EP2195605B1 - Marking paint ball and method for making same - Google Patents

Marking paint ball and method for making same Download PDF

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Publication number
EP2195605B1
EP2195605B1 EP08860824A EP08860824A EP2195605B1 EP 2195605 B1 EP2195605 B1 EP 2195605B1 EP 08860824 A EP08860824 A EP 08860824A EP 08860824 A EP08860824 A EP 08860824A EP 2195605 B1 EP2195605 B1 EP 2195605B1
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oxo
films
biodegradable
marking paint
ball
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German (de)
French (fr)
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EP2195605A1 (en
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David Delhaye
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
    • F42B12/02—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect
    • F42B12/36—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information
    • F42B12/40—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information of target-marking, i.e. impact-indicating type

Definitions

  • the invention relates to a marking paintball and its method of manufacture.
  • a ball of marking paint is understood to mean a capsule generally of spherical shape, which comprises an envelope and a marking paint composition contained in this envelope.
  • the nature of the material constituting the envelope and its dimensional characteristics (in particular the thickness) must be such that the impact caused by a ball on a target causes the envelope to burst and the sprawl of the marking paint composition on the target, indicating that it has been reached.
  • such a ball is made with a gelatin envelope according to a known method conventionally used for the manufacture of medicaments.
  • This method comprises forming by thermoforming two hemispheres, which are assembled together, while the marking composition is introduced into the cavity delimited by the two hemispheres.
  • gelatin since the gelatin is of animal origin, its preparation is delicate and it is difficult to obtain a constant and reproducible composition.
  • manufacture of gelatin beads must be carried out under controlled atmospheric conditions because of the high sensitivity of the gelatin to moisture and temperature. This usually manifests itself as follows: from a certain moisture level, the gelatin softens, while at high temperature it tends to dry. Moreover, in case of frost, the water contained in the gelatin crystallizes, which has the consequence that the gelatin loses some of its mechanical properties.
  • the manufacture of the gelatin beads generally comprises a hemisphere thermoforming step, generally followed by a drying step for a relatively long time, typically between one and several days.
  • the packaging must be made hermetically, for example in a bag which is welded (sometimes under vacuum), in particular because of the high sensitivity of the gelatin to humidity and temperature conditions.
  • ball having a controlled life is meant, within the meaning of the present invention, a ball having a life cycle determined from its manufacture until its bio-assimilation, and whose mechanical properties are controlled.
  • non-aqueous paint compositions based on solvents such as ethylene glycol, polyethylene glycol or polypropylene glycol.
  • solvents such as ethylene glycol, polyethylene glycol or polypropylene glycol.
  • biodegradable substance or product means a product which is biologically degradable in nature by the combined actions of an abiotic oxidative degradation followed by a bio-assimilation by the action of microorganisms. organizations.
  • fragmentable substance is meant, in the sense of the present invention, a substance which fragments molecules by molecules, but which does not change chemically.
  • polystyrene polystyrene molecules are still obtained after degradation of the substance.
  • a product or substance that is environmentally friendly is understood to mean a biologically degradable product or substance without generating toxic residues.
  • an oxo-biodegradable and non-water-soluble polymeric material can be used to make paintball bins, because this material has the same mechanical properties as gelatin.
  • oxo-biodegradable polymeric material means a polymeric material which can degrade biologically in nature, having previously undergone abiotic oxidative degradation under the combined effects of heat and UV, by oxidation of the carbon-hydrogen bonds which causes a drop in the molecular weight of the material. The oxidized material in the presence of microorganisms is then converted to CO 2 , water and non-sterile biomass, without generating toxic residues.
  • the oxo-biodegradable polymeric material also allows the use of aqueous paints which are much more environmentally friendly than the striking paints. based on solvent conventionally used in marking paintballs.
  • the envelope is made of an oxo-biodegradable polymeric material.
  • the envelope thanks to the oxo-biodegradable nature of the envelope, it makes the beads compatible with a use in nature where, if they are abandoned, they degrade after a predetermined time, without generating hazardous components.
  • the oxo-biodegradable polymeric material constituting the envelope is an oxo-biodegradable thermoplastic polymer, which is preferably chosen from oxo-biodegradable polyolefins.
  • oxo-biodegradable polyolefins examples include those described in the scientific publications. "Acquired biodegradability of polyethylenes containing pro-oxidant additives", in Polymer Degradation and Stability 91 (2006) 1495-1503, M. Koutny, M. Sancelme, C. Dabin, N. Pichon, AM Delort, and J. Lemaire (high density and low density polyethylenes) and "Biodegradation of thermally-oxidized, fragmented low-density polyethylenes", in Polymer Degradation and Stability 81 (2003) 341-351, by E. Chiellini, A. Corti and G. Swift (low density polyethylenes (LDPE) only).
  • LDPE low density polyethylenes
  • the oxo-biodegradable polymeric material constituting the envelope advantageously comprises a synthetic polymer and at least one transition metal salt.
  • the synthetic polymer of the oxo-biodegradable polymeric material used in the beads according to the invention is advantageously a thermoplastic polymer, and preferably a polyolefin.
  • low density polyethylenes LDPE
  • high density polyethylenes HDPE
  • polypropylenes may especially be mentioned.
  • transition metals used in the transition metal salts contained in the oxo-biodegradable polymeric materials of the invention mention may notably be made of iron, manganese and cobalt.
  • the casing of the balls according to the invention has a thickness of between 80 and 300 ⁇ m, preferably between 80 and 120 ⁇ m. Such dimensional characteristics lead to optimize the bursting of the ball only during its impact on a target.
  • the marking paint composition contained in the ball according to the invention is aqueous.
  • the marking paint composition contained in the ball according to the invention contains 40 to 60% water, 0 to 5% dyestuffs and 20 to 40% binder.
  • Such an aqueous composition has advantages relating to its environmental quality on the one hand and in terms of costs on the other hand, due to a higher aqueous saturation.
  • the marking paint composition further contains up to 5% sodium chloride, in order to avoid that the paint composition does not freeze when the temperature becomes negative.
  • the ball according to the invention also lends itself well to thermoforming as is the case for beads whose envelope is made of gelatin, but with a considerably simplified process that does not require a drying step.
  • the process of the invention is simplified compared to existing methods conventionally used for the manufacture of gelatin beads by suppressing the drying step. This step is rendered unnecessary by the fact that the oxo-biodegradable polyolefin has, upon cooling after thermoforming, the mechanical properties required for use of the ball in "paint-ball" type applications.
  • the films are made of oxo-biodegradable polyolefin, and the heating temperature of these films, prior to their arrival on the rolls of the drums, is between 100 and 120 ° C.
  • Polyolefin sheets which are orientated, mono-axially or bi-axially, are advantageously used as films, which make it possible to obtain a tendency to shrink the envelope during its cooling, which may lead to pressure prestressing at the same time. ball. This prestressing may cause a fragile rupture of the ball during its impact.
  • the film of oxo-biodegradable polymeric material is a multilayer film comprising a superposition of several monolayers obtained by coextrusion or rolling.
  • a marking paint ball 1 which comprises a casing 10 of spherical shape and containing a marking paint composition 11.
  • a device 100 consisting of an encapsulation unit adapted to the implementation of the process of the invention, which is represented on FIG. figure 2 .
  • this device 100 two films 2, 3 of oxo-biodegradable polyolefin are placed in rolls on the device 100.
  • Each film 2, 3 is unwound, then passes into a furnace 101, 102 to be heated to a temperature between 100 and 120 ° C.
  • each film 2, 3 arrives tangentially on a molding drum 111, 112 which comprises a cylinder 1110, 1120 and hemispherical cavities 1111, 1112, each connected to a vacuum source (not shown in FIG. figure 2 ).
  • the two drums 111, 112 are arranged one beside the other with axes 1112, 1122 parallel to each other, and the drums 111, 112 are joined.
  • a prism 4 filled with marking paint composition 11 is disposed just above the drums 111, 112, so as to cover about a quarter of their respective surface.
  • the premium 4 is provided, at its lower part, with a plurality of orifices capable of injecting the striking paint composition 11 between the two films 2 and 3 when placed on their respective drums 111, 112.
  • the films 23 join the drums 111, 112 at the cylinders 1110, 1120, they are sucked into each cavity 1111, 1121 and take their hemispherical form. Then, by the counter-rotating rotation of the rolls 1110, 1120, the two films 2, 3 are joined together and the marking paint composition 11 is injected simultaneously. The hemispherical portions, then filled with the marking paint composition 11, are welded two by two to form the balls 1 according to the invention.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Paints Or Removers (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Pens And Brushes (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The paint ball (1) has a spherical shaped cover (10) containing an aqueous marking paint composition (11). The cover is made of non-hydrosoluble oxo-biodegradable polymeric material such as oxo-biodegradable polyethylene and oxo-biodegradable polyolefin, where the polymeric material includes synthetic polymer and transition metal salt. The cover has a thickness comprised between 80 to 120 micrometers. The composition contains 40-60, 0-5, 20-40, and 5 percentages of water, coloring substances, a binder and sodium chloride, respectively. An independent claim is also included for a method for manufacturing a paint ball.

