EP1049825A1

EP1049825A1 - Acaricidal polymeric fibres, a method for producing same and their applications

Info

Publication number: EP1049825A1
Application number: EP99900961A
Authority: EP
Inventors: François BELET; Odile Primel; Alain Regad
Original assignee: Rhovyl SA
Current assignee: Rhovyl SA
Priority date: 1998-01-20
Filing date: 1999-01-20
Publication date: 2000-11-08
Also published as: FR2773823B1; FR2773823A1; AU2060399A; JP2002509201A; WO1999036601A1

Abstract

The invention relates to textile products obtained by spinning a solution on a polymer basis and to products obtained by spinning said products, characterized in that they consist of a polymeric material the mass of which contains an effective quantity of at least one acaricidal agent selected from among benzyl benzoate and the carbamates, pyrethroids and pyrethrins. The invention also relates to a method for producing said products and to their use in producing textile articles with acaricidal action. The invention relates especially to chlorofibers.

Description

Polymeric fibers with acaricide character, their manufacturing process and their applications

The invention relates to acaricidal polymer fibers, their manufacturing process and their applications. Dust mites are well known today for causing a number of direct or indirect pathologies in humans and animals. One of the essential scourges that we seek to overcome is that of allergies, in particular allergies to dust mites. It is well known that mites feed mainly on human and animal dander as well as various molds. One of their favorite places for development is made up of textile wall and floor coverings, but also and above all bedding.

At present, to avoid proliferation and get rid of mites, we tend to spray anti-mite and acaricide products on the materials where they develop. Many aerosol products are commercially available to be sprayed on the surface in places where there is a risk of infestation. One of the drawbacks of this type of treatment is the lack of persistence over time, in particular when the materials to be treated are intended to be subsequently subjected to washing operations. Attempts have also been made to incorporate an acaricide product into materials known for their tendency to be infested. Thus, international application WO 92/16683 describes products for covering floors or walls consisting of a backing comprising a polymer matrix in which there is incorporated at least one acaricide agent. Another proposed solution has consisted in treating the fibrous materials so as to fix an acaricidal agent on the surface of their fibers. Such a process is described in particular in European patent EP 0 357 957.

Various documents also describe fibers which can be described as "heart-skin" fibers consisting of a polymeric core and a coating containing the acaricide product. Such fibers are in particular described in Japanese patent application JP 07 054208.

For the sake of simplification, in the present specification, "fibers" will denote both the fibers themselves and all the textile products such as filaments, threads, fibers, hairs, cables, obtained by spinning both dry and wet. polymer solutions. We will include in this definition the spinning products, for example carded, combed or drawn ribbons, fiber yarns, etc.

The term “polymeric fibers” means both fibers consisting of a single polymer or copolymer and fibers consisting of a mixture of polymers and / or copolymers.

Consequently, by polymeric material constituting the polymeric fiber, one also understands mixtures of polymer (s) and / or copolymer (s), when the fibers consist of such a mixture.

The inventors of the present invention have now developed new fibers with acaricidal activity which have the advantage of a high persistence of their acaricidal properties as well as a particularly flexible method of preparation.

More specifically, the inventors of the present invention have developed new polymeric fibers containing, distributed homogeneously within them, well-defined proportions of particular acaricide agents allowing obtaining a residual acaricide activity while allowing a particularly advantageous process for obtaining since these fibers can be obtained by spinning a collodion incorporating within it well-defined proportions of said acaricide agent. Thus, according to one of its essential characteristics, the invention relates to textile products obtained by spinning a solution based on polymers as well as products obtained after spinning of said products, consisting of a polymeric material containing in its mass a effective amount of at least one miticide agent chosen from benzyl benzoate, carbamates, pyrethroids and pyrethrins.

According to an advantageous variant of the invention, the acaricide agent is present in the fiber in proportions of between 1 and 30 phr (per cent of resin), expressed by weight relative to the total weight of the polymeric material. Concentrations of acaricide agent of between 5 and 30 pcr will preferably be chosen, more preferably concentrations of between 10 and 20 pcr.

As indicated previously, the acaricide agent used will be chosen from benzyl benzoate, carbamates, pyrethroids and pyrethrins, compounds which are particularly appreciated for their effectiveness with regard to mites and their harmlessness. Benzyl benzoate will advantageously be chosen for economic reasons. However, other products from the families mentioned above can also be used. Mention will be made, more particularly, of carbaryl and permethrin.

