WO2013072644A2

WO2013072644A2 - Carbo vegetabilis additive for polymer matrix or similar

Info

Publication number: WO2013072644A2
Application number: PCT/FR2012/052657
Authority: WO
Inventors: Jean-Christophe LEGER
Original assignee: Leger Jean-Christophe
Priority date: 2011-11-17
Filing date: 2012-11-19
Publication date: 2013-05-23
Also published as: WO2013072644A3; FR2982869A1

Abstract

The present invention relates to a colouring additive suitable for dispersion in a matrix such as a plastic material, metal, glass, crystal, ceramic material, paint, silicones, plaster, cement, ink, dye, wax, or similar; said colouring additive is remarkable in that it is composed of at least a carbo vegetabilis powder having a granulometry between 0 and 400 μm. The invention also relates to, in particular, a plastic material comprising said colouring additive according to the invention, a master batch for making plastic parts, a master batch for making paints, inks, or similar, and a method for manufacturing foamed plastic parts or similar.

Description

VEGETABLE CHARCOAL POWDER ADDITIVE FOR MATRIX

POLYMER OR THE LIKE

TECHNICAL AREA

The present invention relates to additives for plastics, rubbers, inks, paints or the like, and more particularly to coloring additives. PRIOR ART

In the field of plastics and more particularly in the field of tires, it is well known to use as carbon black coloring filler. Carbon black is one of the amorphous and elemental forms of carbon or in the form of colloidal carbon. Carbon black is massively produced by the petroleum industry or carbochemistry by incomplete combustion of a small amount of vegetable oil and heavy petroleum products such as tar, coal tar or ethylene cracking tar. for example. The most commonly used processes for obtaining carbon black include the so-called "furnace" process, the so-called "channel" method or the plasma process in particular.

Referring to Figure 1, the carbon black is in the form of tiny spheres of carbon, usually in the form of aggregates of these spheres, whose dimensions are generally between 10 and 1000 nm. IUPAC according to the acronym "International Union of Pure and Applied Chemistry" defines carbon black as particles, nodules or aggregates having a size less than 1000 nm. Carbon black is converted into 0.1 to 1 mm granules to facilitate handling and reduce the formation of toxic dust.

The carbon black usually marketed as a coloring filler consists mainly of carbon and traces of aromatic compounds, hydrogen, oxygen, nitrogen and sulfur which are chemically bonded to carbon. The aromatic residues present in the carbon black are polycyclic aromatic hydrocarbons called PAHs and the carbon black also contains nitrates and sulfur-containing PAHs. In addition to the fact that carbon black is expensive, carbon black manufacturing processes produce a large amount of CO2, which is responsible for global warming.

In addition, carbon black poses public health problems. Its toxicity varies according to the diameter and the quantity of particles suspended in the air. Inhalation of carbon black causes irritation of the respiratory tract which may cause pulmonary clearance which may lead to cough, phlegm or chronic bronchitis. Prolonged skin contact with carbon black can cause dermatological problems. In addition, IARC considers that carbon black can be carcinogenic to humans.

In order to overcome this disadvantage, it has already been imagined to substitute carbon black with pulverized charcoal. This is particularly the case of international patent application WO 2005/098103 and US patent applications US 2009062433 and US 2003/157314.

WO 2005/098103 discloses a process for producing synthetic fiber containing charcoal with a high coal content of 5 to 30% by weight by mixing a synthetic resin, which can be converted into a fiber, such as polyester, polypropylene or nylon, with a charcoal powder having a particle size equal to or less than 15 μιη under vacuum to produce crystals in the form of granules, and the melt spinning of the crystals in the form of masterbatches or raw materials.

In order to allow compatibility with the synthetic resin, the process requires a surface treatment of the charcoal particles from a silane-based composition and thus the cost of the process. Moreover, the cohesion of the charcoal particles in the resin is bad.

US Patent Application 2009/062433 discloses a rubber composition simultaneously providing low heat generation and reinforcing properties simultaneously. This composition allows the realization of tires providing low fuel consumption, excellent durability, ease of machining and good surface properties. The rubber composition contains 100 parts by weight of a diene rubber component, 0.5 to 50 parts by weight of bagasse charcoal, having a BET surface area of 10 to 300 m 2 / g, and at least one part by weight of black carbon and silica. The total amount of bagasse charcoal, the black of carbon and silica is preferably from 30 to 100 parts by weight per 100 parts by weight of the diene rubber component.

This type of composition has the disadvantage of requiring the addition of carbon black, particularly toxic, and silica to allow a better compatibility of bagasse charcoal in the rubber.

US 2003/157314 discloses a porous high surface area composite comprising a polymeric material and one or more high surface area fillers. The high surface area fillers consist of carbonaceous materials, mineral and metal particles of high specific surface area such as, for example, Raney metals, rare earth oxides, porous ceramics, perlites, zeolites, clays. The carbonaceous materials may be in the form of powder and are obtained for example from petroleum pitch, phenolic resins, coconut shells and other organic products. A carbonaceous material that can be envisaged is activated carbon.

This type of composite has the disadvantage of requiring the inclusion of polyoxyethylene ensuring a binder function between the active carbon and the polymeric material.

There is therefore a need for a cheaper carbon black substitute product, not presenting a health risk and not requiring an adjuvant to ensure its cohesion in a matrix, such as a polymeric matrix or the like.

SUMMARY OF THE INVENTION

One of the aims of the invention is thus to remedy these drawbacks by proposing a dye additive intended to be dispersed in a matrix such as a plastic material, a rubber, a metal, glass, a crystal, a ceramic, paint, silicones, plaster, cement, ink, stain, polish or the like of simple manufacture which is inexpensive and does not present a risk to health.

