FR2817269A1 - METHOD FOR FIXING ANTI-MITE PRINCIPLES ON FIBERS AND YARNS, ESPECIALLY TEXTILES, ESPECIALLY POLYESTER, AND PRODUCTS THUS OBTAINED - Google Patents

Abstract

The invention relates to a method for imparting anti-mite properties to fibers or yarns, which consists in impregnating said fibers or said yarns with at least one active agent, then fixing this agent by a system of binder (s) and crosslinking agent (s), in particular synthetic fibers or yarns such as polyamide, polyester, polypropylene and I or natural fibers such as wool, cotton, linen, silk and / or artificial fibers or yarns such as viscose, acetate and their mixtures. The binders are preparations based on copolymers of acrylic esters or on polyurethane resins in N-methyl-2-pyrrolidone and the crosslinking agent is a preparation based on amino derivatives including in particular ethylene-imine. Applications in all fields, domestic, hospital and medical, hotel, air transport, maritime and the like, all industrial fields, space, aeronautics and the like, as well for bedding, textile coverings, curtains, covers, and the like., In particular Bedding items (fabrics for the covers of duvets, pillows, box springs and mattress protectors; mattress ticking; filling of duvets, pillows, mattresses and box springs), Decorative and furnishing articles (carpets, curtain fabrics, all fabrics for (furniture, upholstery of armchairs and sofas), Toys (fabrics or knits for envelopes, upholstery) and in particular a three-dimensional polyester textile such as a padding sheet.

Description

Method for fixing anti-mite principles on fibers and threads,

especially textiles, especially

  polyester, and products thus obtained.

  Technical sector of the invention: The present invention relates to the technical sector of technical fibers and threads, and more particularly of synthetic fibers or threads and / or artificial fibers or threads and / or natural fibers to which it is desired to confer anti-mite properties, as well as the products, in particular textiles, thus obtained and having these properties, and their applications in all fields, domestic, hospital and medical, hotel, air, maritime and similar transport, all industrial fields, space, aeronautical and similar, as well for bedding, textile coverings, curtains, covers, and the like, in particular: * Bedding articles: - fabrics for duvet covers, pillows, box springs and mattress protectors, mattress ticking,

  - filling of duvets, pillows, mattresses and box springs.

  * Decorative and furnishing articles: - carpets, curtain fabrics, all furnishing fabrics, upholstery

armchairs and sofas.

  * Toys: woven fabrics or knits, upholstery, and in particular a three-dimensional polyester textile such as a tablecloth

packing.

  By "textile products" is meant throughout this application, including

understood the claims,

  - fibers and yarns, associations of such yarns and / or fibers, fabrics or textiles made wholly or partially from these fibers and yarns and / or these associations, textiles (or fabrics) of natural, synthetic or

  artificial, to which these fibers and / or threads have been integrated, incorporated, etc.

  by all means, and all products similar to "textiles" which have just been described and accessible directly to those skilled in the art, as well as masses of fibers, and the like, not in the form of a flat surface, or on the contrary put in a special form,

  placed in a cover, envelope, or other container, etc ...

  Likewise, "fiber" could designate elementary fibers, but also

  fiber groups or mixtures of fibers of different types.

Technical problem:

  The main problem resides in the fixing of at least one active principle anti

  mites on fibers or threads, and the resistance of this fixation (and therefore of the properties which result therefrom) under various usual conditions such as:

resistance to washing, in particular.

  A particular problem is attached to such treatment of polyester fibers or derivatives. This polyester fiber arouses very great interest among manufacturers

  duvets and pillows. Indeed, the demand for these anti-treatment articles

  mites is growing very fast.

  We know in particular that mites are distributed approximately as follows: 80% in bedding, 15% in textile coverings, 5%

  in other textiles such as curtains and the like.

  However, to date there are great difficulties in obtaining good products, in particular having good activity at acceptable doses of active principle (that is to say sufficiently low with regard to the environment, toxicity, etc. .....) and nevertheless good or very good resistance to washing. This resistance to washing is obviously essential from an industrial and commercial point of view. With current techniques, we do not exceed to this day, at

  better, 10 washes, especially in bedding jobs.

  PRIOR ART: Today only the cover of the duvet or the pillow is treated by impregnation of the fabric in full bath in a solution of permethrin but the filling is not treated because no manufacturer offers fibers for filling thus treated . However, it is in gamrnissage that the

higher population of mites.

  - The company RHOVYLTM has developed and patented under No. FR 2773823 a chlorinated polyvinyl chloride fiber, with acaricide properties, obtained by spinning a polymeric material, in this case PCV collodion, into which has been introduced. beforehand the miticide agent. RHOVYLTM only uses benzyl benzoate as an acaricidal agent, but the patent describes the use of all well-known acaricidal agents: benzyl benzoate but also carbamates, pyrethroids and pyrethrins (families to which

belongs to permethrin).

  It is not a technique of fixing to the surface of the fiber by means of

binders and / or crosslinkers.

  It seems that only 20 to 30% of RHOVYLTM is used.

  In addition, a product like a duvet for example must be both bulky, AND flexible AND light; however, the chlorinated polyvinyl chloride fiber in the patent application cited above does not have the

  resilience and lightness characteristics required by this application.

  Patent EP 0 357 957 has been filed by TEIJIN and describes a technique for fixing acaricidal agents on fibers using different fixatives, employing a thermofixing technique and / or the use of a pore and capillaries. Miticide agents are very different from permethrin or any pyrethroid. Japanese patents JP 07054208 and JP 06272112 show only one

  interest in the technological background, cited in the RHOVYLTM patent.

  These are composite fibers with a core surrounded by an envelope.

