FR2843627A1 - Chemiluminescent light comprises supple envelope containing one chemical compound inside breakable recipient and another in absorbent fibres - Google Patents

Abstract

The chemiluminescent light (1) consists of an outer supple envelope (2) of a transparent or translucent material containing one element able to absorb a liquid, comprising continuous fibres or filaments (9) or powder in a dry or wet form, and two chemical compounds that produce a chemiluminescent reaction when mixed. The chemiluminescent light (1) consists of an outer supple envelope (2) of a transparent or translucent material containing one element able to absorb a liquid, comprising continuous fibres or filaments (9) or powder in a dry or wet form, and two chemical compounds that produce a chemiluminescent reaction when mixed. The first compound is contained in a breakable or tearable receptacle (7), with the second in the fibres or powder surrounding it. The envelope is in the form of a tubular sleeve made, like the fibres or filaments, from thermoplastic materials, allowing it to be extruded and cut to length.

Description

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  CHEMILUMINESCENT LIGHTING DEVICE

  The present invention relates to a lighting device which is said to be chemiluminescent in that it contains chemicals which are capable of reacting with each other to produce a chemiluminescent reaction. The device is inactive when the chemicals are kept separate. However, the device emits light when the chemicals are

  mixed as long as the chemiluminescent reaction develops.

  The great advantage of chemiluminescent lighting devices is that it makes it possible to obtain, temporarily, a light diffusion without

  external energy supply. The implementation of such a principle has been known for a very long time, in particular in document US 2,420. 286 for the temporary identification, at night, of a determined position on the surface of the water.

  In this case it is an oxidation reaction which occurs during the dissolution in water of the chemiluminescent composition which causes the emission of light. Many chemiluminescent compositions have been proposed in very diverse fields of application, which range from military and security applications to leisure, including medical applications. Depending on the application concerned, the constraints may differ to a large extent,

  especially in terms of color, intensity and duration of the light emission.

  US 3,539,794, US 3,994,820, US 4,076,645, US 4,401,585, US 4,547,317, US 4,678,608 and US 4,696,770 describe chemiluminescent compositions which are generally in the form of two components whose mixture allows to develop the reaction

  chemiluminescent proper and therefore the emission of light.

  In the most widely used chemiluminescent compositions, the principle

  The reaction resides in an activation of a compound of oxalic type by a hydroperoxide in the presence of a fluorescent agent, according in particular to the teaching of document US 3,539,794.

  -2- The chemiluminescent lighting devices which have been proposed in this

  document US 3,539,794 comprising a closed outer envelope, made of a material capable of transmitting light and having at least two compartments provided with separation means, each of said 5 compartments containing a part of the chemiluminescent composition. In the standby position, the compartments separate the components and prevent any chemical reaction. The device is implemented by actuating the separation means so that all the components contained in the compartments mix, causing the development of the chemiluminescent reaction.

  In the most simple variant of embodiment, illustrated in FIGS. 1 and 2 of this document, the device is formed of two juxtaposed compartments having a common wall in a material which can be easily broken. It consists of three layers, joined to one another along their peripheral edge 15 by heat sealing, the intermediate layer being in the easily tearable material while the two outer layers being in a transparent or translucent material. The space between each of the outer layers and the intermediate layer acts as a compartment for one of the two components of the chemiluminescent composition. Depending on the composition chosen, the two components may be in the liquid state or

  optionally one can be in the solid state, in the form of a powder.

  Optionally, one of the compartments may contain a support matrix such as a sponge, blotting paper, felt or the like, said support matrix having absorbed the corresponding component either in the wet state or in the dry state. Said support matrix could be transparent and a coating

  reflector could be incorporated on its surface.

  In another alternative embodiment, illustrated in FIGS. 11 to 14 of document US Pat. No. 3,539,794, the chemiluminescent lighting device comprises two compartments, a first compartment which constitutes the external envelope of the device and a second compartment which is completely housed inside the first. The second compartment is made of a material which can be easily broken while the material constituting the first compartment forming the outer envelope of the device is made of a material

transparent or translucent.