For this purpose, and in accordance with the invention, there is provided a coloring additive intended to be dispersed in a matrix such as a plastic material, a rubber, a metal, glass, crystal, a ceramic, plaster, cement, silicones, paint, stain, ink, polish or the like; said additive is remarkable in that it consists of at least one vegetable charcoal powder whose granulometry is included between 0 and 400 μηι and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes.

It will be noted that the molecular structure in the form of parallel planes of polygons and / or in the form of ovoid tubes of the vegetable charcoal particles provides good cohesion of said plant charcoal particles in a matrix such as a plastic material, a rubber or a metal , glass, crystal, ceramics, plaster, cement, silicones, paint, stain, ink, polish or the like, without the need for an adjuvant.

The particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons for a particle size of between 0 and 40 μιη.

The particles of the vegetable charcoal powder have a molecular structure in the form of ovoid tubes for a particle size of between 200 and 400 μιη.

The particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes with a particle size of between 40 and 200 μιη.

The vegetable charcoal powder consists of charcoal powder.

The vegetable charcoal powder consists of charcoal powder obtained by pyrolysis of organic residues.

Another object of the invention relates to a plastic material for producing plastic parts by injection molding, extrusion, extrusion blow molding or extrusion inflation, containing at least one polymer and at least one dye additive which is remarkable in that it comprises at least one 0.2% by weight of a vegetable charcoal powder whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes.

The particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes with a particle size of between 40 and 200 μιη. The vegetable charcoal powder consists of charcoal powder.

The polymer is chosen from the following list of polymers: polycarbonate (PC), polyamide 6 (PA6), polylactic acid (PLA), polypropylene (PP), polyethylene (PE), polyesters block amide (PEBA) or a combination of these polymers .

Said plastic material comprises at least 6% by weight of a vegetable charcoal powder whose particle size is between 0 and 400 μιη to produce parts having a brushed metal appearance.

Alternatively said plastic material comprises at least 6% by weight of a vegetable charcoal powder whose particle size is between 200 and 400 μιη to produce foamed parts.

Another object of the invention relates to a masterbatch for the production of plastic parts by injection molding, extrusion, extrusion blow molding or inflation extrusion, from granules of at least one polymer, said masterbatch is remarkable in that it consists of granules comprising at least one polymer and at least 20% by weight of a vegetable charcoal powder whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes.

The particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons for a particle size of between 0 and 40 μπι.

Alternatively, the particles of the vegetable charcoal powder have a molecular structure in form for a particle size of between 200 and 400 μιη.

Alternatively, the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes for a particle size of between 40 and 200 μιη.

The vegetable charcoal powder consists of charcoal powder.

The polymer is chosen from the following list of polymers: polycarbonate (PC), polyamide 6 (PA6), polylactic acid (PLA), polypropylene (PP), polyethylene (PE), polyether amide block (PEBA) or a combination of these polymers . The granules comprise at least 60% by weight of a vegetable charcoal powder. Another subject of the invention relates to a masterbatch for the production of paints, dyes, liquid inks, or the like which is remarkable in that it consists of at least one liquid solvent and at least 30% by weight. a charcoal powder whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes.

Alternatively, the particles of the vegetable charcoal powder have a molecular structure in the form of ovoid tubes with a particle size of between 200 and 400 μm.

The vegetable charcoal powder consists of charcoal powder.

The vegetable charcoal powder consists of a coal powder obtained by pyrolysis of organic residues.

The solvent is selected from the list of the following solvents: water, aromatic hydrocarbons, esters, ketones, alcohols, glycol ethers or a combination of these solvents.

Said masterbatch comprises at least 60% by weight of a vegetable charcoal powder.

Another subject of the invention relates to a masterbatch for the production of plastic parts by injection molding, extrusion, extrusion blow molding or inflation extrusion, from granules of at least one polymer, and / or for the realization for the production of paints or liquid inks by dissolving in at least one solvent, said masterbatch is remarkable in that it consists of granules comprising at least 90% by weight of vegetable charcoal powder, whose particle size is between 0.degree. and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes, and at most 10% by weight of at least one binder. Said binder is chosen from the list of the following binders: starch, gum arabic, paraffin, potassium nitrate, milk casein or a combination of these binders.

Another object of the invention relates to a method of manufacturing a plastic part by injection molding comprising at least the following steps of:

introducing plastic granules into a feed screw, - heating the pellets in the worm to provide a plastic paste,

injection of the dough into a mold,

said process is remarkable in that the granules consist of at least one polymer and at least 6% by weight of a vegetable charcoal powder, the particle size of which is between 0 and 400 μιη and the molecular structure of which is in the form of parallel planes of polygons and / or in the form of ovoid tubes, and in that said granules are heated to form a viscous paste injected into the mold at an injection speed less than or equal to 25% of the standard injection speed in order to obtain a degassing of the carbon black particles providing foaming of the plastic part.

A final subject of the invention relates to a method of manufacturing a foamed plastic part remarkable in that it comprises at least the following steps: introduction of granules consisting of at least one polymer and at least 6% by weight a vegetable charcoal powder, the particle size of which is between 0 and 400 μm and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes, in a feed screw, heating pellets in the auger to provide a plastics paste without degassing the biobased carbon black particles, injecting the dough into a mold to make a plastic part

thermoforming the plastic part at a speed sufficiently low and at a sufficiently high temperature that the biobased carbon black particles degassed to provide foaming of the plastic part.

The dye additive according to the invention will find numerous applications, in particular for the manufacture of plastic objects, rubber paint, dyeing, cosmetics, inks, synthetic fibers for the production of textile parts, tires or waxing.

