or in the form of a derivative, having an antiseptic activity.
- mercury or mercury derivatives recognized by the pharmacopoeia.
- the content of heavy metal atom, as such or in the form of a derivative having antiseptic properties is at most 1 ⁇ by weight.
- the process of the invention can also be used for the extraction of heavy metals from charged baths.
- the aim is to extract said metals or to purify the bath without particularly seeking the properties of the material obtained.
- a piece of cotton is first treated with 20% sodium hydroxide for 30 minutes, before being rinsed with water, then with alcohol. It is then treated at 80 ° C in ethylene sulfide for 40 hours. After successive rinses with benzene, alcohol and water, the quantity of thiol functions created on the cotton is measured. The rate of thiol functions obtained is of the order of 9%.
- the piece of cotton is then immersed in a solution alcoholic mercurobutol at 50 g / l, expressed at a rate of 90%, for 10 minutes, rinsed with alcohol then with water at room temperature, then dried.
- the mercurobutol content by weight of cotton is 2.8%.
- Example 1 is reproduced, but the cotton is impregnated in a jigger for a one hour cycle with an excess solution of mercurobutol.
- the mercurobutol content by weight of cotton is 11.5%.
- a piece of cotton is first impregnated in the scarf with 4% soda. It is then treated at 80 ° C in ethylene sulfide for 20 minutes. After rinsing, it is brought into contact in a jigger with an aqueous solution of 100 mg / l of mercurobutol solubilized by a surfactant which is for example sodium lauryl sulphate in an amount of 40 g / l.
- a surfactant which is for example sodium lauryl sulphate in an amount of 40 g / l.
Description
La présente invention concerne le traitement de certains matériaux polymériques, en particulier de matériaux textiles tels que le coton, notamment en vue de leur conférer de manière durable des propriétés antiseptiques. Il s'agit précisément de matériaux non-kératiniques polyhydroxylés, ayant peu ou n'ayant pas de fonctions thiols ou de ponts bisulfures dans leur structure polymérique ; parmi les matériaux textiles, la laine est donc exclue . L'invention concerne également les matériaux obtenus par le traitement et comportant des propriétés antiseptiques durables.The present invention relates to the treatment of certain polymeric materials, in particular of textile materials such as cotton, in particular with a view to giving them lasting antiseptic properties. These are precisely polyhydroxylated non-keratin materials, having little or no thiol functions or bisulphide bridges in their polymer structure; among textile materials, wool is therefore excluded. The invention also relates to the materials obtained by the treatment and having lasting antiseptic properties.
On a déjà décrit dans le brevet FR-A-83.00442 un traitement destiné à donner à un matériau des propriétés antiseptiques dans lequel on soumet ledit matériau polymérique à une réaction de greffage dans laquelle intervient également un dérivé du mercurobutol, possédant un groupement fonctionnel, lié au noyau phénolique du mercurobutol , et capable d'intervenir dans une réaction de polymérisation ou de polyaddition. Au cours de la réaction, le dérivé du mercurobutol se place dans le greffon, généralement en bout de chaîne, et apporte au matériau ainsi greffé des propriétés antiseptiques. Dans cette réaction c'est le groupement fonctionnel, lié au noyau phénolique du mercurobutol, qui intervient.Patent FR-A-83.00442 has already described a treatment intended to give a material antiseptic properties in which said polymeric material is subjected to a grafting reaction in which also intervenes a derivative of mercurobutol, having a functional group, bound to the phenolic nucleus of mercurobutol, and capable of intervening in a polymerization or polyaddition reaction. During the reaction, the mercurobutol derivative is placed in the graft, generally at the end of the chain, and provides the material thus grafted with antiseptic properties. In this reaction it is the functional group, linked to the phenolic nucleus of mercurobutol, which intervenes.
Le traitement connu par le brevet précité présente des inconvénients. D'une part il est nécessaire de modifier le mercurobutol et de le transformer en un dérivé capable d'intervenir dans une réaction de polymérisation ou de polyaddition. D'autre part, on a constaté que la présence du noyau phénol présentait des limites dans la conduite de la réaction de polymérisation ; la fonction phénol a une action inhibitrice qui limite le développement de la réaction et en réduit le rendement.The processing known from the aforementioned patent has drawbacks. On the one hand, it is necessary to modify the mercurobutol and to transform it into a derivative capable of intervening in a polymerization or polyaddition reaction. On the other hand, it has been found that the presence of the phenol nucleus has limits in the conduct of the polymerization reaction; the phenol function has an inhibitory action which limits the development of the reaction and reduces its yield.