  In a third alternative embodiment, described in document US Pat. No. 4,814,949, the chemiluminescent lighting device comprises a first thermoplastic film, thermoformed in the form of a cavity, an absorbent nonwoven of polyolefin, polyester or glass fibers which is disposed and substantially matches the bottom of the cavity, a closed and breakable receptacle containing the first component of the chemiluminescent composition, a second thermoplastic film 10 heat-sealed on the periphery of the first film so as to form the cover of the cavity and finally the second component of the chemiluminescent composition which is arranged in the housing formed by the two thermoplastic films and outside the frangible receptacle. The second component can either be in a second receptacle also housed in the cavity or can be absorbed by the nonwoven. It is the first thermoplastic film, forming the cavity which must be transparent or translucent so as to allow the transmission towards outside of the light emitted during the chemiluminescent reaction taking place during the mixing of the two components.

on absorbent nonwoven.

  The present invention provides another alternative embodiment of a chemiluminescent lighting device which differs from the embodiments

  known, in particular by documents US 3,539,794 and 4,814,949.

  It is a device which comprises in a known manner: a) a flexible, transparent or translucent outer shell, b) an element capable of absorbing liquid, c) two chemical components capable of reacting with one another to produce a chemiluminescent reaction, the first component being enclosed in a frangible or tearable container and the second component being outside of said frangible or tearable container. Typically, according to the invention, the absorbent element is in the form of continuous fibers or filaments or

  powder and fills the available interior volume of the envelope.

  The structure of the absorbent element differs from that proposed by the aforementioned documents. This particular structure, in the form of fibers, 5 continuous filaments or powder, has the particularity of increasing the visual effect obtained during the emission of light. This effect could perhaps be explained by reflection or diffraction phenomena on the surface of the fibers, filaments or powders. In addition, the fact that these fibers, filaments or powders occupy the entire available interior volume of the envelope 10 in a way provides a protective mattress for the frangible container or

  tearable, which avoids any risk of breakage or accidental tearing.

  The second component can be either absorbed by the fibers, the filaments or the powder, in the wet or dry state or possibly contained in a

  second breakable or tearable container.

  For the protective effect of the container (s) to be optimal, it is preferable for the container (s) to be completely surrounded by the fibers,

  filaments or powders constituting the absorbent element.

  In a preferred embodiment, the outer envelope is formed by a tubular sheath having a given longitudinal direction and the absorbent element consists of a bundle of continuous fibers or filaments

  arranged inside said sheath in the longitudinal direction thereof.

  The sheath and the continuous fibers or filaments of the bundle are for example in one or more thermoplastic materials and the two ends of the sheath

  are closed by welding the said thermoplastic material (s).

  Being a usable chemiluminescent lighting device

  in particular as a light lure for fishing, at least one of the ends of the sheath is closed by welding in a flattened area which includes means for attaching it to the fishing gear. These hooking means can, in the simplest case, consist of a through hole formed in the flattened area.

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  It is another object of the invention to propose a manufacturing process, automatic continuous or semi-continuous, of the abovementioned chemiluminescent lighting device. This process constitutes: a) continuously displacing a longitudinal bundle of fibers or continuous filaments of a thermoplastic, b) introducing into said bundle, at regular intervals, a succession of first container containing a first component of a chemiluminescent composition , c) extruding on the outer periphery of the bundle a thermoplastic sheath 10 and d) welding and cutting the bundle thus sheathed, according to the same

  regular interval between two successive first containers.

  Preferably, the second component of the composition

  chemiluminescent is sprayed onto the continuous fibers or filaments of bundle 15 before the formation of the thermoplastic sheath.

  The present invention will be better understood on reading the description

  which will be made of a preferred embodiment of a chemiluminescent lighting device usable as a fishing lure, illustrated by the appended drawing in which: - Figure 1 is a schematic plan view of said device, - Figures 2 and 3 are diagrammatic representations in section along the axes respectively II II and III III of FIG. 1 and

  FIG. 4 is a simplified representation of the continuous process for manufacturing the device of FIGS. 1 to 3.

  The chemiluminescent lighting device which will be described below is a luminous lure for fishing. This application is of course not restrictive

of the present invention.