  * There is a patent filed by Avondale Mills in the USA in 1996 (EP 0 787 851) covering a technique to improve efficiency and resistance to

washes of an insecticide cloth.

  The insecticidal agent is permethrin but no acaricidal action is described or suggested and the technique is an absolutely conventional technique of impregnation on fabrics (tent cloths in this case) and not fibers, and does not relate to a fortiori absolutely not the fixation on fibers. In addition, this technique requires the use of high doses of permethrin

  1.25 g of agent / m2, i.e. approx. 7 g / kg of treated fabric.

  * There is also a patent filed by the company ABEILTM in 1997, FR 2 763 928, which describes a technique which consists in treating the covering fabric of the duvet or the pillow with an anti-mite agent, in this case. of permethrin and use for the filling of the antibacterial fiber obtained by joint spinning of the polyester polymer and an antibacterial agent (TriclosanTM or zeolite). This patent therefore does not describe the technique of grafting permethrin onto fiber which will

used for filling.

  There is therefore an important and recognized need for textiles and fabrics

  mites, in particular of polyester or cotton fibers or yarns or comprising such fibers or yarns, having properties which must be strongly

  improved, especially resistance to washing.

  In particular, a problem consists in avoiding the use of a barrier or protective fabric such as a cover, which would be uncomfortable because it also forms a barrier against good ventilation (perspiration problems

humidity etc ...).

  With regard to the known methods for fixing an active principle in or on a fiber, it is possible to carry out a synthesis and indicate that there are currently known three main routes: - solvent process o a collodion (polymer dispersed as colloids in a solvent ) receives the additive which is introduced into a paste or gel (e.g. RHOVYLTM patent), after which it is passed through a

  1 5 die (spinning) to obtain treated fibers.

  melt process, very close to the previous one, except that the additive is introduced into a molten polymer, after which the spinning operation is carried out

  (eg Du Pont TM technology for its antibacterial fibers).

  - chemical or radical grafting techniques on a polymer with

ethylenic double bonds.

  These three techniques currently exist to make a textile anti-mite and are described in more detail below:

  The simple spraying of anti-mite solutions on a textile.

  This technique can be used at home using commercially available sprays or "shampoos", often based on pyrethroids. This very simple technique of implementation presents no

  retention. The anti-mite agent disappears on the first wash.

  The impregnation of woven or knitted textile surfaces with

  acaricide agents in solution such as permethrin.

  This technique can be improved by the joint use of polymeric binders but it has several drawbacks: - it has poor resistance to washing, - it adds an operation after weaving or knitting,

  - it only applies to two-dimensional textiles.

  Three-dimensional textiles and particularly the upholstery used in

  bedding and furnishings cannot be treated this way.

  Joint spinning of a polymeric material and an acaricide agent

previously mixed.

  This technique has been patented by RHOVYLTM under the number 277 3823. It is a mixture of polyvinyl chloride collodion and an acaricide agent chosen from pyrethroids, carbamates and benzyl benzoate. This technique makes it possible to obtain good resistance to washing, but it only concerns fibers from PVC, cellulose acetate, acrylics and viscose. However, the use of these fibers is limited. In particular, the fabrics and upholstery for bedding (sheets, duvet and pillow covers, filling) are made from polyester, cotton or feathers and

natural duvets.

  In addition, these fibers are to be used in a mixture which complicates and increases the costs.

  operations before spinning or carding.

  Furthermore, a technique for fixing acaricide agent directly on synthetic fibers has been described in patent TEIJIN EP 0357 957. However, this is a vaporization technique, without any binder; with very unusual miticides. Rather, it appears to be antibacterial agents (e.g. TriclosanTM). We can therefore very seriously doubt the real anti-mite performance of these fibers and especially the resistance to washing

  which, in the absence of binders, must be close to 0 washing.

  None of the techniques developed to date make it possible to confer durable anti-mite properties to synthetic fibers and threads, in particular polyamide or polyester and / or artificial fibers and threads and / or natural fibers and more particularly, it does not there is no anti-mite fiber perfectly suited for use in filling pillows, duvets and toys and the like. However, it is in the linings that

  1 o most develop house mites.

  The present invention relates to a fourth channel which essentially resides in a direct fixation (which is NOT a grafting) on a

  polymer thanks to a binder / crosslinking system.

  Summary of the invention: The invention relates in its general concept to a process for imparting anti-mite properties to fibers or threads, characterized in that it consists in impregnating said fibers or said threads with at least one active agent then fix

  this agent by a system of binder (s) and crosslinker (s).

  The method is particularly characterized in that it consists in impregnating synthetic fibers or threads such as polyamide, polyester, polypropylene, polytrimethylene terephthalate (PTT), acrylic, modacrylic, aramid, polyvinyl chloride and / or fibers or artificial yarn (s) such as viscose,

  acetate and / or natural fibers such as wool, cotton, linen, silk, etc.

  In a preferred embodiment, the method is particularly characterized in that it consists in impregnating synthetic fibers, in particular polyester or polyester derivative, with at least one active agent, then fixing this

  agent by a system of binder (s) and crosslinker (s).

  Preferably, an acting binder (s) and crosslinker (s) system will be used.

drying the fiber or yarn.

  According to a preferred embodiment, the binders are preparations based on copolymers of acrylic esters or of polyurethane resins in N-methyl-2-pyrrolidone and their levels vary from 1 to 7%, preferably from

  1.5 to 6% of the weight of the dry textile material.

  According to yet another preferred embodiment, the crosslinker is a preparation

  based on amino derivatives including ethyleneimine.

  According to a preferred embodiment, the crosslinker is chosen from preparations based on amino derivatives including ethyleneimine and its application rate varies from 0.10 to 0.70%, preferably from 0.15% to 0.6% of

  weight of the dry textile material.