Description

L'invention concerne une bille de peinture marquante et son procédé de fabrication.The invention relates to a marking paintball and its method of manufacture.

Pour les entraînements militaires ou policiers, ou des activités sportives ou de loisir (notamment de type «Paintball ») on utilise fréquemment des pistolets à gaz comprimé et des billes de peinture marquante.For military or police training, or sports or leisure activities (especially of the "Paintball" type), compressed gas guns and paintballs are frequently used.

Par bille de peinture marquante, on entend, au sens de la présente invention, une capsule généralement de forme sphérique, qui comprend une enveloppe et une composition de peinture marquante contenue dans cette enveloppe.For the purposes of the present invention, a ball of marking paint is understood to mean a capsule generally of spherical shape, which comprises an envelope and a marking paint composition contained in this envelope.

Dans ce contexte, la nature du matériau constitutif de l'enveloppe et ses caractéristiques dimensionnelles (notamment l'épaisseur) doivent être telles que l'impact provoqué d'une bille sur une cible provoque l'éclatement de l'enveloppe et l'étalement de la composition de peinture marquante sur la cible, ce qui indique que celle-ci a été atteinte.In this context, the nature of the material constituting the envelope and its dimensional characteristics (in particular the thickness) must be such that the impact caused by a ball on a target causes the envelope to burst and the sprawl of the marking paint composition on the target, indicating that it has been reached.