SUMMARY DESCRIPTION OF THE FIGURES

Other advantages and features will emerge more clearly from the following description of several variant embodiments, given by way of non-limiting example, of the additive colorant according to the invention, with reference to the appended drawings in which: FIG. 1 is an electron microscope view of carbon black particles of the prior art,

FIG. 2 is a diagrammatic representation of an injection device for molding plastic parts obtained from a polymer and the coloring additive according to the invention,

FIG. 3 is an electron microscope view of carbon black particles having a particle size of less than or equal to 40 μιη according to the invention,

FIG. 4 is an electron microscope view of carbon black particles having a particle size of between 40 and 200 μιη according to the invention,

FIG. 5 is an electron microscope view of carbon black particles having a particle size of between 200 and 400 μιη according to the invention,

FIG. 6 is a representation of the curve of the average viscosity index as a function of the percentage by weight of the dye additive according to the invention in polylactic acid, so-called PLA,

FIG. 7 is a representation of the curve of the average viscosity index as a function of the percentage by weight of the dye additive according to the invention in polypropylene (PP) for different particle sizes of said dye additive, FIG. 8 is a representation of the curve of the average viscosity index as a function of the percentage by weight of the dye additive according to the invention in polyamide (PA) for different particle sizes of the said color additive,

FIG. 9 is a graphical representation of the curve of the density as a function of the percentage by weight of the dye additive according to the invention in polylactic acid (PL A) for different particle sizes of said dye additive,

FIG. 10 is a graphical representation of the curve of the density as a function of the percentage by weight of the dye additive according to the invention in polypropylene (PP) for different particle sizes of said dye additive,

FIG. 11 is a graphical representation of the bending modulus curve as a function of the percentage by weight of the dye additive according to the invention in polylactic acid (PL A) for various particle sizes of said dye additive,

FIG. 12 is a graphical representation of the bending modulus curve as a function of the percentage by weight of the dye additive according to the invention in polypropylene (PP) for different particle sizes of said dye additive,

FIG. 13 is a graphical representation of the curve of flexural modulus as a function of the weight percentage of the dye additive according to the invention in polyamide (PA) for different particle sizes of said dye additive;

FIG. 14 is a graphical representation of the curve of the tensile modulus as a function of the percentage by weight of the dye additive according to the invention in polylactic acid (PL A) for different particle sizes of said color additive,

FIG. 15 is a graphical representation of the curve of the flexural modulus as a function of the percentage by weight of the dye additive according to the invention in polypropylene (PP) for different particle sizes of said dye additive,

FIG. 16 is a graphical representation of the curve of flexural modulus as a function of the percentage by weight of the dye additive according to the invention in polyamide (PA) for different particle sizes of said dye additive,

FIG. 17 is a graphical representation of the elongation at break curve expressed in% as a function of the percentage by weight of the dye additive according to the invention in polylactic acid (PLA) for different particle sizes of said dye additive; ,

FIG. 18 is a graphical representation of the elongation at break curve expressed in% as a function of the percentage by weight of the following color additive; the invention in polypropylene (PP) for different particle sizes of said color additive,

FIG. 19 is a graphical representation of the elongation at break curve expressed in% as a function of the percentage by weight of the dye additive according to the invention in polyamide (PA) for different particle sizes of said dye additive,

FIG. 20 is a graphical representation of the curve of the energy of rupture as a function of the percentage by weight of the dye additive according to the invention in polylactic acid (PL A) for different granulometries of said dye additive,

FIG. 21 is a graphical representation of the curve of the energy of rupture as a function of the percentage by weight of the dye additive according to the invention in polypropylene (PP) for different particle sizes of said dye additive,

FIG. 22 is a graphical representation of the curve of the energy of rupture as a function of the percentage by weight of the dye additive according to the invention in polyamide (PA) for different particle sizes of said dye additive;

FIG. 23 is a graphical representation of the attenuation curve of an electromagnetic wave as a function of the frequency of said wave for a 1.66 mm thick polycarbonate (PC) plate loaded with carbon black, prior art,

FIG. 24 is a graphical representation of the attenuation curve of an electromagnetic wave as a function of the frequency of said wave for a polyether block amide plate (PEBA) and for a polyamide plate with a thickness of 1, 60 mm respectively charged with a dye additive of 12% by weight with a particle size of between 40 and 80 μιη and with a dye additive of 20% by weight with a particle size of between 200 and 400 μιη,

FIG. 25 is a graphical representation of the change in heat flux as a function of the polylactic acid temperature loaded with a color additive according to the invention of 12% by weight with different particle sizes.

DETAILED DESCRIPTION OF THE INVENTION For the sake of clarity, in the rest of the invention, the same elements have been designated by the same references in the various figures. In addition, the various sectional views are not necessarily drawn to scale.

With reference to FIG. 2, the process for manufacturing colored plastic parts consists of introducing granules of a plastic material and a dye additive consisting of at least one vegetable charcoal powder made up of so-called biobased carbon black particles whose particle size is between 0 and 400 μιη and / or a master batch consisting of granules comprising at least one polymer and at least 20% by weight of a vegetable charcoal powder whose particle size is between 0 and 400 μιη, as will be further detailed in a hopper (1) feeding a worm (2) driven in rotation by a motor (3) and extending into a tube (4) heated by heating means (5) positioned along said tube (4). The plastic material is thus subjected to a mechanical treatment (compression and mixing) and a heat treatment (heating) providing a viscous and homogeneous paste which is pushed by the worm in rotation towards an outlet orifice (6). The viscous paste expelled through the orifice fills a mold (7) closed and cooled. In contact with the cold walls of the mold (7), the viscous paste cools and solidifies in the form of the mold (7). Said mold (7) then opens to eject the piece (8) thus produced.

It is obvious that the dye additive according to the invention may also be used in any other manufacturing process, well known to those skilled in the art, from thermoplastics such as, for example, in injection-blowing processes. extrusion, extrusion blow molding, extrusion-inflation, forming, thermoforming, expanding molding, calendering or rotational molding for example without departing from the scope of the invention.

The dye additive according to the invention consists of at least one vegetable charcoal powder whose particle size is between 0 and 400 μιη. Said vegetable charcoal powder consists of charcoal powder and / or coal powder obtained by pyrolysis of organic residues such as cut plants for example.