  A particularly interesting result has been obtained thanks to the combination of a binder of acrylic esters or polyurethane resins and a crosslinker based on ethylene-imine, leading to an excellent resistance to washing tested.

according to standard EN 26330.

  Those skilled in the art will be able, if necessary by a few routine tests, to adapt these systems to the fibers and support wires concerned, and to use systems

equivalents.

  The technique for fixing acaricidal agents according to the invention applies to synthetic fibers or threads and / or artificial fibers or threads and / or fibers

natural etc ...

  A mixture of such fibers or yarns may optionally be used.

  According to a preferred embodiment, all known anti-mite agents will be used, such as preferably permethrin or a pyrethroid and the

  benzyl benzoate and carbamates.

  In particular, pyrethrum, permethrin, deltamethrin, carbamates or

benzyl benzoate.

  The rate of fixation of the anti-mite agent varies from 0.03 to 0.5%, preferably

  from 0.1% to 0.5% of the weight of the dry textile material.

  According to yet a preferred embodiment, the method is characterized in that one operates in solution of the active agent (or of a mixture or combination of active agents) in at least one solvent, or in a suitable solvent system. According to another preferred embodiment, said solution (hereinafter "solvent solution") is emulsified in a known manner, for its

  use in the process according to the invention.

  Emulsion techniques, as well as emulsifiers, are well known to those of skill in the art, and no more specific reference is necessary.

  Detailed description of the invention:

  The invention therefore relates to the process which has just been described, and which will

developed below.

  The present invention has the surprising advantages below:> Flexibility: while the techniques of co-extrusion of a polymer and an anti-mite agent require the use of large quantities of yarn or fiber per operation (approximately 5,000 kg), the fixing technique directly on the fiber or wire allows

minimum of 100 kg per operation.

  > Versatility: this technique can be applied to many types of yarns and fibers which vary according to the material, synthetic or natural, but also according to crimp, section, title, length of cut. Continuous yarns from 17 dtex to 5,000 dtex, of round or multi-lobed section, single or multifilament, unbleached or dyed, of polyamide, polyester, polypropylene, PTT, viscose, acetate can be treated. We can treat staple fibers from 1.5 dtex to 80 dtex, of round, hollow or multi-lobed section, unbleached or dyed, of polyamide, polyester, polypropylene, PTT, PBT, cotton, wool, linen,

viscose, acetate.

  It is the only technique allowing the yarn or fiber to be exactly adapted to

its textile application.

  It is for example the only technique making it possible to make a three-dimensional polyester textile such as a filling ply perfectly anti-mite. > Safety: this technique allows a perfectly homogeneous distribution of the active agent on the fibers and yarns. These are then mixed in the various textile processes, ensuring a perfectly homogeneous distribution of the treatment in the fabric or in

the filling ply.

  This aspect is particularly important when it comes to textiles with a health function. > Economy: two fixing techniques can be used: * application of the active agent, the binder and the crosslinker on fibers already

  cut, in an autoclave then spinning and drying / crosslinking.

  1 1 * application of the active agent, the binder and the crosslinker on continuous cable

  fibers then extraction, drying / crosslinking and cutting.

  These two techniques and more particularly the second offer a significant advantage in production cost thanks to their speed of execution. These yarns and fibers thus treated can be used in numerous applications. The threads will be assembled or not with other conventional threads then woven or

knitted pure or mixed.

  The fibers will either be spun then woven or knitted, pure or mixed, or carded and then used for filling, or intermingled or needled

to make a nonwoven.

  The invention will be better understood on reading the description which follows, and

  non-limiting examples below.

EXAMPLES

MANUFACTURING TECHNIQUE

  Two techniques can be used: - continuous treatment on an impregnation line, drying, crosslinking, cutting.

- batch processing in an autoclave.

  Continuous treatment is the preferable treatment: It consists in passing a continuous cable of synthetic fibers from 20 to 180 ktex or a continuous knitting of threads from 20 g to 180 g / meter in an impregnation tank 10 containing the solution of acaricide agent (s), binder (s) and crosslinker (s); to extract by suction or to express by padding the excess solution carried away to obtain a rate of removal of the solution from 30% to 60%, preferably 45%, then to dry and crosslink the solution in an air oven hot whose temperature is from 80 to 150 C, preferably 100 C; spraying a mineral oil or silicone solution depending on the final application of the fiber or yarn; and finally to cut this fiber cable to the length suitable for the application either from 30 to 150 mm or to unravel and wind the wire on tubes or

on cones.

  This treatment can be done at speeds of up to 100 m / min or more

  by adapting the length of the impregnation tanks.

  2) The batch treatment in an autoclave consists in filling an autoclave either with a mass of cut fibers or with bobbins of threads of which the barrel is drilled and which are threaded on tubes themselves drilled; inject the solution of anti-mite agent (s), binder (s) and crosslinker (s) into the autoclave until complete filling; wring out by centrifugation or by suction the mass of fibers or the spools of threads then dry and crosslink in a static oven. The mineral oil or silicone will either be mixed with the impregnation solution or

sprayed later.

  In this non-limiting example of embodiment, the anti-mite agent is chosen from the family of pyrethroids: pyrethrum, permethrin, deltamethrin, carbamates or benzyl benzoate. Agent fixation rate

  anti-mite varies from 0.03% to 0.5% of the weight of the dry textile material.

  The binder is chosen from preparations based on copolymers of acrylic esters or polyurethane resins. Application rate varies from 1.5

  % to 6% of the weight of the dry textile material.

