WO2003023130A2

WO2003023130A2 - Method of depositing and binding molecules to a support and the support thus obtained

Info

Publication number: WO2003023130A2
Application number: PCT/IB2002/003600
Authority: WO
Inventors: Serge Weibel
Original assignee: Internova International Innovation Company B.V.
Priority date: 2001-09-07
Filing date: 2002-09-06
Publication date: 2003-03-20
Also published as: FR2829407A1; WO2003023130A3; AU2002330688A1

Abstract

The invention relates to a method of depositing and binding molecules, particularly bioactive molecules, colorant molecules or compound molecules having specific physical characteristics, to a support, such as a support made from natural or synthetic fibres. The inventive method consists in using a support (1) having a first electrical polarity (2) and depositing thereon molecules (3) having a second electrical polarity (4) with an opposite sign in such a way as to generate ionic bonds which bind the molecules (3) to the support (1) in a stable and unalterable manner. The support (1) could be made from a textile material which is intended for clothing and the molecules (3) could be insect repellent bioactive molecules, for example. When the inventive method is used, the molecules (3) remain effective, active and, moreover, bound to the support (1) even after numerous repeated washings.

Description

METHOD FOR DEPOSITING AND FIXING MOLECULES ON A SUPPORT AND SUPPORT OBTAINED BY SAID METHOD

Technical area

The present invention relates to a method for depositing and fixing molecules, in particular bio-active molecules, dye molecules or molecules of compounds having specific physical characteristics on a support, such as for example a support based on natural textile fibers. or synthetic.

It also relates to a support based on natural or synthetic textile fibers obtained after the above deposition and fixing process of bio-active molecules, dye molecules and / or molecules having specific physical characteristics according to the above process .

Prior art

There are different methods for depositing and fixing molecules on a support of different nature and / or composition. A first method described in publication EP-A-0 104 608 provides for modifying the chemical nature of a support to allow the attachment and the orientation of the molecules on its surface by using the free radicals of both the molecules and the modified support. The modification of the chemical nature of the support is obtained by means of a plasma and the fixing of the molecules is ensured by the covalent bonds established between the support and the molecules. This first process can cause degeneration of the molecules and / or of the support and does not make it possible to definitively preserve their original chemical nature. This can be particularly troublesome for certain applications requiring the preservation of these original chemical natures.

Another method of depositing and fixing molecules on a support consists in mixing the molecules with a binder, for example an adhesive, and in apply this binder containing the molecules to the support. In this second process, the molecules are trapped in the binder and cannot or only partially confer on the support their specific characteristics. As a result, the molecules, for example bio-active, lose all or at least in part their effect and the treated support has only reduced effectiveness.

Publication US-A-5 618 622 describes a naturally cationic or anionic fibrous surface, such as a nonwoven, covered with an electrically charged natural or synthetic polyelectrolyte, the charges of which retain opposite charges of solid particles by ionic attraction. in a solution to be filtered such as a chemical, pharmaceutical or mineral solution.

Publication EP-A-0 395 476 describes a process for manufacturing a nonwoven intended for example for making clothes and comprising the steps of immersing the nonwoven in a solution bath, of wringing part of the solution, cooking, washing and drying. The nonwoven can be chemically modified beforehand to be ionically absorbent so that ionic bonds are established between it and an active agent contained in the solution. This active agent is intended to be gradually released upon contact with the skin, in a controlled manner according to the degree of humidity of the latter.

The publication US-A-5,536,573 describes a process for obtaining a support carrying successive layers of naturally cationic polymers electrically charged, these layers being linked to each other by non-covalent bonds. The supports thus obtained are used in particular to reduce friction, protect from corrosion, promote lubrication and for their modified electrical and / or optical properties.

Publication WO-A-96 / 31,644 describes a fibrous web comprising a binding agent of polymeric type or not, making it possible to bind the fibers, by example to a super absorbent, while avoiding making them rigid and thus promoting the increase in their density.

It is noted that all of these methods consist in using fibers or naturally ionic molecules, which are weak do not allow strong bonds to be created, without changing their chemical nature and without altering the effectiveness of their action, especially when it is acts of bioactive molecules.

Disclosure of the invention The present invention aims to overcome these drawbacks by proposing a method of depositing and fixing molecules as defined above on a support, making it possible to preserve the original chemical nature of the molecules and to confer the properties specific for these molecules to the support, while guaranteeing a strong bond, unalterable over time and insensitive to external agents and to environmental conditions, of said molecules on said support.

For this purpose, the method according to the invention is characterized in that said support is subjected to a first treatment to give it a first cationic electrical polarity, in that at least part of said molecules is subjected to a second treatment intended to give them a second anionic electrical polarity and in that anionic molecules are deposited on said cationic support in order to generate ionic bonds firmly fixing said molecules on said support.