The polymers constituting said polymeric materials may be synthetic, natural polymers or derivatives of natural polymers. As synthetic polymeric materials constituting the fibers, it is preferable to choose polymers or copolymers chosen from the family consisting of polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, acrylic polymers, cellulose acetate, cellulose and mixtures thereof. The polymeric material will advantageously consist of polyvinyl chloride or a mixture of polyvinyl chloride and chlorinated polyvinyl chloride. Chlorofibres denote fibers based on this type of polymeric material.

An example of a natural polymer which can be used according to the invention is cellulose.

As an example of a polymer derived from a natural polymer, mention will be made of viscose.

The invention relates not only to fibers incorporating therein an acaricidal agent giving them acaricidal properties. It also relates to a process for the preparation of these fibers.

Such a process advantageously comprises a first step of solubilization of the polymer in an appropriate solvent, in which at least one acaricide agent is also dissolved, and a second step of obtaining the fiber with dry or wet extraction of said solvent. The following are understood to mean: - dry extraction, a process in which the solvent is extracted by evaporation,

- wet extraction, a process in which the solvent is extracted by dissolving it in a third body. When such a method is applied to a polymer derived from a natural polymer, the method generally also comprises a step of regenerating said natural polymer.

Thus, according to another of its aspects, the invention also relates to the process intended for the preparation of the fibers described above.

These fibers are advantageously obtained by a process comprising a wet or dry spinning step of a gel in which the acaricide agent defined above is found. This process will also include, where appropriate, a step of spinning the preceding product. Those skilled in the art will choose the type of spinning method, dry or wet, depending on the nature of the polymer used.

For example, the dry route is preferred for the transformation of

PVC (acetone / carbon sulfide solvent or acetone / benzene), and cellulose acetate (acetone solvent), and the wet process is preferred for obtaining acrylic fibers (solvent: dimethylformamide) or cellulose fibers (solvent: N - methyl morpholine oxide or viscose process).

According to a very particularly advantageous variant of the invention, the polymers from the polyvinyl chloride (PVC) family will be chosen, as well as mixtures of polyvinyl chloride and chlorinated polyvinyl chloride.

(PVCC).

We will advantageously choose for the production of fibers based on

PVC, a PVC of molecular weight in number of between 50,000 and 120,000 and the fiber will advantageously be produced according to the method described in European patent EP 0091384, the acaricide agent preferably being dissolved beforehand in the solvent or mixture of solvents before introduction PVC in said solvent or mixture of solvents.

The acaricide agent may be introduced into any fiber based on a mixture of PVC and PVCC, capable of being obtained by wet or dry spinning of a gel containing such a mixture and in which this acaricide agent is dissolved beforehand.

For the production of fibers based on mixtures of PVC and PVCC, it is advantageous to choose mixtures containing from 5 to 80% by weight of a polymer or of a mixture of chlorinated vinyl chloride polymers, having a transition temperature of the second order greater than or equal to 100 ° C. The fibers can then be obtained by any known method of dry or wet spinning of a gel containing this mixture. The acaricide agent is then advantageously dissolved in the solvent used for the preparation of the gel before dissolution of the polymer mixture. According to a particularly advantageous variant of the invention, the

PVCC is present in an amount of 17 to 20% by weight relative to the mixture in said mixture and the fibers are obtained under the conditions described in the European patent application EP-A-0530119.

Furthermore, the polymer fibers can of course contain, in addition to the polymer and the acaricide agent, all the additives conventionally added, in particular in the case of textile fibers. By way of example of such additives, mention will be made of whitening and mattifying agents intended to thermally stabilize polymers, anti UV agents and pigments.

The fibers of the invention may also incorporate products with antibacterial or bactericidal activity intended to confer on said fibers properties complementary to acaricide properties. These products with antibacterial or bactericidal properties will advantageously be chosen from products soluble in the gel used for the preparation of the fibers of the invention.

As seen above, the fibers of the invention can be used, alone or in admixture with other fibers, for the preparation of different materials, in particular knitted, woven or nonwoven textile products.

The invention also relates to fibrous materials incorporating fibers as described above. The term “fibrous materials” means any material incorporating the fibers of the invention, in particular knitted fabrics, woven or nonwoven textiles.