  The crosslinker is chosen from preparations based on amino derivatives including ethylene imine and its application rate varies from 0.15% to 0.6% by weight

dry textile material.

RESULTS:

  1) Treatment on yarn of knitted polyester / cotton fibers.

  Dose: 0.03% permethrin + 5% binder and 0.5% crosslinker Number of mites /% mortality 8 days 4 weeks 6 weeks Control 48 180 775 0 wash test 0/100% 0/100% 0/100% Test after 10 washes - 60 C 0/100% 0/100% 0/100% 2) Treatment on polyester fiber cables treated with 0.5% permethrin, 5% binder and 0.5% crosslinker, cut and then carded in a filling sheet Number of mites /% of mortality 8 days | 4 weeks 6 weeks Control - untreated 50 224 730 0.5% Permethrin% binder 3/94% 0/100% 0/100% 0.5% crosslinking 0 washing 0.5% Permethrin% binder 4/92% 0/100% 0/100% 0.5% crosslinking washes - 60 C

  MEASURING THE EFFICIENCY OF TEXTILE TREATMENTS

  TO FIGHT AGAINST DUST MITES

  Samples 1, 3, 4, 1L5, 3L5, 5, 5L5, 7, 7L5

  KNITTINGS MADE WITH FIBER YARN

POLYESTER / COTTON TREATED

DOSE: 0.03% permethrin

1) PRINCIPLE

  The purpose of this study is to assess the impact of textile treatments on the evolution of a dust mite population (Dermatophagoides

  pteronyssinus) in comparison with a population not subject to the product.

  This research is carried out by depositing mites on supports

  whether or not impregnated with the active ingredients.

  The follow-up is carried out over a period of at least two cycles, ie 6 weeks.

2) ORIGINAL BREEDING OF MITES:

  The mites used (Dermatophagoldes pteronyssinus) come from a laboratory strain raised on a substrate composed of a 50/50 mixture (mass / mass) of wheat germ and brewer's yeast in flakes calibrated by sieving (fragments of smaller size at 1 mm). The temperature is between 23 and 25 C and the relative humidity maintained at 75% by the presence of a saturated solution of ammonium sulfate

  ([(NH4) 2SO4]); the strain is kept in the dark.

  The strain is supplied by the Laboratory of Insects and Mites of Commodities of the National Institute of Agronomic Research of Bordeaux

(I.N.R.A.).

3) EXPERIMENTAL METHOD:

  The experimental unit is made up of a 5 cm diameter enclosure which is dust-proof (no leaks) but allows ventilation (filter paper) and in which: - 0.05 g of nutritive substrate / dust intended to assume the food survival - a patch of textile covering the ground of this arena The research is carried out by depositing 25 pairs of mites in these

1 o devices.

  The mites intended for the tests are sorted beforehand in order to recover

the most active.

  4 repetitions are performed by experimental factor, including for the TEMOIN batches made up of the same device but with the support without

1 5 treatment.

  The experimental units are isolated by factor in "banks" (polypropylene tanks with maintenance of relative humidity) and placed in conditions

  optimal development (idem breeding conditions 2).

4) PROVIDED CONTROLS AND RESULTS:

  Mortality is determined by counting under a binocular magnifying glass (with

  hand counter) thanks to the method developed and validated by the I.N.R. AT.

from Bordeaux.

  Mortality is controlled 8 days, 4 weeks and 6 weeks after deposit

  mites on treated or control supports.

  The measurements will be carried out by the same experimenter and the mortality criteria are as follows: - are classified as dead, the mites unable to move,

  - are classified as alive, the mites capable of moving.

  The results present the parallel evolutions of the populations of mites, subjected or not to the treatment, in order to highlight the impact of the treatment on the developing colony. The efficiency criterion is explained

in paragraph 6.

) EXPERIMENTAL PLAN

  - untreated standard cotton - references: 1,3,4, 1 L5, 3L5, 5, 5L5, 7, 7L5

6) RESULTS

  6.1. Presentation: The counts give the data in number of surviving mites. These values are first converted into% mortality. The

raw data is given in the Annex.

  Since it is a question of comparing what is the impact of the treatment on the evolution of the mite population compared to the "untreated", the expression value used for the graphic expression of the results will be the:

  COEFFICIENT OF POPULATION CONTROL OF MITES = PC

  CP = Population of the untreated - Population of the treated lot x 100 Population of the untreated

  This value will therefore be the efficiency coefficient of the product.

  - the closer this coefficient is to 0, the less effective the treatment

  since the population will grow at the same rate as in the case of non-

  treaty; - the closer this coefficient is to 100, the more effective the treatment will be by eradicating the mite population and halting its process

expansion.

  The tables and graphs on the following pages summarize the

  data for the different experimental series.

  6.2. Analysis: The natural expansion of the untreated batches validates the test insofar as this confirms the extremely favorable conditions to which the test pieces are subjected: the populations of mites not subjected to the treatments have in fact had an increase factor of 12 to 15 (more than 700 individuals

  obtained from 50 at the start).

  NOTE: in the case of a basic treatment, the effectiveness of the treatment is evaluated according to the reduction of the mite population after 2 cycles of

development (6 weeks).

  Comments: Under the conditions of these tests, with the samples, mite strains and methodology used: First series: sample 1 gave excellent results with perfect control of the mite populations over two development cycles. - samples 3 and 4 also led to satisfactory reductions

(86% and 79% respectively).

  Second series: - samples 5, 5L5, 7 and 7L5 gave excellent results with perfect control of mite populations over two development cycles. - samples 1 L5 and 3L5 gave insufficient results for

be usable.