The particles of the vegetable charcoal powder have, with reference to FIG. 3, a molecular structure in the form of parallel planes of polygons with a particle size of between 0 and 40 μιη. These flakes of coal may have any polygonal shape such as a rectangular, triangular, hexagonal shape, etc. .. and have pores, the number and size of pores depending in particular on the wood species used in the manufacture of the charcoal powder and the part of the wood used (sapwood, bark, heart, etc. ...).

With reference to FIG. 4, the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes with a particle size of between 40 and 200 μιη.

With reference to FIG. 5, the particles of the vegetable charcoal powder have a molecular structure in the form of ovoid tubes with a particle size of between 200 and 400 μιη.

It will be noted that the charcoal powder may optionally comprise impurities, in a small quantity, resulting from the pyrolysis of the organic material, the impurities being of the calcium, magnesium, potassium or silicon type, etc.

The addition of the dye additive according to the invention in a plastic matrix such as a thermoplastic material, a thermosetting material or elastomers can be done without specific adjuvant and can improve the physical and / or chemical properties and / or biological materials of said plastics depending in particular on the particle size of the dye additive carbon particles and / or the percentage by weight of said dye additive introduced into the plastic matrix.

With reference to FIG. 6, it can be observed that the average viscosity index, referred to as mvi by the acronym "medium viscosity index", decreases when the percentage by weight of the coloring additive according to the invention increases, regardless of the particle size of the color additive introduced into the polylactic acid matrix (PLA). Said average viscosity index mvi is measured according to ISO 1133, that is to say by heating a sample at a temperature of 230 ° C. with a load of 3.8 kg. This reduction in the average viscosity index mvi is essentially marked for percentages by weight of between 0 and 10%, the average viscosity index mvi being substantially constant between 10 and 20% by weight of coloring additive additive. The addition of the dye additive according to the invention thus makes it possible to increase the viscosity of the PLA and the coloring additive can thus be introduced into polylactic acid in injection or extrusion processes in particular.

With reference to FIG. 7, it can be observed that the average viscosity index mvi, measured according to the ISO 1133 standard, decreases substantially linearly when the percentage by weight of the coloring additive according to the invention increases, whatever the particle size of the color additive introduced into the polypropylene (PP) matrix. Thus, the addition of the dye additive according to the invention makes it possible to increase the viscosity of polypropylene (PP).

In the same way as for polypropylene (PP), with reference to FIG. 8, it is observed that the average viscosity index mvi, measured according to the ISO 1133 standard, decreases substantially linearly when the percentage by weight of the coloring additive according to the invention increases and whatever the particle size of the dye additive introduced into the polyamide matrix (PA). Thus, the average viscosity index mvi is generally stable regardless of the charge and the particle size of the additive according to the invention, said average viscosity index mvi remaining in the range mvi injection and / or injection processes. 'extrusion. In this way, the addition of the additive according to the invention does not require any modification of the parameters of the injection and / or extrusion processes in particular, and whatever the concentration of said additive in polypropylene (PP ). This is valid for a majority of plastics.

However, for certain crystalline polymers such as PC, it will be observed that for a polycarbonate (PC) matrix, the average viscosity index mvi increases strongly, for a concentration of the additive according to the invention of between 5 and 10% and for particle size of said additive between 40 and 80 μιη and between 200 and 400 μιη, so that the polycarbonate becomes too liquid for injection and / or extrusion processes.

With reference to FIGS. 9 and 10, the density measured according to the ISO 1183 standard of polypropylene (PP) polylactic acid (PLA) compounds loaded with different percentages of biobased carbon black particles with particle sizes of between 0 and 40 μιη, between 40 and 80 μιη and between 200 and 400 μιη increases very slightly with the percentage of biobased carbon black particles. In fact, the carbon black particles according to the invention have a density of approximately 1.65 g / cm 3 which is greater than the density of polylactic acid (1.25 g / cm 3) and the density of polypropylene. (0.9 g / cm3).

With reference to FIG. 11, the bending modulus measured according to the ISO 178 standard increases substantially linearly as a function of the percentage of biobased carbon black particles introduced into a polylactic acid (PLA) matrix, whatever the particle size of said particles. particles. Thus, biobased carbon black particles according to the invention substantially rigid plastic parts obtained from polylactic acid loaded with carbon black particles according to the invention.

With reference to FIG. 12, the flexural modulus measured according to ISO 178 increases substantially linearly as a function of the percentage of biobased carbon black particles introduced into a polypropylene (PP) matrix, regardless of the particle size of said particles. Thus, the carbon black particles according to the invention substantially stiffen plastic parts obtained from polypropylene loaded with carbon black particles according to the invention.

With reference to FIG. 13, the bending modulus measured according to ISO 178 increases substantially linearly as a function of the percentage of biobased carbon black particles introduced into a polyamide (PA) matrix, for particle sizes of between 40 and 80 μιη and between 200 and 400 μιη, with the exception of the particle size of between 0 and 40 μιη. Thus, the carbon black particles according to the invention substantially stiffen plastic parts obtained from polyamide charged with carbon black particles according to the invention having a particle size greater than 40 μιη.

With reference to FIG. 14, the tensile modulus measured according to the ISO 527 standard increases substantially linearly as a function of the percentage of biobased carbon black particles introduced into a polylactic acid (PLA) matrix, regardless of the particle size of said particles. particles. Thus, the carbon black particles according to the invention substantially increase the resistance to elongation of plastic parts obtained in polylactic acid loaded with carbon black particles according to the invention, this increase in resistance being able to reach at 45% for a load of 20% by weight of carbon black particles having a particle size of between 0 and 40 μιη.