On connaît par le brevet GB-A-1.178.307 un procédé pour rendre autostérile un article contenant de la kératine. Ce procédé connu consiste dans un premier temps à traiter l'article avec des solutions telles que le thioglycolate d'ammonium afin de rompre les ponts bisulfures ou cysténiques de la kératine pour réaliser des groupes sulphydryl puis dans un deuxième temps à traiter l'article avec une solution d'un sel métallique afin de remplacer les ions hydrogène du groupe sulphydryl par les ions métalliques correspondants. Les ions métalliques sont choisis pour leur action antiseptique (argent, bismuth, cuivre ou mercure).Patent GB-A-1,178,307 discloses a process for making an article containing keratin autosterile. This process known consists firstly in treating the article with solutions such as ammonium thioglycolate in order to break the bisulphide or cystenic bridges of keratin in order to produce sulphydryl groups, then in a second stage in treating the article with a solution a metal salt in order to replace the hydrogen ions of the sulphydryl group with the corresponding metal ions. The metal ions are chosen for their antiseptic action (silver, bismuth, copper or mercury).
Ce procédé est spécifique des matériaux polymériques kératiniques , ayant des fonctions thiols ou des ponts bisulfures dans leur structure.This process is specific for keratin polymeric materials, having thiol functions or disulphide bridges in their structure.
Or on a trouvé et c'est ce qui fait l'objet de l'invention un nouveau procédé de traitement de matériaux polymériques non kératiniques polyhydroxylés ayant notamment pour but de leur conférer de manière durable des propriétés antiseptiques qui pallie les inconvénients du procédé du brevet FR-A-83.00442 et qui ne présente pas les limitations du procédé du brevet GB-A-1.178.307 en ce qu'il est applicable aux matériaux non kératiniques.Now we have found, and this is what is the subject of the invention, a new process for treating polyhydroxylated non-keratinous polymeric materials, in particular with the aim of giving them lasting antiseptic properties which overcomes the disadvantages of the patent process. FR-A-83.00442 and which does not present the limitations of the process of patent GB-A-1,178,307 in that it is applicable to non-keratin materials.
Le procédé de l'invention consiste , le matériau polyhydroxylé n'ayant dans sa structure polymérique pas ou peu de fonctions thiols et/ou de ponts bisulfures , à traiter ledit matériau de manière à fixer dans sa structure polymérique des fonctions thiols en faisant agir le sulfure d'éthylène puis à mettre ledit matériau ainsi traité en présence d'une solution contenant un atome métallique lourd. Ce sera en particulier une solution contenant du mercure ou un dérivé mercuriel ayant une activité antiseptique.The process of the invention consists, the polyhydroxylated material having in its polymeric structure no or few thiol functions and / or bisulphide bridges, in treating said material so as to fix in its polymeric structure thiol functions by causing the ethylene sulfide and then putting said material thus treated in the presence of a solution containing a heavy metal atom. This will be in particular a solution containing mercury or a mercurial derivative having an antiseptic activity.
L'atome métallique lourd, à l'état ionique, par exemple mercure, argent, bismuth, cuivre soit tel quel soit sous forme d'un dérivé se fixe sur les fonctions thiols qui ont été créées dans la structure polymérique du matériau au cours de la première étape du procédé.The heavy metallic atom, in the ionic state, for example mercury, silver, bismuth, copper either as such or in the form of a derivative, binds to the thiol functions which have been created in the polymer structure of the material during the first step in the process.
Le matériau polymérique polyhydroxylé est notamment le coton et la fibranne.The polyhydroxylated polymeric material is in particular cotton and fibranne.
Le dérivé mercuriel en solution est un dérivé ayant des propriétés antiseptiques. Ce peut être en particulier le mercurobutol ou un dérivé du mercurobutol, en particulier le bromomercuri-2 tertio butyl - 4 phénol allyl éther. Ce peut être un autre dérivé mercuriel tel que le phényl borate de mercure ou la mercurescéine, ou un autre dérivé mercuriel reconnu par la pharmacopée.The mercurial derivative in solution is a derivative having antiseptic properties. It may in particular be mercurobutol or a derivative of mercurobutol, in particular bromomercuri-2 tertio-butyl-4 phenol allyl ether. It can be another mercurial derivative such as mercury phenyl borate or mercurescein, or another mercurial derivative recognized by the pharmacopoeia.