  The results are presented in Table 1) below and Table II

TABLE I

  M = dead V = alive% M =% mortality (relative to the total) 8 d 4 weeks 6 weeks number number of mites of mites rep M V% M living alive control 1 1 49 2.0 159 813

2 4 46 8.0 186 695

3 2 49 3.9 198 842

4 4 46 8.0 174 748

avg 5.5 179.3 774.5

1 1 38 12 76.0 1 1 0

  0.03% permethrin 50% polyester 2 3 4 17 66.7 7 0 1% acrylic binder 50% cotton 3 42 8 84.0 5 0 0.1% crosslinker 4 41 9 82.0 3 0 avg = 77.2 6.5 0.0 percentage efficiency = 96.4 100.0

3 1 16 34 32.0 67 128

  0.03% permethrin 50% polyester 2 18 30 37.5 91 115 0% binder 50% cotton 3 21 29 42.0 74 96 0% crosslinker 4 1 3 37 26.0 60 108 avg 34.4 73.0 111 , 8 percent efficiency = 59.3 85.6

4 1 10 40 20.0 94 112

  0.03% permethrin 67% polyester 2 7 43 14.0 71 1 84 0% binder 33% cotton 3 11 38 22.4 89 210 0% crosslinker 4 9 4 1 8.0 75 153 avg 18.6 82.3 164.8 percentage efficiency = 54.1 78.7 Comments concerning table l: The results of sample 1 (0.03% of permethrin - 1% of binder and 0.1% of crosslinker) are fairly satisfactory but the permethrin level should be

  slightly increased to obtain 90% to 100% 8-day mortality.

  The results of samples 3 and 4 (0.03% permethrin, without binder or

  crosslinking) show very insufficient results.

  TABLE II YARNS 50% POLYESTER / 50% COTTON KNITTED WITH 0.03% PERMETHRIN M = dead V = alive% M =% mortality (compared to the total) 8d 6 weeks rep MV% M number of living mites control 1 3 47 6.0 865

2 2 48 4.0 730

3 2 48 4.0 658

4 2 48 4.0 571

avg 4.5 706.0

1 L5 1 23 27 46.0 289

  1% binder 2 21 29 42.0 375 0-1% crosslinker 3 29 20 59.2 268 washed 10 times 60 C 4 24 26 48.0 410 avg 48.8 335.5 percentage of effectiveness = 52.5

3L5 1 8 42 16.0 438

  0% binder 2 1 1 39 22.0 562 0% crosslinker 3 17 34 33 3 417 washed 10 times 60 C 4 15 35 30.0 520 _ _ _ _ _ _ _ _ av_ _ _ _ _t_25.3 484.3 percentage of effectiveness = 31.4

1 44 6 88.0 0

  2.5% binder 2 49 2 96.1 0 0.25% crosslinker 3 42 8 84.0 0

0 WASH 4 50 0 100.0 0

  avg 92.0 0 percentage of effectiveness = 100.0

L5 1 48 2 96.0 0

  2.5% binder 2 43 7 86.0 0 0.25% crosslinking 3 49 1 98.0 0 washes 60 C 4 47 3 94.0 0 ___ ___ _____ _ avg 93.5 _0 percentage of effectiveness = 100, 0

7 1 50 0 100.0 0

  % binder 2 50 0 100.0 0 0.5% crosslinking 3 50 0 100.0 0

0 WASH 4 51 0 100.0 0

  avg 100.0 0 percentage of effectiveness = 100.0

7L5 1 50 0 100.0 0

  % binder 2 50 0 100.0 0 0.5% crosslinking 3 50 0 100.0 0 washes 60 C 4 50 0 100.0 0 avg 100.0 0 percentage of effectiveness = 100.0 Comments on the table II : All samples are 50% cotton / 50% fiber yarn knits

  polyester treated with 0.03% permethrin.

* The results demonstrate that: - the use of a binder and a cross-linking agent is essential to obtain sufficient resistance of the treatment to washing - the binder rate must be greater than 2.5%. 5% gives very good results with a 100% mortality at 8 days even after 10 washes at C - the level of crosslinker must be greater than 0.25%. 0.5% gives very good results with a mortality of 100% at 8 days even after 10 washes at 60 C - for a two-dimensional textile application such as these knitted fabrics of fibers, a very low rate of permethrin of 0.03 % is sufficient if a binder and crosslinker are used

  MEASURING THE EFFICIENCY OF TEXTILE TREATMENTS

  TO FIGHT AGAINST DUST MITES

  POLYESTER BURNER POLYESTER B AND C

  B: 0.03% permethrin + 5% acrylic binder C 0.1% permethrin 0.5% crosslinking

1) PRINCIPLE

  The purpose of this study is to assess the impact of textile treatments on the evolution of a population of dust mites (Dermatophagoides pteronyssinus) in comparison with a population not subject to the product. This research is carried out by depositing mites on supports

  whether or not impregnated with active ingredients.

  The follow-up is carried out over a period of at least two cycles, ie 6 weeks.

2) ORIGINAL BREEDING OF MITES:

  The mites used (Dermatophagoides pteronyssinus) come from a laboratory strain raised on a substrate composed of a 50/50 mixture (mass / mass) of wheat germ and brewer's yeast in flakes calibrated by sieving (fragments of smaller size at 1 mm). The temperature is between 23 and 25 C and the relative humidity maintained at 75% by the presence of a saturated sulfate solution

  ammonia ([(NH4) 2SO4]); the strain is kept in the dark.

  The strain is supplied by the Laboratory of Insects and Mites of Commodities of the National Institute of Agronomic Research of Bordeaux

(I.N.R.A.).