With reference to FIG. 15, the tensile modulus measured according to the ISO 527 standard increases substantially linearly as a function of the percentage of biobased carbon black particles introduced into a polypropylene (PP) matrix, whatever the particle size of said particles. Thus, the carbon black particles according to the invention substantially increase the resistance to elongation of plastic parts obtained in polypropylene loaded with carbon black particles according to the invention, this increase in resistance up to 72 % for a charge of 20% by weight of carbon black particles having a particle size of between 40 and 80 μιη.

With reference to FIG. 16, the tensile modulus measured according to the ISO 527 standard varies only very slightly regardless of the percentage by weight of the carbon black filler according to the invention having a particle size of between 0 and 40 μιη in a polyamide matrix (PA). On the other hand, said tensile modulus increases substantially linearly as a function of the percentage of biobased carbon black particles, having a particle size of between 40 and 80 μιη or a particle size of between 200 and 400 μιη, introduced into a polyamide matrix. Thus, the carbon black particles according to the invention having a particle size of between 40 and 80 μιη or a particle size of between 200 and 400 μιη substantially increase the resistance to elongation of plastic parts obtained in polypropylene loaded with black particles. According to the invention, this increase in resistance can reach up to 60% for a load of 20% by weight of biobased carbon black particles having a particle size of between 200 and 400 μιη.

With reference to FIG. 17, the elongation at break of samples obtained in polylactic acid (PLA) comprising different percentages by weight of a charge of carbon black particles according to the invention for different sizes. This elongation at break was measured in tensile tests according to ISO 527. The elongation at break of the PLA samples decreases substantially linearly when the weight percentage of the carbon black particles according to the invention increases. regardless of the particle size of said particles.

With reference to FIG. 18, for samples obtained in polypropylene (PP), it is found that the elongation at break increases when the percentage by weight of the biobased carbon black filler increases from 0% to about 8%. , then said elongation at break decreases from 8% by weight of the charge of particles of carbon black, regardless of the particle size. However, it will be observed that the larger the particle size, the greater the decrease in elongation at break.

With reference to FIG. 19, for samples obtained in polyamide (PA), it is found that the elongation at break decreases linearly when the percentage by weight of the charge of biobased carbon black particles increases from 0 to about 8. %>, whatever the particle size of the following carbon black particles the invention. At about 8%, the elongation at break is almost zero and it remains substantially zero up to a percentage by weight of 20% of the carbon black particles according to the invention. Thus, polyamide parts comprising a filler greater than or equal to 8% by weight of carbon black particles according to the invention have a very low resistance to elongation, the slightest deformation in elongation causing rupture of the parts.

Referring to Figure 20, Charpy impact bending tests were performed in accordance with ISO 179. For samples obtained in polylactic acid (PLA), there is a decrease in impact resistance when the percentage by weight of the charge of biobased carbon black particles increases regardless of the particle size of said particles.

In the same manner as above, with reference to FIG. 21, for samples obtained in polypropylene (PP), there is a decrease in impact resistance when the percentage by weight of the biobased carbon black particle charge increases. and whatever the particle size of said particles.

With reference to FIG. 22, for samples obtained in polyamide (PA), there is a decrease in the impact resistance when the percentage by weight of the charge of biobased carbon black particles increases for a particle size of the black particles. carbon between 0 and 40 μιη and for a particle size of between 200 and 400 μιη. For a particle size of said particles of biobased carbon black between 40 and 80 μιη, the impact resistance increases to a weight percentage of 8%, then it decreases when the percentage by weight of the charge of carbon black particles according to the invention increases.

Thus, besides the fact that the charge of carbon black particles according to the invention makes it possible to black color plastic parts, the quantity of particles as well as the particle size of these particles provide modifications of the mechanical characteristics of the plastics without the need for addition of other adjuvants.

In addition, the carbon black particles according to the invention also provide a significant increase in the hardness of the plastics in which they are introduced. The table below records the Shore D hardness values measured for polypropylene (PP) samples comprising 0.8, 12 and 20% by weight of a charge of biobased carbon black particles having a particle size between 40 and 80 μηι. Shore hardness measurements were made according to ISO 868 with a penetration type D durometer.

It thus appears that the carbon black particles according to the invention significantly improve, by about 16%, the shore hardness of polypropylene (PP) thus improving the scratch resistance of polypropylene, but also of polyethylene (PE), polylactic acid (PLA) and poly (n-butylacrylate) (PBAX). In general, biobased carbon black particles significantly improve the scratch resistance of all polymers.

In addition, the carbon black particles of the dye additive according to the invention exhibit adsorption properties of the gases so that said carbon black particles according to the invention allow, after integration into a plastic matrix in particular, significantly reduce emissions of volatile organic compounds known as VOCs, thus reducing the odors and toxicity of plastics. Indeed, the adsorption properties of the carbon black particles according to the invention makes it possible to reduce the emissions of volatile organic compounds (VOCs) below the regulatory exposure limit values (TLVs). These gas adsorption properties are also valid for rubbers, paints, inks, dyes, or cosmetic products in particular in which biobased carbon black particles are introduced, the biobased carbon black particles adsorbing the solvents. some products.

Moreover, the carbon black particles according to the invention provide modifications of the physical properties of the plastics into which they are introduced.