A l'heure actuelle, une telle bille est réalisée avec une enveloppe en gélatine selon un procédé connu classiquement utilisé pour la fabrication de médicaments. Ce procédé comprend la formation par thermoformage de deux hémisphères, qui sont assemblés l'un avec l'autre, tandis que la composition marquante est introduite dans la cavité délimitée par les deux hémisphères.At present, such a ball is made with a gelatin envelope according to a known method conventionally used for the manufacture of medicaments. This method comprises forming by thermoforming two hemispheres, which are assembled together, while the marking composition is introduced into the cavity delimited by the two hemispheres.

Cette bille pose toutefois de nombreux problèmes liés à la nature de l'enveloppe.This ball, however, poses many problems related to the nature of the envelope.

En effet, étant donné que la gélatine est d'origine animale, sa préparation est délicate et il est difficile d'obtenir une composition constante et reproductible. En outre, la fabrication de billes en gélatine doit être effectuée dans des conditions atmosphériques contrôlées en raison de la grande sensibilité de la gélatine à l'humidité et à la température. Celle-ci se manifeste généralement comme suit : à partir d'un certain taux d'humidité, la gélatine se ramollit, tandis qu'à température élevée, elle a tendance à sécher. Par ailleurs, en cas de gel, l'eau contenue dans la gélatine se cristallise, ce qui a pour conséquence que la gélatine perd une partie de ses propriétés mécaniques.Indeed, since the gelatin is of animal origin, its preparation is delicate and it is difficult to obtain a constant and reproducible composition. In addition, the manufacture of gelatin beads must be carried out under controlled atmospheric conditions because of the high sensitivity of the gelatin to moisture and temperature. This usually manifests itself as follows: from a certain moisture level, the gelatin softens, while at high temperature it tends to dry. Moreover, in case of frost, the water contained in the gelatin crystallizes, which has the consequence that the gelatin loses some of its mechanical properties.

La fabrication des billes en gélatine comprend généralement une étape de thermoformage d'hémisphères, généralement suivie d'une étape de séchage pendant une durée relativement élevée, typiquement entre un et plusieurs jours.The manufacture of the gelatin beads generally comprises a hemisphere thermoforming step, generally followed by a drying step for a relatively long time, typically between one and several days.

En outre, pour ce qui concerne le conditionnement de ces billes une fois fabriquées, le conditionnement doit être réalisé de manière hermétique, par exemple dans un sachet qui est soudé (parfois sous vide), notamment en raison de la grande sensibilité de la gélatine aux conditions d'humidité et de température.In addition, as regards the packaging of these beads once manufactured, the packaging must be made hermetically, for example in a bag which is welded (sometimes under vacuum), in particular because of the high sensitivity of the gelatin to humidity and temperature conditions.

Par ailleurs, selon l'environnement de ces billes lors de leur utilisation, leurs propriétés mécaniques, en particulier leur aptitude à l'éclatement lors de l'impact sur la cible, ainsi que leurs dimensions peuvent varier, ce qui les rend imprécises, voire inutilisables, de sorte qu'il devient difficile de contrôler leur durée de vie.Furthermore, depending on the environment of these beads during their use, their mechanical properties, in particular their ability to burst during the impact on the target, as well as their dimensions may vary, which makes them imprecise, even unusable, so that it becomes difficult to control their life.

Par bille ayant une durée de vie contrôlée, on entend, au sens de 1a présente invention, une bille ayant un cycle de vie déterminé depuis sa fabrication jusqu'à sa bio-assimilation, et dont on contrôle les propriétés mécaniques.By ball having a controlled life is meant, within the meaning of the present invention, a ball having a life cycle determined from its manufacture until its bio-assimilation, and whose mechanical properties are controlled.

Enfin, la sensibilité de la gélatine à l'humidité impose d'utiliser des compositions de peinture non aqueuses à base de solvants tels que l'éthylène-glycol, le polyéthylène-glycol ou le polypropylène-glycol. Ces compositions peintures non aqueuses se présentent généralement sous forme de gels visqueux et contiennent des solvants qui ne sont absolument pas respectueux de l'environnement.Finally, the sensitivity of gelatin to moisture requires the use of non-aqueous paint compositions based on solvents such as ethylene glycol, polyethylene glycol or polypropylene glycol. These non-aqueous paint compositions are generally in the form of viscous gels and contain solvents which are absolutely not environmentally friendly.

Pour résoudre les problèmes précités liés à l'utilisation de gélatine dans la fabrication de l'enveloppe des billes, l'homme du métier a cherché un autre matériau qui ne présente pas les inconvénients de la gélatine.To solve the aforementioned problems related to the use of gelatin in the manufacture of the casing beads, the skilled person has sought another material that does not have the disadvantages of gelatin.

Ainsi, il est connu de la demande de brevet européen EP 0 609 298 une bille de peinture marquante dont l'enveloppe est en polystyrène avec des lignes moléculaires orientées le long de lignes circonférentielles entre deux pôles. Ces lignes sont fragilisées, ce qui est favorable à l'éclatement de la bille lors de son impact sur une cible. La bille est réalisée par l'assemblage de deux hémisphères par injection sous pression, puis collage ou soudage. Même si une telle bille peut s'affranchir des problèmes de stabilité que rencontrent usuellement les billes dont les enveloppes réalisées en gélatine, sa fabrication reste onéreuse car elle fait appel à une technique d'injection sous pression et nécessite de manipuler les hémisphères avant leur assemblage.Thus, it is known from the European patent application EP 0 609 298 a marking paintball with a polystyrene envelope with molecular lines oriented along circumferential lines between two poles. These lines are weakened, which is favorable to the bursting of the ball during its impact on a target. The ball is made by assembling two hemispheres by injection under pressure, then gluing or welding. Even if such a ball can overcome the stability problems that usually meet the balls whose envelopes made of gelatin, its manufacture is expensive because it uses a pressure injection technique and requires handling the hemispheres before assembly .