  This device 1 is composed of an envelope 2 of generally cylindrical shape with two end zones 3, 4 flattened and each pierced with a through hole 5, 6. At least the cylindrical middle part 2a of the envelope -6 -

  2, which extends between the two flattened end zones 3, 4 contains on the one hand a breakable or tearable container 7 and on the other hand a bundle 8 of continuous filaments 9. In the example illustrated and preferably the receptacle 7 is disposed centrally with respect to the cylindrical part 2a of the outer casing 2, being completely surrounded by continuous filaments 9 of the bundle 8, as is clearly seen on examining FIG. 3.

  The container 7 is for example a breakable glass bulb which is

  filled with a liquid which is one of the two components of a chemiluminescent composition the other component of which is impregnated in the wet or dry state 10 in the bundle 8 of continuous filaments 9.

  The outer envelope of said device 1 is a tubular sheath of a flexible thermoplastic material. Thus, it is possible for the user to exert a flexion on the cylindrical part 2a of the envelope 2 in order to break the bulb 7 and thus release the first liquid component so that it diffuses by capillarity between the continuous filaments 9 of bundle 8 throughout the available volume thereof between the two end zones 3, 4. It is for this reason that the bundle of filaments is considered to be an absorbent element, even so the material constituting the filaments would not in itself have an absorption property with respect to the liquid component (for example not being hydrophilic with respect to an aqueous component). The absorbent nature of the fibers, filaments or powder is linked to their capacity to allow the diffusion and the retention of the component or components of the chemiluminescent composition throughout the volume they occupy. This diffusion is mainly linked to the capillarity of the three-dimensional network formed by the fibers, filaments or powder, but it can also be linked to the absorbent nature specific to the material, in particular

being natural fibers.

  The chemiluminescent reaction can then develop by emitting the

  desired light. Of course, the material constituting the sheath 2 is transparent or possibly translucent so that the light emitted by the reaction is perfectly visible from the outside of the device 1.

  -7- There is a perfect diffusion of the first liquid component throughout the interior volume of the tubular part 2a of the casing 2 thanks to the

  capillarity inherent in the multifilament structure of the bundle 8.

  In a precise and non-exhaustive example of embodiment, the bundle 8 of 5 continuous filaments 9 was a cable of polypropylene fibers of the crimped type making of the order of 50,000 deniers, or 5,500 tex. The total length L of the device was of the order of 140 mm. The diameter d of the device in the cylindrical part 2a of the envelope 2 was of the order of 13 to 14 mm, said envelope

  2 having a thickness of the order of 400 μm.

  The end zones 3, 4 realize the sealed closure of the tubular casing 2 and, also, allow the attachment of the device 1. In the present case, of a light decoy, this attachment is done simply by the presence in each end zone 3, 4 of a through hole 5, 6 which allows the fixing of the light lure on the fishing equipment. Optionally, one or other of the end zones 3, 4 may have a configuration

  particular, by cutting, making more complex attachment means.

  Figure 4 shows schematically and without the proportions being respected an automatic manufacturing mode of the chemiluminescent lighting device 1 which has just been described. This process is particularly advantageous from the economic point of view because it is carried out continuously. It comprises four main stations which are specific to the present invention, namely a station A for introducing the containers 7 containing the first component 10 of the chemiluminescent composition, a station B for spraying the second component 11 of the chemiluminescent composition, a sheathing station C in bundle 8 equipped with a head

  extrusion, for example at an angle, and a welding and cutting station D.

  The bundle 8 of continuous filaments 9 is supplied from a station not shown towards the sheathing station C, more particularly towards the extrusion head 12. During this feeding, the bundle 8 has a generally conical shape, converging towards the extrusion head 12, the filaments 9 being distributed in the space around the station A so that the receptacles 7 containing the first component 10 can be introduced into the core of the bundle 8 during its movement towards the extrusion head 12. This introduction can be done for example by projection of each container 7 along the longitudinal axis of the bundle 8 with a sufficient speed so that said container comes to be embedded 5 between the filaments and is trapped in the core of the bundle 8 during its passage in the extrusion head 12. The introduction of the containers 7 is done in a sequenced manner, with a determined interval between two adjacent containers 7 . At spraying station B, the bundle 8 is impregnated with the second component 11 of the chemiluminescent composition before it is introduced into

the extrusion head 12.