The surface resistivity varies in particular according to the percentage by weight of the carbon black particles according to the invention and the particle size of said particles as can be seen in the table below. 0-40 μιη 40-80 μηι 200-400 μηι

0% 8% 12% 20% 0% 8% 12% 20% 0% 8% 12% 20%

PLA 10 ^Λ 12 5.10 ^Λ 10 6.10 ^Λ 10 7.10 ^Λ 10 10 ^Λ 12 1.10 ^Λ 1 1 9.10 ^Λ 10 9.10 ^Λ 10 10 ^Λ 12 2.10 ^Λ 1 1 1.10 ^Λ 1 1 2.10 ^Λ 12

PC 2.10 ^Λ 16 2.10 ^Λ 1 1 2.10 ^Λ 1 1 No 2.10 ^Λ 16 No No No 2.10 ^Λ 16 2.10 ^Λ 1 1 No No

PA 4.10 ^Λ 1 1 5.10 ^Λ 10 6.10 ^Λ 10 7.10 ^Λ 10 4.10 ^Λ 1 1 2.10 ^Λ 1 1 6.10 ^Λ 10 8.10 ^Λ 10 4.10 ^Λ 1 1 2.10 ^Λ 1 1 2.10 ^Λ 1 1 2.10 ^Λ 1 1

PP 10 ^Λ 14 1.10 ^Λ 1 1 1.10 ^Λ 1 1 4.10 ^Λ 1 1 10 ^Λ 14 6.10 ^Λ 1 1 2.10 ^Λ 1 1 2.10 ^Λ 1 1 10 ^Λ 14 6.10 ^Λ 1 1 4.10 ^Λ 1 1 2.10 ^Λ 10

TPE 10 ^Λ 12 6.10 ^Λ 10 3.10 ^Λ 10 3.10 ^Λ 10 10 ^Λ 12 7.10 ^Λ 10 7.10 ^Λ 10 5.10 ^Λ 10 10 ^Λ 12 8.10 ^Λ 10 1.10 ^Λ 1 1 6.10 ^Λ 10

Despite their low conductivity, plastics loaded with carbon black particles according to the invention tend to conduct electrostatic charges, in the same way as metals, so that said plastics loaded with carbon black particles according to the invention. have anti-static properties.

Electrostatically charged paint spraying tests were carried out on plastic plates loaded with carbon black particles according to the invention, under the same conditions as for metal plates, and, despite a weak conduction of said plastic plates, the paint has correctly adhered to said plastic plates.

It is therefore possible to paint plastics loaded with carbon black particles according to the invention, without the addition of other additives and without the application of a primer attached to plastics, with electrostatically charged paints.

The adhesion and displacement properties of the electrostatic charges of the plastics charged with carbon black particles according to the invention thus make it possible, without prior treatment, to carry out electroplating or electroplating operations such as, for example, nickel plating, chromium plating, copper plating, tin plating, gilding, silver plating or the like.

With reference to FIGS. 23 and 24, the attenuation of a 1.6 mm thick polyamide (PA) plate loaded with 20% by weight of carbon black particles according to the invention having a particle size of between 200 and 400 μιη and a 1.6 mm thick PEBA sheet loaded with 12% by weight of carbon black particles according to the invention having a particle size of between 40 and 80 μιη (FIG. 24) is substantially similar to the attenuation of a polycarbonate (PC) plate having a thickness of 1.6 mm charged with carbon black of the prior art, said carbon black of the prior art having been selected for conduction. In addition, the addition of carbon black particles according to the invention in a plastic matrix such as polyamide (PA), polyethylene amide blocks (PEBA), polypropylene (PP), etc. does not modify the thermal behavior. during the cooling phase of the plastics whatever the particle size of the carbon black particles and regardless of the percentage by weight of said particles in said plastic.

However, with reference to FIG. 25, this lack of modification of the thermal behavior is not valid when the plastic matrix consists of polylactic acid (PLA). Indeed, as can be seen in the curves of Figure 25, the particle size between 200 and 400 μιη has a strong influence. Upon cooling, the crystallization temperature is increased by about 5 ° C so that the crystallinity of the PLA is increased and the amorphous portion of said PLA is decreased. Thus, it is possible to increase the so-called HdT load deflection temperature according to the acronym "Heat Distortion Temperature", that is to say the softening temperature of the PLA, by maintaining a temperature in the mold or at the outlet of the extrusion die close to the crystallization temperature of 91.5 ° C. of the PLA loaded with carbon black particles according to the invention.

Finally, it should be noted that a percentage by weight of 1.5% of carbon black particles according to the invention with a particle size of between 0 and 100 μιη is sufficient to provide a black coloration to the plastic matrix in which they are introduced. In addition, depending on the particle size, the percentage by weight of carbon black particles, but also as a function of the injection or extrusion temperature and the injection or extrusion speed, it is possible to obtain different types of surface effect such as glossy, varnished, matte, metallic, brushed metal, a surface providing good paint adhesion, including for plastics such as polypropylene (PP) or polyethylene (PE) for example, which traditionally do not allow sufficient adhesion of paints, etc ...

It will be noted that, for a smaller particle size, such as a particle size of between 0 and 40 μm, for example, a black coloration may be obtained with a percentage by weight of the carbon black particles according to the invention of less than 1.5%. , while the carbon blacks of the prior art stain black in the mass from 0.2 or 0.3% by weight.

It is obvious that the plastic matrix in which the carbon black particles according to the invention are introduced may consist of any material thermoplastic such as polycarbonate (PC), polyamide 6 (PA6), polylactic acid (PLA), polypropylene (PP), polyethylene (PE), polyether amide block (PEBA), polystyrene (PS), polyacetals or polyoxymethylene (POM) or polyvinyl chloride (PVC) for example, in any thermosetting plastic material such as polyurethanes (PUR), unsaturated polyesters, phenoplasts (PF) or aminoplasts (MF), epoxys by example, or else in elastomers and rubbers. It will be appreciated that the introduction of carbon black particles according to the invention into rubber significantly increases the anti-abrasive properties of the rubber with respect to the anti-abrasive properties of a carbon black filled rubber of the prior art.

In addition, the carbon black particles according to the invention may be introduced into any other type of solid or liquid matrix such as rubber, metal, glass, crystal, ceramic, paint, silicones, plaster, cement, ink, stain, polish or the like without departing from the scope of the invention.