En outre, contrairement à ce qui est affirmé dans la demande de brevet européen EP 0 609 298 , le polystyrène n'est pas biodégradable, mais seulement fragmentable. Une bille biodégradable est connue du US 2006/0005732 A1 .In addition, contrary to what is stated in the European patent application EP 0 609 298 , the polystyrene is not biodegradable, but only fragmentable. A biodegradable ball is known from US 2006/0005732 A1 .

Par substance ou produit biodégradable, on entend, au sens de la présente invention, un produit qui est dégradable biologiquement dans la nature par les actions conjuguées d'une dégradation abiotique oxydative, suivie d'une bio-assimilation par l'action de micro-organismes.For the purposes of the present invention, the term "biodegradable substance or product" means a product which is biologically degradable in nature by the combined actions of an abiotic oxidative degradation followed by a bio-assimilation by the action of microorganisms. organizations.

Par substance fragmentable, on entend, au sens de la présente invention, une substance qui se fragmente molécules par molécules, mais qui ne se transforme pas chimiquement. Ainsi, dans le cas du polystyrène, on obtient encore, après dégradation de la substance, des molécules de polystyrène.By fragmentable substance is meant, in the sense of the present invention, a substance which fragments molecules by molecules, but which does not change chemically. Thus, in the case of polystyrene, polystyrene molecules are still obtained after degradation of the substance.

C'est donc l'un des objectifs de l'invention de proposer une bille à peinture marquante dont la durée de vie est contrôlée, qui est peu sensible aux conditions atmosphériques, simple à fabriquer et qui est véritablement respectueuse de l'environnement, tant au niveau du contenant (c'est-à-dire l'enveloppe), que du contenu, c'est-à-dire la composition de peinture marquante qui peut être aqueuse.It is therefore one of the objectives of the invention to provide a marking paint ball whose life is controlled, which is insensitive to atmospheric conditions, simple to manufacture and is truly environmentally friendly, both at the level of the container (that is to say the envelope), only content, that is to say the marking paint composition which can be aqueous.

Par produit ou substance véritablement respectueux (se) de l'environnement, on entend au sens de la présente invention, un produit ou une substance dégradable biologiquement sans générer de résidus toxiques.For the purposes of the present invention, a product or substance that is environmentally friendly is understood to mean a biologically degradable product or substance without generating toxic residues.

La demanderesse a en effet découvert de manière surprenante qu'un matériau polymérique oxo-biodégradable et non hydrosoluble peut être utilisé pour réaliser des enveloppes de billes de peinture marquante, car ce matériau présente les mêmes propriétés mécaniques que la gélatine.The Applicant has in fact surprisingly discovered that an oxo-biodegradable and non-water-soluble polymeric material can be used to make paintball bins, because this material has the same mechanical properties as gelatin.

Par matériau polymérique oxo-biodégradable, on entend, au sens de la présente invention, un matériau polymère qui peut se dégrader biologiquement dans la nature, après avoir au préalable subi une dégradation oxydative abiotique sous les effets combinés de la chaleur et des UV, par une oxydation des liaisons carbone-hydrogène qui entraine une baisse du poids moléculaire de la matière. La matière oxydée en présence de microorganismes est alors convertie en CO2, en eau et en une biomasse non stérile, sans générer de résidus toxiques.For the purposes of the present invention, the term "oxo-biodegradable polymeric material" means a polymeric material which can degrade biologically in nature, having previously undergone abiotic oxidative degradation under the combined effects of heat and UV, by oxidation of the carbon-hydrogen bonds which causes a drop in the molecular weight of the material. The oxidized material in the presence of microorganisms is then converted to CO 2 , water and non-sterile biomass, without generating toxic residues.

Le matériau polymérique oxo-biodégradable permet en outre l'utilisation de peintures aqueuses qui sont beaucoup plus respectueuses de l'environnement que les peintures marquantes. à base de solvant classiquement utilisées dans les billes de peinture marquante.The oxo-biodegradable polymeric material also allows the use of aqueous paints which are much more environmentally friendly than the striking paints. based on solvent conventionally used in marking paintballs.

La présente invention a donc pour objet une bille de peinture marquante comprenant :

  • une enveloppe en un matériau polymérique non hydrosoluble et de forme sensiblement sphérique, et
  • une composition de peinture marquante contenue dans ladite enveloppe.
The present invention therefore relates to a marking paintball comprising:
  • an envelope made of a non-water soluble polymeric material and of substantially spherical shape, and
  • a striking paint composition contained in said envelope.

Selon l'invention, l'enveloppe est constituée d'un matériau polymérique oxo-biodégradable.According to the invention, the envelope is made of an oxo-biodegradable polymeric material.

L'avantage d'une telle bille est qu'elle présente des propriétés équivalentes à celles de la gélatine lorsqu'elle celle-ci est utilisée pour la fabrication de billes de peinture marquante (notamment pour des applications de type « paint-ball »). Les propriétés mécaniques et les caractéristiques dimensionnelles de cette bille restent constantes quelles que soient les conditions hygrométriques rencontrées lors du conditionnement ou l'utilisation de la bille.The advantage of such a ball is that it has properties equivalent to those of gelatin when it is used for the manufacture of paint marking beads (especially for "paint-ball" type applications) . The mechanical properties and the dimensional characteristics of this marble remain constant whatever the hygrometric conditions encountered during conditioning or use of the ball.