  At the sheathing station C, the bundle 8 surrounding the succession of containers 7 is coated on its periphery with the outer casing 2 by extrusion of a thermoplastic sheath which may also be made of polypropylene. We therefore obtain, continuously, a set 13 formed

  of an outer sheath surrounding a multifilament bundle in which is trapped, at regular intervals, a succession of breakable or tearable containers containing a first component of a chemiluminescent composition, the second component being distributed by impregnation in the multifilament bundle.

  It is from this assembly 13 that the devices 1 described above and illustrated in FIGS. 1 to 3 are produced, thanks to the station D of welding and cutting. The welding is done by hot compression of the assembly 13 or possibly by compression and application of ultrasound. Of course, in the process sequence, compression and welding necessarily take place in an area of the assembly 13 which does not include containers 7, preferably at an equal distance between two adjacent containers. During compression, the sheath and the bundle are flattened and during the application of heat or ultrasound, a localized fusion of the thermoplastic materials constituting the sheath and of the bundle filaments is obtained. This fusion achieves an intimate connection of the sheath and of the filaments in the aforementioned flattened configuration and, consequently, the sealed closure of the assembly 13. The individualization of the device 1 is obtained by cutting off the assembly 13 by successive cuts along a transverse line 14 in the localized compression and fusion zone. 5 One can, in the same operation, also make two circular cuts 15, 16, in the same fusion zone located near and on either side of the transverse cutting line 14, so as to form the holes

through 5, 6 of the device 1.

  It should be noted that, the bundle or cable of filaments or fibers being of the crimped type, the blooming of the bundle prior to its introduction into the extrusion head increases the multidirectional nature of the filaments or fibers and therefore promotes the diffusion capacity liquid in the interior volume

available from the device.

  Preferably, the spraying of the second component 11 at station B is also sequenced so that the impregnation of the bundle 8 is located only in the useful volume of the bundle 8 which corresponds to the cylindrical part 2a of the envelope 2 In fact, if the spraying is done continuously, the second component 11, being in the end zones 3, 4 will not be accessible to the first component 10 when the lighting device is actuated, the second component 11 which cannot diffuse by capillary action in these end zones 3, 4 o the filaments 9 are no longer really individualized but embedded in the thermoplastic mass resulting from the localized melting of said filaments and of the sheath. In addition, the presence of this second component can hinder the desired localized fusion at station D. In a specific embodiment, the first component of the

  chemiluminescent composition, contained in container 7, included dibutylphthalate, an oxalate and a colorant, while the second component included hydrogen peroxide, terbutanol and also dibutylphthalate.

  More specifically, the oxalate was trichlorocarbopentoxyphenyl oxalate (CPPO). 30 As an indication, the proportions were as follows: -101st component: - dibutylphthalate: 2.31 cm3 - CPPO: 0.28 cm3 - dye: 0.0023 g 2nd component: - dibutylphthalate: 0.75 cm3 - hydroperoxide (water oxygenated): 0.05 cm3 - terbutanol: 0.19 cm3 We can very easily vary the relative proportions of the two

  components by modifying the dibutyphthalate content of both.

  The present invention is of course not limited to this example of a two-component chemiluminescent composition. It is up to the person skilled in the art to determine in particular among all the chemiluminescent compositions known in the aforementioned documents those which are suitable for the desired application, with the distribution of said composition in at

at least two suitable components.

  As indicated above, the second component may not be absorbed by the fibers, filaments or powder filling the available interior volume of the envelope, but may also be contained in a second breakable or tearable container which, too, will preferably be disposed at the

  heart of fibers, filaments or powder.

  In the example described, the bundle of fibers or filaments was of the type used in the manufacture of cigarette filters. Such bundles, in the form of cables, are manufactured by the American firms FILTRONA and German BAUMGARTNER. It can also be bundles of fibers or filaments such as those used in writing articles of the marker type to constitute a fibrous ink reservoir. This type of beam

  fibers is produced in particular by the Italian firm DE MARTINI.