Furthermore, the carbon black particles according to the invention allow the quick and easy manufacture of foamed plastic parts. The method of manufacturing such parts consists at least in the following steps of:

injection of the dough in a mold

The granules consist of at least one polymer and at least 6% by weight of a vegetable charcoal powder whose particle size is between 0 and 400 μιη and in that said granules are heated to form a viscous paste injected into the mold at an injection speed less than or equal to 25% of the injection speed of the unfilled plastic, in order to obtain a degassing of the carbon black particles providing foaming of the plastic part. In this way, the carbon black particles according to the invention degass and provide at the outlet of the extruder a viscous paste comprising gas bubbles, the number and size of these bubbles depending in particular on the particle size of the particles, the amount of particles introduced into the plastic matrix, the temperature and the extrusion rate. It will be observed that the slower the injection speed, the greater the concentration of carbon black particles according to the invention, the greater the particle size of the carbon black particles according to the invention and the higher the injection temperature. will be high, the more the foaming effect will be important.

It will be noted that the foaming process may also be used in the context of a thermoforming process. In this case, a first step consists in forming polymer plates loaded with at least 6% by weight of carbon particles according to the invention, said particles of carbon black having a particle size of between 0 and 400 μιη, such whereby said carbon black particles do not degass to prevent foaming. Then, the polymer plates loaded with carbon black particles according to the invention are thermo formed at a sufficiently low speed and at a sufficiently high temperature so that the carbon black particles according to the invention degassed to provide foaming parts. in plastic.

Another object of the invention relates to a masterbatch for the production of plastic parts by injection molding, extrusion, extrusion blow molding or inflation extrusion, from granules of at least one polymer. Said masterbatch consists of granules comprising at least one polymer and at least 20% by weight of a vegetable charcoal powder whose particle size is between 0 and 400 μιη. The particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons with a particle size of between 0 and 40 μιη, a molecular structure in the form of ovoid tubes with a particle size of between 200 and 400 μιη and a molecular structure. in the form of parallel planes of polygons and in the form of ovoid tubes for a particle size of between 40 and 200 μιη.

Said vegetable charcoal powder consists of charcoal powder and preferably in charcoal powder obtained by pyrolysis of organic residues.

Said polymer is chosen from the following list of polymers: polycarbonate (PC), polyamide 6 (PA6), polylactic acid (PLA), polypropylene (PP), polyethylene (PE), polyether amide block (PEBA) or a combination of these polymers .

The granules of the masterbatch preferably comprise at least 60% by weight of a vegetable charcoal powder.

Another subject of the invention relates to a masterbatch for the production of paints, dyes, liquid inks or the like consisting of at least one liquid solvent and at least 30% by weight of a vegetable charcoal powder whose granulometry is between 0 and 400 μιη. In the same way as above, the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons for a particle size of between 0 and 40 μιη, a molecular structure in the form of ovoid tubes with a particle size of between 200 and and 400 μιη and a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes for a particle size of between 40 and 200 μιη. Said vegetable charcoal powder consists of charcoal powder and preferably in charcoal powder obtained by pyrolysis of organic residues.

The solvent of the masterbatch is selected from the list of the following solvents: water, aromatic hydrocarbons, esters, ketones, alcohols, glycol ethers or a combination of these solvents.

In addition, the masterbatch comprises at least 60% by weight of a vegetable charcoal powder.

According to an alternative embodiment, the masterbatch for the production of plastic parts by injection molding, extrusion, extrusion blow molding or extrusion inflation, from granules of at least one polymer, and / or for the realization for the production of paints or liquid inks by dissolving in at least one solvent, can consist of granules comprising at least 90% by weight of vegetable charcoal powder whose particle size is between 0 and 400 μιη and at most 10% by weight of at least one binder. The particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons with a particle size of between 0 and 40 μιη, a molecular structure in the form of ovoid tubes with a particle size of between 200 and 400 μιη and a molecular structure. in the form of parallel planes of polygons and in the form of ovoid tubes for a particle size of between 40 and 200 μιη.

The binder is preferably selected from the list of the following binders: starch, gum arabic, paraffin, potassium nitrate, milk casein or a combination of these binders. Note that this type of binder allows a complete and rapid dissolution of biobased carbon black particles in the solid or liquid matrix without impairing the mechanical and physical properties of the end products.

Finally, it is obvious that the examples which we have just given are only particular illustrations in no way limiting as to the fields of application of the invention

Claims

1. Additive dye intended to be dispersed in a matrix such as plastic, rubber, metal, glass, crystal, ceramic, plaster, cement, silicones, paint, dye, ink, waxing or the like characterized in that it consists of at least one vegetable charcoal powder whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and or in the form of ovoid tubes.

2. dye additive according to claim 1 characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons for a particle size between 0 and 40 μιη.

3. dye additive according to claim 1 characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of ovoid tubes for a particle size of between 200 and 400 μιη.

4. dye additive according to claim 1 characterized in that the particles of the charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes for a particle size of between 40 and 200 μπι.

5. dye additive according to any one of claims 1 to 4 characterized in that the vegetable charcoal powder consists of charcoal powder.

6. dye additive according to any one of claims 1 to 4 characterized in that the vegetable charcoal powder consists of charcoal powder obtained by pyrolysis of organic residues.

7. Plastic material for producing plastic parts by injection molding, extrusion, extrusion blow molding or extrusion inflation, containing at least one polymer and at least one coloring additive characterized in that it comprises at least 0.2% by weight. mass of a charcoal powder whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes.

8. Plastic material for the production of plastic parts according to claim 7 characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons for a particle size between 0 and 40 μιη.

9. Plastic material for the production of plastic parts according to claim 7, characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of ovoid tubes for a particle size of between 200 and 400 μm.

10. Plastic material for the production of plastic parts according to the claim

Characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes for a particle size of between 40 and 200 μιη.

11. Plastic material for the production of plastic parts according to any one of claims 7 to 10 characterized in that the plant charcoal powder consists of charcoal powder.

12. Plastics material for producing plastic parts according to any one of claims 7 to 10, characterized in that the vegetable charcoal powder consists of charcoal powder obtained by pyrolysis of organic residues.