En outre, grâce à la nature oxo-biodégradable de l'enveloppe, on rend les billes compatibles avec une utilisation dans la nature où, si elles sont abandonnées, elles se dégradent après un temps déterminé, sans générer de composants dangereux.In addition, thanks to the oxo-biodegradable nature of the envelope, it makes the beads compatible with a use in nature where, if they are abandoned, they degrade after a predetermined time, without generating hazardous components.

De manière avantageuse, le matériau polymérique oxo-biodégradable constitutif de l'enveloppe est un polymère thermoplastique oxo-biodégradable, qui est de préférence choisi parmi les polyoléfines oxo-biodégradables.Advantageously, the oxo-biodegradable polymeric material constituting the envelope is an oxo-biodegradable thermoplastic polymer, which is preferably chosen from oxo-biodegradable polyolefins.

A titre d'exemples de polyoléfines oxo-biodégradables utilisables dans les billes selon l'invention, on peut notamment citer les polyéthylènes oxo-biodégradables tels que ceux décrits dans les publications scientifiques « Acquired biodegradability of polyethylenes containing pro-oxidant additives », in Polymer Degradation and Stability 91 (2006) 1495-1503, de M. Koutny, M. Sancelme, C. Dabin, N. Pichon, A.M. Delort, et J Lemaire (polyéthylènes haute densité et basse densité) et « Biodegradation of thermally-oxidized, fragmented low-density polyethylenes », in Polymer Degradation and Stability 81 (2003) 341-351, de E. Chiellini, A. Corti et G. Swift (polyéthylènes basse densité (LDPE) uniquement).As examples of oxo-biodegradable polyolefins that can be used in the beads according to the invention, mention may be made especially of oxo-biodegradable polyethylenes such as those described in the scientific publications. "Acquired biodegradability of polyethylenes containing pro-oxidant additives", in Polymer Degradation and Stability 91 (2006) 1495-1503, M. Koutny, M. Sancelme, C. Dabin, N. Pichon, AM Delort, and J. Lemaire (high density and low density polyethylenes) and "Biodegradation of thermally-oxidized, fragmented low-density polyethylenes", in Polymer Degradation and Stability 81 (2003) 341-351, by E. Chiellini, A. Corti and G. Swift (low density polyethylenes (LDPE) only).

Le matériau polymérique oxo-biodégradable constitutif de l'enveloppe comprend avantageusement un polymère synthétique et au moins un sel de métal de transition.The oxo-biodegradable polymeric material constituting the envelope advantageously comprises a synthetic polymer and at least one transition metal salt.

Le polymère synthétique du matériau polymérique oxo-biodégradable utilisé dans les billes selon l'invention est avantageusement un polymère thermoplastique, et de préférence une polyoléfine.The synthetic polymer of the oxo-biodegradable polymeric material used in the beads according to the invention is advantageously a thermoplastic polymer, and preferably a polyolefin.

A titre de polyoléfines utilisables dans le matériau polymérique selon l'invention, on peut notamment citer les polyéthylènes basse densité (LDPE), les polyéthylènes haute densité (HDPE), et les polypropylènes.As polyolefins that may be used in the polymeric material according to the invention, low density polyethylenes (LDPE), high density polyethylenes (HDPE) and polypropylenes may especially be mentioned.

A titre d'exemples de métaux de transition utilisés dans les sels de métaux de transition contenus dans les matériaux polymériques oxo-biodégradables de l'invention, on peut notamment citer le fer, le manganèse, et le cobalt.As examples of transition metals used in the transition metal salts contained in the oxo-biodegradable polymeric materials of the invention, mention may notably be made of iron, manganese and cobalt.

De manière avantageuse, l'enveloppe des billes selon l'invention présente une épaisseur comprise entre 80 et 300 µm, de préférence entre 80 et 120 µm. De telles caractéristiques dimensionnelles conduisent à optimiser l'éclatement de la bille uniquement lors de son impact sur une cible.Advantageously, the casing of the balls according to the invention has a thickness of between 80 and 300 μm, preferably between 80 and 120 μm. Such dimensional characteristics lead to optimize the bursting of the ball only during its impact on a target.

Avantageusement, la composition de peinture marquante contenue dans la bille selon l'invention est aqueuse.Advantageously, the marking paint composition contained in the ball according to the invention is aqueous.

De préférence, la composition de peinture marquante contenue dans la bille selon l'invention contient 40 à 60% d'eau, 0 à 5% de substances colorantes et 20 à 40% de liant.Preferably, the marking paint composition contained in the ball according to the invention contains 40 to 60% water, 0 to 5% dyestuffs and 20 to 40% binder.

Une telle composition aqueuse présente des avantages relatifs à sa qualité environnementale d'une part et en termes de couts d'autres part, en raison d'une saturation aqueuse plus élevée.Such an aqueous composition has advantages relating to its environmental quality on the one hand and in terms of costs on the other hand, due to a higher aqueous saturation.