3) EXPERIMENTAL METHOD

  The experimental unit is made up of a 5 cm diameter enclosure which is dust-proof (no leaks) but allows ventilation (filter paper) and in which: - 0.05 g of nutritive substrate / dust intended to ensure the food survival - a portion of the nonwoven covering the ground of this arena The research is carried out by depositing 25 pairs of mites in these devices. The mites intended for the tests are sorted beforehand in order to recover

the most active.

  4 repetitions are performed by experimental factor, including for the TEMOIN batches made up of the same device but with the support without treatment. The experimental units are isolated by factor in "banks" (polypropylene tanks with maintenance of relative humidity) and placed in conditions

  optimal development (idem breeding conditions 2).

4) PROVIDED CONTROLS AND RESULTS:

  Mortality is determined by counting under a binocular magnifying glass (with

  hand counter) thanks to the method developed and validated by 'I.N.R.A.

from Bordeaux.

  Mortality is controlled 8 days and 6 weeks after deposit of the mites

  on treated or control media.

  The measurements will be carried out by the same experimenter and the mortality criteria are as follows: - are classified as dead, the mites unable to move,

  - are classified as alive, the mites capable of moving.

  The results present the parallel evolutions of the populations of mites, subjected or not to the treatment, in order to highlight the impact of the treatment on the developing colony. The efficiency criterion

is explained in paragraph 6.

) EXPERIMENTAL PLAN

  - non-woven polyester filling sheets B and C (sent from 22.06.00) laboratory witness (untreated and washed cotton)

6) RESULTS

  6.1. Presentation The counts give the data in number of surviving mites. These values are first converted into% mortality. The

raw data is given in the Annex.

  Since it is a question of comparing what is the impact of the treatment on the evolution of the mite population compared to the "untreated", the expression value used for the graphic expression of the results will be the:

  COEFFICIENT OF POPULATION CONTROL OF MITES = PC

  CP = Population of the untreated - Population of the treated lot x 100 Population of the untreated

  This value will therefore be the efficiency coefficient of the product.

  - the closer this coefficient is to 0, the less effective the treatment since the population will grow at the same rate as in the case of the untreated; - the closer this coefficient is to 100, the more effective the treatment will have been by eradicating the mite population and halting its expansion process. The tables and graphs on the following pages summarize the

  data for the different experimental series.

  6.2. Analysis: The natural expansion of the untreated batches validates the test insofar as this confirms the extremely favorable conditions to which the test pieces are subjected: the populations of mites not subjected to the treatments have indeed had a factor of increase 12 to 15 (more than

  700 individuals obtained from 50 at the start).

  NOTE: in the case of a basic treatment, the effectiveness of the treatment is evaluated according to the reduction of the mite population after 2 cycles of

development (6 weeks).

  Comments: Under the conditions of these tests, with the samples, mites strains and methodology used: - the two layers showed excellent efficiency by completely controlling the populations of developing mites (layer C), or by limiting them

up to 92% (tablecloth B).

Results in Table III

TABLE III

  M = dead V = alive% M =% mortality (relative to the total) 8 d 4 serm 6 wk number number of mites of mites re p MV / __ l living alive control 1 2 49 3.9 251 758 (cotton not -processed) 2 3 48 5.9 218 699

3 3 47 6.0 196 743

4 5 45 10.0 230 712

_ avg 6.5 223.8 728.0

B 1 32 18 64.0 51 89

2 39 il 78.0 23 40

0.03% 3 34 17 66.7 17 58

  permethrin 4 37 13 74.0 63 46 ______________ av 70.7 38.5 58.3 percentage efficiency = 82.8 92.0

C 1 27 23 54.0 0 0

2 29 20 59.2 0 0

0.1% 3 28 22 56.0 0 0

  permethrin 4 25 25 50.0 0 0 _____________moy _____ _ _54.8 0.0 0.0 percent effectiveness = 100.0 100.0 Comments on Table III: These results demonstrate that: - Despite the use of binder acrylic at 5% and crosslinking at 0.5%, maximum rate so as not to alter the textile properties of the fiber, the permethrin levels of 0.03% and 0.1% are insufficient to cause

  mortality at 20% / 1,00% after 8 days.

  This is linked to the very airy structure of the filling ply compared to a two-dimensional textile such as fabrics and knits. This structure leaves

mite survival spaces.

  o It is therefore necessary to increase the doses of miticide agents for three-dimensional applications.

  MEASURING THE EFFICIENCY OF TEXTILE TREATMENTS

  TO FIGHT AGAINST DUST MITES

  Anti-mite polyester filling sheet A DOSE: 0.5% permethrin% acrylic binder

0.5% crosslinker.

1) PRINCIPLE

  The purpose of this study is to assess the impact of textile treatments on the evolution of a population of dust mites (Dermatophagoides pteronyssinus) in comparison with a population not subject to the product. This research is carried out by depositing mites on supports

  whether or not impregnated with active ingredients.

  The follow-up is carried out over a period of at least two cycles, ie 6 weeks.

2) ORIGINAL BREEDING OF MITES:

  The mites used (Dermatophagoides pteronyssinus) come from a laboratory strain raised on a substrate composed of a 50/50 mixture (mass / mass) of wheat germ and brewer's yeast in flakes calibrated by sieving (fragments of smaller size at 1 mm). The temperature is between 23 and 25 C and the relative humidity maintained at 75% by the presence of a saturated sulfate solution

  ammonia ([(NH4) 2SO4]); the strain is kept in the dark.

  The strain is supplied by the Laboratory of Insects and Mites of Commodities of the National Institute of Agronomic Research of Bordeaux

(I.N.R.A.).