13. Plastic material for the production of plastic parts according to any one of claims 7 to 12 characterized in that the polymer is selected from the list of polymers according to: polycarbonate (PC), polyamide 6 (PA6), polylactic acid (PLA) ), polypropylene (PP), polyethylene (PE), amide block polyesters (PEBA) or a combination of these polymers.

14. Plastic material for the production of plastic parts according to any one of claims 7 to 13 characterized in that it comprises at least 6% by weight of a charcoal powder whose particle size is between 0 and 400 μιη to make pieces with a brushed metal appearance.

15. Plastics material for producing plastic parts according to any one of claims 7 to 13, characterized in that it comprises at least 6% by weight of a vegetable charcoal powder whose particle size is between 200 and 400 μm. to make foamed parts.

16. Master mix for producing plastic parts by injection molding, extrusion, extrusion blow molding or extrusion inflation, from granules of at least one polymer, characterized in that it consists of granules comprising at least one polymer and at least 20% by weight of a vegetable charcoal powder whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes.

17. Master blend according to claim 16 characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons for a particle size between 0 and 40 μιη.

18. master batch according to claim 16 characterized in that the particles of the charcoal powder have a molecular structure in the form of ovoid tubes for a particle size of between 200 and 400 μιη.

19. Master blend according to claim 16 characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes for a particle size between 40 and 200 μιη.

20. Master batch according to any one of claims 16 to 19, characterized in that the vegetable charcoal powder consists of charcoal powder.

21. Master batch according to any one of claims 16 to 19, characterized in that the vegetable charcoal powder consists of charcoal powder obtained by pyrolysis of organic residues.

22. Master mixture according to any one of claims 16 to 21, characterized in that the polymer is chosen from the following list of polymers: polycarbonate (PC), polyamide 6 (PA6), polylactic acid (PLA), polypropylene (PP) , polyethylene (PE), polyether amide block (PEBA) or a combination of these polymers.

23. Master batch according to any one of claims 16 to 22 characterized in that the granules comprise at least 60% by weight of a vegetable charcoal powder.

24. Masterbatch for the production of paints, dyes, liquid inks, or the like, characterized in that it consists of at least one liquid solvent and at least 30% by weight of a vegetable charcoal powder. whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes.

25. master batch according to claim 24 characterized in that the particles of the charcoal powder have a molecular structure in the form of parallel planes of polygons for a particle size between 0 and 40 μιη.

26. Master blend according to claim 24 characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of ovoid tubes for a particle size of between 200 and 400 μιη.

27. Master blend according to claim 24 characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes for a particle size of between 40 and 200 μπι.

28. Master batch according to any one of claims 24 to 27, characterized in that the vegetable charcoal powder consists of charcoal powder.

29. Master batch according to any one of claims 24 to 27, characterized in that the vegetable charcoal powder consists of a charcoal powder obtained by pyrolysis of organic residues.

30. Master mixture according to any one of claims 24 to 29, characterized in that the solvent is chosen from the list of the following solvents: water, aromatic hydrocarbons, esters, ketones, alcohols, glycol ethers or a combination of these solvents.

31. Master mixture according to any one of claims 24 to 30 characterized in that it comprises at least 60% by weight of a vegetable charcoal powder.

32. Master mix for the production of plastic parts by injection molding, extrusion, extrusion blow molding or extrusion inflation, from granules of at least one polymer, and / or for the realization for the production of paints or liquid inks by dissolution in at least one solvent, characterized in that it consists of granules comprising at least 90% by weight of vegetable charcoal powder whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of planes parallel polygons and / or form of ovoid tubes, and at most 10%> by weight of at least one binder.

33. Master mixture according to claim 32 characterized in that the binder is selected from the list of the following binders: starch, gum arabic, paraffin, potassium nitrate, milk casein or a combination of these binders.

34. The masterbatch according to claim 32, wherein the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons with a particle size of between 0 and 40 μιη.

35. master batch according to any one of claims 32 or 33 characterized in that the particles of the charcoal powder have a molecular structure in the form of ovoid tubes for a particle size of between 200 and 400 μιη.

36. A master batch according to claim 32 or 33, characterized in that the particles of the vegetable charcoal powder have a molecular structure in the form of parallel planes of polygons and in the form of ovoid tubes with a particle size of between 40 and 200 μm.

37. A method of manufacturing a plastic part by injection molding comprising at least the following stages of:

introducing plastic granules into a feed screw, heating the pellets in the auger to provide a plastic paste,

injection of the dough in a mold

characterized in that the granules consist of at least one polymer and at least 6% by weight of a vegetable charcoal powder whose particle size is between 0 and 400 μιη and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes, and in that said granules are heated to form a viscous paste injected into the mold at an injection speed less than or equal to 25% of the standard injection speed in order to obtain degassing the carbon black particles providing foaming of the plastic part.

38. A method of manufacturing a foamed plastic part characterized in that it comprises at least the following stages of:

introduction of granules consisting of at least one polymer and at least 6% by weight of a vegetable charcoal powder, the particle size of which is between 0 and 400 μm and whose molecular structure is in the form of parallel planes of polygons and / or in the form of ovoid tubes, in a feed screw, heating the pellets in the auger to provide a plastic paste without degassing the biobased carbon black particles, injecting the dough into a mold to make a plastic part

39. Application of the color additive according to any one of claims 1 to 6 to a plastic object.

40. Application of the color additive according to any one of claims 1 to 6 to a rubber object.

41. Application of the dye additive according to any one of claims 1 to 6 to a paint or a dye.

42. Application of the color additive according to any one of claims 1 to 6 to an ink.

43. Application of the dye additive according to any one of claims 1 to 6 to synthetic fibers for producing textile parts.

44. Application of the color additive according to any one of claims 1 to 6 to a polish.

45. Application of the color additive according to any one of claims 1 to 6 to a tire.