Selon un perfectionnement de la présente invention, la composition de peinture marquante contient en outre jusqu'à 5% de chlorure de sodium, afin d'éviter que la composition de peinture ne se fige lorsque la température devient négative.According to an improvement of the present invention, the marking paint composition further contains up to 5% sodium chloride, in order to avoid that the paint composition does not freeze when the temperature becomes negative.

La bille selon l'invention se prête également bien à une fabrication par thermoformage comme c'est le cas pour des billes dont l'enveloppe est en gélatine, mais avec un procédé considérablement simplifié ne nécessitant pas d'étape de séchage.The ball according to the invention also lends itself well to thermoforming as is the case for beads whose envelope is made of gelatin, but with a considerably simplified process that does not require a drying step.

Ainsi, la présente invention a également pour objet un procédé de fabrication d'une bille de peinture marquante comprenant une enveloppe contenant une composition de peinture marquante, comprenant les étapes suivantes:

  • la fourniture de deux films de matière semblable ;
  • la disposition de ces films dans une unité d'encapsulation comportant deux tambours de moulage, qui comprennent chacun un cylindre dans lequel est formée une pluralité de cavités hémisphériques, ces tambours étant disposés de manière à ce que leurs axes soient parallèles et leurs cylindres jointifs et les films défilant en continu dans l'unité d'encapsulation de manière à arriver de manière tangentielle sur les cylindres des tambours ;
  • la transformation des films en parties de capsule de forme sensiblement hémisphérique par rotation contrarotative des cylindres des tambours de moulage, et l'introduction simultanée de la composition de peinture marquante dans lesdites parties de capsule ;
  • la fermeture desdites parties de capsule pour former lesdites enveloppes remplies de composition de peinture marquante ;
ledit procédé étant caractérisé en ce que les films sont en matériau polymérique non hydrosoluble et oxo-biodégradable, et
en ce que préalablement à l'arrivée des films sur les cylindres des tambours, on chauffe les films à une température comprise entre 90 et 140°C.Thus, the present invention also relates to a method of manufacturing a marking paintball comprising an envelope containing a marking paint composition, comprising the following steps:
  • the supply of two films of similar material;
  • the arrangement of these films in an encapsulation unit comprising two molding drums, each of which comprises a cylinder in which is formed a plurality of hemispherical cavities, these drums being arranged so that their axes are parallel and their cylinders contiguous and the films continuously moving in the encapsulation unit so as to arrive tangentially on the cylinders of the drums;
  • transforming the films into capsule portions of substantially hemispherical shape by counter-rotating the rolls of the molding drums, and simultaneously introducing the marking paint composition into said capsule portions;
  • closing said capsule portions to form said envelopes filled with a striking paint composition;
said method being characterized in that the films are of non-water soluble and oxo-biodegradable polymeric material, and
in that prior to the arrival of the films on the rolls of the drums, the films are heated to a temperature of between 90 and 140 ° C.

Le procédé de l'invention est simplifié par rapport aux procédés existants classiquement utilisés pour la fabrication de billes en gélatine par suppression de l'étape de séchage. Cette étape est rendue inutile par le fait que la polyoléfine oxo-biodégradable présente, dès le refroidissement suivant le thermoformage, les propriétés mécaniques requises pour une utilisation de la bille dans des applications de type « paint-ball ».The process of the invention is simplified compared to existing methods conventionally used for the manufacture of gelatin beads by suppressing the drying step. This step is rendered unnecessary by the fact that the oxo-biodegradable polyolefin has, upon cooling after thermoforming, the mechanical properties required for use of the ball in "paint-ball" type applications.

De manière avantageuse, les films sont en polyoléfine oxo-biodégradable, et la température de chauffage de ces films, préalablement à leur arrivée sur les cylindres des tambours, est comprise entre 100 et 120°C.Advantageously, the films are made of oxo-biodegradable polyolefin, and the heating temperature of these films, prior to their arrival on the rolls of the drums, is between 100 and 120 ° C.

De préférence, on utilise comme films des feuilles en polyoléfine orientée, mono-axialement ou bi-axialement, qui permettent d'obtenir une tendance au retrait de l'enveloppe lors de son refroidissement, ce qui peut conduire à une précontrainte en pression à la bille. Cette précontrainte peut occasionner une rupture fragile de la bille lors de son impact.Polyolefin sheets which are orientated, mono-axially or bi-axially, are advantageously used as films, which make it possible to obtain a tendency to shrink the envelope during its cooling, which may lead to pressure prestressing at the same time. ball. This prestressing may cause a fragile rupture of the ball during its impact.

Avantageusement, le film de matériau polymérique oxo-biodégradable est une feuille multicouche comprenant une superposition de plusieurs monocouches obtenue par co-extrusion ou laminage.Advantageously, the film of oxo-biodegradable polymeric material is a multilayer film comprising a superposition of several monolayers obtained by coextrusion or rolling.

L'invention sera mieux comprise et d'autres particularités et avantages apparaîtront à la lecture de la description qui va suivre, la description faisant référence aux dessins annexés parmi lesquels :

  • la figure 1 est une vue en coupe d'une bille conforme à l'invention,
  • la figure 2 est une vue en coupe d'un dispositif utilisé pour la mise en oeuvre du procédé de fabrication de billes selon l'invention.
The invention will be better understood and other features and advantages will become apparent on reading the description which follows, the description referring to the appended drawings among which:
  • the figure 1 is a sectional view of a ball according to the invention,
  • the figure 2 is a sectional view of a device used for the implementation of the bead manufacturing method according to the invention.