C'est un autre objet de l'invention que de protéger un matériau polymérique non-kératinique polyhydroxylé ayant des propriétés antiseptiques durables, obtenu selon le procédé précité, et qui comporte dans sa structure polymérique des fonctions thiols liées à un atome métallique lourd, seul ou sous forme de dérivé, ayant une activité antiseptique. En particulier il s'agit du mercure ou de dérivés mercuriels reconnus par la pharmacopée.It is another object of the invention to protect a polyhydroxylated non-keratin polymeric material having lasting antiseptic properties, obtained according to the above-mentioned process, and which comprises in its polymeric structure thiol functions linked to a heavy metal atom, alone or in the form of a derivative, having an antiseptic activity. In particular, it is mercury or mercury derivatives recognized by the pharmacopoeia.
De préférence pour cette application précise visant à l'obtention d'un matériau non-kératinique polyhydroxylé à propriété antiseptique, la teneur en atome métallique lourd, tel quel ou sous forme de dérivé ayant des propriétés antiseptiques est au plus de 1‰ en poids.Preferably for this precise application aimed at obtaining a polyhydroxylated non-keratin material with antiseptic property, the content of heavy metal atom, as such or in the form of a derivative having antiseptic properties is at most 1 ‰ by weight.
Le procédé de l'invention est utilisable également pour l'extraction de métaux lourds de bains chargés. Dans ce cas le but est d'extraire lesdits métaux ou d'épurer le bain sans rechercher particulièrement les propriétés du matériau obtenu.The process of the invention can also be used for the extraction of heavy metals from charged baths. In this case the aim is to extract said metals or to purify the bath without particularly seeking the properties of the material obtained.
L'invention et les avantages qu'elle apporte seront mieux compris à la lecture de la description qui va être faite de trois exemples de mise en oeuvre du procédé de l'invention appliqué au coton.The invention and the advantages which it brings will be better understood on reading the description which will be given of three examples of implementation of the method of the invention applied to cotton.
Un morceau de coton est d'abord traité avec de la soude à 20 % pendant 30 minutes , avant d'être rincé à l'eau, puis à l'alcool.
Il est ensuite traité à 80°C dans du sulfure d'éthylène pendant 40 heures. Après des rinçages successifs au benzène, à l'alcool et à l'eau on dose la quantité de fonctions thiols créées sur le coton.
Le taux de fonctions thiols obtenu est de l'ordre de 9%.
Le morceau de coton est ensuite plongé dans une solution alcoolique de mercurobutol à 50 g /l , exprimé à un taux de 90%, pendant 10 minutes , rincé à l'alcool puis à l'eau à température ambiante, puis séché. La teneur pondérale du coton en mercurobutol est de 2,8 %.A piece of cotton is first treated with 20% sodium hydroxide for 30 minutes, before being rinsed with water, then with alcohol.
It is then treated at 80 ° C in ethylene sulfide for 40 hours. After successive rinses with benzene, alcohol and water, the quantity of thiol functions created on the cotton is measured.
The rate of thiol functions obtained is of the order of 9%.
The piece of cotton is then immersed in a solution alcoholic mercurobutol at 50 g / l, expressed at a rate of 90%, for 10 minutes, rinsed with alcohol then with water at room temperature, then dried. The mercurobutol content by weight of cotton is 2.8%.
L'exemple 1 est reproduit mais l' imprégnation du coton se fait en jigger pendant un cycle d'une heure avec une solution de mercurobutol en excès. La teneur pondérale du coton en mercurobutol est de 11,5 %.
Ces deux premiers exemples illustrent la capacité , par un coton ayant des fonctions thiols, d'extraction de grandes quantités d'un dérivé tel que le mercurobutol contenu dans une solution.Example 1 is reproduced, but the cotton is impregnated in a jigger for a one hour cycle with an excess solution of mercurobutol. The mercurobutol content by weight of cotton is 11.5%.
These first two examples illustrate the capacity, by a cotton having thiol functions, of extracting large quantities of a derivative such as mercurobutol contained in a solution.