These fibers can be used, alone or in admixture with other types of fibers, to prepare different fibrous materials, for the production in particular of wall fabrics, floor coverings (carpets, rugs), bedding items such as sheets, duvet and upholstery covers, in particular for filling mattresses, pillows, duvets. Miticide fibers can be used for the manufacture of knitted, woven or non-woven articles.

The fibers and materials of the invention find a particularly advantageous application for the production of various products for filling household objects, such as in particular pillows, cushions, mattresses, duvets.

These fibers and materials are particularly advantageous because of their acaricidal properties vis-à-vis dust mites.

The examples which follow are given purely by way of illustration of the invention, they present methods of preparing fibers according to the invention with different types of polymers and different concentrations of acaricide agents. They also illustrate the acaricidal properties of the fibers and fibrous materials obtained. EXAMPLES

Example 1: Preparation of Different Chlorofibers Based on PVC / PVCC Mixtures a) A PVC / PVCC fiber is prepared from PVC with a viscosity index of between 113 and 115 (measured according to standard NFT 51013) and from PVCC to 69 % of chlorine and viscosity index of the order of 100 measured according to standard NFT 51013.

The two polymers are mixed in proportions of 80 parts by weight of PVC for 20 parts by weight of PVCC.

A gel containing approximately 30% by weight of polymer is prepared by dissolving in a mixer at room temperature, the corresponding amount of mixture of the two polymers in a solvent consisting of an acetone / carbon sulphide mixture in a 50/50 by volume ratio. , in which a quantity of benzyl benzoate representing 5 pcr, expressed by weight relative to the resin, has previously been dissolved, in the proportions given below. This test is noted A in Table 1 given in Example 5 below.

The gel is then stirred for 8 h, then filtered and heated to 80 ° C, then extruded through a die of 900 holes. The solvent is extracted by evaporation in hot air. The cable is then drawn at 100 ° C. in water, stabilized with steam, under a pressure of 1.3 bar relative, sized, shrunk with steam, crimped and dried. b) Fibers incorporating 7.5 parts of benzyl benzoate relative to the weight of polymer are prepared in an analogous manner (test noted B in Table 1 given in Example 5 below).

EXAMPLE 2 Preparation of PVC-Based Chlorofibers

2. a) A chlorofiber is prepared from a PVC with a viscosity index of between 113 and 115 (measured according to standard NFT 51013).

A mixture of solvents consisting of acetone and CS2 in proportions 50-50 by volume is introduced into a mixer fitted with a marine propeller, and 5 parts by weight are then added relative to the benzoate resin (pcr). benzyl.

The above mixture is homogenized for 24 h. PVC is introduced into this mixture at a rate of 30% by weight. The PVC / solvent mixture is stored in a buffer mixer and the procedure is then carried out according to European patent EP-034 548 introduced here by reference. The gel is then heated to 120 ° C, filtered, cooled to 80 ° C, then extruded through a die of 1,200 holes. The solvent is extracted by evaporation in hot air. The cable is then stretched at 100 ° C in water, vapor stabilized under

0.8 bar relative, sized, steam shrunk, then crimped and dried. This test is noted C in Table 2 of Example 5. b) Other fibers are prepared in the same way using a benzyl benzoate concentration of 7.5 pcr. The test is noted D in Table 2 of Example 5. c) Other fibers are prepared in the same way using a benzyl benzoate concentration of 10 pcr. The test is noted E in Table 2 of Example 5. d) Fibers are prepared in the same way using the carbaryl agent as acaricide at a concentration of 20 pcr. The tests are noted as F and the results are given in Table 3 of Example 5. e) Fibers are prepared in the same way by using permethrin as a miticide agent at a concentration of 20 pcr. The tests are noted G and the results appear in Table 3 of Example 5.

EXAMPLE 3 Cellulose Acetate Fiber A cellulose acetate gel 2.5 to 30% by weight is produced in acetone, into which 10 phr of benzyl benzoate are introduced. This gel is extruded through a die of 80 holes with a diameter of 60 μm. Drying is ensured by air circulation at 80 ° C under the die. The recovered yarn is dried. The test is noted H in Table 4 of Example 5.

Example 4: Acrylic fiber

An acrylic fiber is prepared containing 10 phr of benzyl benzoate relative to the acrylic polymer, by operating as follows.