On a représenté sur la figure 1 une bille 1 à peinture marquante conforme à l'invention, qui comporte une enveloppe 10 de forme sphérique et contenant une composition de peinture marquante 11.We have shown on the figure 1 a marking paint ball 1 according to the invention, which comprises a casing 10 of spherical shape and containing a marking paint composition 11.

Pour fabriquer des billes 1 conformes à l'invention, on utilise un dispositif 100 consistant en une unité d'encapsulation adaptée à la mise en oeuvre du procédé de l'invention, qui est représentée sur la figure 2. Dans ce dispositif 100, deux films 2, 3 de polyoléfine oxo-biodégradable sont placés en rouleaux sur le dispositif 100. Chaque film 2, 3 est déroulé, puis passe dans un four 101, 102 pour y être chauffé à une température comprise entre 100 et 120°C. Puis, chaque film 2, 3 arrive tangentiellement sur un tambour de moulage 111, 112 qui comprend un cylindre 1110, 1120 et des cavités hémisphériques 1111, 1112, chacune reliée à une source de vide (non représentée sur la figure 2). Les deux tambours 111, 112 sont disposés l'un à côté de l'autre avec des axes 1112, 1122 parallèles entre eux, et les tambours 111, 112 sont jointifs. Un prisme 4 rempli de composition de peinture marquante 11 est disposé juste au-dessus des tambours 111, 112, de manière à en recouvrir environ un quart de leur surface respective. Le prime 4 est muni, au niveau de sa partie inférieure, d'une pluralité d'orifices aptes à injecter la composition de peinture marquante 11 entre les deux films 2 et 3 lorsqu'ils sont placés sur leurs tambours respectifs 111, 112.In order to manufacture balls 1 according to the invention, a device 100 consisting of an encapsulation unit adapted to the implementation of the process of the invention, which is represented on FIG. figure 2 . In this device 100, two films 2, 3 of oxo-biodegradable polyolefin are placed in rolls on the device 100. Each film 2, 3 is unwound, then passes into a furnace 101, 102 to be heated to a temperature between 100 and 120 ° C. Then, each film 2, 3 arrives tangentially on a molding drum 111, 112 which comprises a cylinder 1110, 1120 and hemispherical cavities 1111, 1112, each connected to a vacuum source (not shown in FIG. figure 2 ). The two drums 111, 112 are arranged one beside the other with axes 1112, 1122 parallel to each other, and the drums 111, 112 are joined. A prism 4 filled with marking paint composition 11 is disposed just above the drums 111, 112, so as to cover about a quarter of their respective surface. The premium 4 is provided, at its lower part, with a plurality of orifices capable of injecting the striking paint composition 11 between the two films 2 and 3 when placed on their respective drums 111, 112.

Lorsque les films 2 3 rejoignent les tambours 111, 112 au niveau des cylindres 1110, 1120, ils sont aspirés dans chaque cavité 1111, 1121 et prennent leur forme hémisphérique. Puis, par la rotation contrarotative des cylindres 1110, 1120, les deux films 2, 3 sont réunis et la composition de peinture marquante 11 est injectée simultanément. Les portions hémisphériques, alors remplies de la composition de peinture marquante 11, sont soudées deux à deux pour former les billes 1 selon l'invention.When the films 23 join the drums 111, 112 at the cylinders 1110, 1120, they are sucked into each cavity 1111, 1121 and take their hemispherical form. Then, by the counter-rotating rotation of the rolls 1110, 1120, the two films 2, 3 are joined together and the marking paint composition 11 is injected simultaneously. The hemispherical portions, then filled with the marking paint composition 11, are welded two by two to form the balls 1 according to the invention.

Claims (13)