For this purpose also, the support based on textile fibers according to the invention is characterized in that said molecules are fixed to said support by strong ionic bonds and give it the physical or chemical properties which are specific to them. According to an advantageous embodiment, said first treatment consists in impregnating said support by passing it through at least one first bath called impregnation bath composed of a solution which can be polymerized and / or crosslinked and having said first cationic electrical polarity.

Preferably, said solution which can be polymerized and / or crosslinked is obtained by mixing at least one first material which can be polymerized and / or crosslinked nonionically with at least one second material having said cationic electrical polarity.

Said solution which can be polymerized and / or crosslinked is advantageously an adhesive having said cationic electrical polarity.

The first impregnation bath advantageously contains at least one catalyst arranged to fix at least said solution which can be polymerized and / or crosslinked to said support.

Advantageously, said molecules can be deposited on said support by passing said support through at least one second bath, called deposition bath, composed of a solution containing at least said molecules.

Another embodiment may consist in depositing said molecules on said support by spraying the solution which contains them.

After the molecules have been deposited and fixed, the support is preferably dried.

The support based on textile fibers preferably has applications in the field of clothing, in the field of furniture and in the field of building. In this latter field, this support can be a covering of a ceiling or a wall having, for example, properties bio active, anti-bacterial, anti-insect, physical properties, for example reflective, luminescent, absorbent or the like.

Brief description of the drawings The present invention and its main advantages will appear more clearly in the following description of an exemplary embodiment, with reference to the accompanying drawings, in which:

FIG. 1 schematically represents the support based on textile fibers and the molecules to be fixed on this support according to the invention before deposition and fixing,

FIG. 2 schematically represents the support based on textile fibers and the molecules to be fixed in FIG. 1 after deposition and fixing, and

FIG. 3 schematically illustrates the method of treatment according to the invention of the support based on textile fibers in a bath known as an impregnation bath.

With reference to FIGS. 1 and 2, the present invention relates to a method for depositing and fixing bioactive molecules 3, dye molecules or molecules of compounds having specific physical characteristics on a support 1, such as for example a support based on natural or synthetic textile fibers and the support 10 after treatment according to this process, carrying the said molecules 3.

Very schematically, the method of depositing and fixing the molecules 3 on the support 1 consists in depositing on this support having a first electrical polarity 2 the molecules 3 having a second electrical polarity 4 of sign opposite to the first. In practice, the first electrical polarity 2 is cationic and the second electrical polarity 4 is anionic. The supports based on textile fibers are often neutral and the; molecules to be fixed can be neutral or naturally slightly anionic. To make the support cationic, it is subjected to a treatment which will be described in more detail below. To make the molecule; anionic when they are neutral or to reinforce their anionic character when they are naturally and weakly anionic, they are subjected to a treatment which will be described below.

The support 1 based on textile fibers can be intended for all kinds of uses, the confection of clothes, the manufacture of camping equipment, the realization of bio active mosquito nets having a destructive effect on certain dangerous insects, the production of bands textiles intended to make stretch ceilings or wall coverings

This support can be woven, non-woven or knitted. It can be raw, white, dyed or printed and can be in the form of a strip or tube of raw textile material or in the form of a worked or made or finished product. It can comprise fibers or threads of natural or synthetic origin or a mixture of the two and contain, for example, cotton, polyester, polyamides, wool, silk, or mixtures of these different fibers.

This first treatment could consist, for example, and as illustrated by FIG. 3, of immersing the support 1 in at least one first so-called impregnation bair bath 5, for example liquid, contained in a tank 6, this first impregnation bath 5 having the first cationic electrical polarity 2. This first impregnation bath 5 consists of a solution which can be polymerized and / or crosslinked, obtained for example by mixing at least one first material capable of being polymerized and / or crosslinked nonionically with at least one second material having said first cationic electrical polarity 2. In this way it is possible to obtain a cationic support 1 starting from a neutral support. Said first material can being polymerized and / or cross-linked nonionically can for example consist of binders based on styrene butadiene, polyurethane and vinyl acetate or mixtures of several of these materials. Resins of the DMDHEU (DiMethylolDiHydroxyEthylèneUrée), DMU (DiMethylolUrée) and MF (Mélamine Formol) type or mixtures of several of these materials can also be used. By way of example, as the second cationic material, it is possible to use quaternary ammonium compounds, modified polysilicic acids, products derived from chromium complex. It is possible, for example, to use a mixture of 50 to 80 g / l of an aqueous solution of a nonionic acrylic polymer and of 50 to 100 g / l of an aqueous solution of a cationic quaternary polyamine or any other highly cationic. It is also possible to use a solution which can be polymerized and / or crosslinked cationic ready for use previously prepared, for example based on quaternary amine.