A commercial acrylic polymer based on acrylonitrile, methyl methacrylate and sodium sulfonate is suspended in DMF, in which the acaricide has previously been dissolved. This suspension is carried out at a temperature of 3 ° C to allow degassing, then dissolution is brought about by increasing the temperature up to 20 ° C. The gel formed contains 25% of acrylic polymer. It is extruded through a die of 150 holes 55 μm in diameter. The wire then undergoes the following treatment:

- Coagulation in a bath containing 40% water and 60% DMF at 20 ° C,

- Drawing in air at a rate of 2.1, - Washing with water,

- Relaxation in boiling water (rate of 0.8),

- Drawing in boiling water (3.5 times),

- Drying.

The test is noted I in Table 4 of Example 5.

EXAMPLE 5 Laboratory Evaluation of the Effectiveness of Several Textile Samples for the Control of Dust Mites (Dermatophagoids Farinae and Pteronyssinus)

a) Principle of the evaluation test

This involves measuring the mortality of dust mites in contact with different textile samples. In the event of manifest effectiveness, reinfestations spread over time will provide information on the persistence of the action.

The species used for the tests is Dermatophagoid farinae.

b) Protocol and apparatus

This research is carried out by infestation of standard surfaces (7 x 7 cm).

The mites used come from laboratory strains raised under the following conditions: 25 ° C - 75% relative humidity (RH). Four test tubes (repetitions) per product are infested. A series of untreated surfaces (filter paper) is produced for each of the supports.

Mites are removed from breeding environments and sorted using a heat gradient in order to recover the most active individuals, then are deposited on the surfaces (approximately 100 to 200).

These experimental units are stored randomly and put in culture conditions (25 ° C, 75% RH, photoperiod 12/12). The remaining textile samples are unfolded and suspended in the storage room under the same conditions as those mentioned above.

Reinfestations take place 30, 60 and 90 days (noted time T30, T60, T90 in the tables below) after the first infestation with healthy mites and mortality is monitored 24 hours a day after 24 hours after these contacts.

The controls are carried out by counting under a binocular magnifier; this count is not an estimate because all the mites are counted. The mortality percentages obtained will be considered validated if the mortality of the control lots is less than 15%.

c) Results

Tables 1, 2 and 3 below respectively give the results obtained with knits produced with the fibers of Example 1 (A and B), of Example 2a, 2b and 2c (C, D and E) and of Example 2d and 2e (F and G) in comparison with a control product and with a knitted fabric of control fibers denoted respectively T1 and T2 obtained respectively with the same collodions and under the same conditions as in Examples 1 and 2 but do not containing no miticide agent.

Table 3 gives the results obtained with knits produced with the fibers of Examples 3 and 4 (tests H and I) in comparison with a control product.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

Claims

1. Textile products obtained by spinning a polymer-based solution and products resulting from the spinning of said products, characterized in that they consist of a polymeric material containing in its mass an effective amount of at least one agent acaricide chosen from benzyl benzoate, carbamates, pyrethroids and pyrethrins.

2. Products according to claim 1, characterized in that said (said) miticide agent (s) represents (s) 1 to 30 pcr expressed as percentage by weight relative to the total weight of polymeric material.

3. Products according to one of claims 1 or 2, characterized in that said acaricide agent is benzyl benzoate, carbaryl or permethrin.

4. Products according to one of claims 1 to 3, characterized in that said polymeric material consists of a polymer or copolymer or a mixture of polymers and / or copolymers capable of forming a spinnable gel with a solvent in which said miticide agent is soluble.

5. Products according to one of claims 1 to 4, characterized in that said polymeric material consists of at least one polymer or copolymer chosen from the family consisting of polyvinyl chloride, chlorinated polyvinyl chloride, acetate cellulose, acrylic polymers and viscose.

6. Products according to one of claims 1 to 5, characterized in that said polymeric material is a polyvinyl chloride or a mixture of polyvinyl chloride and chlorinated polyvinyl chloride.

7. A method of manufacturing a product according to one of claims 1 to 6, characterized in that it comprises a step of spinning by dry or wet a gel in which is dissolved at least one acaricide agent selected among benzyl benzoate, carbamates, pyrethroids and pyrethrins.

8. Material of fibrous type, characterized in that it comprises products according to one of claims 1 to 6 or obtained according to the method of claim 7.

9. Use of the products according to one of claims 1 to 6 or obtained according to the process of claim 7 or of the materials according to claim 8 for the production of textile articles having acaricidal activity, in particular against acarids of the dust.

10. Use according to claim 9, characterized in that said products or materials are used for the filling of household objects such as cushions, pillows, mattresses, quilts.