  1. Marking paint ball (1) comprising:
    - a shell (10) made of non-water-soluble polymer material and having a substantially spherical shape, and
    - a marking paint composition contained in said shell (10),
    characterised in that the shell (10) consists of an oxo-biodegradable polymer material.
  2. Ball according to claim 1, characterised in that the oxo-biodegradable polymer material is an oxo-biodegradable thermoplastic polymer.
  3. Ball according to claim 2, characterised in that the oxo-biodegradable thermoplastic polymer is an oxo-biodegradable polyolefin, preferably an oxo-biodegradable polyethylene.
  4. Ball according to any of the above claims, characterised in that the oxo-biodegradable polymer material comprises a synthetic polymer and at least one transition metal salt.
  5. Ball according to any of the above claims, characterised in that the shell (10) thickness is between 80 and 300 µm, preferably between 80 and 120 µm.
  6. Ball according to any of the above claims, characterised in that the marking paint composition (11) is water-based.
  7. Ball according to claim 6, characterised in that the marking paint composition (11) contains 40 to 60% water, 0 to 5% colouring substances and 20 to 40% binder.
  8. Ball according to claim 7, characterised in that the marking paint (11) further contains up to 5 % sodium chloride.
  9. Method for producing a marking paint ball (1) comprising a shell (10) containing a marking paint composition (11), comprising the following steps:
    - providing two films (2, 3) of similar material;
    - arranging said films (2, 3) in an encapsulation unit (100) comprising two moulding drums (111, 112), each comprising a cylinder (1110, 1120) wherein a plurality of hemispherical cavities (1111, 1121) are formed, said drums (111, 112) being arranged such that the axes (1112, 1122) thereof are parallel and the joined cylinders, said films (2, 3) feeding continuously in the encapsulation unit (11) so as to arrive tangentially on the drum cylinders (1110, 1120);
    - transforming the films (2, 3) into capsule portions having a substantial hemispherical shape by means of counter-rotating rotation of the moulding drum (111, 112) cylinders, and the simultaneous introduction of the marking paint composition (11) into said capsule portions; and
    - closing said capsule portions to form said shells (10) filled with marking paint composition (11), said method being characterised in that the films (2, 3) are made of oxo-biodegradable non-water-soluble polymer material, and
    in that, prior to the arrival of the films (2, 3) on the drum (111, 112) cylinders (1110, 1120), said films (2, 3) are heated to a temperature between 90 and 140°C.
  10. Method according to claim 9, characterised in that:
    - said films (2, 3) are made of oxo-biodegradable polyolefin, and
    - the heating temperature of said films (2, 3), is between 100 and 120°C.
  11. Method according to claim 10, characterised in that said films (2, 3) are sheets made of monoaxially or biaxially-oriented polyolefin.
  12. Method according to any of claims 9 to 11, characterised in that it is devoid of any drying process following the thermoforming of the hemispheres.
  13. Method according to any of claims 9 to 12, characterised in that the sheet of polymer material is a multi-layer sheet comprising a superposition of a plurality of single layers obtained by means of coextrusion or rolling.
EP08860824A 2007-09-21 2008-09-18 Marking paint ball and method for making same Active EP2195605B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0757747A FR2921474A1 (en) 2007-09-21 2007-09-21 MARKING PAINT BALL AND METHOD OF MANUFACTURING THE SAME
FR0854309A FR2921475B1 (en) 2007-09-21 2008-06-27 MARKING PAINT BALL AND METHOD OF MANUFACTURING THE SAME
PCT/FR2008/001310 WO2009074732A1 (en) 2007-09-21 2008-09-18 Marking paint ball and method for making same

Publications (2)

Publication Number Publication Date
EP2195605A1 EP2195605A1 (en) 2010-06-16
EP2195605B1 true EP2195605B1 (en) 2011-05-04

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EP08860824A Active EP2195605B1 (en) 2007-09-21 2008-09-18 Marking paint ball and method for making same

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US (1) US8342099B2 (en)
EP (1) EP2195605B1 (en)
AT (1) ATE508341T1 (en)
DE (1) DE602008006751D1 (en)
FR (2) FR2921474A1 (en)
PT (1) PT2195605E (en)
WO (1) WO2009074732A1 (en)

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Publication number Priority date Publication date Assignee Title
FR2993864B1 (en) * 2012-07-27 2015-04-24 Polytek Innovations METHOD AND MACHINE FOR FORMING CAPSULES CONTAINING FLUID.
FR3018268B1 (en) 2014-03-07 2016-03-11 Polytek Innovations METHOD AND SYSTEM FOR MANUFACTURING CAPSULE
US10184765B1 (en) * 2015-04-21 2019-01-22 Briana Gardell Throwable paint balls and method of manufacture
US11226183B1 (en) * 2015-04-21 2022-01-18 Mezzimatic LLC Throwable paint balls, kit, and method of manufacture
US20180156588A1 (en) * 2016-12-07 2018-06-07 Russell LeBlanc Frangible Projectile and Method of Manufacture
FR3107667A1 (en) * 2020-02-27 2021-09-03 Melchior Material And Life Science France UNIT DOSES FOR THE RELEASE OF AN AQUEOUS FORMULATION

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Publication number Priority date Publication date Assignee Title
BE630044A (en) * 1962-04-16 Energa
FR2034212A2 (en) * 1969-02-25 1970-12-11 France Etat Water colour marker released from crashed - aircraft
US5254379A (en) 1991-10-21 1993-10-19 Perfect Circle Paint Ball Inc. Paint ball
US5353712A (en) * 1991-12-31 1994-10-11 Olson Christy L Marking pellet gun and rigid, fracturable pellet therefor
US6574945B2 (en) * 2001-03-21 2003-06-10 Lumitek Llc Method for manufacturing a projectile containing chemiluminescent compounds
US20050217527A1 (en) * 2004-02-06 2005-10-06 Ciesiun Paul M Bioluminescent paintball
US20060005732A1 (en) * 2004-07-06 2006-01-12 Glenn Forster Blow-molded paintball and method of manufacture thereof
US7905181B2 (en) * 2005-02-05 2011-03-15 Ciesiun Paul M Bioluminescent paintball
US20060288898A1 (en) * 2005-06-24 2006-12-28 Sung Ho Byun Paintball
CA2659450A1 (en) 2006-08-03 2008-08-07 Dow Global Technologies Inc. New fill compositions and method for making the same
CA2623684A1 (en) * 2007-03-06 2008-09-06 X.O. Industries Inc. Spreader box apparatus and method of forming bi-laminar paintball shell material and paintballs for use with paintball gun

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US20100258024A1 (en) 2010-10-14
DE602008006751D1 (en) 2011-06-16
PT2195605E (en) 2011-08-18
ATE508341T1 (en) 2011-05-15
FR2921475B1 (en) 2009-11-20
FR2921474A1 (en) 2009-03-27
EP2195605A1 (en) 2010-06-16
WO2009074732A8 (en) 2010-05-06
FR2921475A1 (en) 2009-03-27
US8342099B2 (en) 2013-01-01
WO2009074732A1 (en) 2009-06-18

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