Although not very common, it would be possible to obtain an anionic support 1 starting from a neutral support, using a first impregnation bath 5 containing a solution which can be polymerized and / or crosslinked anionically such as for example the mixture of 50 to 80 g / l of an aqueous solution of an anionic acrylic polymer and 20 to 40 g / l of an aqueous solution of carboxy-methylcellulose or any other highly anionic product. It is also possible to use a solution which can be polymerized and / or anionic crosslinked ready for use previously prepared.

The concentration of the various materials will be chosen as a function of the carrying rate of the support corresponding to the quantity in liters / kg of bath absorbed by the support 1 after spinning.

In order to fix the solution which can be polymerized and / or crosslinked on the support 1, it is possible to incorporate a catalyst into the first impregnation bath 5. Similarly, if the support 1 to be treated has a character hydrophobic, can be added to the first impregnation bath 5 a nonionic surfactant such as most alcoholic compounds such as isopropyl alcohol.

If necessary, the support 1 can pass through several successive baths containing the same solution which can be polymerized and / or crosslinked or different solutions. The speed of passage of the support 1 in the impregnation bath (s) 5 depends on the type of support, the type of solution which can be polymerized and / or crosslinked used and the type of treatment desired. It is also possible to interrupt the scrolling of the support in order to make it remain in the impregnation bath 5 for a period determined according in particular to its characteristics and those of the impregnation bath 5.

This first treatment can be carried out at room temperature and preferably at a temperature below 50 ° C. After this first treatment, the support 1 can be subjected, as required, to a spin and then a first heat treatment. One can for example dry the support 1 at a temperature between 100 and 250 ° C and preferably about 200 ° C for less than 15 seconds, or from 190 to 199 ° C for 15 to 30 seconds and so on.

The molecules 3 to be deposited and fixed on said support 1 are usually neutral or naturally weakly anionic. To prepare these molecules, they will be subjected to a second treatment intended to give them the second anionic electrical polarity 3. This involves preparing a solution containing the molecules to be deposited, in particular the bio-active or other molecules which will have to give the support the desired physical and chemical properties.

Several techniques can be used to deposit the molecules 3 on the support I. A first technique consists in passing the support 1 in at least a second bath 7, said deposition bath, for example liquid and contained in a tank 8 similar to tank 6 containing the impregnation bath 5, and containing a solution comprising at least the molecules 3. The products incorporated in this second deposition bath may be in the form of an emulsion or an aqueous dispersion and the molecules 3 may be soluble, emulsifiable or simply miscible. In the case of molecules 3 in the form of an emulsion, the solution may contain a dispersant or an emulsifier such as condensation products of sulfonic acids, carboxy-methylcellulose making it possible to maintain a stable emulsion without separation of the phases, without settling or deposition of an aggregate.

According to this treatment method, the support based on textile fibers passes successively through the two baths 5 and 7, driven by rollers 9, respectively 11, mounted in the two tanks 6 and 8. This equipment is especially intended for the treatment of strip textiles, the tension of the strip being provided by the tension rollers 12 and 13 and by a take-up spool (not shown) on which the textile strip is wound after treatment. An intermediate drying and / or spinning operation may be required between the treatment in tank 8 and the take-up reel.

A second technique consists in spraying a solution containing the molecules 3 onto the support 1, for example by means of one or more nozzles, a rotary centrifuge system or any other equivalent means.

Once the molecules 3 deposited on the support 1 their fixing is ensured automatically and instantaneously by the ionic bonds being established between the first electrical polarity 2 of the support 1 and the second electrical polarity 4 of the molecules 3. These ionic bonds make it possible to ensure stable and lasting fixation of the molecules 3 on the support 1. After the molecules 3 have been deposited on the support 1, the support 10 obtained carrying the molecules 3 can be dried in an oven or by any other means at more or less high temperature. The drying temperature will depend on the sensitivity and the heat resistance of the molecules 3 and / or of the support 1. The heat resistance of the support 10 obtained will depend in particular on the melting point and the softening point respectively of 170 ° C. and Î45 ° C for a support 1 of polypropylene for example.

This method of depositing and fixing molecules 3 can be applied to any type of support 1 of various natures and properties and can have many applications. It is possible, for example, to deposit on textiles, for example intended for making clothes, molecules of the bioactive type which have curative, preventive, repellent and / or comfort properties. The major advantage of this process lies in the fact that the bioactive molecules thus deposited are not trapped and made inactive in a binder but remain close to the surface of the support, which allows them to remain active and to exercise their action effectively. In addition, their attachment to the support is durable over time and resistant, in particular to washing or any other mechanical or chemical treatment, or to exposure to environmental conditions. When the process is applied to fibers or threads, the latter can be easily woven or knitted after treatment, without altering the effectiveness of the bioactive molecules. In addition, the textile serving as a support can be treated in the raw state, that is to say in a strip or in the state of a worked or made-up product. In this case the drive mechanisms inside the tanks should be adapted.