3) EXPERIMENTAL METHOD:

  The experimental unit is made up of a 5 cm diameter enclosure which is dust-proof (no leaks) but allows ventilation (filter paper) and in which: - 0.05 g of nutritive substrate / dust intended to ensure the food survival - a portion of the nonwoven covering the ground of this arena The research is carried out by depositing 25 pairs of mites in these

devices.

  The mites intended for the tests are sorted beforehand in order to recover

the most active.

  4 repetitions are performed by experimental factor, including for the TEMOIN batches made up of the same device but with the support without treatment. The experimental units are isolated by factor in "banks" (polypropylene tanks with maintenance of relative humidity) and placed under conditions

  optimal development (idem breeding conditions 2).

4) PROVIDED CONTROLS AND RESULTS:

  Mortality is determined by counting under a binocular magnifying glass (with

  hand counter) thanks to the method developed and validated by the I.N.R. AT.

from Bordeaux.

  Mortality is controlled 8 days and 6 weeks after deposit of the mites

  on treated or control media.

  The measurements will be carried out by the same experimenter and the mortality criteria are as follows: - are classified as dead, the mites unable to move,

  - are classified as alive, the mites capable of moving.

  The results present the parallel evolutions of the populations of mites, subjected or not to the treatment, in order to highlight the impact of the treatment on the developing colony. The efficiency criterion

is explained in paragraph 6.

) EXPERIMENTAL PLAN

  - non-woven polyester filling tablecloths A (sent from 22.06.00) - laboratory control (untreated and washed cotton)

6) RESULTS

6.1. Presentation

  The counts give the data in number of surviving mites.

  These values are first converted into% mortality. The

raw data is given in the Annex.

  Since it is a question of comparing what is the impact of the treatment on the evolution of the mite population compared to the "untreated", the expression value used for the graphic expression of the results will the:

  COEFFICIENT OF POPULATION CONTROL OF MITES = PC

  CP = Population of the untreated - Population of the treated lot x 100 Population of the untreated

  This value will therefore be the efficiency coefficient of the product.

  - the closer this coefficient is to 0, the less effective the treatment since the population will grow at the same rate as in the case of the untreated; - the closer this coefficient is to 100, the more effective the treatment will have been by eradicating the mite population and halting its expansion process. The tables and graphs on the following pages summarize the

  data for the different experimental series.

  6.2. Analysis: The natural expansion of the untreated batches validates the test insofar as this confirms the extremely favorable conditions to which the test pieces are subjected: the populations of mites not subjected to the treatments have indeed had a factor of increase 12 to 15 (more than

  700 individuals obtained from 50 at the start).

  NOTE: in the case of a basic treatment, the effectiveness of the treatment is evaluated according to the reduction of the mite population after 2 cycles of

development (6 weeks).

  Comments: Under the conditions of these tests, with the samples, mite strains and methodology used: - the tablecloth showed excellent efficiency by fully controlling the

  developing mite populations.

  The results are collated in Table IV below

TABLE IV

  TEST anti-mite polyester filling plies with 0.5% permethrin, 5% binder, 0.5% crosslinker M = dead V = alive% M =% mortality (relative to total) 8 i 4 weeks 6 weeks number of mites number of mites rep MV% / M living alive control 1 2 49 3.9 251 758 (untreated cotton) 2 3 48 5.9 218 699

3 3 47 6.0 196 743

4 5 45 10.0 230 712

avg - 6.5 223.8 728.0

A 1 47 3 94.0 0 0

2 45 5 90.0 0 0

3 47 2 95.9 0 0

4 49 1 98.0 0 0

  _ _ _ _ _ avg 94.5 0.0 0.0 percentage efficiency = 100.0 100.0 Comments on Table IV: It can be seen that the association of a rate of permethrin at 0.5%, 5% binder and 0.5% crosslinker, provides excellent structural results

  aerated three-dimensional such as the filling sheet.

  These results were confirmed after 10 washes at 60 C.

  Conclusions on Tables I to IV: - In all application cases, the use of an acrylic or polyurethane binder and a crosslinker based on amino derivatives is necessary to attach the active agent permethrin to the fiber support or yarn - The more ventilated the final textile structure, the more the rate must be increased

  active agent, in this case permethrin.

  A permethrin level of 0.03% is sufficient for a two-dimensional fabric or knit structure if there is a combination of binder and crosslinker

  at the respective rates of 5% and 0.5%.

  A permethrin level of 0.5% is necessary for a very airy three-dimensional structure such as a packing sheet, with a combination of% of binder and 0.5% of crosslinker. The resistance to washing was measured excellent after 10 cycles at 60 ° C. but these results make it possible to reasonably believe that the resistance

  should be 20 washes at 60 C.

  The invention also covers all the embodiments and all the applications which will be directly accessible to those skilled in the art on reading the present application, their own knowledge, and possibly simple routine tests.

Claims (18)