  It will have been noted that there is no fundamental difference between the terms continuous fibers and filaments, the essential difference being a question of length, the term fiber being used when the filiform element in question has a controlled medium length of relatively small size, from a few millimeters to a few centimeters, while this length is

  more important and random in the case of the continuous filament.

  In the example described and illustrated above, the sheath forming the envelope

  outer was continuously extruded around the bundle of fibers or filaments.

  This is not exclusive, the sheath can be formed independently and the

  beam introduced, semi-continuously in sheath sections.

  Likewise, the use of fibers or filaments is not restrictive of the present invention, the absorbent element filling the available interior volume of the envelope can also be in the form of a powder. It can in particular be an ultra high weight micronized powder

  molecular, as produced by the firm TICONA, sintered or not.

  The technique of closing the outer envelope by welding, whether it is thermo-welding or ultrasonic welding, is not limiting either.

the present invention.

  This closure can indeed take place by any appropriate means and in

particular by gluing.

  It should be noted that in the process described above, the 20 containers are introduced into the core of the bundle in an area where it is relatively open, that is to say in an area where it occupies a large volume. more important than the one it has when it passes through the extrusion head. This opening of the bundle can be made difficult in the case of a cable of the crimped type because of the relative attachment between the filaments constituting

the cable.

  In this case it may be preferable to proceed with the manufacture of the device in semi-continuous, namely by first carrying out the sheathing of the beam, by cutting sections of the beam thus sheathed, by impregnating said 30 sections with the second component and finally by inserting in each section a breakable or tearable container containing the first component before

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  closing the two ends of said section by any means, in particular welding or bonding.

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Claims (9)

  1. A chemiluminescent lighting device comprising: a) a flexible, transparent or translucent outer casing (2), b) an element capable of absorbing liquid, c) two chemical components (10,11) capable of reacting with the other to produce a chemiluminescent reaction, the first component (10) being enclosed in a breakable or tearable container (7) and the second component (11) being outside of said breakable or tearable container (7), characterized in the absorbent element is in the form of continuous fibers or filaments (9) or powder and   fills the available interior volume of the envelope (2).   2. Device according to claim 1 characterized in that the second component (11) is absorbed by the fibers, the filaments (9) or the powder, in the wet or dry state.   3. Device according to claim 1 characterized in that the second component   is contained in a second breakable or tearable container.   4. Device according to one of claims 1 to 3 characterized in that the said container (s) (7) are completely surrounded by fibers, filaments (9) or powders.   5. Device according to one of claims 1 to 4 characterized in that the outer envelope (2) is formed of a tubular sheath having a given longitudinal direction and the absorbent element consists of a bundle (8) of continuous fibers or filaments (9) disposed inside said sheath in the longitudinal direction thereof.   6. Device according to claim 5 characterized in that the sheath (2) and the fibers or continuous filaments (9) of the bundle (8) are in one or more thermoplastic materials and the two ends (3,4) of the sheath ( 2) are closed by   welding of said thermoplastic material (s).   7. Device according to claim 6 usable in particular as a light lure for fishing, characterized in that at least one of the ends of -14- the sheath is closed by welding according to a flattened area (3,4) which includes means for attaching it to fishing gear, for example a hole   through (5,6) formed in said flattened area (3,4).   8. A method of manufacturing, automatic continuously or semi-continuously, 5 chemiluminescent lighting devices according to one of claims 5 to 7 characterized in that it comprises the following steps, consisting of:   a) continuously moving a longitudinal bundle (8) of continuous fibers or filaments (9), preferably thermoplastic, b) introducing into said bundle, at regular intervals, a succession of first breakable or tearable container (7) containing a first component (10) of a chemiluminescent composition, c) to extrude on the outer periphery of the bundle (8) a thermoplastic sheath (2) and d) to weld and cut the bundle thus sheathed (13) into sections, according to the 15 same said regular interval, between two successive first containers   (7), each section constituting a lighting device.   9. Method according to claim 8 characterized in that the second component (11) of the chemiluminescent composition is sprayed onto the continuous fibers or filaments (9) of the bundle (8) before the formation of the thermoplastic sheath (2).