Un morceau de coton est d'abord imprégné au foulard avec de la soude à 4%. Il est ensuite traité à 80°C dans du sulfure d'éthylène pendant 20 minutes. Après rinçage, il est mis en contact en jigger avec une solution aqueuse de 100 mg/l de mercurobutol solubilisée par un tensioactif qui est par exemple du lauryl sulfate de sodium à raison de 40g/l. On obtient un épuisement du mercurobutol à 90% et une teneur pondérale du coton en mercurobutol de 0,2 ‰. Ce tissu de coton présente des propriétés antiseptiques durables.A piece of cotton is first impregnated in the scarf with 4% soda. It is then treated at 80 ° C in ethylene sulfide for 20 minutes. After rinsing, it is brought into contact in a jigger with an aqueous solution of 100 mg / l of mercurobutol solubilized by a surfactant which is for example sodium lauryl sulphate in an amount of 40 g / l. We obtain an exhaustion of mercurobutol at 90% and a weight content of cotton in mercurobutol of 0.2 ‰. This cotton fabric has long-lasting antiseptic properties.
Claims (6)
- Process for the treatment of a nonkeratinous polyhydroxylated polymeric material, characterized in that it consists in binding thiol functional groups to its polymeric structure by reacting ethylene sulphide with the said material and by placing the material thus treated in contact with a solution containing a heavy metal atom, either as such or in the form of a derivative.
- Process according to Claim 1, characterized in that, with a view to imparting antiseptic properties to the polymeric material, the heavy metal atom, by itself or its derivative, has antiseptic properties.
- Process according to Claim 2, characterized in that the solution of metal is a solution of a mercury derivative such as mercurobutol or a mercurobutol derivative.
- Process according to Claim 3, characterized in that the mercurobutol derivative is 2-bromomercuri-4-tert-butylphenol allyl ether.
- Polyhydroxylated nonkeratinous polymeric material which has antiseptic properties, obtained according to the process of Claim 2, characterized in that it contains thiol functional groups bonded to mercurobutol or one of its derivatives, in which the weight content of mercury derivatives is not more than 0.1 %.
- Process for the purification of a bath laden with heavy metals with the aid of a nonkeratinous polyhydroxylated polymeric material, characterized in that it consists in binding thiol functional groups to the polymeric structure of the said material by reacting ethylene sulphide with the said material and extracting the heavy metals from the laden bath by placing the material thus treated in contact with the said bath.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8901567A FR2642445B1 (en) | 1989-01-31 | 1989-01-31 | PROCESS FOR TREATING POLYMERIC MATERIALS WITH A VIEW TO PROVIDING ANTISEPTIC PROPERTIES AND MATERIALS OBTAINED |
| FR8901567 | 1989-01-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0390616A1 EP0390616A1 (en) | 1990-10-03 |
| EP0390616B1 true EP0390616B1 (en) | 1995-09-20 |
Family
ID=9378556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19900400245 Expired - Lifetime EP0390616B1 (en) | 1989-01-31 | 1990-01-30 | Process for the antiseptic treatment of non-keratinous textile materials |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0390616B1 (en) |
| DE (1) | DE69022460D1 (en) |
| FR (1) | FR2642445B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317445C (en) * | 2003-12-02 | 2007-05-23 | 中国科学院东北地理与农业生态研究所 | Method for preparing mercapto cotton |
| CN106319754A (en) * | 2016-09-08 | 2017-01-11 | 河南工程学院 | Functional antibacterial composite wool flocculus and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2396957A (en) * | 1944-01-27 | 1946-03-19 | Du Pont | Treatment of polymeric materials with dithioglycidol |
| CH462775A (en) * | 1966-02-01 | 1968-09-30 | Semi S A | Manufacturing process of a self-sterile brush |
-
1989
- 1989-01-31 FR FR8901567A patent/FR2642445B1/en not_active Expired - Fee Related
-
1990
- 1990-01-30 EP EP19900400245 patent/EP0390616B1/en not_active Expired - Lifetime
- 1990-01-30 DE DE69022460T patent/DE69022460D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2642445B1 (en) | 1991-08-16 |
| EP0390616A1 (en) | 1990-10-03 |
| DE69022460D1 (en) | 1995-10-26 |
| FR2642445A1 (en) | 1990-08-03 |
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