  1 Method for imparting anti-mite properties to fibers or yarns, characterized in that it consists in impregnating said fibers or said yarns with at least one active agent, then fixing this agent by a system of binder (s) and of crosslinker (s).   2 Method according to claim 1 characterized in that said fibers or said threads are synthetic fibers or threads such as polyamide, polyester, polypropylene, polytrimethylene terephthalate (PTT), acrylic, modacrylic, aramid, polyvinyl chloride and / or artificial fibers or yarn (s) such as viscose, acetate and / or natural fibers such   than wool, cotton, linen, silk and possibly a mixture of these fibers or threads.   3 Method according to claim 1 or 2 characterized in that said fibers are synthetic fibers, in particular polyester or derived from 1 5 polyester.   4 Method according to any one of claims 1 to 3 characterized   in that we will use a binder (s) and crosslinking system (s) acting at fiber drying.   Process according to any one of Claims 1 to 4, characterized in   that the binders are preparations based on copolymers of acrylic esters or polyurethane resins in N-methyl-2-pyrrolidone and their levels vary from 1 to 7%, preferably from 1.5 to 6% by weight of the dry textile material.   6 Method according to any one of claims 1 to 4 characterized in   what the crosslinker is a preparation based on amino derivatives including especially ethyleneimine.   7 Method according to any one of claims 1 to 6 characterized in   that the crosslinker is chosen from preparations based on amino derivatives including ethyleneimine and its application rate varies from 0.10 to 0.70   %, preferably from 0.15% to 0.6% of the weight of the dry textile material.   8 Method according to any one of claims 1 to 7 characterized in   what is used the combination of a binder of acrylic esters or polyurethane resins and a crosslinker based on ethylene imine.   9 Method according to any one of claims 1 to 8 characterized in   which all known anti-mite agents will be used, such as preferably permethrin or a pyrethroid. and benzyl benzoate and carbamates, in particular, pyrethrum, permethrin, deltamethrin,   carbamates or benzyl benzoate.   Process according to any one of Claims 1 to 9, characterized in   that the rate of fixation of the anti-mite agent preferably varies from 0.03 to   0.5%, preferably 0.1% to 0.5% by weight of the dry textile material.   11 Method according to any one of claims 1 to 10 characterized   in that one operates in solution of the active agent (or of a mixture or combination of active agents) in at least one solvent, or in a system suitable solvent.   12 Method according to any one of claims 1 to 11 characterized   in that said solution (hereinafter "solvent solution") is emulsified in a known manner   13 Method according to any one of claims 1 to 12 characterized   in that continuous yarns of 17 dtex to 5,000 dtex, of round or multi-lobed section, single or multifilament, unbleached or dyed, of polyamide, polyester, polypropylene, PTT, viscose, acetate can be treated. We can treat staple fibers from 1.5 dtex to 80 dtex, of round, hollow or multi-lobed section, unbleached or dyed, of polyamide, polyester, polypropylene, PTT, PBT,   cotton, wool, linen, viscose, acetate.   14 Method according to any one of claims 1 to 13 characterized   in that two fixing techniques can be used:% 8, * application of the active agent of the binder and of the crosslinker on fibers or threads already cut, in an autoclave then wringing and drying / crosslinking; or * application of the active agent, the binder and the crosslinker on continuous cable of   fibers or threads then extraction, drying / crosslinking and cutting.   15 Method according to any one of claims 1 to 14 characterized   in that the threads will be assembled or not with other conventional threads then woven or knitted in pure or in mixture, and the fibers will be either spun and then woven or knitted, in pure or in mixture, or carded and then used in filling, or intertwined or   needled to make a nonwoven.   16 Method according to any one of claims 1 to 15 characterized   in that a continuous treatment is carried out which consists in passing a continuous cable of synthetic fibers from 20 to 180 ktex or a continuous knitting of threads of 20 g to 180 g / meter in an impregnation tank containing the solution miticide (s), binder (s) and crosslinking agent (s); to extract by suction or to express by padding the excess solution carried away to obtain a rate of removal of the solution from 30% to 60%, preferably 45%, then to dry and crosslink the solution in an air oven hot whose temperature is from 80 to 150 C, preferably 100 C; spraying a mineral oil or silicone solution depending on the final application of the fiber or yarn; and finally to cut this fiber cable to the length suitable for the application either from 30 to mm or to unravel and wind the wire on tubes or cones, this treatment can be done at speeds up to 100 m / min even more by adapting the length of impregnation tanks.   17 Method according to any one of claims 1 to 15, characterized   in that a batch treatment is carried out in an autoclave which consists in filling an autoclave either with a mass of cut fibers or with spools of threads the barrel of which is drilled and which are threaded onto tubes themselves drilled; inject the solution of anti-mite agent (s), binder (s) and crosslinker (s) into the autoclave until complete filling; wring out by centrifugation or by suction the mass of fibers or the spools of threads then dry and crosslink in a static oven. The mineral oil or silicone will either be mixed with the solution   impregnation is sprayed later.   18 Synthetic fibers or threads, artificial fibers or threads, natural fibers and their mixtures in various combinations, in particular of polyamide, polyester, cotton, wool, silk, viscose and acetate including fibers and threads, associations of such fibers and / or fibers, characterized in that they are   have been treated by a method according to any one of claims 1   to 17 "fibers" which can denote elementary fibers, but also   fiber groups or mixtures of fibers of different types.   19 Textile anti-mite products, characterized in that they have been manufactured or contain fibers or threads according to claim 16, - including fibers and threads, combinations of such threads and / or fibers, fabrics or textiles produced totally or partially from these fibers and yarns and / or from these associations, textiles (or fabrics)) of synthetic or artificial natural type, in which these fibers and / or yarns will have been integrated, incorporated by any means, and all products similar to "textiles" - as well as masses of fibers, and the like, not in the form of a flat surface, or on the contrary put in a special form,   placed in a cover, envelope, or other container.   Applications of the process and of fibers and yarns and products according to one   any of claims 1 to 19 in all fields, domestic,   hospital and medical, hotel, air, maritime and similar transport, all industrial, space, aeronautical and similar fields, as well for bedding, textile coverings, curtains, covers, and the like., in particular: * Bedding articles: - duvet cover fabrics, pillows, box springs and mattress protectors, mattress ticking, 4 / o   - filling of duvets, pillows, mattresses and box springs.   * Decorative and furnishing articles: - carpets, curtain fabrics, all furnishing fabrics, upholstery armchairs and sofas.   For Toys: woven fabrics or knits, upholstery, and in particular a three-dimensional polyester textile such as a tablecloth.