The bioactive molecules 3 of curative type can for example be used to improve the circulation of the blood, to desensitize a subject against allergies, to quit smoking or certain drugs, etc. The bioactive molecules 3 of preventive type can for example be used to protect a subject against the rays of the sun, serve as a vaccine, etc.

The bioactive molecules 3 of repellant type can for example be used to protect a subject against insect bites, against mosquitoes in general and the risks of malaria associated therewith, against mites, against bacteria, against microbes such as isothiazolinone, against fungal infections, etc.

The so-called comfort bio-active molecules 3 can for example play the role of thermal barrier, be perfumed, tinted so as to change color depending for example on the temperature. The bioactive tinted molecules are particularly suitable for the inkjet printing technique.

The bioactive molecules 3 mentioned above can be deposited and fixed on any support other than textile, for example supports made of synthetic material, paper, cardboard, etc.

One can cite a particularly interesting application in the field of anti-mosquito treatment for clothing and mosquito nets. At present, existing treatments require periodic maintenance and re-impregnation after each washing of the treated article. These re-impregnations make the use of these articles complicated especially in remote geographic areas. In addition, reimpregnation techniques generate significant risks of environmental pollution and dermal toxicity for a limited time. With the process according to the invention, a permanent impregnation is obtained without risk of contamination for humans or for the environment. The bioactive molecules used are preferably chosen according to the geographic area of destination of the article and therefore the type of mosquito. To date, there are several bioactive molecules in this field. Mention may be made of permethrin which acts directly on the nervous center of mosquitoes and is particularly well suited to this application. Tests have made it possible to demonstrate that the effectiveness of the protection conferred by a mosquito net treated with the method according to the invention is five times greater than that of an untreated mosquito net. Likewise, garments treated with this process have an effectiveness not achieved to date and keep this efficiency even after numerous washes. By way of nonlimiting example, to treat using bio-active insect repellent molecules based on permethrin, a cotton fabric having a density of 320 g / m ² and a carrying rate of 65%, the concentration of permethrin solution 50% of the impregnation bath can be approximately 26 g / l.

This description clearly highlights the fact that the method according to the present invention makes it possible to fix effectively and durably any type of molecules on any type of support using the ionic bonds created between the support and the molecules, without altering the proper functions. molecules which is essential especially when using bioactive molecules.

The present invention is not limited to the embodiments described but extends to any modification and variant obvious to a person skilled in the art while remaining within the scope of the protection defined in the appended claims.

Claims

claims

1. Method for depositing and fixing molecules, in particular bio-active molecules, dye molecules or molecules of compounds having specific physical characteristics on a support, such as for example a support based on natural or synthetic textile fibers, characterized in that said support (1) is subjected to a first treatment to give it a first cationic electrical polarity (2), in that at least part of said molecules (3) are subjected to a second treatment intended to give them a second anionic electric polarity and in that anionic molecules (3) are deposited on said cationic support to generate ionic bonds firmly fixing said molecules (3) on said support (1).

2. Method according to claim 1, characterized in that said first treatment consists in impregnating said support (1) by passing it through at least one first bath called impregnation bath (5) composed of a solution which can be polymerized and / or crosslinked and having said first cationic electrical polarity (2).

3. Method according to claim 2, characterized in that said solution which can be polymerized and / or crosslinked is obtained by mixing at least one first material which can be polymerized and / or crosslinked nonionic with at least one second material having said polarity cationic electric (2).

4. Method according to claim 2, characterized in that said solution which can be polymerized and / or crosslinked is an adhesive having said cationic electrical polarity (2).

5. Method according to claim 2, characterized in that said first impregnation bath (5) contains at least one catalyst arranged to fix at least said solution which can be polymerized and / or crosslinked to said support (1).

6. Method according to claim 1, characterized in that said molecules (3) are deposited on said support (1) by passing said support through at least a second bath (7) said deposition bath composed of a solution containing at least said molecules.

7. Method according to claim 1, characterized in that said molecules (3) are deposited on said support (1) by spraying.

8. Method according to claim 1, characterized in that one proceeds to a drying of said support (1) after the deposition and fixing of the molecules (3).

9. Support based on natural or synthetic textile fibers obtained after the deposition and fixing treatment of bio-active molecules, dye molecules and / or molecules having specific physical characteristics according to the method of any one of the preceding claims , characterized in that said molecules (3) are fixed to said support (1) by strong ionic bonds and give it the physical or chemical properties which are specific to them.

10. Support based on textile fibers according to claim 9, characterized in that it has applications in the field of clothing.

11. Support based on textile fibers according to claim 9, characterized in that it has applications in the field of furniture.

12. Support based on textile fibers according to claim 9, characterized in that it has applications in the field of construction.

13. Support based on textile fibers according to claim 12, characterized in that the application in the field of building is a coating of ceiling or wall wall.